Unit 1-Solutions

Some important formulae of different methods of Concentrations:

%
1.Molality(M)= ( )
2. Molality(M)=

%
3.Normality(N)= . ( )
4.Normality (N) = .

5. molality (m) = 6. mole fraction (x2)= ; x1= ; x1+x2=1

Henry’s Law: Partial pressure of a gas in the solution is directly proportional to the mole fraction of
the gas in the solution.
PA= KH. x
 Higher the value of KH , lower is the solubility.
 Value of KH increases with increase in Temperature
Applications of Henry’s Law: a) Scuba divers carry oxygen cylinder which contains
b) Soda water bottle are filled with CO2 with high pressure.
c) People living at high altitude suffer with disease of anoxia.
Raoult’s Law: Partial pressure of a volatile liquid in the solution is directly proportional to its mole
fraction. PA= P0. xA Ptotal = PA + PB
Ideal & Non-ideal solution
Ideal solution Non- ideal solution
The solution which obeys raoult’s law The solution which does not obey raoults
law
∆ Hmix =0 ∆ Hmix =0
∆ Vmix =0 ∆ Vmix =0
The intermolecular force of attraction The intermolecular force of attraction
between liquid A & liquid B are equal between liquid A & liquid B is equal
before & after mixing are the same before & after mixing are not same.

Type of Non-ideal solutions:

a) Solutions showing positive deviation b) Solutions showing negative deviation
Solutions showing positive deviation Solutions showing negative deviation
∆ Hmix >0 ∆ Hmix <0
∆ Vmix >0 ∆ Vmix <0
The intermolecular force of attraction The intermolecular force of attraction
between molecules of liquid A & liquid between molecules of liquid A & liquid
B after mixing are weaker than before B after mixing are weaker than before
mixing mixing

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*** when the solution obtained by mixing two liquids becomes hot, that solution shows a negative
deviation.
*** when the solution obtained by mixing two liquids becomes cold, that solution shows a positive
deviation.

Azeotropes: it is a mixture of two liquids which at a particular composition shows constant boiling
point known as azeotropes.

Types of Azeotropes: a) Azeotropes showing minimum boiling point: Non-ideal

solutions with positive deviation form azeotropes showing minimum boiling point.

b) Azeotropes showing maximum boiling point: Non-ideal solutions with negative

deviation form azeotropes showing minimum boiling point.

Raoult’s Law for non-volatile solute: When a non-volatile solute is added to solvent, vapour
pressure of the solution decreases.
°
°
= x2 ; P0= V.P of solvent; Ps = v.p. of solution
°
°
= Relative lowering of V.P.

P0- Ps= lowering of V.P.

Colligative Properties: The properties which depend on the number of particles of solute are
known as colligative properties.

Colligative Properties : 1. Relative lowering of Vapour Pressure. :

° °
°
= x2 °
=

for dilute solution: n1+n2= n1

° °
then °
= : °
=

2. Elevation in Boiling Point:

∆Tb = Kb.m ; ∆Tb =Tb- Tb0
Tb0 = Boiling point of solvent; Tb= Boiling point of solution;
Kb= Molal elevation constant
𝐰𝟐𝐱 𝟏𝟎𝟎𝟎
∆Tb = Kb. 𝐌𝟐𝐱 𝐰𝟏

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 3. Depression in freezing point:

∆Tf = Kf.m : ∆Tf= Tf0 - Tf

Tf0 = freezing point of solvent; Tf= freezing point of solution;
Kf= molal cryoscopic constant

∆Tf = Kf

 Salt is sprayed over road to remove the snow from road as it decreases the
freezing point of water and it is easy to remove snow from road.
 Similarly ethylene glycol is added to radiator of car traveling in sub-zero
temperature zone.

4. Osmotic Pressure: it is the minimum excess pressure applied on the conc. solution to stop the
osmosis when the two solutions of different concentrations are separated by semipermeable
membrane known as osmotic pressure.
Depending on osmotic pressure the solutions are of 3 types
a) Isotonic solution: the solution of same osmotic pressure are called isotonic solutions. Eg. 0.9%
solution of NaCl is isotonic with R.B.C.
b) Hypertonic solution: The solution with higher osmotic pressure are known as hypertonic solution.
E.g. more than 0.9% NaCl solution is hypertonic with R.B.C.
c) Hypotonic solution: The solution with lower osmotic pressure are known as hypotonic solution. E.g.
less than 0.9% NaCl solution is hypertonic with R.B.C.
 When R.B.C. placed in Hypertonic solution; the RBC shrinks due to exosmosis.
 When R.B.C. placed in Hypotonic solution; the RBC bursts due to endosmosis.
 When R.B.C. placed in isotonic solution; the RBC remains intact.
Π= CRT ; C- molar concentration ; R – gas constant (0.0821 L atm/K/mol)

Π= RT ; Π= RT ; Π= RT

** The best method to determine the molecular mass of macro molecules through various colligative
properties is by using osmotic pressure as the colligative properties are inversely proportional to
molecular mass of solute.
a) The very small value of osmotic pressure can be measured as molecular mass of macro molecules is
very high
b) The osmotic pressure is measured at room temperature where as other two colligative properties
are not measured at room temperature

Van’t Hoff factor (i) it is the ratio of calculated molecular mass to the observed molecular mass.
i=

Van’t Hoff factor is used when solute (electrolyte) undergo either association or dissociation.
**If i> 1, then electrolyte undergo dissociation; i< 1 then electrolyte undergo association
i=1 neither association nor dissociation.
Degree of dissociation or association ( α) : it is the fraction of molecules undergo dissociation.
𝑵𝒐.𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒅𝒊𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒆𝒅𝒐𝒓 𝒂𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒆𝒅
Degree of dissociation (α )= 𝒕𝒐𝒕𝒂𝒍 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔
degree of dissociation (α)= ; where n= number of ions produced by an electrolyte .
e.g. for NaCl value of n is 2; CaCl2 n is 3

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 𝒏 (𝟏 𝒊)
Degree of association (α) = 𝒏 𝟏 for dimer n=2, trimer n=3
Q. Calculate the i for AlCl3 which undergo 70% dissociation.
Ans: AlCl3 Al+3 + 3 Cl-
n=4
(α)=
Α= 70/100= .70 ; .70= ; .70= ; 3*.70= i-1 ; 2.1=i-1 i= 2.1+1= 3.1

SECTION A ( MCQ TYPE)

1. One kilogram of sea water sample contains 6 mg of dissolved O2. The concentration of O2 in
ppm in the sample is
(a) 0.06 (b) 60 (c) 6 (d) 0.6
2. The value of Henry’s constant KH is _____________.
(a) greater for gases with higher solubility. (b) greater for gases with lower solubility.
(c) constant for all gases. (d) not related to the solubility of gases.
3. The vapour pressure, at a given temperature, of an ideal solution containing 0.2 mole of a non-
volatile solute and 0.8 mole of solvent is 60 mm of Hg. The vapour pressure of the pure solvent at
the same temperature is
(a) 150 mm of Hg (b) 60 mm of Hg (c) 75 mm of Hg (d) 120 mm of Hg
4. Which of the following statements is false
(a) Units of atmospheric pressure and osmotic pressure are the same.
(b) In reverse osmosis, solvent molecules move through a semipermeable membrane from a region of
lower concentration of solute to a region of higher concentration.
(c) The value of molal depression constant depends on nature of solvent.
(d) Relative lowering of vapour pressure, is a dimensionless quantity
5. The value of van’t Hoff factor for ethanoic acid in benzene is
(a) 1.0 (b) 1.5 (c) 0.5 (d) 2
6. Consider the figure and mark the correct option.
a) water will move from side (A) to side (B) if a pressure lower than
osmotic pressure is applied on piston (B).
(b) water will move from side (B) to side (A) if a pressure greater
than osmotic pressure is applied on piston (B).
(c) water will move from side (B) to side (A) if a pressure equal to
osmotic pressure is applied on piston (B).
(d) water will move from side (A) to side (B) if pressure equal to
osmotic pressure is applied on piston (A)
7. We have three aqueous solutions of NaCl labelled as ‘A’, ‘B’ and ‘C’ with concentrations 0.1 M,
0.01 M and 0.001 M, respectively. The value of van’t Hoff factor for these solutions will be in the
order ___________.
(a) iA < iB < iC (b) iA > iB > iC (c) iA = iB = iC (d) iA < iB > iC
8. The van’t Hoff factor (i) for a dilute aqueous solution of the strong electrolyte barium
hydroxide is
(a) 0 (b) 1 (c) 2 (d) 3
9. What is the mass percentage of carbon tetrachloride if 22g of benzene is dissolved in 122g of
carbon tetrachloride?
(a) 84.72% (b) 15.28 % (c) 50% (d) 44%
10. Which of the following 0.10 M aqueous solution will have the lowest freezing point?
(a) Al2(SO4 )3 (b)C5H10 O 5 (c) KI (d)C12H22O11
Answer Key

Q.N. 1 2 3 4 5 6 7 8 9 10
Ans c b c b c b b d b a

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 Section B (ASSERTION REASON TYPE QUESTIONS)
In the following questions, two statements are given—one labelled Assertion (A) and the other labelled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given
below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation
of the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement.
1. Assertion (A) : The boiling point of 0.1 M urea solution is less than that of 0.1 M KCl solution.
Reason (R) : Elevation of boiling point is directly proportional to the number of species present in the
solution.
2. Assertion (A) : Non-ideal solutions always form azeotropes.
Reason (R) : Boiling point of an azeotrope may be higher or lower than boiling points of both
components
3. Assertion (A) : If one component of a solution obeys Raoult’s law over a certain range of composition,
the other component will not obey Henry’s law in that range.
Reason (R) : Raoult’s law is a special case of Henry’s law
4. Assertion : If a liquid solute more volatile than the solvent is added to the solvent, the vapour
pressure of the solution may increase i.e., Ps > Po.
Reason : In the presence of a more volatile liquid solute, only the solute will form the vapours and
solvent will not.
5. Assertion : When methyl alcohol is added to water, boiling point of water increases.
Reason : When a volatile solute is added to a volatile solvent elevation in boiling point is observed.
Answer Key

Q.N. 1 2 3 4 5
Ans a b b c b

SECTION C (2 MARKS QUESTIONS)

1. How is it that measurement of osmotic pressures is more widely used for determining molar
masses of macromolecules than the elevation in boiling point or depression in freezing point of
their solutions?
Ans. because (i) Osmotic pressure is measured at the room temperature and the molarity of solution is
used instead of molality.
(ii) Compared to other colligative properties, its magnitude is large even for very dilute solutions.
2.(a) Out of two 0.1 molal aqueous solutions of glucose and of potassium chloride, which one will
have a higher boiling point and why?
Ans. 0.1 m KCl solution will have higher boiling point as KCl dissociates in the solution.
b) What will happen to freezing point of a potassium iodide aqueous solution when mercuric
iodide is added to solution?
Ans. HgI2 + 2KI K2HgI4 Mercuric iodide forms a complex with potassium iodide, therefore, the
number of solute particles (KI) in the solution decreases resulting in the decrease in the value of ∆Tf ,
i.e., depression in the freezing point. As a result, the freezing point (Tf = T f o + ∆Tf) of the solution will
increase.
3. (a) Why is an increase in temperature observed on mixing chloroform and acetone?
Ans. The bonds between chloroform molecules and molecules of acetone are dipole-dipole interactions
but on mixing, the chloroform and acetone molecules, they start forming hydrogen bonds which are
stronger bonds resulting in the release of energy. This gives rise to an increase in temperature.
(b) Why does sodium chloride solution freeze at a lower temperature than water?
Ans. When a non-volatile solute is dissolved in a solvent, the vapour pressure decreases. As a result, the
solvent freezes at a lower temperature.

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4. (a)Gas (A) is more soluble in water than Gas (B) at the same temperature. Which one of the two
gases will have the higher value of KH (Henry’s constant) and why?
Ans. According to Henry’s law, p = KH x, i.e., higher the value of KH lower is the solubility of the gas in the
liquid. Therefore, Gas B will have higher value of KH than gas A.
(b) Which of the following aqueous solutions should have the highest boiling point?
Solution A 1.0 M NaOH , Solution B 1.0 M Na2SO4, Solution C 1.0 M NH4NO3, Solution d 1.0 M KNO3
Ans. Solution B as it produced more number of particles.
5. a) Why do gases always tend to be less soluble in liquids as the temperature is raised?
Ans. With the increase in temperature, value of KH increases, the solubility of gases decreases
b) why do aquatic animal feel comfort in winter as compared to summer?
Ans. As the solubility of gases decreases with increase in temperature, so in summer less oxygen is
dissolved in water as compared to winter. That’s why the aquatic animals feel comfort in winter as
compared to summer.
6. When 1.5 g of a non-volatile solute was dissolved in 90 g of benzene, the boiling point of
benzene raised from 353.23 K to 353.93 K. Calculate the molar mass of the solute. (Kb for
benzene = 2.52 K kg mol–1)
Ans. ∆Tb = 353.93 K – 353.23 K = 0.7 K
Substituting WB = 1.5 g, WA = 90 g, ∆Tb = 0.7 K, Kb = 2.52 K kg mol–1 in the expression,
. .
∆Tb = Kb ; 0.7 = :; on solving the value of M2= 60 g/mol
7. Give reasons: (a) Cooking is faster in pressure cooker than in cooking pan.
Ans. The use of pressure cooker reduces cooking time because the weight over the lid does not allow the
steam to go out. As a result, pressure inside the cooker becomes high. Higher the pressure, higher is
the boiling point and faster is the cooking
(b) Red Blood Cells (RBC) shrink when placed in saline water but swell in distilled water.
Ans. As the concentration of saline solution is higher than the concentration inside the cell. Thus water
will move outside the cytoplasm and the cell will shrink while, distilled water is hypotonic, when
RBCs are placed in distilled water, water will enter the cell through simple diffusion and lead to cell.
8. The dissolution of ammonium chloride in water is an endothermic process but still it dissolves
in water readily. Why?
Ans. This is because of entropy change. In this case, ∆S is +ve. NH4Cl(aq) NH4 + (aq) + Cl– (aq) The
ions that were held together in crystalline solid are free and moving in all possible directions. Its
entropy has increased and this makes T∆S > ∆H, i.e., ∆G = –ve.
9. Explain why the depression in freezing point of water observed for the same amount of acetic
acid, tri-chloroacetic acid and trifluoroacetic acid increases in the order as given CH3COOH <
Cl3CCOOH < F3CCOOH.
Ans. The depression in freezing point is the order of CH3COOH < Cl3CCOOH < F3CCOOH.
because Fluorine, being the most electronegative, has the highest negative inductive effect. As a
result of this, trifluoroacetic acid is the strongest acid while acetic acid is the weakest acid. Hence,
trifluoroacetic acid ionises to the largest extent while acetic acid ionises to the minimum extent to
give ions in their solutions in water. Greater the ions produced, greater is the depression in freezing
point. Hence, the depression in freezing point is the maximum for the trifluoroacetic acid and
minimum for acetic acid
10. (a) Why is an increase in temperature observed on mixing chloroform and acetone?
Ans. The bonds between chloroform molecules and molecules of acetone are dipole-dipole interactions
but on mixing, the chloroform and acetone molecules, they start forming hydrogen bonds which are
stronger bonds resulting in the release of energy. This gives rise to an increase in temperature.
(b) Why does sodium chloride solution freeze at a lower temperature than water?
Ans. When a non-volatile solute is dissolved in a solvent, the vapour pressure decreases. As a result, the
solvent freezes at a lower temperature.

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 SECTION D (3 Marks Questions)
1. Benzene and toluene form ideal solution over the entire range of composition. The vapour
pressures of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg respectively.
Calculate the mole fraction of benzene in the vapour phase if 80 g of benzene is mixed with 100 g of
toluene.
Ans. Molar mass of benzene (C6H6) = 78 g mol–1 ; Molar mass of toluene (C7H8) = 92 g mol–1
V.P of Benzene (P01) = 50.71 mm Hg ; V.P of toluene (P02) = 32.06 mm Hg
n1(C6H6) = = 1.026 mol ; n2(C7H8) = = 1.087 ;
total number of moles ( n1 + n2) = 1.026+1.087= 2.113
.
x1 = . = .486 ; x2 = 1-0.486= .514
P1= P01 x1 = 50.71x .486= 24.65 mm Hg
Ptotal = P01 x1 + P20 x2 = 50.71x .486 + 32.06 x .514 = 41.13 mm Hg
.
Y1 = = .
= .60
2. When 1.5 g of a non-volatile solute was dissolved in 90 g of benzene, the boiling point of
benzene raised from 353.23 K to 353.93 K. Calculate the molar mass of the solute. (Kb for
benzene = 2.52 K kg mol–1)
Ans. ∆Tb = 353.93 K – 353.23 K = 0.7 K
W2 = 1.5 g, W1 = 90 g, ∆Tb = 0.7 K, Kb = 2.52 K kg mol–1
M2= ∆
, substituting the values in the formula we get M2 = 60 g mol–1
3. A solution of glucose (Molar mass = 180 g mol–1) in water has a boiling point of 100.20°C.
Calculate the freezing point of the same solution. Molal constants for water Kf and Kb are 1.86
K kg mol–1 and 0.512 K kg mol–1 respectively.
Ans. ∆Tb = 100.20°C – 100°C = 0.20°C or 0.20 K
∆ .
∆Tb = Kb . m ⇒ m = =. = .39 mol/kg
∆Tf = Kf . m = 1.86 x .39= .725 K
∆Tf = Tf0- Tf ⇒ Tf= Tf0- ∆Tf
Tf = 273.15 K – 0.725 K = 272.425 K
4. 3.9 g of benzoic acid dissolved in 49 g of benzene shows a depression in freezing point of 1.62 K.
Calculate the van’t Hoff factor and predict the nature of solute (associated or dissociated).
(Given: Molar mass of benzoic acid = 122 g mol–1, Kf for benzene = 4.9 K kg mol–1)
Ans. W2 = 3.9 g, W1 = 49 g, ∆Tf = 1.62 K, Kf = 4.9 K kg mol–1
∆Tf = , substituting the values in the formula we get i = .507
As the value of i < 1 so the solute undergoes association
5. A solution containing 1.9 g per 100 mL of KCl (M = 74.5 g mol–1) is isotonic with a solution
containing 3 g per 100 mL of urea (M = 60 g mol–1). Calculate the degree of dissociation of KCl
solution. Assume that both the solutions have same temperature
Ans. Isotonic solutions are those solutions which have the same osmotic pressure. If the osmotic
pressures are equal at the same temperature, concentrations must also be equal. So,
For non-electrolyte Urea; 𝛱 = CRT For electrolyte KCl; 𝛱 = i CRT Thus,
C urea RT =iCKCl RT = C urea = iCKCl
C urea = = 0.5 M
.
C KCl = .
= .25 M
C urea = iC KCl = .50 = i x .25 i= 2
Now, KCl K +Cl
+ –

0.25 0 0
0.25 – α α α
Total moles after dissociation = 0 .25 – α + α + α = = 0 .25 + α

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 i=
.
i= .
α= 2X .25 - .25 = .25 i.e 25%
6. Given alongside is the sketch of a plant for
carrying out a process. (i) Name the process
occurring in the given plant.
(ii) To which container does the net flow of
solvent take place?
(iii) Name one SPM which can be used in this
plant.
(iv) Give one practical use of the plant.
Ans. (i) Reverse osmosis. (ii) Fresh water container. (iii) Cellulose acetate placed on a suitable support.
(iv) Desalination of sea water.
7. a) On mixing liquid X and liquid Y, volume of the resulting solution decreases. What type of
deviation from Raoult’s law is shown by the resulting solution? What change in temperature
would you observe after mixing liquids X and Y?
Ans. The solution will show negative deviation from Raoult’s law. The temperature will rise.
What happens when we place the blood cell in water (hypotonic solution)? Give reason
Ans. Due to osmosis water enters into the cell and blood cell will swell.
8. Why is an increase in temperature observed on mixing chloroform and acetone?
Ans. (a) The bonds between chloroform molecules and molecules of acetone are dipole-dipole
interactions but on mixing, the chloroform and acetone molecules, they start forming hydrogen
bonds which are stronger bonds resulting in the release of energy. This gives rise to an increase in
temperature.
(b) Why does sodium chloride solution freeze at a lower temperature than water?
(b) When a non-volatile solute is dissolved in a solvent, the vapour pressure decreases. As a result, the
solvent freezes at a lower temperature.
9. State Henry’s law. Write its one application. What is the effect of temperature on solubility of
gases in liquid?
Ans. It states that the partial pressure of a gas in vapour phase (p) is proportional to the mole fraction of
the gas (x) in the solution. p ∝ x or p = KH x where KH is the Henry’s constant.
Application of Henry’s law: To increase the solubility of CO2 in soft drinks and soda water, the
bottle is sealed under high pressure.
Effect of temperature on solubility: As dissolution is an exothermic process, therefore, according
to Le Chatelier’s principle solubility should decrease with rise in temperature
10. Give reason for the following:
a) glycol and water mixture used in car radiators in cold countries
Ans. Ethylene glycol lowers the freezing point of water. Due to this, coolant in radiators will not freeze.
b) The vapour pressure of a solution of glucose in water is lower than that of water
Ans. This is due to decrease in the escaping tendency of the water molecules from the surface of solution
as some of the surface area is occupied by non-volatile solute, glucose particles.
c) ) Red Blood Cells (RBC) shrink when placed in saline water but swell in distilled water
Ans. As the concentration of saline solution is higher than the concentration inside the cell. Thus water
will move outside the cytoplasm and the cell will shrink while, distilled water is hypotonic, when
RBCs are placed in distilled water, water will enter the cell through simple diffusion and lead to cell
swelling.
SECTION D(5 MARKS QUESTIONS)
1. (a) A solution containing 15 g urea (molar mass = 60 g mol–1) per litre of solution in water has the same
osmotic pressure (isotonic) as a solution of glucose (molar mass = 180 g mol–l) in water. Calculate the mass of
glucose present in one litre of its solution.

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Ans 𝑤2 = 15 g, M2 (urea)= 60 g/mol M2 (glucose)= 180 g/mol ; w2 (glucose)= ?
Π (urea)= RT ; Π (glucose)= RT for isotonic solutions
Π (urea) = Π (glucose)
=
w2 (glucose) = 45 g
b) What type of deviation is shown by a mixture of ethanol and acetone? What type of azeotrope is formed
by mixing ethanol and acetone?
Ans. A mixture of ethanol and acetone shows positive deviation and the azeotrope formed by this mixture is
minimum boiling azeotrope.
2. a) Define the following terms:
(i) Abnormal molar mass (ii) van’t Hoff factor
Ans. (i) When the molar mass of a substance determined by using any of the colligative properties comes
out to be different than the theoretically expected molar mass, the substance said to show abnormal
molar mass.
(ii) van’t Hoff factor. It may be defined as the ratio of observed colligative property to calculated
colligative property. It gives the extent of association or dissociation of the solute particles in the
solution
b) Write two differences between a solution showing positive deviation and a solution showing
negative deviation from Raoult’s law.
Solutions showing positive deviation Solutions showing negative deviation
∆ Hmixing >0 ∆ Hmixing <0
∆ Vmixing >0 ∆ Vmixing <0
The intermolecular force of attraction The intermolecular force of attraction
between molecules of liquid A & between molecules of liquid A &
liquid B after mixing are weaker liquid B after mixing are weaker
than before mixing than before mixing

SECTION E (CASE STUDY BASED QUESTIONS)

1. Observe the graph between mole fraction of HCl gas dissolved in cyclohexane Vs equilibrium pressure
of HCl(g) and answer the questions based on graph.
(a) Which law is depicted by this graph?
Ans. Henry’s law.
(b) What is mathematical expression for Henry’s law?
Ans. Pgas = KH .Xgas Where Pgas = Partial pressure of gas X gas = Mole
fraction of gas KH = Henry’s law constant
(c) What does slope represent?
Ans. Slope = KH, Henry’s law constant.
(d) What is effect of temperature and pressure on
solubility of gas in liquid?
Ans. Solubility of gas in liquid increase with increase in pressure. Solubility of gas in liquid increase with
decrease in temperature.

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(e) Name two factors which affect the value of KH?
Ans. (i) Nature of gas (ii) Temperature
2. . Observe the table in which azeotropic mixtures are given along with their boiling points of pure
components and azeotropes and answer the questions that follow.

(a) What type of deviation is shown by minimum boiling azeotropes?

Ans. Positive deviation from Raoult’s law.
(b) Why does H2O and HCl mixture form maximum boiling azeotropes?
Ans. It is because force of attraction between H2O and HCl is more than H2O—H2O and HCl—HCl.
(c) How can be separate azeotropic mixture?
Ans. Azeotropic distillation. Add benzene to water and ethanol, all three will get separated.
(d) Give one example of ideal solution. What type of liquids form ideal solutions?
Ans. Hexane and heptane form ideal solution. Those compounds of same family having similar forces of
attraction form ideal solution.
(e) What are azeotropes?
Ans. These are constant boiling mixtures which distill out unchanged in their composition.

Unit 2-ELECTROCHEMISTRY
1.Electrochemistry is the branch of chemistry which deals with the relationship between electrical
energy and chemical energy and inter-conversion of one form into another.
2. An electrochemical cell consists of two metallic electrodes dipped in electrolytic solutions. The cells
are of two types:
(a) Electrolytic cells (b) Galvanic cells
3. A galvanic cell consists of two half cells. Each half cell contains an electrolytic solution and a metallic
electrode. The electrode at which- oxidation takes place is called an anode and the electrode at which
reduction takes place is called the cathode. The half-cells are separated from each other by means of a
porous pot or a salt bridge.
4. The passage of current from one electrode to the other indicates the existence of potential
difference between them. This difference of potential which causes current to flow from the electrode of
higher negative potential is called the electromotive force (emf).
5. Electrical energy = Emf (volts) x Quantity of electricity (coulombs)
6. The potential of SHE is assigned an arbitrary value of zero. E° = 0 V. It is used as a reference electrode
for measuring the standard electrode potentials. .
7. When the elements are arranged in order of their standard electrode potentials, a series known as
electrochemical series is obtained.
8. Standard emf of a cell,
E0cell =E0cathode – E0node = E0Riglit – E0Left
9. ΔG° = -nFE0cell
If E0cell is positive, ΔG° would be negative and reaction would be spontaneous. If E0cell is
negative, ΔG° would be positive and the reaction would be non-spontaneous.
10. A species with higher standard reduction potential has greater tendency to accept electrons to
undergo reduction or vice versa.
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11. The potential of an electrode in contact with its ions in solution varies with the concentration of
the ion. Thus, for a redox reaction,

Mn+ + ne- → M(s), Nernst equation E = E0Mn+/M + ln[Mn+]

12. For an electrochemical cell for which the overall reaction is
aA + bB↔ cC + dD
. [ ] [ ]
Ecell = E0cell - log[ ] [ ]
, At 298 K , 2.303RT/nF = 0.0591/n
. [ ] [ ]
So the equation becomes Ecell = E0cell - log[ ] [ ]

13. The equilibrium constant of cell can be relate to standard emf of cell
.
E0cell = logKc =0.059/n log Kc at 298 K ; ∆G0 = -nFE0cell = -2.303 RTlogKc
14. Resistance is the measure of obstruction to the flow of current.
R∞ l/A ; R =Sxl /A

where S = specific resistance or resistivity. Unit of R is ohm.

15. Resistivity is defined as the resistance of a conductor of 1cm length and having an area of cross-
section equal to 1cm2.
unit of resistivity is ohm-cm
16. Conductance is reciprocal of resistance, i. e.,
Unit of conductance is ohm-1 or mho or Siemen(S).
17. Specific conductance Λsp is reciprocal of specific resistance.
Λsp = 1/S = l/RA
Specific conductance is thus defined as the conductance of a solution taken in a cell whose electrodes are
at unit distance apart from each other and each having an area equal to 1 cm2. Unit of specific
conductance is ohm-1 cm-1 or S cm-1.
18. Molar conductance (Λm) is defined as the conductance of the volume of solution which contains one
mole of the solute and is placed between two parallel electrodes which are one centimetre apart and
having sufficient area to hold the whole of the solution.
Unit of molar conductance is Ω-1 cm2 mol-1 or S cm2 mol-1
19.Λm = 1000/C x Λsp
where C = concentration of solution in moles per litre (or Molarity).
20. The electrical conductance through metals decreases with increase in temperature.
21. The electrolytic conductance increases with increase of temperature.
22. Effect of Dilution on
(а) Equivalent conductance: The value of equivalent conductance increase with dilution and attains a
maximum value at infinite dilution.
(b) Specific conductance: The value of specific conductance decreases with dilution as the number of
current carrying particles i.e., ions present per cm3 of solution decreases on dilution.
(c) Molar conductance: The value of molar conductance increases with dilution and finally attains a
maximum value at infinite dilution.
23. Variation of molar conductance with concentration:
(a) Strong electrolytes:
Conductance at infinite dilution (Λ m∞) , Λ m = Λ m∞ when C→ 0,

The variation of Λ m with concentration is given by Λ m = Λ m∞ - b√C ( b = constant )

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B) Weak electrolytes : The variation of Λ m with √C is very large and so much so that we can not obtain
molar conductance at infinite dilution (Λ m∞) by extrapolation of the Λ m vs √C plots.
24. According to Kohlrausch law of independent migration of ions, the limiting molar conductivity of
an electrolyte can be expressed as the sum of the contributions of the cation and the anion of the
electrolyte. Λ 0 = 𝜐 + 𝜆 +0 + 𝜐 - 𝜆 -0
where v+, v– are the number of cat ions and anions per unit formula of the electrolyte respectively; λ0+,
and λ0– are the limiting molar conductivities of the cation and anion respectively.
25. Faraday’s laws of electrolysis:
(a) First law: The amount of a substance deposited or liberated at an electrode is directly proportional
to the quantity of electricity passed through the electrolyte. Mathematically,
Q∞ It, m= Zit, I = current in amperes, t= time in sec. Z cont. called electrochemical equivalent.
where m = mass of substance deposited or liberated.
Mass of substance A deposited or liberated Mass of substance B deposited or liberated current in
amperes t = time in seconds, and Z = constant called electrochemical equivalent.
(b) Second law: When the same quantity of electricity is passed through solutions of different
electrolytes, the weight of different substances deposited or liberated at the respective electrodes are
proportional to their chemical equivalent weights.
26.Equivalent weight of metal = Atomic mass of metal / Number of electrons required to reduce to
cation to metal.
27. The charge on one mole of electrons is approximately equal to 96500 coulombs. This quantity of
electricity is called Faraday constant (F).
28. A battery consists of two or more galvanic cells connected in series. There are two kinds of batteries:
(a) Primary batteries: In primary batteries, when the reactants have been converted into
products, no more electricity is produced. The cell reaction cannot be reversed and the battery becomes
dead.
(b) Secondary batteries: In secondary batteries (or cells), the cell reaction can be reversed by passing
electricity through the battery (charging). It means that the battery can be used again and again through
a large number of discharging and charging cycles.
29. The most common example of secondary battery is the lead storage battery.
30. Electrical cells that are discharged to convert the energy from the combustion of fuels (hydrogen,
carbon monoxide, methane, etc.) directly into the electrical energy are called fuel cells.
31. The corrosion of metals is an electrochemical process. It occurs in presence of water and oxygen
(present in the environment)
32. Prevention of corrosion : oiling, painting, galvanisation, sacrificial protection, Making alloy.
33. Galvanisation : Making the coating of zinc over the articles of iron in order to prevent corrosion.

Questions :
A. MULTIPLE CHOICE QUESTIONS ( 1 MARK EACH) :
1. Which of the following is not a good conductor ?
a) Cu metal b) NaCl (aq) c) NaCl (molten) d) NaCl (s)
2. The SI units of molar conductivity are :
a) S m2 mol-1 b) S m-1 mol-1 c) S m-2 mol d) S m2 mol-1
3. For a redox reaction to proceed in a cell , the e.m.f. must be :
a) positive b) negative c) zero d) fixed

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4. Which of the following statements is incorrect about electrochemical cell ?
a) Electrons are released at anode.
b) Chemical energy is converted into electrical energy.
c) Salt bridge maintains the electrical neutrality of the electrolytes.
d) Cell can work infinitely.
5. In a galvanic cell, which one of the following statements is not correct ?
a) Anode is negatively charged. b) Cathode is positively charged.
c) Reduction takes place at the anode. d) Reduction takes place at the cathode.
6. For the electrode reaction - Mn+ (aq) + ne- → M (s)
Nernst equation is :
a) E = E0 + RT/ nF log 1/[Mn+} b) E0 = E + RT ln [ Mn+}
c) E = E0 + RT/nF ln [Mn+] d) E/E0 = RT/nF ln [ Mn+]
7. Rust is a mixture of :
a) FeO and Fe(OH)3 b) FeO and Fe(OH)2
c) Fe2O3 and Fe(OH)3 d) Fe3O4 and Fe(OH)3
8. When lead storage battery discharges :
a) SO2 is evolved b) PbSO4 is consumed c) Lead is formed d) H2SO4 is consumed
9. Electrode potential data are given below
Fe3+ (aq) + e- → Fe2+ (aq) ; E0 = + 0.77V
Al3+ (aq) + 3e- → Al (s) ; E0 = - 1.66V
Br2 (aq) + 2e- → 2 Br- (aq) ; E0 = + 1.08 V
Based on the data , the reducing power of Fe2+ , Al and Br – will increase in the order
a) Br - ‹ Fe2+ ‹ Al b) Fe2+ ‹ Al ‹ Br - c) Al ‹ Br - ‹ Fe2+ d) Al ‹ Fe2+ ‹ Br –
10. In the cell reaction
Cu (s) + 2Ag+(aq) → Cu2+ (aq) + 2Ag (s)
E0 cell = 0.46 V. By doubling the concentration of Cu2+ , Ecell is :
a) Doubled b) Halved c) Unchanged d) Decreased by small fraction.

Answer:
1. (d) 2. (a) 3. (a) 4. (d) 5. (c) 6. (c) 7. (c) 8. (d) 9. (a) 10. (d)

B. Assertion reason based questions :

The questions given below consist of an Assertion and a Reason. Use the following key to choose the
appropriate answer.
a) If both assertion and reason are CORRECT, and reason is the CORRECT explanation of the assertion.
b) If both assertion and reason are CORRECT, but reason is NOT THE CORRECT explanation of the
assertion.
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c) If assertion is CORRECT, but reason is INCORRECT .
d) If assertion is INCORRECT, but reason is CORRECT .
1. Assertion : Equivalent conductance of all electrolytes decreases with increasing concentration.
Reason : Lesser number of ions are available per gram equivalent at higher concentration.
2. Assertion: Iron is protected from corrosion by connecting magnesium metal with it.
Reason : Iron acts as a cathode and magnesium as anode which gradually disappears.
3. Assertion : Zinc can liberate H2 from aqueous solution of HCl.
Reason : Zinc has +ve reduction potential.
4. Assertion : In electrolysis, the quantity of electricity needed for depositing 1 mole of silver is different
from that , required for 1 mole of copper.
Reason : The molecular weight of silver and copper are different.
5. Assertion : For a cell reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) : at the equilibrium, voltmeter
gives zero reading.
Reason : At the equilibrium, there is no change in the concentration of Cu2+ and Zn2+ ion.

Answer : 1. (c) 2. (a) 3. (c) 4.(b) 5. (a)

C. VERY SHORT ANSWER TYPE QUESTIONS : (2 MARKS EACH)
1. Define the following terms with units : a) Conductivity b) Molar Conductivity.
2. What is the function of salt bridge in an electrochemical cell ?
3. Distinguish between electromotive force and potential difference.
4. In a simple electrochemical cell, the half cell reaction with their standard electrode potentials are :
Pb(s) – 2e - → Pb2+(aq) ; E0 = - 0.13V
Ag(s) – e - → Ag+(aq) ; E0 = + 0.80V
Which of the following reactions take place ? Also calculate the e.m.f. of the cell :
i) Pb2+(aq) + 2Ag(s) → 2Ag+(aq) + Pb(s) ii) Pb2+(aq) + Ag(s) → Ag+(aq) + Pb(s)
iii) Ag+(aq) + Pb(s) → Ag(s) + Pb2+(aq) iv) 2Ag+(aq) + Pb(s)→ 2Ag(s) + Pb2+(aq)
5. How does conductivity and molar conductivity vary with concentration? Give reasons for their
variations.
6. What are fuel cells? Discuss H2- O2 fuel cell. List some advantages of fuel cells over other cells.
7.Depict the galvanic cell in which the following reaction takes place: Zn(s) + 2Ag+(aq) → Zn2+ (aq) +
2Ag(s) . Also write which of the electrodes is negatively charged?
8. Can we store:
i) CuSO4 solution in zinc vessel?
ii) FeSO4 solution in silver vessel? Give suitable explanation in support of your answer.
9. Calculate e.m.f of the cell at 298 K
Zn/Zn2+ (0.01M)// Cd2+ (0.01M)/ Cd ; Given E0(Zn2+/Zn) = -0.76V, E0(Cd2+/Cd) = -0.40V
10. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5amperes. What is the mass of
copper deposited at the cathode?

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Answer :
1. Conductivity of an electrolytic solution can be defined as the conductance of a solution of 1 cm length
with area of cross section equal to 1 cm2 . , SI Unit : S m-1
Molar conductivity of an electrolyte solution can be defined as the conducting power of all the ions
produced by dissolving one gram mole of the electrolyte placed between two electrodes at one
centimeter apart. SI Unit : S m2 mol-1.
2. a) Salt bridge completes the electrical circuit.
b) Salt bridge maintains the electrical neutrality of two half cell solutions.
3. E.M.F Potential difference
1. It is the potential difference between It is the potential difference between the
the two electrodes when no current is two electrodes when the cell is sending
flowing in the circuit. current through the circuit.
2. It is the maximum voltage obtainable It is less than the maximum voltage
from the cell. obtainable from the cell.
3. The work calculated from e.m.f. is the The work calculated from potential
maximum work obtainable from the cell. difference is less than the maximum work
obtainable from the cell.
4. It is responsible for the flow of steady It is not responsible for the flow of steady
current in the cell. current in the cell.
4. i) Pb2+(aq) + 2Ag(s) → 2Ag+(aq) + Pb(s)
E0cell = E0cathode – E0anode = 0.13 – (-0.80) = 0.93 V
5. Conductivity decreases with the decrease in concentration, this is because the number of ions per unit
volume that carry the current in the solution decreases on dilution.
Molar conductivity increases with the decrease in concentration or increase in dilution. This is because
the total volume of solution containing one mole of electrolyte increases with increase in dilution. It has
been found that the decrease in 𝜅 on dilution of a solution is more than compensated by increase in its
volume.
6. Fuel Cells : These are voltaic cells in which the reactants are continuously supplied to the electrodes.
These are designed to convert the energy from the combustion of fuels such as H2, CO, CH4 etc. directly
into electrical energy.
H2-O2 Fuel cell: In this cell H2 & O2 are bubbled through a porous C electrode into Conc NaOH or KOH . H2
is fed into anode for oxidation and O2 is fed into cathode for reduction. Anode: 2[H2(g) + 2OH-
(aq)→2H2O(l) + 2e- ]
Cathode: O2(g) + 2H2O(l) + 4e- → 4OH-(aq) ; OVERALL : 2H2(g) + O2(g) → 2H2O (l)
Advantages : i) High efficiency ii) Continuous source of energy iii) Pollution free working.
7. Zn/Zn2+(aq)//Ag+(aq)/Ag ; Anode [Zn/Zn2+(aq)]
8. CuSO4 solution can’t be stored in zinc vessel. Because Zn + Cu2+ → Zn2+ + Cu
FeSO4 solution can be stored in silver vessel because Fe2+ does not react with Ag.
9. E0cell = E0cathode – E0anode = - 0.40 – (- 0.76) = 0.36 V ; Ecell = E0cell – 0.059/2 log [zn2+/Cd2+] at 298 K = 0.36
– 0.059/2 log0.01/0.01 = 0.36 V
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10. I = 1.5A, t = 10x60=600sec, Q = Ixt =1.5 A x 600s = 900C, Cu is deposited as Cu2+ + 2 e - → Cu(s) ; 2 mol
of electrons or 2x 96500C of current deposit copper= 63.56g; 900 C of current will deposit copper =
.
x 900 = 0.296g

D. SHORT ANSWER TYPE QUESTIONS : ( EACH CARRIES 3 MARKS )

1. a) Write the statement of Kohlrausch’s law of independent migration of ions.
b) The molar conductivity at infinite dilution for HCl, KCl and CH2ClCOOK are 4.26 x 10-2 , 1.50 x 10-2 and
1.13 x 10-2Sm2mol-1 respectively. Calculate the molar conductivity at infinite dilution for CH2ClCOOH.
2.Calculate the potential for half-cell containing 0.10M K2Cr2O7(aq), 0.20M Cr3+(aq) and 1.0 X 10 -4 M
H+(aq). The half cell reaction is Cr2O72- (aq) + 14 H+(aq) + 6 e- →2 Cr3+ (aq) + 7 H2O (l) and the
standard electrode potential is given as E0 = 1.33V .
3. a) Write Faraday’s first law of electrolysis.
b) Calculate how long it will take to deposit 1.0 g of chromium when a current of 1.25A flows through a
solution of chromium (III) sulphate. ( Molar mass of Cr = 52g ).
4.Predict the products of electrolysis in each of the following :
a) An aqueous solution of AgNO3 with silver electrode. b) An aqueous solution of AgNO3 with platinum
electrode. c) An aqueous solution of CuCl2 with platinum electrode.
5. Predict if the reaction between the following is feasible : i) Fe3+ (aq) and I- (aq)
ii) Ag+ (aq) and Cu(s) iii) Ag(s) and Fe3+ (aq) ; Given standard electrode potentials : E01/2 I2/I- = 0.54 V,
E01/2 Cu2+/Cu = 0.34 V, E01/2 Ag+/Ag= 0.80 V, E01/2 Fe3+/Fe2+ = 0.77 V.
6. Cu2+ + 2e- → Cu E0 = + 0.34 V ; Ag+ + e_ → Ag E0 = + 0.80 V
i) Construct a galvanic cell using the above data.
ii) For what concentration of Ag+ ions will the e.m.f. of the cell be zero at 250C if the concentration of Cu2+
is 0.01M ? ( log 3.919 = 0.593)
7. What is corrosion ? Explain the sacrificial protection of metals from corrosion.
8. Write cell reactions which occur in lead storage battery
i) When battery is in use ii) When the battery is on charging
9. Write Nernst equation for the cell in which the following reaction takes place :
2 Fe3+(aq) + 2 I- (aq) → 2 Fe2+ (aq) + I2 (s) ; Given E0cell = 0.236 V at 298 K. Calculate the standard Gibbs
energy and the equilibrium constant of the cell reaction. ( Antilog 7.983 = 9.62 x 107 )
10. Explain how rusting of iron is envisaged as setting up of an electrochemical cell.

Answer :
1.a) It states that the limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte. b) Λ0CH2ClCOOH = Λ0CH2ClCOOK + Λ0HCl -
Λ0KCl = 1.13 x 10-2 + 4.26 x 10-2 – 1.50 x 10-2 = 3.89 x 10-2 S m2 mol-1
2. For half cell reaction, Cr2O72-(aq) + 14H+(aq) + 6e-→ 2Cr3+(aq) + 7H2O(l)
[ ] . ( . )
Ecell = E0cell – 0.059/n log[ ][ ]
= 1.33V - log( . )( )
= 1.33V – 0.059/6 log(4x1055)
= 1.33V – 0.059/6 [log4 + log1055] = 1.33 V – 0.059/6 [2log2 + 55log10] = 1.33V – 0.059/6 [2x 0.3 +55]
= 1.33V – 0.548V = 0.782V
16 | P a g e
3. a) Faraday’s 1st law of electrolysis : The amount of any substance deposited or liberated at any electrode
is directly proportional to the quantity of electricity passed through the electrolytic solution.
b) Cr3+ + 3e- → Cr(s); 3mol or 3x 96500 C of electricity are needed to deposit 1 mol or 52 g of Cr ; 52 g Cr
require current = 3x 96500 C ; 1g Cr will require current = 3x96500/52 C = 5567.3 C , as
Q = It , so t = 5567.3C / 1.25A = 4453.8s = 1.24 hr.
4. a) AgNO3(s) + nH2O → Ag+ (aq) + NO3- (aq) ; H2O ↔ H+ + OH- Cathode : Ag+ ions have lower discharge
potential than H+ ions. So Ag+ will deposit as Ag. Anode : As Ag electrode is attacked by NO3- ions, Ag
anode will dissolve to form Ag+ in solution.
b) Cathode : Same as above.
Anode : Since Ag is not attacked, out of OH- and NO3- , OH- has lower discharge potential and so OH- will
be discharged, These OH- will produce O2 OH-(aq)→ OH + e- ; 4OH → 2 H2O(l) + O2 (g)
c) CuCl2(s) + water → Cu2+ (aq) + 2Cl- (aq); H2O → H+ + OH-
Cathode : Cu2+ will reduce in preference to H+ Cu2+ + 2e- → Cu
Anode : Cl – will be oxidised in preference to OH- ions ; Cl- → Cl + e- ; Cl + Cl → Cl2 , Copper will deposit on
cathode and Cl2 gas liberates from anode.
5. A reaction is feasible if EMF of the cell is positive.
i) Fe3+ (aq) + I – (aq) → Fe2+ (aq) +1/2 I 2 ; E0cell = E0 (Fe3+/Fe2+) - E0 (1/2 I2 /I - ) = 0.77- 0.54 = 0.23 V ,
Reaction is feasible.
ii) 2Ag+(aq) + Cu(s) → 2 Ag(s) + Cu2+ (aq) ; E0cell = E0 (Ag+/Ag) - E0 (Cu2+ /Cu ) =0.80 – 0.34 = 0.46 V ,
Feasible.
iii) Ag(s) + Fe3+(aq) → Ag+(aq) + Fe2+(aq) , E0cell = E0 ( Fe3+/Fe2+) - E0 (Ag+/Ag) = 0.77- 0.80 = -0.03V ,
Reaction is not feasible.
6. Cu/Cu2+//Ag+/Ag , Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s);
[ ]
E0cell = 0.80 – 0.34 = 0.46 V ; Ecell = E0cell - 0.059/2 log[ ]
,
.
As E0cell = 0, 0 = 0.46V -0.059/2 log ,
0.46V = 0.059/2 [log10-2 – 2logx], 0.46x2/0.059 = -2-2logx ,
-2logx =17.6, log x = -8.8 , x = 10-8.8 , [Ag] = 10 -8.8 M
7. Corrosion is a process of deterioration of a metal as a result of its reaction with air or water
(environment) surrounding it.
Sacrificial protection : In this method iron is protected from rusting by covering it with a layer of a metal
more active than iron. This prevents loss of electrons from iron. The active metal loses electrons in
preference to iron. So the covering metal is consumed with time but as long as it is present on the surface
of iron, the later is not rusted. This process of protection of iron from corrosion is known as sacrificial
protection. Iron can be coated with zinc or tin etc. In case of zinc coating, iron can be prevented even if
the coating of zinc gets any scratch, because zinc oxidises in preference to iron if both are exposed which
is not possible in case of the coating of tin, because iron oxidises in preference to tin.
8. When lead storage battery is in use : Anode : Pb(s) →Pb2+(aq) + 2e-
Pb2+(aq) + SO42-(aq) → PbSO4(s) : The overall anode reaction: Pb(s) + SO42- (aq) → PbSO4(s) + 2e-
Cathode : PbO2(s) + 4H+ +2e- → Pb2+(aq) + 2H2O
Pb2+(aq) + SO42_(aq) → PbSO4(s) ;
The overall cathode reaction is : PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- → PbSO4 (s) + 2H2O (l)
Thus the complete reaction is : Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
Recharging the battery : 2PbSO4(s) + 2H2O(l) → Pb(s) + PbO2(s) + 2H2SO4(aq)
17 | P a g e
 . [ ]
9. Ecell = E0cell - log[ ] [ ]

E0cell = 0.236 V ; ∆G0 = -nFE0 , n= 2, F = 96500C, ∆G0 = 2 x (96500C) x (0.236V) = - 45548 J = - 45.55 kJ ; ∆r
.
G0 = -2.303RT log Kc ; log Kc = - .
=𝑥 = . .
= 7.983 ;
Kc = antilog (7.983 ) = 9.62 x 107
10. Water layer present on the surface of iron (particularly during rainy season ) dissolves acidic oxides
present in air such as CO2, SO2 etc. to form acids which dissociate to give H+ ions : H2O + CO2 → H2CO3 ↔
2H+ + CO32- ; In the presence of H+ ions, iron starts losing electrons at a particular spot of iron object to
form ferrous ions. Therefore, oxidation takes place and that spot behaves as anode. Fe(s) → Fe2+ (aq) +
2e- ; The electrons released at anodic spot move through the metal to reach another spot where H+ ions
and the dissolved oxygen take up these electrons and reduction takes place. Hence this spot behaves as
cathode : O2(g) + 4H+ (aq) + 4e- → 2 H2O (l) , The overall reaction is : 2Fe(s) + O2(g) + 4H+(aq) → 2
Fe2+(aq) + 2H2O(l) ; Thus, an electrochemical cell sets up on the surface. Ferrous ions are further oxidised
by atmospheric oxygen to ferric ions which combine with water molecules to form hydrated ferric ions
which combine with water molecules to form hydrated ferric oxide, Fe2O3.xH2O , which is rust.

D. LONG ANSWER TYPE QUESTIONS : (5 MARKS EACH)

1.Consider the figure given below and answer the following questions :

a) Write the direction of electron flow. b) Is silver plate anode or cathode ?

c) What will happen if salt bridge is removed ? d) When will the cell stop functioning ?
e) How will concentrations of Zn2+ and Ag+ ions be affected when the cell functions and when it becomes
dead ?
2. At 291 K , the molar conductivities at infinite dilution of NH4Cl , NaOH and NaCl are 129.8 , 217.4 and
108.9 S cm2 mol -1 respectively. If the molar conductivity of a centinormal solution of NH4OH is 9.33 S cm2
mol -1 , what is the percentage dissociation of NH4OH at this dilution ? Also calculate the dissociation
constant of NH4OH.
Answer :
1. a) Electrons move from Zn to Ag, b) Cathode c) Cell will stop functioning d) If Ecell becomes zero e)
Concentration of Zn2+ will increase and concentration of Ag+ will decrease when cell functions but at
equilibrium state concentration of ions will remain unchanged.
2. Λ0m for NH4OH = 𝜆 0NH4+ + 𝜆 0OH- = Λ 0m (NH4Cl) + Λ0m(NaOH) - Λ0m(NaCl) = [129.8 + 217.4 -108.9 ] S
cm2 mol-1 = 238.3 S cm2 mol-1 , Degree of dissociation 𝛼 = Λcm / Λ0m = 9.33/238.3 = 0.0392 ; %
dissociation = 0.0392 x 100 = 3.92% ;
NH4OH ↔ NH4+ + OH-
Initial Conc. C 0 0
Equilibrium conc. C-c𝛼 c𝛼 c𝛼
( . )( . ) ( . )
K= ( )
= .
= .
= 1.599 x 10-5

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E . CASE BASED QUESTIONS :
Read the following passage and answer the given questions :
PASSAGE -1
In case of strong electrolytes, molar conductivity increases slowly with dilution and there is a tendency
for molar conductivity to approach a certain limiting value when the concentration approaches zero i.e.
when the dilution is infinite. The molar conductivity when the concentration approaches zero is called
molar conductivity at infinite dilution. Variation of molar conductivity with concentration for strong and
weak electrolytes are shown in the following 2 figures :

Molar conductance of weak electrolyte depends upon its degree of dissociation. Higher the degree of
dissociation , larger is the molar conductance . With increase in dilution, the conductance increases and
at infinite dilution, the electrolyte is completely dissociated so that degree of dissociation becomes one.
Thus measuring the molar conductance at any concentration helps to calculate degree of dissociation if
molar conductance at infinite dilution is known.
1. Solutions of 2 electrolytes ‘A’ and ‘B’ are diluted. The limiting molar conductivity of ‘B’ increases to a
smaller extent while that of ‘A’ increases to a much larger extent comparatively. Which of the two is a
strong electrolyte? Justify your answer.
2. Calculate the degree of dissociation of 0.0024 M acetic acid if conductivity of this solution is 8.0 x 10 -5 S
cm-1 . [ Given 𝜆0H+ = 349.6 S cm2 mol-1 ; 𝜆0CH3COO- = 40.9 S cm2 mol-1

Answer :
1. Electrolyte B is strong electrolyte.
Limiting molar conductivity increases only to a smaller extent for a strong electrolyte as the number of
ions does not increase appreciably on dilution and only mobility of ions increases due to decrease in
interionic attractions.
Limiting molar conductivity increases to a larger extent for a weak electrolyte, as on dilution degree of
dissociation increases, therefore the number of ions in the solution increases.

2. Here C = 0.0024M, 𝜅 = 8 x 10-5 S cm-1, Λcm = = .

= 33.33 S cm2 mol-1 ; .
Λ0m(CH3COOH) = 𝜆0H+ + 𝜆0CH3COO- = (349.6 + 40.9 ) Scm2 mol-1 = 390.5 S cm2mol-1 ; 𝛼 = . Λcm /. Λ0m =
33.33/390.5 = 0.085 ; 𝛼 = 8.5%

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 Unit 3-Chemical Kinetics
Some important Points
1.RATE OF REACTION
The change in concentration of either reactant or product per unit time.
Example : N2 + 3H2 → 2NH3
Unit of rate mol L-1 S-1
2.Rate Law
The expression of rate of reaction in term of concentration of reactant
aA + bB →Product
Rate=K[A]x [B]y
Rate Constant=K
3. Specific Rate of reaction :-Rate of reaction when concentration are taken as
unity Rate=K[A]x[B]
[A]=1 [B]=1 Rate=K
Unit of rate =constant
4. N - Order of reaction
Order of reaction
The sum of power of concentration of reactant in rate law expression
aA + bB →Product Rate=K[A]x[B]y Order of reaction = x+y
It may be Zero, Positive or Negative or fraction. It is experimental quantity.
Difference between order and molecularity of a reaction.
Molecularity Order
1 It is the total number of species taking part in It is the sum of the powers of the concentration
a chemical reaction. terms of reacting species in the rate law
equation.
2 It is derived from the mechanism of reaction. It is derived from the rate expression.
3 It a theoretical concept It is an experimental quantity.
4 It can neither be zero nor fractional; It is It may be zero, fractional or any integer value.
always a whole number.
5 It is applicable only to elementary reactions. It is applicable to elementary as well as complex
The overall molecularity of a complex reactions.
reaction has no significance.
5. Mechanism of Reaction
Elementary reaction:-Chemical reactions which complete in single step and have exponent in rate law
expression equal to their stochiometric coefficient .Zero order reaction can not be an elementary
reaction.
Complex Reaction:- For the complex reaction, The overall reaction is controlled by the slowest step.
Integrated Rate equations-
For zero order-
K=[R0]-[R]/k

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Graph for 0 order reaction
Half life period for a zero order reaction:
The half-life of a reaction is the time in which the concentration of a
reactant is
reduced to one half of its initial concentration. It is represented as t½
Examples of zero order reactions;- (a)The decomposition of gaseous
ammonia on a hot platinum surface is a zero order reaction at high
pressure(b)The thermal decomposition of HI on gold surface.

For first order-k=2.303/t log[A0]/[A]

Graphical representation for first order reaction
Half life period for a First order reaction :
t½=0.693/k
(For a first order reaction, half-life period is constant,
it does not depend on initial concentration of the
reactant)
Examples of first order reaction:-All natural and
artificial radioactive decay of unstable nuclei take
place by first order kinetics.
Rate equation for radioactive decay-
𝑘=2.303/t ×N0/Nt (N0 is initial number of atoms
and Nt is number of atoms after t time)

In the above graph A0 =initial concentration of reactant.

Pseudo first order reaction
A chemical reaction which seems to be higher order but actually they are of first order
For these reaction, Order of reaction is one but molecularity is more than one
Example :-Hydrolysis of ester in acidic medium,
(a)CH3COOC2H5 + H2O →CH3COOH + C2H5OH, Rate =K[CH3COOC2H5][ H2O]
When water is in excess then K’[CH3COOC2H5]
(b)Inversion of cane sugar in acidic medium C12H22O11+H2O → C6H12O6 + C6H12O6
Rate =K[C12H22O11][ H2O]
Factors affecting rate of reaction-
1. Nature of reactant:-
Chemical Nature of Reactant:-Reaction having less value of activation energy , Will takes place faster
2. Concentration of Reactant:- Rate of reaction α Conc. Of Reactant
3. Temperature:-On increasing temperature, rate of reaction increases
Whether the reaction is exothermic or endothermic because KE of molecule Increase on increases
temperature which led to increasing activated Molecule.

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4. Relation between rate constant and temperature
Generally it is found that for every 100 C rise in temperature rate of Reaction become 2 times.
5. Presence of catalyst:-In the presence of catalyst, Ea(Activation energy) Decreases therefore rate of
reaction increases .

6. Exposure of radiation:-Rate of some reaction increases on exposure of

Radiation. These reaction are called photochemical reaction For Example:-
Arrhenius equation -It shows the relationship between activation energy and rate constant and effect of
temp on rate constant.
7. Collision theory-The reactant molecules are assumed to be hard spheres .
Reaction occurs when molecules collide with each other
Rate=ZAB the number of collisions per second unit volume of the reaction mixture.
e-Ea/RT the fraction of molecules with energies equal to or greater than Ea
The proper orientation of reactant molecules lead to bond formation improper orientation makes them
simply bounce back and no products are formed
In collision theory activation energy and proper orientation of the molecules together determine the
criteria for an collision and hence the rate of a chemical reaction.

Multiple Choice Questions

Q.No Questions
1. The rate of a chemical reaction tells us about - 1
(a)the reactants taking part in the reaction (b)the products formed in the reaction
(c)how slow or fast the reaction is taking place (d)none of the above
2 In the rate equation, when the concentration of reactants is unity then the rate is equal to - 1
(a)specific rate constant (b)average rate constant
(c)instantaneous rate constant (d)None of the above
3. The average rate and instantaneous rate of a reaction are equal - 1
(a)at the start (b)at the end
(c)in the middle (d)when two rates have a time interval equal to zero
4. Which of the following observations is incorrect about the order of a reaction? 1
(a)Order of a reaction is always a whole number
(b)The stoichiometric coefficient of the reactants doesn’t affect the order
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 (c)Order of reaction is the sum of power to express the rate of reaction to the concentration
terms of the reactants.
(d)Order can only be assessed experimentally
5. The rate constant of zero-order reactions has the unit - 1
(a)s-1 (b)mol L-1s (c)L2 mol-2 s-1 (d)L mol-1
6. In the reaction 2A + B → A2B, if the concentration of A is doubled and that of B is halved, 1
then the rate of the reaction will -
(a)increase 2 times (b)increase 4 times(c)decrease 2 times (d)remain the same
7. When the rate of the reaction is equal to the rate constant, the order of the reaction is- 1
(a)zero order (b)first order (c)second order (d)third order
8. A substance ‘A’ decomposes by a first-order reaction starting initially with [A] = 2.00M and 1
after 200min, [A] becomes 0.15M. For this reaction t1/2 is -
(a)53.72 min (b)50.49 min (c)48.45 min (d)46.45 min
9. In the Haber process for the manufacture of ammonia the following catalyst is used 1
(a)Platinized asbestos (b)Iron with molybdenum as a promoter
(c)Copper oxide (d)Alumina
10. A catalyst alters, which of the following in a chemical reaction? 1
(a)Entropy (b)Enthalpy (c)Activation energy (d)Internal Energy

Answers :1 (c) 2(a) 3(d) 4(a) 5(b) 6 (a) 7(a) 8(a) 9(b) 10(c)
Read the statements given as assertion & reason both and choose the correct option as per
the following instructions.
(A) if both assertion & reason are correct statements and reason is the correct explanation
of assertion.
(B) if both assertion & reason are correct statements and reason is not the correct
explanation of assertion.
(C) if the assertion is the correct statement & the reason is an incorrect statement.
(D) if the assertion is incorrect statement and reason is the correct statement.

1. Assertion: The order of reaction can be zero or fractional. 1

Reason: The order of a reaction cannot be determined from a balanced chemical reaction.
2. Assertion: The order and molecularity of a reaction are always the same. 1
Reason: Order is determined experimentally whereas molecularity by a balanced
elementary reaction.
3. Assertion: Rate constant of a zero-order reaction has the same unit as the rate of a reaction. 1
Reason: Rate constant of a zero-order reaction does not depend upon the concentration of
the reactant.
4. Assertion: In a first-order reaction, the concentration of the reactant is doubled, its half-life 1
is also doubled.
Reason: The half-life of a reaction does not depend upon the initial concentration of the
reactant in a first-order reaction.
5. Assertion: Average rate and instantaneous rate of a reaction have the same unit. 1
Reason: Average rate becomes an instantaneous rate when the time interval is too small.
Answers of Assertion and Reason Type Questions.
(1)b(2)d(3)a(4)d(5)b
VERY SHORT ANSWER TYPE QUESTIONS(2MARKS)
1. For the reaction at 500 K 2
(i) NO2(g) + NO2 (g) → NO + NO3 (slow)
(ii) NO3 + CO → CO2 + NO2 (fast)
What is the rate law for the reaction? GIVE REASON.
Ans- The slow step of the reaction mechanism is:
NO2 + NO2 →NO + NO3
Hence, the rate of reaction is,
23 | P a g e
 Rate = k [NO2] [NO2]
Or rate = k [NO2]2
SLOWEST STEP OF THE MECHANISM DECIDES THE RATE OF THE REACTION.

2. Q.A first order reaction takes 69.3 minutes for 50% completion. How much time will be 2
needed for 80% completion?
Answer. t1/2 = 69.3 minutes
K = 0.693/69.3 = 10-2 min-1
Now t = 2.303/k log a/(a – x)
= 2.303/10-2 x 0.6990 = 160.9 minutes.
3. In a certain first order reaction, half the reaction was decomposed in 500 seconds. How long 2
will it take for 90% completion?
Answer. K = 0.693/(t1/2) = 0.693/500
= 0.001386 sec-1
Now, t = 2.303/0.001386 x log (100)/10
= 1661 sec.
4. Find the two-third life, t2/3, of a first order reaction in which k = 5.4 x 10-14 s-1 2
Answer: Formula; t2/3 = ( 2.303 / k) log (a / a- x)
Here, x = 2a/ 3 and k = 5.4 x 10-14 s-1
Thus, t2/3 = [2.303 / 5.4 x 10-14 s-1] ( log [a /( a - 2a / 3)]
t2/3 = [ 2.303 / 5.4 x 10-14] log3
= 0.4264 (0.4771) (1014) s
= 0.2034 x 1014 s
5. Q. Find the value of rate constant for the reaction, A + B → AB, if the rate of the reaction is 5 2
x 10-5(mole/L)min-1 and |A| and |B| are 0.05 and 0.01 mol/L respectively.
Ans. A + B → AB
R = K[A][B]
K = (5 x 10-5)/(0.05 x 0.01)
= 0.1 (mol/l)-1min-1
6. Can a reaction have a) zero activation energy b) negative activation energy? 2
Ans. a) No; if Ea is zero all collisions will lead to product formation, which is not possible.
b) If Ea is negative than K>>A which is not possible.
7. Q-What is meant by effective collision? 2
Ans. Those collisions results into product formation are called effective collisions. The
molecules must cross 1) energy barrier 2) orientation barrier for the formation of the
products.
8. Following reaction takes place in one step- 2
2NO +O2⟶2NO3
How will the rate of above reaction change if the volume of the reaction vessel is
diminished to one third of its original volume? Will there be any change in order of reaction
with the reduced volume?
Ans-Rate of the reaction will become 27 times, order will remain unchanged.
9. Q- For the reaction 2
NO2 + CO → CO2+ NO
Rate law is Rate = K [NO2]2 Propose mechanism of this reaction.

24 | P a g e
 Ans. Mechanism of reaction is
(a) NO2 + NO2 → NO + NO3 (slow)
(b)NO3 + CO → CO2 + NO2 (fast)
10. Q- A first order reaction is 15% complete in 20 minutes. How long will it take to be 60% 2
complete?
Ans- k= 2.303/20 log a/a-0.15a =2.303/20 log 1/0.85 =2.303/20 x0.0706 = 0.00813 /min.
K=2.303 /t log a/a-0.6a
T= 2.303/0.00813 log a /0.4a =2.303/ 0.00813 x 0.3979 = 112.71 min.

Short Answer Type Questions -3Marks

1. Q. The rate of decomposition of a substance A becomes 8 times when its concentration is 3
doubled . What is the order of the reaction?
Ans- Rate= k [A]n
r = k [A]n …..…………….(i)
8r= k [2A]n ……………(ii)
Dividing (ii) by (i) => 8r/r = k [2A]n / k [A]n
8 =[2]n
n=3 so-order is 3
2. The kinetics of the reaction: A + 2B → Products; obeys the rate equation Rate = k [A]x [B]y. 3
For it, find
a) Order of the reaction
b) Apparent molecularity of reaction
c) Order of reaction when B is in large excess.
A.1) a) x+y b) 3 c) x

3. In the start of summer, a given sample of milk turns sour at room temperature (300K) in 3
48 hours. In a refrigerator at 275K, milk can be stored three hours longer before it sours.
Calculate activation energy of the souring of milk.
Ans. Ea = 30.146 kJ mol –1
4. Q-. What is activation energy? The rate constant of a first order reaction becomes 5 times 3
when the temperature is raised from 350 K TO 400K. Calculate the activation energy of the
reaction.
Ans. Activation energy is the minimum energy which must supplied to the reactant
molecule so that the collision between the reactant molecules is effective and can produce
the chemical change.
From Arrhenius equation
Logk2/k1 =Ea /2.303 R[1/T1-1/T2 ]
Log of 5x/x =Ea/(2.303 x8.314) x [1/350-1/400]
Log5 = Ea /(2.303 x8.314)[50/350x400]
Ea = (log 5 x 2.303 x8.314 x 350x400) /50
= 37480J/mol
=37.480KJ/mol

5. (i)Write order of a chemical reaction, which proceeds at a uniform rate.? 3

Ans(i)Zero

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 (ii) State any one condition under which a bimolecular reaction may be kinetically of first
order.
Ans (ii) When one reactant is present in large excess.
(iii)If half-life of a reaction is inversely proportional to initial concentration of the
reactant, what is the order of the reaction?
Ans(iii) Second order
6. (i)Entropy of activation is usually negative. Why? 3
Ans-(i)With the formation of transition state there is loss in the randomness of the reacting
molecule.
(ii)In some cases it is found that a large number of colliding molecules have energy more
than threshold energy, yet the reaction is slow. Why?
A-ii Because reacting molecules are not having proper orientation.
(iii) Liquid bromine reacts slowly as compared to the bromine vapours .Why?
A-iii More the surface area more is the rate of reaction.
7. For a first order reaction, show that time required for 99% completion is twice the time 3
required for the completion of 90% of reaction.
Ans-The time required for 99% completion of a first order reaction is twice the time
required for 90% of the reaction.
8. (a) For a reaction A + B →P, the rate is given by rate = k[A][B]2 3
(i) How is the rate of reaction affected in the concentration of B is doubled? Ans. Rate will
become 4 times.
(ii). What is the overall order of reaction if A is present in large excess? Ans-1
(b) A first order reaction takes 30 minutes for 50% completion. Calculate the time required
for 90% completion of the reaction. Given rate=[A] [B]2 k=2.0 X 10-6 mol-2 L2s-1
Ans-100.13 min.
9. (a)Define ‘rate of a reaction’. 3
Answer: Rate of a reaction: The change in the concentration of any one of the reactants or
products per unit time is called rate of a reaction. Or, The rate of a chemical reaction is the
change in the molar concentration of the species taking part in a reaction per unit time
(b)Distinguish between ‘rate expression’ and ‘rate constant’ of a reaction.
Answer:
Rate expression: The expression which expresses the rate of reaction in terms of molar
concentrations of the reactants with each term raised to their power, which may or may not
be same as the stoichiometric coefficient of that reactant in the balanced chemical equation.
Rate constant: The rate of reaction when the molar concentration of each reactant is taken
as unity.

10. (a)Define ‘activation energy’ of a reaction. 3

Answer: The minimum extra amount of energy absorbed by the reactant molecules to form
the activated complex is called activation energy.
The activation energy of the reaction decreases by the use of catalyst.
Define the following-
i) Elementary step in a reaction
(ii) Rate of a reaction
Answer:(i) Elementary step in a reaction: Those reactions which take place in one step
are called elementary reactions.
Example : Reaction between H2, and I2 to form 2HI
H2 + I2 → 2HI

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 (ii) Rate of a reaction: The change in the concentration of any one of the reactants or
products per unit time is called rate of reaction.

Long Answer Type Questions

1. Define order of reaction. Show graphical representation for 0 and 1 order reaction. Derive 5
the equation for half life period of 1 order reaction.
Ans1.Order of a reaction: It is the sum of the powers to which reactant terms must be raised
to express the rate of reaction completely.

(a)For 0 order reaction (b) For 1 order reaction

For Half life period k = 0.693/T1/2]

2. 5

.
(a)What is order of reaction shown in graph ?
Ans(a) zero order
(b)What is slope in graph II?
Ans.(b)k/2.303
(c)How does t1/2 vary with initial concentration in zero order reaction.
(c)Directly proportional to the initial concentration.
(d)If initial concentration of a first order is increased by 2 times then what will be the effect
on half life period of the reaction? Give reason to support your answer.
Ans-No effect .
Reason-As half life of first order reaction is independent of initial concentration.
(e)What is t1/2 of zero order reaction in terms of ‘k’?
Ans.(e) t1/2 =[Ro]/2k
CASE STUDY BASED QUESTION 4
The half-life of a reaction is the time required for the concentration of reactant to decrease
by half, [At]=[A]/2
For first order reaction, t1/2=.693/k
this means t1/2 is independent of initial concentration. The figure shows a typical variation
of concentration of reactant exhibiting first-. It may be noted that though the major portion
of the first-order kinetics may be over in a finite time, the reaction will never cease as the
concentration of reactant will be zero only at infinite time.

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Order kinetics.

(i)A first-order reaction has a rate constant k = 3.01 × 10–3 /s. How long it will take to
decompose half of the reactant?
(a) 2.303 s (b) 23.03 s
(c) 230.3 s (d) 2303 s
Ans-(c)
(ii)The rate constant for a first-order reaction is 7.0 × 10–4 s–1. If the initial concentration of
reactant is 0.080 M, what is the half-life of the reaction?
(a) 990 s (b) 79.2 s
(c) 12375 s (d) 10.10 × 10–4 s
Ans.(a)
(iii)For the half-life period of a first-order reaction, which one of the following statements is
generally false?
(a) It is independent of initial concentration.
(b) It is dependent on the rate of the reaction.
(c) At t1/2, the concentration of the reactant is reduced by half.
(d) None of these
Ans.(b)
(iv)The rate of a first-order reaction is 0.04 mol L–1 s–1 at 10 minutes and 0.03 mol L–1 s–1 at
20 minutes after initiation. The half-life of the reaction is
(a) 4.408 min (b) 44.086 min
(c) 24.086 min (d) 2.408 min
Ans.(c)

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 Unit 4-d and f Block elements
d Block elements(Transition elements) : Group 3-12 in periodic table.
f-block elements (inner transition elements): consists of elements in which 4f and 5f orbitals are
progressively filled. They are placed in a separate panel at the bottom of the periodic table.
3d series I transition series (Sc-Zn) 4d series II transition series (Y -Cd)
5d series III transition series (La Hf -Hg)6d series IV transition series (Ac from Rf -Cn)
Definition of transition elements :‟elements which have incomplete d subshell( i.e less than 10 e) either
in neutral atom or in their ions″.
Electronic configuration for 3d series: General electronic configuration Ar (n-1)d 1– 10 ns 1–2except for
Pd 4d105s0 .Stable electronic configuration.( d0 empty, d5 half filled d10 filled filled)

Sc21 Ti 22 V 23 Cr 24 Mn 25 Fe 26 Co 27 Ni 28 Cu 29 Zn 30

3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc

Exceptional electronic configuration: For Cr , should have been 3d4 4s2, for Cu should have been 3d9
4s2. . But to achieve stable electronic configuration.ie 3d5 ,3d10 (as there is very little energy diff between
3d and 4s orbital) so Cu and Cr have exceptional electronic configuration. But while forming cation
electron is removed first from 4s then from 3d In 3d series all elements have incompletely filled d
orbitals in their ground state so they fit to this definition except Cu, Zn ,for Cu and Zn Although both have
completely filled d orbitals in their ground state but

Cu, Ag are transition element Zn, Cd Hg are not transition elements

Cu(3d104s1) in +2 oxidation state it has Zn in ground state(3d104s2) and in +2 oxidation state

electronic configuration as 3d9 has ,3d10 has completely filled d orbitals. similarly for Cd Hg.
incompletely filled d orbitals. Same for Ag But Zn Cd Hg are studies along with d block elements

General properties of Transition elements

PHYSICAL PROPERTY: Metallic properties: show metallic properties like high tensile strength, ductility,
malleability, thermal and electrical conductivity and luster, exceptions of Zn, Cd, Hg and Mn
•Metallic bonding directly proportional to unpaired electron so increases till Cr and decreases since
after that pairing occurs. •Enthalpy of atomisation is directly proportional to metallic bonding •Zn, Cd,
Hg no unpaired electrons so less metallic bonding hence soft, not with high melting and boiling point.
Variation in Atomic and Ionic Sizes of Transition Metals: Ionic radii decreases along the period due to
increase in effective nuclear charge, d orbital give a very poor shielding effect.
Observation Ionic radii increase from the first (3d) to the second (4d) series of the elements but the radii
of the third (5d) series are virtually the same as those of corresponding members of the second series.
Reason: Due to lanthanoid contraction.
LANTHANOID CONTRACTION The filling of 4f before 5d orbital results in a regular decrease in atomic radii
called Lanthanide contraction. Due to this 4d and 5d series elements have same size Zr and Hafnium has
similar atomic size due to lanthanide contraction
IONISATION ENTHALPIES: General trend ionisation enthalpy increases along a period, due to increase in
effective nuclear charge., nuclear charge increases from Sc to Zn but electrons are added to the orbital of
inner subshell Therefore, the atomic radii decrease less rapidly. Stable electronic configuration also affects
29 | P a g e
ionisation enthalpy as for Mn+2 third ionisation enthalpy is high, Fe+3 fourth ionisation enthalpy is
high(3d54s0), it is difficult to remove another electron. (3d54s0)
Oxidation States: The lowest common oxidation state of these metals is +2. Exception Scandium it shows
only one oxidation state +3.Low oxidation state means few electron to loose / share for eg Sc 3+, Ti4+.Or too
many electrons so less vacant orbitals to share electrons.
Oxidation state vs electronic configuration• Scandium(II) is unknown(Sc+3 has d0 configuration hence
more stable• titanium (IV) is more stable than Ti (III) or Ti(II).(Ti +4 is 3d04s0).•Only oxidation state of zinc
is +2 (no d electrons are involved)( Zn+2 3d10 4s0 hence stable (d10)•Mn has maximum oxidation state
Difference in oxidation state of transition and non transition series:
TRANSITION ELEMENTS: •their oxidation states differ from each other by unity, e.g., for Mn it is +2,+3,+4
so on •Higher oxidation states are more stable
NON TRANSITION ELEMENTS: •their oxidation states differ from each other by 2 inert pair effect, •lower
oxidation states are more stable due inert pair effect, Sn +2 oxidation state is more stable than +4
Trends in the M2+/M Standard Electrode Potentials
Electrode potential is reduction potential
E0 value higher. tendency to get reduced reduced form more stable behave as oxidising agent
higher
E0 value lower tendency to get oxidise oxidised form more stable behave as reducing agent
E0 M2+/M means •reduction potential for M2+ →M, •tendency of ion to get reduced from 2+ to M high
•E0 M2+/M high implies tendency to reduce from M+2 to M0 to high,. M more stable than M+2
E0 value is the sum of:(i)Sublimation enthalpy(positive ) (ii)Enthalpy of atomisation(positive)
(iii)Ionisation enthalpy(positive ) (iv)Hydration enthalpy(negative)
• Overall sum positive then E0 positive (∆Hhyd value.< other enthalpies) •Overall sum Negative means E0
negative (∆Hhyd value.> other enthalpies).So E0 value depend on all of the above factor and on electronic
configuration.
Facts on E0 values (those with stable electronic configuration in 2+oxidation state will have a low
tendency to get reduced to M)
1.The E0(M2+/M) value for copper is positive (+0.34V) due to low hydration enthalpy high enthalpy of
atomisation
2. Mn , Zn negative E0 value means less tendency to get reduced oxidised form +2 is more stable (d5 and
d10 ).
Trends in the M3+/M2+Standard Electrode Potentials
E0 M3+/M2+ means reduction potential for M3+ →M2+
tendency of ion to get reduced from 3+ to 2+, E0 high tendency to reduce to +2 high ion Stable in 2+
oxidation state will easily get reduced from +3 to +2 oxidation state, (E0 high) while stable in +3 stable will
not have tendency to get reduced so E0 low or more negative
Facts on E0 M3+/M2+values (Stable electronic configuration d0 ,d5 ,d10, d3) •The low value for Sc reflects
it dont want to get reduced to 2+( Sc3+ Ar 3d0 4s0). •The highest value for Zn reflects tendency to get
reduced to Zn2+ d10 configuration of Zn2+ .•.The comparatively high value for Mn shows that Mn2+(d5) is
particularly stable •low value for Fe shows the extra stability of Fe3+ (d5) •The comparatively low value for
V is related to the stability of V2+ (d3)
Trends in Stability of Higher Oxidation States Higher oxidation states are shown in florides or oxides :The
ability of oxygen to stabilise these high oxidation states exceeds that of fluorine. Thus the highest Mn
fluoride is MnF4 whereas the highest oxide is Mn2O7,Mn in 7 oxidation states For fluorides: The ability of
30 | P a g e
fluorine to stabilise the highest oxidation state is due to either higher lattice energy as in the case of CoF3,
or higher bond enthalpy covalent compounds, e.g., VF5 and CrF6 For oxides: The ability of oxygen to form
multiple bonds to metals . fluorides instability in the low oxidation states e.g., VX2.many copper (I)
compounds are unstable in aqueous solution and undergo disproportionation. 2Cu+ → Cu2+ + Cu, The
stability of Cu2+ (aq) rather than Cu+(aq) is due to the much more negative ∆Hhyd of Cu2+(aq) than Cu+,
which more than compensates for IInd ionisation enthalpy of Cu.

KMnO4( potassium permangnate) PURPLE K2Cr2O7 (potassium dichromate)orange

Mangnate ion(MnO42–)green, Permangnate ion(MnO4–) purple ChromateCrO4– yellow, Dichromate Cr2O72–
orange

preparation MnO2→ K2MnO4→K2MnO4 FeCr2O4 → Na2CrO4 → Na2CrO7→ K2Cr207

2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O 3MnO4 1.4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8Na2CrO4+
2– + 4H+ → 2MnO4– + MnO2 + 2H2O 2Fe2O3 + 8 CO2
2.2Na2CrO4 +2H+ → Na2Cr2O7 + 2 Na+ + H2O
3.Na2Cr2O7 +2 KCl → K2Cr2O7 + 2 NaCl

Structure:pi bonding takes place by overlap of p orbitals of oxygen Conversion of chromate an dichromate ion
with d orbitals are e by changing pH
of manganese. CrO4– increased pH(yellow)
OH– ⇅ H+
Cr2O72– decreased pH (orange)

Paramagnetic (unpaired e–) diamagnetic(paired e–)

MnO4– + 4H+ + 3e– → MnO2 + 2H2O (EV =+ 1.69 V)
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
Cr2O72– + 14H+ + 6e–→ 2Cr3+ + 7H2O

• 2 MnO4– + 16H+ + 5C2O4 → 2Mn2+ + In neutral or faintly alkaline 6I– → 3I2 + 6e– ;3 Sn2+ →
8H2O +10CO2 solutions: 3Sn4++6e–
•MnO4– + 8H+ + 5Fe2+ Mn2+ + 4H2O + (a) 2MnO4– + H2O + I– —>2MnO2 + 3 H2S →6H+ +3S + 6e– ; 6 Fe2+ →
5Fe3 2OH– + IO3– 6Fe3+ + 6 e–
•2 MnO4– + 16H+ + 10I– → 2Mn 2+ + (b) Thiosulphate is oxidised almost Combining ox half and red half
8H2O +5I2 to sulphate:8 MnO4– + 3S2O32– + H2O
Cr2O72– + 14 H+ + 6 Fe2+ → 2 Cr3+ +
——> 8MnO2 + 6SO42– + 2OH–
• 5NO2 - +2 MnO4 +6H+ → Mn 2+ + 6 Fe3+ + 7 H2O
3H2O +5NO3 – (c) Manganous salt is oxidised to
MnO2:
•10I- + 2MnO4 – + 16H+→ 2Mn2+ +
8H2O+ 5I2 2MnO4– + 3Mn2+ + 2H2O ——>
5MnO2 + 4H+
5S2- + 2 MnO4– +16H+→ Mn2+ +8H2O
+5S
vii)5SO3 2-+2MnO4 – + 6H+ 2 Mn2+ +
3H2O +5SO4 2 –

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Chemical Reactivity and E0Values: The E0 Values for M2+/M indicate a decreasing tendency to form
divalent cations across the series because of increase in the sum of the first and second ionisation
enthalpies
E0values for Mn, Ni and Zn are more negative than expected refer to earlier explanation
E0 M3+/M2+for Mn3+ and Co3+ aq ions reflects that they are the strongest oxidising agents The ions
Ti2+, V2+ and Cr2+ are strong reducing agents
↿⇂ ↿⇂ ↿⇂ ⇂ ⇂

.Magnetic Properties: Spinning and revolving electron causes magnetic momentum, spin angular
momentum and orbital angular momentum. only unpaired e contribute to magnetic moment, in fig All the
d electrons will not contribute to magnetic moment only 2 unpaired e will contribute. DIMAGNETIC:
repelled by the applied field( no unpaired electron) PARAMAGNETIC: Attracted by the applied
field(unpaired electron), the magnetic moment is determined by the number of unpaired electrons and is
calculated by using the ‘spin-only’ formula, i.e. μ =⎷n(n + 2)where n is the number of unpaired electrons
and μ is the magnetic moment unit Bohr magneton (BM). Observed magnetic moment give data about
unpaired electron
Formation of Coloured Ions: There is splitting of d orbital in the presence of ligand (ligands are atoms /
ions bonded to transition metal), 2 energy levels are created one is t2g and other as eg , from all five d
orbitals. if transition element is in non bonded state splitting don’t happen. When an electron from a lower
energy level is excited to a higher energy level, it absorbs radiation when it comes back to ground state it
releases energy in complementary to the frequency of light absorbed, lies in the visible region. Atoms
withd0 and d10 configuration will be colourless • d0 (Sc+3) NO electrons to jump to higher level , d10 (Zn
+2)all orbitals filled no space in higher level for lower level electron to jump

Formation of Complex Compounds: Transition elements form Complex compound (central atom bonded
with ligands(atoms / ions) reason: due to availability of d orbitals for bond formation the ,smaller sizes of
the metal ions, their high ionic charges eg.[Fe(CN)6]3–
Catalytic Properties: Reason: transition elements can adopt multiple oxidation states and to form
complexes , so they can change oxidation states eg Vanadium(V) oxide (in Contact Process), finely divided
iron (in Haber’s Process), and nickel (in Catalytic Hydrogenation) iron(III)
Formation of Interstitial Compounds: Definition: Interstitial compounds are those which are formed
when small atoms like H, C or N are trapped inside the crystal lattices of metals., TiC, Mn4N, FeH, VH0.56 and
TiH1.7, etc. Characteristics :(i)They have high melting points, hard higher than pure metals. metallic
conductivity and chemically inert
Alloy Formation: An alloy is a blend of metals i.e homogeneous solid solutions in which the atoms of one
metal are distributed among the atoms of the other. Metal mixed should be comparable in metallic radii
Transition elements form alloys: Reason : Because of similar radii of transition metals eg steel brass
(copper-zinc) and bronze (copper-tin),
OXOANIONS OF TRANSITION ELEMENT ( Manganese and chromium)
LANTHANOIDS The 14 elements after Lanthanum having atomic number 58 to 71 are known as
Lanthanoids. The general electronic configuration is [Xe] 4f1-14, 5d0-1 ,6s2 .
•LANTHANOID CONTRACTION The overall decrease in atomic and ionic radii from lanthanum to
lutetium is due to poor shielding of 4f electrons is known as lanthanoid contraction: conseques: basic
character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3, Sizes of 4d and 5d metal pair like
Zr and Hf; Nb and Ta are almost similar. OXIDATION STATES: common oxidation state of these elements
is +3, However, occasionally +2 Eu+2 and Yb+2)and +4 ions (Ce+4 and Tb+4) in solution or in solid
compounds are also obtained. COLOUR :Many trivalent lanthanoid ions are coloured both in the solid state
and in aqueous solutions. (unpaired electrons in f subshell.) 16. MAGNETIC BEHAVIOUR: The lanthanoid
ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+) are all paramagnetic. .alloy
is mischmetal which consists of a lanthanoid metal(~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al
used in Mg-based alloy to produce bullets, shell and lighter flint. ACTINOIDS 1. The 14 elements after
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Actinium having atomic number 90 to 113 are collectively known as Actinoids or actinides are 15
consecutive chemical elements in the periodic table from actinium to lawrencium
Like lanthanoids contraction, there is actinoids contraction.
These contractions are due to poor shielding of 5f and 4f electrons in
lanthanoids and actinoids respectively
Property Lanthanoids Actinoids
Oxidation state Show mainly +3, except +3 and show higher
in a few cases where it is oxidation state +4,+5,+6+7.
+2 ,+4
Shielding effect 4f electrons have greater 5f electrons have poor
shielding effect. shielding effect. Contraction
Contraction in their ionic in their ionic radii is more.
radii is less.
Basic character Less basic More basic
Tendency to They do not form Oxo They form Oxo ions UO2+,
ions NpO2+,PuO2+
form Oxo ions
Colours Most of their ions are Most of the actinoids ions are
colourless.
coloured. UO2+ (yellow)

PRACTICE QUESTIONS:
MCQ
1 Which of the following element is not a transition element
(i)Sc(ii) Ti(iii)Zn (iv)Cu

2 Although Zirconium belongs to 4d transition series and Hafnium to 5d transition series even then
they show similar physical and chemical properties because___________.
(i)both belong to d-block. (ii)both have same number of electrons.(iii)both have similar atomic
radius.(iv) both belong to the same group of the periodic table

3 Which of the following has the maximum number of unpaired electrons?

(a) Mg2+(b) Ti3+(c) V3+(d) Fe2+

4 When acidified K2Cr2O7 solution is added to Sn2+ salts then Sn2+ changes to
(i) Sn (ii) Sn3+ (iii) Sn4+ (iv) Sn+

5 Which of the following would be diamagnetic?

(a) Cu2+(b) Ni2+(c) Cd2+(d) Ti3+.

6 Highest oxidation state of manganese in fluoride is +4 (MnF4 ) but highest oxidation state in
oxides is +7 (Mn2O7 ) because ____________.
(i)fluorine is more electronegative than oxygen. (ii) fluorine does not possess d-orbital
(iii) fluorine stabilises lower oxidation state. (iv)in covalent compounds fluorine can form single bond
only while oxygen forms double bond

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7 Lanthanides and actinides resemble in
(a) electronic configuration(c) ionisation energy
(b) oxidation state(d) formation of complexes
8 The radius of La3+ (At. No. of La = 57) is 1.06 A°. Which one of the following given values
will be closest to the radius of Lu3+.
(a) 1.40 Å(b) 1.06 Å (c) 0.85 Å(d) 1.60 Å
9 Gadolinium belongs to 4f series. It’s atomic number is 64. Which of the following is the correct
electronic configuration of gadolinium?
(a) [Xe] 4f 75d1 6s2 (b) [Xe] 4f 65d26s2 (c) [Xe] 4f86d2 (d) [Xe] 4f 95s1
10 Among the following pairs of ions the lower oxidation state in aqueous solution is more
stable than the other.
(a) Tl+, Tl3+ (c) Cr3+(b) Cu+, Cu2+(d)none of these
Ans 1.(iii)Zn 2. both have similar atomic radius. 3(d) Fe2 + 4.(iii) Sn4+5 (c) Cd2+
wers
6. (iv)in covalent compounds fluorine can form single bond only while oxygen forms
7.(a) electronic configuration double bond 8.(c) 0.85 Å 9(i) [Xe] 4f 75d1 6s2

1 Assertion : Cu2+ iodide is not known. Reason : Cu2+ oxidises I – to iodine.

2 Assertion : Actinoids form relatively less stable complexes as compared to lanthanoids.
Reason : Actinoids can utilise their 5f orbitals along with 6d orbitals in bonding but
lanthanoids do not use their 4f orbital for bonding
3 Assertion: Cu cant liberate H2from acids. Reason :Because it has positive electrode potential
4 Assertion : Separation of Zr and Hf is difficult. Reason :Because Zr and Hf lie in the same group
of the periodic table.
5 Assertion : Magnetic property of Mangnate ion and Permangnate ion is different
Reason : Paramagnetism arises due to unpaired electron.
ans 1.(a) 2(ii)3 (iii)4(i) 5(b)
1 Why Cu is a transition elements but Zn , Cd Hg are not transition elements
Cu(3d104s1) in +2 oxidation state it has electronic configuration as 3d9 has incompletely filled d
orbitals. Zn in ground state(3d104s2) and in +2 oxidation state ,3d10 has completely filled d orbitals.
similarly for Cd Hg.

2 why are they called transition elements

The very name ‘transition’ given to the elements of d-block is only because of their position between s–
and p– block elements

3 Why do the transition elements exhibit higher enthalpies of atomization? Ans(Due to

strong intermetallic boding)

4 In the series Sc(Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest or why Zn ,
Cd , Hg are soft metal
ans. Zn, Cd, Hg no unpaired electrons so less metallic bonding hence soft , not with high melting and
boiling point)

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5 Zr and Hf exhibit similar properties. Why?(ans. Due to lanthanoid contraction)
6 How would you account for the irregular variation of ionization enthalpies (I & II) in the
first series of the transition elements?
Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of
different 3d-configurations (e.g., d 0 , d 5 , d 10 are exceptionally stable).
7 Zn+2 , Cu+ , Sc+3salts are white ,but Cu+2 are blue. Why?
Atoms withd0 and d10 configuration will be colorless • d0 (Sc+3) NO electrons to jump to higher
level , d10 (Zn +2)all orbitals filled no space in higher level for lower level electron to jump
8 Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their+3 state?
Electronic configuration of Mn2+ is 3d5. This is a half-filled configuration and hence stable. Therefore,
third ionization enthalpy is very high, i. e., third electron cannot be lost easily. Electronic configuration of
Fe2+ is 3d6. It can lose one electron easily to achieve a stable configuration 3d5.
9 Predict which of the following will be coloured in aqueous solution?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+, Co2+.
Only those ions will be coloured which have incomplete d-orbitals. The ions with either empty
or filled d-orbitals are colourless. Keeping this in view, the coloured ions among the given list
are : Ti3+(3d1), V3+(3d2), Mn2+(3d5), Fe3+(3d5), Co2+ (3d7) Sc3+ (3d°) and Cu+ (3d10) ions are
colourless.
10 Mn , Zn show negative E0 value. Why?
Mn , Zn negative E0 value, means less tendency to get reduced, oxidised form +2 is more stable
(d5 and d10 )
SHORT QUESTIONS AND ANSWERS
1. Sc21 Ti 22 V 23 Cr 24 Mn 25 Fe 26 Co 27 Ni 28 Cu 29 Zn 30

3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc

(i)Which elements exhibits only one oxidation state(ansSc,3)

(ii)Which element exhibits maximum oxidation state and Paramagnetism. (ans. Mn)
(iii)Which element show exceptional electronic configuration (ans. Cu, Cr)
2 How is the variability in oxidation states of transition metals different from that of the non-
transition metals? Illustrate with examples.
The transition metals show a number of variable oxidation states due to the participation of (n – 1) d
electrons in addition to ns electrons in the bond formation. They therefore, exhibit a large number of
variable oxidation states. On the other hand, the non-transition metals generally belonging to s-block do
not show variable oxidation states because by the loss of valence s-electrons, they acquire the
configuration of the nearest noble gas elements.

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3 When an oxide of manganese (A) is fused with KOH in the presence of an oxidising agent
and dissolved in water, it gives a dark green solution of compound (B). Compound (B)
disproportionates in neutral or acidic solution to give purple compound (C). An alkaline
solution of compound (C) oxidises potassium iodide solution to a compound (D) and
compound (A) is also formed. Identify compounds A to D and also explain the reactions
involved
Ans. A = MnO2 (B) K2MnO4 (C) KMnO4 (D) KIO3
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O (A) (B)
3MnO4 2– + 4H+ → 2MnO4 – + MnO2 + 2H2O
2MnO4 – + H2O + KI → 2MnO2 + 2OH– + KIO3 (A) (D)
4 Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate

Potassium dichromate is prepared from chromate, which in turn is obtained by the fusion of
chromite ore (FeCr2O3) with sodium or potassium carbonate in free excess of air. The reaction
with sodium carbonate occurs as follows:

The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr,07.2H20 can be crystallised.

Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.

Orange crystals of potassium dichromate crystallise out. The chromates and dichromates
depending upon pH of the solution. If pH of potassium dichromate is increased it is converted to
yellow potassium chromate.
5 Describe the oxidising action of potassium dichromate and write the ionic equations for its
reaction with:(i) iodide (ii)iron (II) solution and(iii)H2S
K2Cr207is a powerful oxidising agent. In dilute sulphuric acid medium the oxidation state of Cr changes
from+6 to + 3. The oxidising action can be represented as follows:

Describe the preparation of potassium permanganate. How does the acidified permanganate solution
react with (i) iron (II) ions (ii) S02 and (iii) oxalic acid? Write the ionic, equations for the reactions.
ans Potassium permanganate (KMn04) is prepared by the fusion of a mixture of pyrolusite
(Mn02),potassium hydroxide and oxygen, first green coloured potassium manganate is formed.
2MnO2 + 4KOH + 02 —> 2K2Mn04+2H20 The potassium manganate is extracted by water, which then
undergoes disproportionation in neutral or acidic solution to give potassium permanganate.

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7 Compare the chemistry of actinoids with that of the lanthanoids with special reference
to(i)electronic configuration, (ii)atomic and ionic sizes and(iii)oxidation state

ans (i) Electronic configuration: The general electronic configuration of lanthanoids is [Xe]54 4f1-14 5d0-
1 6s2 and that of actinoids is [Rn]86 5f0-14 6d0-1 7s2, lanthanoids . belong to 4 f series whereas
actinoids belong to 5f-series.
(ii) Atomic and ionic sizes: Both lanthanoids and actinoids show decrease in size of their atoms or ions in
+ 3 oxidation state as we go from left to right. In lanthanoids, the decrease is called lanthanoid
contraction whereas in actinoids, it is called actinoid contraction. The contrition is greater from element
to element in actinodes due to poorer shielding by 5f electrons.
(iii)Oxidation state: Lanthanoids show limited oxidation states (+ 2, + 3, + 4) out of which + 3 is most
common whereas actinoids show +3, +4, +5, +6, +7 oxidation states. This is because of large energy gap
between 4f 5d and 6s orbitals. However, actinoids show a large number of oxidation states because of
small energy gap- between 5f 6d and Is orbitals..
How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing.
(ii) How would you account for the increasing oxidising power in the series VO2 + < Cr2O7 2–<
MnO4– (iii) The E V (M2+/M) value for copper is positive (+0.34V). What is possible reason for
this
(i)Cr2+ is reducing as its configuration changes from d 4 to d 3 , the latter having a half-filled t2g level.
On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d 5 ) configuration which has
extra stability(ii)This is due to the increasing stability of the lower species to which they are
reduced(iii)consider its high ∆aH V and low ∆hyd H V )

8 Define Disproportionation
Reactions are those in which the same substance undergoes oxidation as well as reduction, i.e., oxidation
number of an element increases as well as decreases to form two different products

9 What can be inferred from the Answer:

magnetic moment values of the
following complex species?

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10 Give examples and suggest reasons for the following features of the transition metal
(i) The lowest oxide of transition metal is basic the highest is amphoteric/ acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal
(i) The lower oxide of transition metal is basic because the metal atom has low oxidation state whereas
higher once are acidic due to high oxidation state. For example, MnO is basic whereas Mn2O7is acidic.
Oxides in lower oxidation state are ionic hence basic. Oxides in higher oxidation state are covalent hence
acidic
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides because oxygen and
fluorine are highly electronegative elements, small in size and strongest oxidising agents. For example,
osmium shows an oxidation states of + 6 in O5F6and vanadium shows an oxidation states of + 5 in V2O5.
(iii) Oxo metal anions have highest oxidation state, e.g., Cr in Cr2072- has an. oxidation state of + 6
whereas Mn in Mn04– has an oxidation state of + 7. This is again due to the combination of the metal with
oxygen, which is highly electronegative and oxidizing agent.

LONG QUESTIONS
1 Explain giving reasons:
(i)Transition metals and many of their compounds show paramagnetic behaviour.
(ii)Transition metals form alloys. (iii)The transition metals generally form coloured
compounds(iv)Transition metals and their many compounds act as good catalyst.
(v) Why Cu undergo disproportionation reaction in aq sol
(i)Due to presence of unpaired electron(ii)Due to similarity in size
(iii) d-d transition, electron from lower energy level jumps to higher energy level
(iv) Due to variable oxidation
(v)the ion is unstable in an aqueous medium and undergoes the disproportionation reaction, and gives C
u 2 + and as the product. It gets oxidized to give cuprous ion and reduced to give copper metal. The
chemical reaction can be depicted as: 2 Cu + (aq ) → Cu ( s ) + Cu 2 + ( aq )

2 Observed and calculated values for the standard electrode potentials of elements from Ti to Zn

(i) The general trend towards less negative Eo values across the series
(ii) Explain the irregularity in the above values
(iii)More negative Eo values of Mn and Zn
(iv)Why is the E V value for the Mn3+/Mn2+ couple much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+? Explain
(v)Explain why Cu+ ion is not stable in aqueous solutions
(i)The general trend towards less negative E0 values along the series is due to the general increase in the
sum of first and second ionization enthalpies.
(ii)The E0(M2+/M) values are not regular which can be explained from the irregular variation of
ionisation enthalpies and also the sublimation enthalpies which are relatively much less for manganese
and vanadium

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 (iv)Much larger third ionisation energy of Mn (where the required change is d 5 to d 4 ) is mainly
responsible for this. This also explains why the +3 state of Mn is of little importance
(v)Cu+ (aq) is not stable, while Cu2+ (aq) is stable. This is because ΔhydH of Cu2+(aq) is much higher
than that of Cu+(aq) and hence it compensates for the 2nd IE of Cu. Thus, many Cu(I) compounds are
unstable in aqueous solution and undergo disproportionation as follows : 2 Cu+ —–> Cu2+ + Cu

1. CASE BASED QUESTIONS

The Following questions are case based questions carries 4 (1+1+2) marks. Read the
given passage carefully and answer the questions that follow:
The transition metals react with a number of non-metals like oxygen, nitrogen, sulphur and
halogens to form binary compounds. The first series transition metal oxides are generally formed
from the reaction of metals with oxygen at high temperatures. These oxides dissolve in acids and
bases to form oxometallic salts. Potassium dichromate and potassium permanganate are common
examples. Potassium dichromate is prepared from the chromite ore by fusion with alkali in
presence of air and acidifying the extract. Pyrolusite ore (MnO2) is used for the preparation of
potassium permanganate. Both the dichromate and the permanganate ions are strong oxidising
agents.
a) What happens when Manganate ions (MnO42- ) undergoes disproportionation reaction in acidic
medium?
[Ans :- MnO42- ions disproportionate in acidic medium to give Permanganate ions and
Manganese(IV) oxide. 3MnO4 2- + 4 H+ → 2MnO4 - + MnO2 + 2H2O
b) Explain why the colour of KMnO4 disappears when oxalic acid is added to its solution in acidic
medium.
[Ans :- This is a redox titration. The deep purple colour of KMnO4 disappears due to the formation
of MnSO4]
c) When an orange solution containing Cr2O72– ion is treated with an alkali, a yellow solution is
formed and when H+ ions are added to a yellow solution, an orange solution is obtained. Explain
why does this happen?
[ Ans:- When Cr2O7 2- ion is treated with an alkali :
Cr2O7 2– (orange) + 2 OH-→2CrO4 2–(yellow) + H2O
When the yellow solution is treated with an acid, we get back the orange solution:
2 CrO4 2– (yellow)+ 2H+→Cr2O7 2–(orange) + H2O
OR
A solution of KMnO4 on reduction yields either colourless solution or a brown precipitate or a
green solution depending on the pH of the solution. What different stages of the reduction do
these represent and how are they carried out?
[Ans:- In acidic medium, permanganate changes to manganous ion which is
colourless. MnO4– + 8H+ + 5e--------------- Mn2+ (colourless) + 4H2O
In alkaline medium, permanganate changes to manganate, which is a green solution
MnO4-+ e- → MnO42- (green)
In a neutral medium, permanganate changes to manganese dioxide which is a brown
precipitate,
MnO4– + 2H2O + 3e-→ MnO2 (brown) + 4OH-

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 Unit -5 COORDINATION COMPOUNDS
Coordination compounds are a special class of compounds in which the central metal atom is
surrounded by ions or molecules beyond their normal valency. These compounds are widely present in
the minerals, plants and animals and play many important functions. Many biologically important
compounds are Coordination compounds in which complicated organic species are bound to metal ions.
The common examples are: Hemoglobin which is a Coordination compound of Iron, Chlorophyll
which is a Coordination compound of Magnesium and Vitamin B12 which is a Coordination compound
of Cobalt etc. The Coordination compounds are also finding extensive applications in metallurgical
processes, analytical chemistry, industrial catalysts, textile dyeing, electroplating and medicinal
chemistry.
Coordination compounds are molecular compounds which are formed from the combination oftwo
or more simple stable compounds and retain their identity in the solid as well as in the dissolved state.
For example, when aqueous ammonia is added to green solution of nickel chloride, NiCl2, the colour
changes to [Ni (NH3)6] Cl2 purple crystals. Such a compound is calledCoordination compounds.
NiCl2 (Green) + 6NH3 [Ni (NH3)6] Cl2 (Purple)
When the compound [Ni (NH3)6] Cl2 is dissolved in water it ionizes to give a new species. Suchan ion is
called complex ion [Ni (NH3)6]2+.
[Ni (NH3)6] Cl2 [Ni (NH3)6]2+ + 2Cl-
Coordination compounds are the compounds in which the central metal atom is bound to a number
of anions or neutral molecules by coordinate bonds.
Coordination entity: A coordination entity constitutes a central metal atom or ion bounded to afix
number of oppositely charged ions or neutral molecules. For example, [Co Cl3 (NH3)3]
Coordination sphere: The central metal atom or ion and the molecules or ions bonded to it are
enclosed in a square bracket and a collectively called the Coordination sphere.
Central atom or ion: The atom or ion to which a fixed number of neutral molecules or ions areattached
in the coordination entity is called Central atom or ion.
Ligands: The neutral molecules or ions bonded to the central atom or ion in the coordinationentity
are called ligands. For example,
[Ni (NH3)6]2+: Central atom = Ni2+, ligands = NH3 molecules
Types of ligands:
(i) Unidentate or monodentate ligands: When a ligand is bound to a metal ion througha single
donor atom, as with Cl–, H2O or NH3, the ligand is said to be Unidentate ligands.
(ii) Didentate or Bidentate ligands: When a ligand can bind through two donor atoms as in
H2NCH2CH2NH2 (ethane-1, 2-diamine) or C2O42– (oxalate), the ligand is said to beDidentate ligands.
(iii) Polydentate ligands: Ligands having more the two donor atoms present in the
molecule, the ligands are said to be Polydentate ligands.
Diethylene triamine acts as tridentate ligand having three donor N atoms.
Triethylene tetra amine acts as tetradentate ligand having four donor N atoms. Ethylenediamine
triacetate ion acts as Pentadentate ligand having two N atoms and three Oatoms.
Ethylenediaminetetraacetate ion (EDTA4–) is an important hexadentate ligand. It can bindthrough two
nitrogen and four oxygen atoms to a central metal ion.
When a di- or Polydentate ligand uses its two or more donor atoms simultaneously to bind a single
metal ion, it is said to be a chelate ligand. The number of such ligating groups is called the denticity of
the ligand. Such complexes, called chelate complexes tend to be more stable thansimilar complexes
containing Unidentate ligands.
Ligand which has two different donor atoms and either of the two ligates in the complex is called
ambidentate ligand.
Examples of such ligands are the NO2 – and SCN– ions. NO2 – ion can coordinate either throughnitrogen
or through oxygen to a central metal atom/ion.
Similarly, SCN– ion can coordinate through the sulphur or nitrogen atom.

40 | P a g e
 Coordination number: The total number of ligands attached to a central metal atom or ion is called
the Coordination number of that metal atom or ion. For example,
[Ni (NH3)4]2+: C.N. of Ni2+ = 4 [Co Cl3 (NH3)3]: C.N. of Co3+ = 6
IUPAC nomenclature of coordination compounds: Write the IUPAC names of the following
coordination compounds:
(a) [Pt (NH3)2 Cl (NO2)] (a) Diamminechloridonitrito-N-platinum (II)
(b) K3 [Cr (C2O4)3] (b) Potassium trioxalatochromate (III)
(c) [Co Cl2 (en)2]Cl (c) Dichloridobis (ethane-1, 2-diamine) cobalt (III) chloride
(d) [Co (NH3)5(CO3)] Cl (d) Pentaamminecarbonatocobalt (III) chloride
(e) Hg [Co (SCN)4] (e) Mercury (I) tetrathiocyanato-S-cobaltate (III)
(f) [Cr (NH3)3 (H2O)3] Cl3 (f) Triamminetriaquachromium (III) chloride
(g) [Co (H2NCH2CH2NH2)3]2 (SO4)3 (g) Tris (ethane-1,2–diamine)cobalt(III) sulphate
(h) [Ag (NH3)2][Ag(CN)2] (h) Diamminesilver (I) dicyanidoargentate (I)

Werner's theory: Werner proposed the concept of a primary valence and a secondary valencefor a
metal ion. Binary compounds such as CrCl3, CoCl2 or PdCl2 have primary valence of 3, 2 and 2
respectively.
In a series of compounds of cobalt (III) chloride with ammonia, it was found that some of the chloride
ions could be precipitated as AgCl on adding excess silver nitrate solution in cold butsome remained in
solution.
1 mol CoCl3.6NH3 (Yellow) gave 3 mol AgCl1 mol CoCl3.5NH3 (Purple) gave 2 mol AgCl1 mol
CoCl3.4NH3 (Green) gave 1 mol AgCl1 mol CoCl3.4NH3 (Violet) gave 1 mol AgCl
Werner proposed the term secondary valence for the number of groups bound directly to themetal ion;
in each of these examples the secondary valences are six.
Formulation of Cobalt (III) Chloride-Ammonia Complexes:
Colour Formula Solution conductivity corresponds to
Yellow [Co (NH3)6]3+ 3Cl- 1:3
Purple [Co Cl (NH3)5] 2Cl
2+ - 1:2
Green [Co Cl2 (NH3)4]+ Cl- 1:1
Violet [Co Cl2 (NH3)4] Cl
+ - 1:1
The main postulates are:
1. In coordination compounds metals show two types of linkages (valences)-primary andsecondary.
2. The primary valences are normally ionisable and are satisfied by negative ions.
3. The secondary valences are non ionisable. These are satisfied by neutral molecules or negativeions.
The secondary valence is equal to the coordination number and is fixed for a metal.
4. The ions/groups bound by the secondary linkages to the metal have characteristic
Partial arrangements corresponding to different coordination numbers.

Valence Bond Theory (VBT) for bonding in Coordination Compounds:

The main assumptions of this theory are listed below:
1. The central metal ion in the complex makes available a number of empty orbitals for the
formation of coordination bonds with suitable ligands.
2. The number of empty orbitals made available for this purpose is equal to coordination number
of the central metal ion. For example, if coordination number is 6, six empty orbitals are made
available and if coordination number is 4, four empty orbitals are madeavailable in the central
metal ion.
3. The appropriate atomic orbitals (s, p and d) of the metal hybridize to give a set of equivalent
orbitals of definite geometry such as square planar, tetrahedral and octahedraland so on.
4. The d-orbitals involved in the hybridization may be either inner d-orbitals i.e. (n-1) d or outer
d-orbitals i.e. nd. For example, in case of octahedral hybridization. The orbitals maybe two 3d,
one 4s and three 4p (d2sp3) or one 4s, three 4p and two 4d (sp3d2)
5. Each ligand has at least one orbital (of donor atom)) containing a lone pair of electrons.
6. The empty hybrid orbitals of metal ion overlap the filled orbitals of the ligand to formmetal-
ligand coordinate covalent bonds.
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Number of Orbitals, Types of Hybridizations and Magnetic Properties of Coordination
Compounds:
Coordinatio Type of Complex/ion Geometry No. of Magnetic Character
nnumber hybridization unpaired
electrons
4 sp3 [NiCl4]2- Tetrahedral 2 Paramagnetic
4 dsp2 [Ni(CN)4]2- Square planar 0 Diamagnetic
6 sp3d2 [CoF6]3– Octahedral 4 Paramagnetic
6 d2sp3 [Co(NH3)6]3+ Octahedral 0 Diamagnetic

CRYSTAL FIELD THEORY (CFT): The crystal field theory (CFT) is an electrostatic model which
considers the metal-ligand bond to be ionic arising purely from electrostatic interactions between the
metal ion and the ligand. Ligands are treated as point charges in case of anions or point dipoles in case
of neutral molecules. The five d orbitals in an isolated gaseous metal atom/ion have same energy, i.e.,
they are degenerate. This degeneracy is maintained if a spherically symmetrical field of negative
charges surrounds the metal atom/ion. However, when this negative field is due to ligands (either
anions or the negative ends of dipolar molecules like NH3 and H2O) in a complex, it becomes
asymmetrical and the degeneracy of the d orbitals is lifted. It results in splitting of the d orbitals. The
pattern of splitting depends upon the nature of the crystal field.
The conversion of five degenerate d-orbitals of the metal ion into different sets of orbitals having
different energies in the presence of electric field of ligand is called crystal field splitting.
(a) Crystal field splitting in octahedral coordination entities:

d orbital splitting in an octahedral crystal field (fig. 9.8 ncert)

Spectrochemical series: ligands can be arranged in a series in the order of increasing field
strength as given below:
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O4 2– < H2O < NCS– < edta4– < NH3 < en < CN– < CO
For d4 ions, two possible patterns of electron distribution arise:
(i) The fourth electron could either enter the t2g level and pair with an existing electron, or
(ii) It could avoid paying the price of the pairing energy by occupying the eg level. Which of these
possibilities occurs, depends on the relative magnitude of the crystal field splitting, ∆o andthe pairing
energy, P (P represents the energy required for electron pairing in a single orbital). The two options
are:
If ∆o < P, the fourth electron enters one of the eg orbitals giving the configuration t2g3 eg1
Ligands for which ∆o < P are known as weak field ligands and form high spin complexes.
If ∆o > P, it becomes more energetically favourable for the fourth electron to occupy a t2g
orbital with configuration t2g4 eg0 Ligands which produce this effect are known as strong field ligands
and form low spin complexes.
(b) Crystal field splitting in tetrahedral coordination entities:

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In tetrahedral coordination entity formation, the d orbital splitting (Fig. 9.9) is inverted and is smaller
as compared to the octahedral field splitting. For the same metal, the same ligands andmetal-ligand
distances, it can be shown that ∆t = (4/9) ∆o.
Colour in Coordination Compounds: The crystal field theory attributes the colour of the
coordination compounds to d-d transition of the electron. Relationship between the Wavelength of Light
absorbed and the Colour observed in someCoordination Entities:

Coordination Wavelength of Colour of light Colour of

entity light absorbed absorbed coordinationentity
(nm)
[Co(CN)6]3– 310 Violet Pale Yellow
[Co(NH3)6]3+ 475 Blue Yellow Orange
[Co(NH3)5(H2O)]3+ 500 Blue Green
Red
[Ti(H2O)6]3+ 510 Blue Green
Purple
[Co Cl(NH3)5]2+ 535 Yellow Violet
[Cu(H2O)4]2+ 600 Red Blue
Isomerism in Coordination Compounds:
Two or more compounds having the same molecular formula but different arrangement of atomsare
called isomers and the phenomenon is called Isomerism
Two types of isomerism are: (a) Structural isomerism (b) Stereoisomerism
(a) Structural isomerism: The isomers which have same molecular formula but different structural
arrangement of atoms or groups of atoms around the central metal ion are calledstructural isomers.
(i) Ionization isomerism: The compounds which have same molecular formula but give differentions
in solution are called ionization isomers. For example:
[Co (NH3)5 (SO4)]Br and [Co (NH3)5Br] SO4 .
(ii) Solvate isomerism: The compounds which have same molecular formula but differ in thenumber
of solvent molecules present as ligands and as free solvent molecules in the crystal lattice are called
solvate isomers. This form of isomerism is known as ‗hydrate isomerism in case where water is
involved as a solvent. For example:
[Cr (H2O)6]Cl3 (violet) and its solvate isomer [Cr (H2O)5 Cl]Cl2.H2O (grey-green).
(iii) Coordination isomerism: This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex. For example:
[Co (NH3)6][Cr(CN)6 ], in which the NH3 ligands are bound to Co3+ and the CN– ligands to Cr3+.In its
coordination isomer [Cr (NH3)6][Co(CN)6 ], the NH3 ligands are bound to Cr3+ and the CN–ligands to
Co3+.
(iv) Linkage isomerism: The compounds which have same molecular formula but differ in the mode of
attachment of a ligand to the metal atom or ion are called linkage isomers. Linkage isomerism arises
in a coordination compound containing ambidentate ligand. For example: Complexes containing the
thiocyanate ligand, which may bind through sulphur to give M–SCN.Isothiocyanate ligand through the
nitrogen to give M–NCS.
[Co (NH3)5 (NO2)]Cl2 the ligand is bound through nitrogen (–NO2). [Co (NH3)5 (ONO)]Cl2 the ligand is
bound through oxygen (–ONO).
(b) Stereoisomerism: Stereoisomers have the same chemical formula and chemical bonds butthey have
different spatial arrangement of atoms.
Two types of isomerism are: (a) Geometrical isomerism (b) Optical isomerism
(a) Geometrical isomerism: This type of isomerism arises in heteroleptic complexes due to ligands
occupying different positions around the central ion. The ligands occupy positions either adjacent to
one another or opposite to one another. These are referred to cis- form (ligand occupy adjacent
position) and trans-form (ligand occupy opposite position). For example:
Geometrical isomers (cis and trans)
of Pt [NH3)2 Cl2]

Cis- trans-

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(b) Optical isomerism: Optical isomers are mirror images that cannot be superimposed on oneanother.
These are called as enantiomers.
The molecules or ions that cannot be superimposed are called chiral.
The two forms are called dextro (d) and laevo (l) depending upon the direction they rotate theplane of
polarized light in a polarimeter (d rotates to the right, l to the left).
Optical isomerism is common in octahedral complexes involving Didentate ligands.
Optical isomers of [PtCl2 (en)2] 2+

Importance and Applications of Coordination Compounds:

The coordination compounds are of great importance. These compounds are widely present in the
mineral, plant and animal worlds and are known to play many important functions in the area of
analytical chemistry, metallurgy, biological systems, industry and medicine. These are described
below:
• Coordination compounds find use in many qualitative and quantitative chemical analyses.Examples
of such reagents include EDTA, DMG (dimethylglyoxime), etc.
Ni2+ ions are detected by adding DMG (dimethylglyoxime) in the presence of NH4OH to nickelsalt
solution, red precipitates are formed.
• Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and Mg2+ ions form stable
complexes with EDTA. The selective estimation of these ions can be done due to difference in the
stability constants of calcium and magnesium complexes.
• Some important extraction processes of metals, like those of silver and gold, make use of complex
formation. Gold, for example, combines with cyanide in the presence of oxygen andwater to form the
coordination entity [Au (CN)2] – in aqueous solution
• Purification of metals can be achieved through formation and subsequent decomposition of their
coordination compounds.
For example, impure nickel is converted to [Ni (CO)4], which is decomposed to yield purenickel.
• Biological importance: Coordination compounds are of great importance in biological systems.The
pigment responsible for photosynthesis, chlorophyll, is a coordination compound of magnesium.
Haemoglobin, the red pigment of blood which acts as oxygen carrier is a coordination compound of
iron.
Vitamin B12, cyanocobalamine, the anti– pernicious anemia factor, is a coordination compound of
cobalt.
• In catalyst: Coordination compounds are used as catalysts for many industrial processes.Examples
include rhodium complex, [(Ph3P)3 Rh Cl], a Wilkinson catalyst, is used for the hydrogenation of
alkenes.
• Articles can be electroplated with silver and gold much more smoothly and evenly from solutions of
the complexes, [Ag (CN)2] – and [Au(CN)2 ] – than from a solution of simple metalions.
• In black and white photography: The developed film is fixed by washing with hypo solutionwhich
dissolves the undecomposed AgBr to form a complex ion, [Ag (S2O3)2] 3–.
• In medicine: Complexing agents are used for removal of metal poisoning. A platinum complex,[Pt Cl2
(NH3)2] known as cis-platin has been used in cancer therapy.

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 MCQ (Multiple Choice Question)
Q.1 The solution of the complex [Cu(NH3)4] SO4 in water –
(A) Will give the tests of Cu2+ ions (B) Will give the tests of NH3
(C) Will give the tests of SO42– ions (D) Will not give the tests of any of the above species [C]
Q.2 The donor atoms in EDTA are –
(A) Two N and Two O (B) Two N and four O
(C) Four N and Two O (D) Three N and three O [B]
Q.3 Which of the following ligands is not a chelating agent –
(A) EDTA (B) en
(C) Oxalate (D) Pyridine [D]

Q.4 The co-ordination number of Cr in the complex ion [Cr(H2O)6]3+ is –

(A) Zero (B) 3 [C]

(C) 6 (D) None of these
Q.5 The oxidation number of platinum in [Pt(NH3)5 Cl]Cl3 is –

(A) 2 (B) 3
(C) 4 (D) 6 [C]
Q.6 An ambidentate ligand is one which –

(A) is linked to the metal atom at two points

(B) has two donor atoms but only one of them has the capacity to form a coordinate bond

(C) Has two donor atoms but either of the two can form a co-ordinate bond

(D) forms chelate rings [C]

Q.7 Coordination number and oxidation number of Cr in K3[Cr(C2O4)3] are, respectively –

(A) 4 and + 2 (B) 6 and + 3

(C) 3 and + 3 (D) 3 and 0 [B]
Q.8 All ligands are –
(A) Lewis acid (B) Lewis base [B]
(C) Neutral (D) None of these
Q.9 In SCN ligand if N is attached to central atom, the name of ligand is –
(A) Thiocyanato-N (B) Cyanato-N
(C) Thiocyanato-S (D) Cyanato-S [A]
Q.10 In [Co(NH3)4Cl2]Cl the co-ordination number of cobalt is –

(A) 4 (B) 6 (C) 2 (D)7 [B]

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 ASSERTION AND REASONING QUESTIONS
1. Assertion: Toxic metal ions are removed by the chelating ligands.
Reason: Chelate complexes tend to be more stable.
Answer: a
2. Assertion: Linkage isomerism arises in coordination compounds containing ambidentate ligand.
Reason: Ambidentate ligand has two different donor atoms.
Answer: a
3. Assertion: Complexes of MX6 and MX5L type (X and L are unidentate) do not show geometrical
isomerism.
Reason: Geometrical isomerism is not shown by complexes of coordination number 6.
Answer: c
4. Assertion: [Fe(CN)6]3– ion shows magnetic moment corresponding to two unpaired electrons.
Reason: Because it has d2sp3 type hybridization.
Answer: d

SHORT ANSWER TYPE QUESTION

Q1. Write the formulas for the following coordination compounds:
(a) Tetraammineaquachloridocobalt (III) chloride
(b) Potassium tetrahydroxidozincate (II)
(c) Potassium trioxalatoaluminate (III)
(d) Dichloridobis (ethane-1, 2-diamine) cobalt (III) ion
(e) Tetracarbonylnickel (0)
Ans.:
(a) [Co (NH3)4(H2O) Cl] Cl2
(b) K2 [Zn (OH)4]
(c) K3 [Al (C2O4)3]
(d) [Co Cl2 (en)2] +
(e) [Ni (CO)4]
Q2. Write the IUPAC names of the following coordination compounds:
(a) [Pt (NH3)2Cl (NO2)]
(b) K3 [Cr (C2O4)3]
(c) [Co Cl2 (en)2] Cl
(d) [Co (NH3)5(CO3)] Cl
(e) Hg [Co (SCN)4]
Ans.:
(a) Diamminechloridonitrito-N-platinum (II)
(b) Potassium trioxalatochromate (III)
(c) Dichloridobis (ethane-1, 2-diamine) cobalt (III) chloride
(d) Pentaamminecarbonatocobalt (III) chloride
(e) Mercury (I) tetrathiocyanato-S-cobaltate (III)

Q3. Draw structures of geometrical isomers of [Fe (NH3)2(CN)4]–Ans.

Q4. Indicate the types of isomerism exhibited by the following complexes and draw thestructures for
these isomers:
(i) K [Cr (H2O)2(C2O4)2]
(ii) [Co(en)3]Cl3
(iii) [Co (NH3)5(NO2)](NO3)2
(iv) [Pt(NH3)(H2O)Cl2]

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Ans. (i) Both geometrical (cis and trans) and optical isomers for cis. (ii)Two optical isomers
(iii)Geometrical, ionization and linkage isomers.
(iv)Geometrical (cis and trans)
Q5. Give evidence that [Co (NH3)5Cl] SO4 and [Co (NH3)5(SO4)] Cl are ionization isomers.
Ans. (NH3)5Cl] SO4 + BaCl BaSO4 (white ppt)
[Co (NH3)5(SO4)] Cl + AgNO3 AgCl (white ppt)
Q6. The spin only magnetic moment of [MnBr4]2– is 5.9 BM. Predict the geometry of thecomplex ion?
Ans. Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either tetrahedral
(sp3 hybridization) or square planar (dsp2 hybridization). But the fact that the magnetic moment of the
complex ion is 5.9 BM, it should be tetrahedral in shape rather thansquare planar because of the
presence of five unpaired electrons in the d orbitals.
Q7. Predict the number of unpaired electrons in the square planar [Pt (CN)4]2– ion.Ans. Pt = 5d9 6s1
Pt (II) = 5d8, square planar geometry and dsp2 hybridization.
Q8. Explain on the basis of valence bond theory that [Ni (CN)4]2– ion with square planarstructure is
diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is paramagnetic.Ans. [Ni (CN)4]2– square
planar geometry and dsp2 hybridization.
[NiCl4]2– Tetrahedral geometry and sp3 hybridization.
Q 9. [Fe (H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly paramagnetic.Explain.
Ans. In both the complexes, Fe is in +3 oxidation state.
CN- is strong field ligand, inner d-orbitals are involved, d2sp3 hybridization, one unpaired electron,
weakly paramagnetic.
H2O is weak field ligand, outer d-orbitals are involved, sp3d2 hybridization, five unpairedelectrons,
strongly paramagnetic.
Q10. Explain [Co (NH3)6]3+ is an inner orbital complex whereas [Ni (NH3)6]2+ is an outer orbital
complex.
Ans. [Co (NH3)6]3+ is an inner orbital complex, d2sp3 hybridization.[Ni (NH3)6]2+ is an outer orbital
complex, sp3d2 hybridization.

3 MARKS QUESTIONS
1. What is meant by crystal field splitting energy? On the basis of crystal field theory, write the
electronic configuration of d4 in terms of t2g and eg in an octahedral field when (i) Δ0 > P (ii) Δ0 < P

Ans: The difference between energies of two sets of d-orbitals t2g and e is called crystal field splitting
energy (Δ0).
If Δ0 > P, the configuration will be t2g4, eg0. Ligands will produce strong field and pairing takes place.
If Δ0 < P, the configuration will be t2g3, eg1 and it is in the case of weak field ligands and pairing will
not take place
2. i. Nickel (II) does not form low spin octahedral complexes.
ii. [Fe(CN)6]4- and [Fe(H2O)6]2 + are of different colours in dilute solutions.

Ans: i. Ni2+ has unpaired electrons, therefore, forms high spin complex as pairing of electrons does not
take place because after pairing only one d-orbital will be left which cannot be used in octahedral
complex.
(ii) They absorb different wavelengths from visible light, undergo d-d transitions and radiate
complementary colour. CN- is stronger ligand than H2O.
3. Name the following coordination compounds according to IUPAC system of nomenclature.
1. [CO(NH3)2 (H2O) Cl] Cl2
2. [Cr Cl2(en)2] Cl, (en = ethane-1,2-diamine)
Answer:
1. Tetraammineaquachlorido cobalt(III) chloride.
2. Dichlorido bis(ethane 1, 2-diamine) chromium (III) chloride.
4. Describe the shape and magnetic behaviour of following complexes:
1. [CO(NH3)6]3+
2. [Ni(CN)4]2-
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 Answer: It is octahedral, d2sp3 hybridised, diamagnetic in nature.
It is square planar, dsp2 hybridised, diamagnetic in nature
5. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization isomers?
ANS. When they are dissolved in water, they will give different ions in the solution which can be tested
by adding AgNo3 solution and BaSO4 solution. when cl ions are counter ions a white ppt will be
obtained AgNo3 solution, If SO42- ions are counter ions a white ppt will be obtained with BaCl2 solution
6. [Fe(H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6 ]3- is weakly paramagnetic ? why
ANS. In both the complexes Fe is in +3 oxidation state with the configuration 3d5. CN- is a strong ligand.
In Its presence, 3d electron s pair up leaving only one unpaired electron. The hybridisation is d2sp3
forming Inner orbital complex. H2O is a weak ligand , In its presence, 3d electron do not pair up . The
hybridisation is sp3d2 forming an outer orbital complex containing five unpaired electrons. Hence it is
strongly paramagnetic.
7. [NiCl4]2- is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral ,why ?
ANS. In[NiCl4]2-, Ni is +2 oxidation state with the configuration 3d84S0 ,Cl- is weak ligand . it cannot
pair up the electron in 3d orbitals, Hence it is paramagnetic. In [NI(CO)4],Ni is in zero oxidation state
with the configuration 3d84s2,In the presence of CO ligand , the 4s electrons shift to 3d to pair up 3d
electron s .thus ,there is no unpaired electron present . Hence it is diamagnetic.
8. A complex is prepared by mixing CoCl2 and NH3 In the molar ratio of 1:4, 0.1M solution of this
complex was found to freeze at -0.372°c. what is the formula of the complex? Given that molal
depression constant of water (kf)=1.86c/m
ANS. Theoretical change in temperature =kfxm =1.86x0.1=0.186 Observed change in
temperature(freezing)=0.372 As observed value is double of the theoretical value This show that each
molecule of the complex dissociates to form two ions. This can be so only if the formula of the complex
is [Co(NH3)4Cl2]Cl
9. Calculate the over all complex dissociation equilibrium constant for the [Cu(NH3)4]2+ion , given
that B4 for this complex is 2.1 x(10)13?
ANS. Overall stability constant (B)=2.1x(10)13
Overall dissociation constant is the reciprocal of the overall stability constant .Hence overall
dissociation constant= 1\B4= 1\2.1X(10)13=4.7X(10)-14.
10. Write down the applications of coordination compound?
ANS (a) In analytical chemistry
(b) In metallurgy
(c) In purification of metal
(d) In Industry
(e) In medical field
11. Define the following terms;
(a) Homoleptic complex
(b) Hetroleptic complex
(c) Coordination sphere ;
ANS. Homoleptic complex-; complexes in which the metal atom or ion is linked to only one type of
ligands are called homoleptic complexes, eg ,[Co(NH3)6]3+
Hetroleptic complexes- complexes in which the metal atom or ion is linked to more than one kind of
ligands are called hetroleptic complexes .eg ;[Co(NH3)4Cl2]+
(c )Coordination sphere ;--The central atom and the ligands which are directly attached to it are
enclosed in square brackets and are collectively termed as the coordination sphere.

48 | P a g e
 12. ( i) What type of isomerism is shown by the complex [Cr (H2O)6]Cl3 ?
(ii) On the basis of CFT , write the electronic configuration for d4 ion if Δ0 > P .
(iii) Write the hybridization and shape of [CoF6]3- . [ atomic number of Co=27]
ANS. (I) Hydrate isomerism.
(ii) Δ0 > P so t2g4 eg0
(iii)sp3d2 hybridization and Octahedral shape.

5. MARKS QUESTIONS
1. Write the name of the structure and the magnetic behaviour of each one of the following complexes
(At. nos. Co = 27, Ni = 28, Pt = 78)
i. [Pt(NH3)2Cl(NO2)] ii. [Co(NH3)4 Cl2] Cl iii. Ni(CO)4
Answer:
i. Diamminechloridonitrito-N-platinum(II). It is square planar and diamagnetic.
ii. Tetraamminedichlorido cobalt(III) chloride. It is octahedral and diamagnetic.
iii. Tetracarbonylnickel(O). It is tetrahedral and diamagnetic complex.
2. For the complex [Fe(en)2Cl2]Cl, identify the following:
i. Oxidation number of iron. ii. Hybrid orbitals and shape of the complex.
iii. Magnetic behaviour of the complex. iv. Number of its geometrical isomers.
v. Whether there may be optical isomer also. vi. Name of the complex.
Answer:
i. +3 (III) ii. d2sp3, octahedral
iii. paramagnetic iv. Two geometrical isomers
v. Yes, there may be optical isomer also due to presence of polydentate ligand.
vi. Dichloridobis-(ethane 1, 2-diamine) Iron (III)
3. Write the name, the state of hybridization, the shape and the magnetic behaviour of the following
complexes: [CoCl4]2-, [Cr(H2O)2(C2O4)2]- , [Ni(CN)4]2-
(At. No. : Co = 27, Ni = 28, Cr = 24)
Answer.

CASE BASED QUESTIONS

1. Complex compounds play an important role in our daily life. Werner’s theory of complex compounds
says every metal atom or ion has primary valency (oxidation state) which is satisfied by –vely charged
ions, ionisable where secondary valency (coordination number) is non-ionisable, satisfied by ligands
(+ve, –ve, neutral) but having lone pair. Primary valency is non-directional, secondary valency is
49 | P a g e
directional. Complex compounds are name according to IUPAC system. Valence bond theory helps in
determining shapes of complexes
Based on hybridisation, magnetic properties, outer or inner orbital complex. Complex show ionisation,
linkage, solvate and coordination isomerism also called structural isomerism. Some of them also show
stereoisomerism i.e. geometrical and optical isomerism. Ambidentate ligand are essential to show linkage
isomerism. Polydentate ligands form more stable complexes then unidentate ligands. There are called
chelating agents. EDTA is used to treat lead poisoning, cis-platin as anticancer agents. Vitamin B12 is
complex of cobalt. Haemoglobin, oxygen carrier is complex of Fe2+ and chlorophyll essential for
photosynthesis is complex of Mg2+.
a. What is the oxidation state of Ni in [Ni(CO)4]?
Ans. Zero
b. Out Cis – [Pt(en)2 Cl2]2+ and trans[ (Pt(en)2Cl2)]2+ which one shows optical isomerism?
Ans. Cis – [Pt(en)2 Cl2]2+ shows optical isomerism.
c. What is hybridisation of [CoF6]3–? [Co = 27] Give its shape and magnetic properties.
Ans. sp3d2, octahedral, paramagnetic. It is outer orbital complex.
2. Transition metals form complex compounds which play a very important role in our daily life.
Complexes are also formed by other groups elements e.g. Chlorophyll is coordination compound of Mg.
Organometallic compounds like Grignard reagent is most useful in organic chemistry. Complexes are
used in medicines, analytical chemistry, qualitative analysis, electroplating, biological processes. Stability
of complexes depends upon charge on central metal ion, strength of ligand. Counter ions outside the
coordination entity are ionisable but inside the coordination sphere are not ionisable.
a. Name a complex used as anticancer agent?
Ans. Cis-platin
b. What is coordination number of Co in[Co(en)3]3+ and why?
Ans. Coordination number of Co is 6 because ‘en’(ethane 1, 2-diammine) is bidentate ligand.
c. Name a complex used for determining hardness of water. What is its denticity?
Ans. EDTA, it is hexadentate ligand, denticity =6
3. Negative ion or Neutral molecule which bound to the metal ion by secondary valency is called as
ligand. In complex , metal ion acts as Lewis acid and ligand act as Lewis base. Ligands are classified
according to number of electron pair in them.
The ligand which can donates one e pair to the metal atom is called Unidentate ligand . The ligand which
can donate two electron pair to the Metal ion is called didentate ligand. The ligand in which two or more
coordination sites are there is called polydentate ligand.
Polydentate ligand forms cyclic structure with metal ion and form Chelate.
(i) In complex compound ligand is also known as:
(a) Lewis acid (b) Lewis base (c) Bronsted acid (d) Bronsted base
(ii) Number of unidentate ligand is complex compound is known as:
(a) Oxidation number (b) primary valency (c) Secondary valency (d) tertiary valency
(iii) Which ligand can not form chelate ?
(a) SO42- (b) Ox2- (c) O2- (d) CO32-
(iv) Among the given ligands which one has the highest number of coordination site ?
(a) en (b) Pn (c) Ptn (d) EDTA
(v) EDTA has coordination number of ?
(a) 4 (b) 5 (c) 6 (d) 7
Answer - (i) b (ii) c (iii) c (iv) d (v) c

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 Unit 6 HALOALKANES AND HALOARENES
Alkyl halides : General formula is RX, where R = alkyl group.
General methods of preparation :
≫ From alcohols : Alkyl halides can be prepared from alcohols in a number of ways :
– Action of hydrogen halides :

• Order of reactivity of halogen acids towards the above reaction is :

HI >HBr>HCl
• Order of reactivity of different alcohols towards the above reaction is :
allyl benzyl > tertiary > secondary > primary
Action of phosphorus halides :

– Action of thionyl chloride (Darzen’s process) :

≫ Halogenation of alkanes :

– Abstraction of hydrogen for a particular halogen follows the orderallylic> 3° > 2° > 1° > CH4–
Reactivity of halogens for the above reaction follows the order :F2 > Cl2 > Br2 > I2
≫ Halide exchange method :

This is known as Finkelstein reaction.

– Fluoroalkanes can also be prepared by halide exchange method by reacting alkyl chloride with
inorganic fluorides. This is known as Swart’s reaction.

≫ Action of hydrogen halides on ethers :

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 Addition of hydrogen halides to alkene :Alkenes add on a molecule of hydrogen halide to form alkyl
halide. Reaction follows electrophilic addition mechanism and takes place as per Markownikoff’s rule.
However, in presence of peroxide addition of HBr takes place as per anti-Markownikoff’s rule.

Anti-Markownikoff’s rule is also known as Peroxide effect or Kharasch effect. HCl and HI do not show
peroxide effect. Physical properties :
≫ Alkyl halides being polar in nature are insoluble in water as they cannot break H-bonding already
existing in water.
≫They have higher melting and boiling points. For the same alkyl group boiling point follows the order
as : R I > R Br > R Cl> R F
≫ Decreasing order of boiling points among the isomeric alkyl halides follows the order : 1° > 2° > 3°
alkyl halides
≫ Decreasing order of density among the alkyl halides is RI >RBr>RCl> RF.
For alkyl iodide decreasing order of density is as follows :
CH3I > CH3CH2I > CH3CH2CH2I.
≫ Bond strength of C X bond follows the order
CH3F > CH3Cl > CH3Br > CH3I
i.e., bond strength of C X bond decreases as the size of halogen atoms increases.
≫ Correct stability order of RX is as follows :
R F > R Cl> R Br > R I Chemical properties :
≫Dehydrohalogenation :

≫Friedel Crafts reacton :

≫Reaction with Mg metal :

≫Wurtz reaction :

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≫Wurtz Fittig reaction :

≫Fittig reaction :

≫Reduction of alkyl halides :

HALOARENES Aryl halides : General formula is ArX, where Ar = aryl group.

General methods of preparation :
≫By Raschig process :

From benzene diazonium salt :

By direct halogenation of benzene :

Physical properties :

≫Aryl halides are colourless stable liquids with pleasant odour.

≫These are insoluble in water but readily miscible with organic solvents.
≫Most of them are steam volatile, heavier than water.
≫Their boiling points are higher than corresponding alkyl halides. The boiling points rise gradually
from fluoro to iodo compounds.
Chemical properties :
≫Nucleophilic substitution reactions : The presence of an electron withdrawing group ( NO2) at ortho-
and para-positions increases the reactivity of haloarenes

Electrophilic substitution reactions :

– Halogenation :

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Nitration :

Sulphonation :

Friedal-Crafts reaction :

SN1 Reaction SN2Reaction

It take place in two steps It takes place in one step
SN1 reaction is a unimolecular reaction SN2 reaction is a bimolecular reaction
SN1 reaction leads to racemization SN2reaction leads to optical inversion
Primary allylic and primary benzylic halides show higher reactivity in SN1 reactions than other primary
alkyl halides due to the greater stabilisation of allylic and benzylic carbocation intermediates by
resonance.
≫Vinylic and aryl halides are unreactive in nucleophilic substitution reactions. This is because of
double bond character of C-X bond due to resonance.
Optical isomerism/Enantiomerism :
≫Optical isomer is known as dextrorotatory isomer (latin : dexter means right) (d-form or +ve) if it
rotates the plane polarised light to the right (clockwise) and laevorotatory isomer (latin : laevo means
left) (l-form or –ve) if it rotates the plane polarised light to the left (anticlockwise).
≫An equimolar mixture of the d- form and l-form will be optically inactive and is called racemic
mixture (or dl- form or (±)-mixture).
≫The process of conversion of an enantiomer into racemic mixture is known as racemisation.
≫Chirality : The compound is said to have chirality if the central carbon atom is attached to four
different groups and this centre is called chiral (asymmetric) centre or stereogenic centre or stereo
centre.
≫Achirality : The compound is said to have achirality if the central carbon atom have at least two
identical groups and this centre is called achiral (symmetric).
≫If molecule has a plane of symmetry it is achiral (not chiral) and if molecule has no plane of symmetry
it is chiral.
≫Enantiomers/d and l isomers : They are the optical isomers which are non-superimposable mirror
images (or dissymmetric).
≫Diastereomers : They are the optical isomers which are not mirror images of each other. They have
different physical properties and magnitude of specific rotation.
≫Mesocompounds : These compounds which have two or more even number of chiral carbon atoms
and have an internal plane of symmetry.
They are optically inactive due to internal compensation

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 QUESTIONS

S.No MULTIPLE CHOICE QUESTIONS

1 Increasing order of reactivity of following compound toward aromatic electrophic
substitution reaction is A) Chlorobenzene, B) Anisole, C) Toluene, D) Cyanobenzene
a) D < A < C < B b) B < C < A < D c) A < B < C < D d) D < B < A < C Ans (a)
2 Which of the following molecules is chiral?
(a) Butan-2-ol(b) Propan-2-ol(c) 1-chlorobutane(d) Butanamine Ans (a)
3 Which of the following compounds will have highest melting point?
(a) Chlorobenzene (b) o-Dichlorobenzene (c) m-Dichlorobenzene (d) p-Dichlorobenzene (d)
4 Which of the following will have the maximum dipolemoment?
(A) CH3F(B) CH3Cl(C) CH3Br(D) CH3I Ans (a)
5 Fittig reaction can be used to prepare
(a) Toluene(b) Acetophenone(c) Diphenyl(d) Chlorobenzene Ans (c)
6 Identify A CH3CH2I + AgCN --------->A
(A) A = C2H5NC(B) A= C2H5CN(C) A = C2H4(D) A= C3H7CN Ans (a)
7 Methyl bromide reacts with AgF to give methyl fluoride and silver bromide. This reaction is
called (a) Fittig reaction (b) Swarts reaction (c) Wurtz reaction (d) Finkelstein reaction
Ans (b)
8 Bromination of Ethane in presence of sunlight is
a) Nucleophilic substitution b) Electrophilic substitution
c) Free radical substitution d) Addition reaction Ans (c)
9 Toluene reacts with a halogen in the presence of FeCl3 giving ortho and para compounds. The
reaction is
a) Electrophilic elimination reaction b) Electrophilic substitution reaction
c) Free radical addition reaction d) Nucleophilic substitution reaction Ans (b)
10 SN1 reaction of alkyl halide leads to
(a) Retention of configuration (b) Racemisaton
(c) Inversion in configuration (d) None of the above. Ans (b)

S.No ASSERTION REASON TYPE QUESTIONS

A) Both Assertion and reason are true and reason is correct explanation of assertion.
(B) Assertion and reason both are true but reason is not the correct explanation of assertion.
(C) Assertion is true, reason is false.
(D) Assertion is false, reason is true.
1 Assertion: Nitration of chlorobenzene leads to the formation of m-nitrochlorobenzene.
Reason: -NO2 group is a meta directing group. Ans (d)
2 ASSERTION: Tertiary alkyl halides are most reactive towards SN1 reaction.

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 REASON: In SN1 reaction rate of reaction depends only on the concentration of alkyl halide
Ans (b)
3 ASSERTION: KCN reacts with methyl chloride to give methyl isocyanide.
REASON: CN- is an ambident nucleophile. Ans (d)
4. Assertion: C – X bond in aryl halides is less polar than the C – X bond in alkyl halides.
Reason: In aryl halides, the electron withdrawing inductive effect is opposed by electron
releasing resonance effect Ans(a)
5. ASSERTION: Presence of a nitro group at ortho or para position increases the reactivity of
haloarenes towards nucleophilic substitution reaction.
REASON: Nitro group, being an electron withdrawing group decreases the electron density
over benzene ring Ans (a)

I) VERY SHORT ANSWER TYPE QUESTIONS CONSIST OF 2 MARKS EACH

1. In the following pair of compounds, which will react faster by SN1 mechanism and why?

Ans reacts faster by SN1 mechanism as it is a tertiary halide

and it produces a stable tertiary carbocation.
2. Which one in the following pairs of substances undergoes SN2 substitution reaction faster and
why?

3 Complete the following reaction equations

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4. Haloalkanes undergo nucleophilic substitution whereas haloarenes undergo electrophilic
substitution. Explain.
Ans Haloarenes (say chlorobenzene) is a resonance hybrid of the following five structures

Resonance leads to lowering of energy and hence greater stability. On the other hand, no such
resonance is possible in haloalkanes. Halogens directly attached to benzene ring are o, p-
directing in electrophilic substitution reactions. This is due to greater electron density at these
positions in resonance
5 Draw the structure of major mono-halo product in each of the following reactions :

6. Which compound in each of the following pairs will react faster in SN2 reaction with —OH?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
Ans-(i) CH3I: Because Iodide is better leaving group than bromide.
(ii) CH3Cl : Carbon atom leaving group is less hindered
7. Give reasons :
(a) n-Butyl bromide has higher boiling point than f-butyl bromide.
(b) Racemic mixture is optically inactive
Ans a) n-Butyl bromide has higher boiling point than f-butyl bromide because it has larger
surface area hence have more Van der Waals’ forces.
(b) Rotation due to one enantiomer is cancelled by another enantiomer

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8. In the following pairs of the halogen compounds which compound undergoes faster SN1
reaction.

Ans

9 Account for the following :

(a) Haloalkanes, though polar, are insoluble in water.
(b) Arrange the following compounds in increasing order of reactivity towards SN2
displacement:
Ans (a) They fail to form hydrogen bonds with water. More energy is required to break
hydrogen bonds in water and less energy is released when new attractions are set up.
(b) 2-Bromo-2-Methylbutane < 2-Bromopentane < 1-Bromopentane
10. Which alkyl halide from the following pair is chiral and undergoes faster SN2 reaction?

Ans

SHORT ANSWER TYPE QUESTIONS CONSIST OF 3 MARKS EACH

1. Rearrange the compounds of each of the following sets in order of reactivity towards SN2
displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) l-Bromo-3-methylbutane, 2-Bromo-2-methyl-butane, 3-Bromo-2-methylbutane
(iii) 1-Bromobutane, l-Bromo-2,2-dimethyl-propane, l-Bromo-2-methylbutane
Answer:
(i) 1-Bromopentane > 2-Bromopentane > 2-Bromo-2-methylbutane
(ii) 1-Bromo-3-methylbutane > 3-Bromo-2 methylbutane> 2-Bromo-2-methylbutane
(iii) 1-Bromobutane > 1-Bromo-2-methylbutane > 1-Bromo-2, 2-dimethylpropane
2 Give reasons for the following :
(i) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
(ii) (±) 2-Butanol is optically inactive.
(iii) C—X bond length in halobenzene is smaller than C—X bond length in CH3—X.

2. Answer: (i) I, is better leaving group/C—I bond is weaker than C—Br bond.
(ii) (±)-Butan-2-ol is optically inactive because in racemic mix one type of rotation is cancelled
by other.
(iii) In halobenzene, halogen atom is attached to the sp2 hybrid carbon atom while in CH3-X
halogen atom is attached to sp3 hybrid carbon atom. Hence C-X bond length in halo benzene is
smaller than CH3-X.

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3. Give reasons :
(a) n-Butyl bromide has higher boiling point than f-butyl bromide.
(b) Racemic mixture is optically inactive.
(c) The presence of nitro group (-NO2) at o/p positions increases the reactivity of haloarenes
towards nucleophilic substitution reactions.
Answer:
(a) n-Butyl bromide has higher boiling point than f-butyl bromide because it has larger surface
area hence have more Van der Waals’ forces.
(b) Rotation due to one enantiomer is cancelled by another enantiomer.
(c) The presence of nitro group (-NO2) at ortho and para positions withdraws the electron
density’ from benzene ring and thus facilitating the attack of nucleophile.

4 How can the following conversions be carried out :

(i) Aniline to bromobenzene (ii) Chlorobenzene to 2-chloroacetophenone(iii) Chloroethane to
butane
Answer: (i) Aniline to bromobenzene

5 What happens when

(i) CH3—Cl is treated with aqueous KOH?
(ii) CH3—Cl is treated with KCN?
(iii) CH3—Br is treated with Mg in the presence of dry ether?

Answer:

6. Following compounds are given to you:

2-Bromopentane, 2-Bromo-2-methylbutane, 1-Bromopentane
(i) Write the compound which is most reactive towards SN2 reaction.
(ii) Write the compound which is optically active.
(iii) Write the compound which is most reactive towards β – elimination reaction
Answer:
(i) 1-Bromopentane is most reactive towards SN2 reaction.
(ii) 2-Bromopentane is optically active.
(iii) 2-Bromo-2-methylbutane is most reactive towards β -elimination reaction.

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8. The following compounds are given to you:
2-Bromopentane, 2-Bromo-2-methylbutane, 1-Bromopentane
(i) Write the compound which is most reactive towards SN2 reaction.
(ii) Write the compound which is optically active.
(iii) Write the compound which is most reactive towards P-elimination reaction.
Answer:
(i) 1-Bromopentane CH3CH2CH2CH2Br is most reactive towards SN2 reaction.

9. (i) o-nitrophenol has lower b.p. than p-nitro-phenol. Explain.

(ii) Give reasons : n-Butyl bromide has higher boiling point than f-butyl bromide.
Answer: (i) Ortho-nitrophenol has lower boiling point due to formation of intramolecular H-
bonding whereas p-nitrophenol forms intermolecular H-bonding.
(ii) n-Butyl bromide has higher boiling point than f-butyl bromide because it has larger surface
area hence have more Van der Waals’ forces.

10. How would you differentiate between SN1 and SN2 Reaction ?Give one example of each?.
Answer:

Long Answer Type Questions Carrying 5 marks each

1. Compound ‘A’ with the molecular formula C4H9Br is treated with aq. KOH solution. The rate of
this reaction depends upon the concentration of the compound ‘A’ only. When another
optically active isomer ‘B’ of this compound was treated with aq.KOH solution, the rate of
reaction was found to be dependent on concentration of compound and KOH both.

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 (i) Write down the structural formula of both compounds ‘A’ and ‘B’.

(ii) Out of these two compounds, which one will be converted to the product with inverted
configuration?

Answer: Alkyl halides on treatment with aq. KOH gives alcohol as the major product.

C4H9Br + KOH(aq) → C4H9OH + KBr

In the case of compound .A. rate of reaction depends upon the concentration of .A. only, the
reaction proceeds through the SN mechanism. Since the SN1 mechanism is favoured by 3° alkyl
halides. A should be

In the case of compound B. which is an optically active isomer of .A., rate of

reaction depends upon the concentration of .B. as well as KOH. Therefore, the reaction occurs
by SN mechanism which is favoured by 1∘ and 2∘ alkyl halides.

The compound B is

2. (a) What are ambident nucleophiles? Explain with an example.

(b) Haloalkanes easily dissolve in organic solvents, why?
(c) What is known as a racemic mixture? Give an example.
(d) Of the two bromoderivatives, C6H5CH (CH3)Br and C6H5CH(C6H5)Br, which one is
more reactive in SN1 substitution reaction and why?
ANS (a) An ambident nucleophile is a nucleophile that can form new bonds at two or more
spots in its structure, usually due to resonance contributors. Example: S = C = N– can act as a
nucleophile with either the S or N attacking
Ans (b) Because the new forces of attraction set up between haloalkanes and solvent
molecules are of the same strength as the forces of attraction being broke
Ans (c) A mixture that contains the equal proportions of two enantiomers of a compound in
equal proportions is called a racemic mixture. Example: (±) butan-2-ol
Ans (d) Since the reactivity of SN1 reactions increases as the stability of intermediate
carbocation increases. Of the two 2° bromides, the carbocation intermediate derived from
C6H-CH(C6H5)Br i.e. C6H5CHC6H5 is more stable as compared to the
carbocation C6H+5CHCH3 obtained from C6H5CH(CH3)Br because it is stabilized by two
phenyl groups due to resonance

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 CASE BASED QUESTION

Aryl halides are extremely less reactive towards nucleophilic substitution reactions due
to the following reasons: (i) In haloarenes, the electron pairs on halogen atom are in
conjugation with π-electrons of the ring. (ii) In haloalkane, the carbon atom attached to
halogen is sp3 hybridised while in case of haloarene, the carbon atom attached to
halogen is sp2 -hybridised. (iii) In case of haloarenes, the phenyl cation formed as a
result of self-ionisation will not be stabilised by resonance.

1.The polarity of C-X bond in Haloarenes is less than C-X bond in Haloalkanes:
(a) Due to sp3 hybridized orbital (b) Due to sp2 hybridized orbital
(c) Haloalkanes are less reactive than haloarenes (d) Due to double bond character in haloarenes
Ans (b)

2.Haloarenes are less reactive towards Nucleophilic substitution reaction due to

(a) Hybridisation of Carbon (b) polarity of C-X bond
(c) Resonance effect (d) All of the above

Ans (d)

3. Haloarenes shows SN1 __ reaction mechanism when: -

(a) An electron releasing group is attached to the benzene ring.
(b) An electron withdrawing group is attached to benzene ring.
(c) A stronger Nucleophile approaches haloarenes.
(d) No Haloarenes does not show nucleophilic reaction at all.

Ans (b)

4.Haloarenes are less reactive than haloalkanes towards nucleophilic substitution

reactions due to
a)Nucleophile attacks an electron deficient carbon ring centre
b)bond length of C-X is longer in haloarenes
c)bond length of C-X is shorter in haloarenes
d)sp3 hybridised C in haloarenes is more electronegative and hold electron pair of C-x
tightly

Ans (c)

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 Unit 7 ALCOHOLS, PHENOLS AND ETHERS
1. Hydroxyl (− OH) derivatives of alkane are called alcohols.
2. Alcohols are classified as 1º, 2º and 3º.
3. −OH group is attached to sp3 hybridized carbon.
Alcohols further may be monohydric, dihydric and polyhydric on the basis of OH group.
4. Phenols : Compounds containing – OH group bound directly to benzene ring.
General Methods of Preparation :
1. Acid catalysed hydration of alkene

2. From Aldehyde and ketones: Reducing eagent may be H2 in presence of Ni, Pd or Pt, NaBH4 or LiAlH4.

3. From Carboxylic acid and Ester:

4.From Grignard Reagent:

i. Formaldehyde produces primary alcohol.

ii. Any other aldehyde produces secondary alcohol.
iii. Ketone produces tertiary alcohol.

Preparation Of Phenols:
1. From Chlorobenzene

2. From Benzenesulphonic acid:

3. From Diazonium Salts:

4. From Cumene:

Industrial process.

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-Primary, secondary and tertiary alcohols Lucas reagent test: If it is a primary alcohol, no turbidity
appears at room temperature. Turbidity appears only on heating. If it is a secondary alcohol, turbidity
appears in 5 minutes. If it is a tertiary alcohol, turbidity appears immediately.

i. Phenols are more

acidic than alcohol.
ii. The presence of e-
withdrawing group such
as nitro enhances the
acidic strength of
phenol, however
presence of e- releasing
group soch as methoxy
decreases acidic
behaviour. This effect is
more pronounced when
the substituent is
present at ortho and
para positions.
Reactions of Phenol :-

Physical properties of
ethers:
a) Miscibility:
Miscibility of ethers
with water
resembles those of
alcohols of the same

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 molecular mass. This is due to the fact that just like alcohols, oxygen of ether can also form
hydrogen bonds with water molecule.
b) Boiling points: Ethers have much lower boiling points than alcohols. This is due to the presence of
hydrogen bonding in alcohols. Hydrogen bonding is absent in ethers.

Preparation Of Ethers :
(a) by dehydration of alcohols

(b) Williamson‘s synthesis: Only primary alkyl halides when react with sodium alkoxide give ether
while tertiary alkyl halides give alkene due to steric hindrance.

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MCQ
1.The major product obtained on interaction of phenol with NaOH and CO2 is
(a) Benzoic acid (b) Salicyladehyde
(c) Salicylic acid (d) Pthalic acid

2.Which of the following alcohol on dehydration with conc H2SO4 gives but-2-ene ?
(a) 2-methylpropan-2-ol (b) Butan-1-ol
(c) 2-methyl propan-1-ol (d) Butan-2-ol
3.Which of the following alcohol give iodoform test?
(a) Butan-1-ol (b) Propan-1-ol
(c) Propan-2-ol (d) Butan-2-ol

4. An ether is more volatile than alcohol having the same molecular formula. This is due to
(a) intermolecular hydrogen bonding in alcohols.
(b) dipolar character of ethers
(c) alcohols, having resonance structures
(d) intermolecular hydrogen bonding in ethers.
5. Lucas reagent is used to identify
(a) nitro alkane (b) alcohol
(c) alkene (d) alkyl amine

6.. Phenol is less acidic than -

(a) ethanol (b) o-nitrophenol
(c) o-methyl phenol (d) o-methoxyphenol

7. The most acidic among the following is

(a) Benzyl alcohal (b) cyclohexanol
(c)phenol (d) m-chlorophenol

8. Monochlorination of toluene in sunlight followed by hydrolysis with aq. NaOH yields:

(a) o-cresol (b) 2,4-dihydroxytoluene
(c) m-cresol (d) benzyl alcohol
9. IUPAC name of m-cresol is:
(a) 3-methylphenol (b) benzene-1,3-diol
(c) 3-chlorophenol (d) 3-methoxyphenol

10. Arrange the following compounds in increasing order of boiling point.

Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(a) propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(b) propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(c)pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
(d) pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol

ANSWERS : 1(c) 2(b & d) 3(c) 4(a) 5(b) 6(b) 7(d) 8(d) 9(a) 10(a)

Assertion and Reason Type Questions:

In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is given.
Choose the correct answer out of the following choices:

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 (a) Assertion and Reason both are correct and Reason is the correct explanation of Assertion.
(b). Both Assertion and Reason are correct but Reason is not the correct explanation of Assertion
(c) Assertion is correct but Reason is wrong.
(d) Assertion is wrong but Reason is correct.

1.Assertion (A): Bond angle in ethers is slightly less than the tetrahedral angle.
Reason (R): There is a repulsion between the two bulky (-R) groups.

2..Assertion: In Lucas test, 3º alcohols react immediately.

Reason: An equimolar mixture of anhyd. ZnCl2 and conc. HCl is called Lucas reagent

3.Assertion: The reactivity of halogen acids with alcohols to form haloalkanes follows the order: HI>
HBr> HCI
Reason: The nucleophilicity of halide ions increases as I< Br<CI

4.Assertion: Addition reaction of water to but-1-ene in acidic medium yields butan-2-ol.

Reason: Addition of water in acidic medium proceeds through the formation of primary carbocation.
(both x)

5.Assertion: p-nitrophenol is more acidic than phenol.

Reason: Nitro group help in the stabilization of phenoxide ion by dispersal of negative charge due to
resonance. (both correct)

ANSWERS : 1(d) 2(b) 3(a) 4(b) 5(a)

2-Mark Questions:
1.Arrange the following compounds in the increasing order of their acid strengths: 4-
nitrophenol, phenol, 2,4,6-trinitrophenol.
Ans. Phenol < 4-nitrophenol < 2,4,6-trinitrophenol
2. Write the structure of the molecule of a compound whose IUPAC name is
(i) 1- Phenylpropan-2-ol (ii) 2- methyl-2-ethoxypentane
(i) (ii)

3. Why do electron withdrawing atoms or groups on the benzene ring increase the acidic
strength of phenols?
Ans: They stabilize the phenoxide ion more by dispersing the negative charge relative to phenol, i.e.,
proton release becomes easy.

4. Account for the following :

(i) Phenol has a smaller dipole moment than methanol.
(ii) Phenol goes electrophilic substitution reactions.
Ans. (i) Due to – ve charge on oxygen in delocalized by resonance.
(ii) Due to greater electron density than benzene.
5.Write chemical equations when :
i. Ethyl chloride is treated with aqueous KOH
ii. Chlorobenzene is treated with CH3COCl in presence of anhydrous AlCl3

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Ans.

6. What is denatured alcohol?

Ans. Alcohol is made unfit for drinking by mixing some copper sulphate and pyridine to it. This process
is called denaturation of alcohol and alcohol mixed with copper sulphate and pyridine is called
denatured alcohol.

7. Why is C—OH bond length in CH3OH longer than C—OH bond length in phenol?
Ans. It is due to resonance in phenol, there is a double bond character in C=O bond, therefore shorter
than the single bond in methanol. In phenol, C to which –OH is attached is sp2 hybridised.

8. How is phenol obtained from aniline ?

Ans:

9. Write IUPAC name of the following compound :

Ans: (i)2,5-Dimethylhexane-1, 3 diol. (ii) 1- Phenylpropan-2-ol

10. Complete the following reaction and write the name of the product :

Ans: 2, 4, 6-Trinitro phenol (Picric acid)

3-Mark Questions:
1. Write a chemical test to distinguish between following :
(a) Primary, secondary and tertiary alcohols
(b) Ethanol and methanol
(c) Ethanol & phenol
Ans : (a) Primary ,secondary and tertiary alcohols : LUCAS TEST
When10 , 20 , 30 alcohol treated with Lucas reagent [Conc HCl + anhydrous ZnCl2] at room temp
i)If turbidity appears immediately alcohol is 30
ii)If turbidity appears in five minutes alcohol is 20
iii)10 alcohol does not react with Lucas reagent at room temp
(b) Ethanol and methanol –
Halo form test :
Compounds treated with NaOI, yellow ppt of iodoform will be given by molecule having – CO – CH3
group. Ethanol gives yellow ppt.
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(c) Ethanol & phenol :
Neutral ferric chloride test .
Ethanol on treating with NaOH and I2 give yellow coloured iodoform but not 1-propanol Phenol gives
violet colour when we treated it with neutral ferric chloride.
2. How will you convert :
(i) Phenol to cyclohexanol
(ii) Benzyl chloride to benzyl alcohol
(iii)Anisole to phenol

Ans :
3. How would you obtain the following?
(i) Benzoquinone from phenol
(ii) 2-methylpropan-2-ol from methyl magnesium bromide
(iii) Propan-2-ol from propene

Ans: (i)
(ii)CH3MgBr +CH3COCH3 ---(CH3)3OMgBr –H2O-----(CH3)3C-OH
(iii) CH2 = CH –CH3 ----------------------CH3CH(OH)CH3
4. Account for the following:
(i) The boiling point of ethanol is higher than that of methanol.
(ii) Phenol is a stronger acid than an alcohol.
(iii) Propanol has higher boiling point than Butane
Ans: (i) Boiling point of alcohols increases with increase in the number of carbon atoms (increase in van
der Waals' forces). That's why boiling point of ethanol is higher than that of methanol.
(ii) (ii) The greater acidic nature of phenols as compared to alcohols can be explained on the basis of
resonance. Due to positive charge on oxygen atom, it attracts the electron pair of O-H bond strongly
towards itself and thus, facilitates the release of H+.
In contrast, alcohol is not stablised by resonance.
(iii) The molecules of propanol are held together by intermolecular hydrogen bonding while the
molecules of butane have only weak van der Waals' forces of attraction. Hydrogen bonds are much
stronger so the boiling point of propanol is much higher than butane.
5. Explain the following observations:
(i) The boiling point of ethanol is higher than of methoxy methane.
(ii) Phenol is more acidic than ethanol.

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(iii) o-and p-nitrophenols are more acidic than phenol.
Ans. (i)This is due to the reason that ethanol is exists as associated molecules due to strong
intermolecular H-bonding, methoxy methane is not associated with such strong intermolecular H-
bonding.
(ii) acidic nature of phenols as compared to alcohols can be explained on the basis of resonance. Ethanol
is not stabilized by resonance.
(iii) NO₂ being an electron withdrawing group when present at ortho and para positions withdraws
electron density from benzene ud ring thereby decreasing the electron density of O-H bond and thus,
make the release of proton easier.
6. Name the reagents which are used in the following conversions:
(i) A primary alcohol to an aldehyde
(ii) Butan-2-one to butan-2-ol
(iii) Phenol to 2,4,6-tribromophenol
Ans : (i) Pyridinium chlorochromate (PCC)
(ii) Ni/H2 or LiAlH4
(iii) Bromine Water

7.Write one chemical reaction to illustrate the following :

(i) Reimer-Teimann reaction
(ii) Williamson’s synthesis
(iii) Kolbe’s reaction
Ans: (i) (ii)

(iii)

8. Draw the structure and name of the product formed if the following alcohols are oxidized.
Assume that and excess of oxidizing agent is used.

(i) CH3CH2CH2CH2OH (ii) 2-butenol (iii) 2-methyl-1-propanol

9. Account for the following:

i. The boiling points of alcohols decrease with increase in branching of the alkyl chain.
ii. Phenol does not give protonation reaction readily.
iii. Phenylmethyl ether reacts with HI to give Phenol and Methyl iodide and not
Iodobenzene and methyl alcohol.

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Ans: i. It is because branched chain alcohols have minimum surface area therefore minimum force of
attraction, hence, they have lower boiling point.
ii. It is due to +ve charge on 3 out of 5 resonating structures of Phenol. It cannot be protonated easily.
iii. It is because phenoxide ion is stabilized by resonance, whereas, methoxide ion is not.
10. How will you convert:
a) Propene to Propan-2-ol?
b) Ethanal to Propan-2-ol?
c) Propan-2-ol to propanone
Ans:

(iii) CH3CH(OH)CH3 ---CrO3---------- CH3COCH3

5-Mark Questions:
1. A compound ‘A’ with molecular formula C4H10O is a unreactive towards sodium metal. It does
not discourse Bromine water and does not react with NaHSO3 solution. On refluxing ‘A’ with excess of
HI gives ‘B’ which react with aq. NaOH to form ‘C’. ‘C’ can be converted into ‘B’ by reacting with P and I2 .
‘C’ on heating with conc. H2SO4 forms ‘D’ decolorizes bromine water. Identify A to D and write the
reactions involved.

Ans: A is not alcohol therefore it does not react with Sodium metal. ‘A’ is not aldehydes and ketones as it
does not react with NaHSO3 ‘A’ is not unsaturated hydrocarbon as it does not add Br2 (aq) . It is likely to
be ether.
CH3CH2OC2H5 + 2HI ------- 2C2H5I + H2O
‘A’ excess ‘B’
C2H5I + NaOH (aq) ------ C2H5OH + NaI
‘B’ ‘C’
C2H5OH + (P/I2) ------- C2H5I
C B
C2H5OH + Conc. H2SO4 ---- C2H4
C D
2. (a) Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with
that of ethanol.
Ans: (i) Phenol reacts with sodium to give sodium phenoxide, liberating H2.
(ii) Phenol reacts with sodium hydroxide to give sodium phenoxide and water as by products.
The acidity of phenol is more than that of ethanol. This is because after losing a proton,
the phenoxide ion undergoes resonance and gets stabilized whereas ethoxide ion does not.

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Case Based Question :
I. Read the passage given below and following questions:
Treatment of sodium salt of phenol with carbon dioxide under pressure brings about substitution of the
carboxyl group, -COOH, for hydrogen of the ring. This provides a path of conversion of phenol into
hydroxy carboxylic acids. The acids formed are industrially very important compounds and form many
useful compounds such as aspirin, salol, methyl salicylate (constituent of oil of winter green), etc.
The following are multiple choice questions. Choose the most appropriate answer.
(i) The name of the reaction is
(a) Reimer Tiemann reaction (b) Kolbe's reaction
(c) Friedel Crafts Reaction (d) Canizaro Reaction

(ii) In the reaction, CO, acts as

(a) Catalyst (b) Electrophile (c) Nucleophile (d) Reaction initiator
(iii) The product of the above reaction can also be prepared by reacting
(a) phenol with chloroform in the presence of aq. KOH
(b) phenol with carbon tetrachloride in the presence of aq. KOH
(c) cumene in the presence of O2
(d) benzoic acid with methanol

(iv) The product can be converted into aspirin by treating with

(a) acetic anhydride in the presence of H2SO4
(b) phenol in the presence of POCI3
(c) methanol in the presence of HCI
(d) chloroform in the presence of KOH

ANSWERS : 1(b) 2(b) 3(b) 4(a)

Space for Notes:

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 Unit -8 Aldehydes, Ketones and Carboxylic Acids

Aldehydes and Ketones

Depending upon the atoms or group of atoms attached on either side of the carbonyl group, carbonyl
compounds are divided into three major classes, i.e. aldehydes, ketones and carboxylic acids.

The compounds, which contain ' =C=O ' group are called carbonyl compounds.
Aldehydes and ketones have same molecular formula CnH2nO, and are functional isomers of each other.

Nomenclature
The word 'al' and 'one' replaces the ending 'e' of corresponding alkanes while naming the open chain
aliphatic aldehydes and ketones, respectively.

Common and IUPAC names of some aldehydes and ketones

ALDEHYDE
Structural formula Common Name IUPAC Name
HCHO Formaldehyde Methanal
CH3-CHO Acetaldehyde Ethanal


CH3-CH2-CH-CHO
-methyl butyraldehyde 2-methylbutanal
|
CH3

3-bromobenzenecarbaldehyde or
3-bromobenzaldehyde
m-bromobenzaldehyde

CH3-CH = CH-CHO Crotonaldehyde But-2-enal

KETONES
CH3-COCH3 Acetone Propanone

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 Di isopropyl ketone
CH3-CH(CH3)-CO-CH(CH3)- CH3 2, 4-dimethylpentan-3-one

Benzophenone Diphenyl ketone

Preparation of Aldehyde’s and Ketones

(i) Controlled oxidation of alcohols in the presence of K2CrO7 / dil. H2SO4,KMnO4/dil. H2SO4 Or Cu metal
at 573 K result in the formation of aldehydes and ketones.
(ii) Dry distillation of some calcium salts of acid gives simple ketones.
(iii) Mixture of calcium salts of formic acid and calcium salts of any other carboxylic acid on dry
distillation gives an aldehyde.
(iv) Addition of Grignard's reagents to alkyl or aryl cyanides followed by hydrolysis with dil. acids gives
ketones while with HCN, aldehydes are formed.
(v) Addition of H2O on alkynes in presence of H2SO4 and HgSO4 yields aldehydes (by terminal alkynes)
and ketones (by non-terminal alkynes).
General Properties of Aldehydes and Ketones
(i) Boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of comparable
molecular masses.
(ii) The lower members of aldehydes and ketones are miscible with water in all proportions, because
they form hydrogen bond with water.
(iii) Aldehydes and ketones generally undergo nucleophilic addition reactions.
(iv) Aldehydes are more reactive than ketones toward nucleophiles due to more +l and steric effects in
ketones.

Chemical Properties of aldehyde and ketones

(1) Aldehydes and ketones undergo a number of addition reactions due to the presence of polar
carbonyl group (the carbonyl carbon bears partial positive charge, thus, undergoes nucleophilic
addition reactions). Common nucleophilic addition reactions are :

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(ii) Aldehydes and ketones also react with ammonia derivatives like:
(i)NH2OH (hydroxylamine) to give oximes.
(ii) NH2- NH2 (hydrazine) to give hydrazones.
(iii) NH2 -NH - (phenyl hydrazine) to give phenyl hydrazones.
(iii) Reaction with 2, 4-DNP can be used to identify the presence of a carbonyl group.
(iv) Clemmensen reduction of aldehydes and ketones (Zn-Hg/conc. HCI) gives alkanes.
(v) Wolff-Kishner reduction The carbonyl group of aldehydes and ketones is reduced to -CH2 group on
treatment with hydrazine followed by heating with KOH in ethylene glycol.
(vi) Aldehydes give positive Tollens’ test, Fehling's test, Benedict's test and Schiff's test.
(vii) Aldehydes can be distinguished from ketones by Tollens’ reagent, Fehling's solution and Benedict's
solution.
(viii) Tollens’ reagent is an ammoniacal silver nitrate (AgNO3 + NH4OH) solution. It is a mild oxidising
agent.
(ix) Aromatic aldehydes do not reduce Fehling's solution.
(x) Iodoform test is given by CH3CO—or CH3CH(OH)- group containing compounds.
(xi) Aldol condensation is given by aldehydes and ketones that have -hydrogen atom in the presence of
dilute alkali. It involves carbanion as an intermediate.
(in) Aldehydes and ketones also react with
(xii) Cannizzaro reaction is given by those aldehydes which do not have -hydrogen atom (like GH3CHO,
HCHO) in the presence of concentrated alkali.
(xiii)Aromatic aldehydes and ketones undergo electrophilic substitution at the ring in which the carbonyl
group acts as a deactivating and meta-directing group.
Uses
Formaldehyde is well known as formalin (40%) solution used to preserve biological specimens and to
prepare polymeric products. Benzaldehyde is used in perfumery and in dye industries.

Carboxylic Acids
1. The carbon compounds containing - COOH group( -COOH) are known as carboxylic acids. The carboxyl group,
consists of a carbonyl group attached to a hydroxyl group, hence it is named as carboxyl.
-C=O, + -O-H ----› COOH
Carbonyl Hydroxyl Carboxyl
2. The general formula of carboxylic acid is. CnH2nO2.
3. Higher aliphatic acids are also known as fatty acids.

Nomenclature
Aliphatic carboxylic acids are named by replacing the ending - e in the name of the corresponding
alkane with -oic acid.

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Names and structures of some carboxylic acids
Structure Common name IUPAC name
НСOОН Formic acid Methanoic acid
CH3COOH Acetic acid Ethanoic acid
CH3CH2COOH Propionic acid Propanoic acid
CH3CH3CH2COOH Butyric acid Butanoic acid
(CH3)2CHCOOH Isobutyric acid 2- methyl propanoic acid
HOOC-COOH Oxalic acid Ethanedioic acid
Benzoic acid Benzene carboxylic acid (Benzoic
acid)

Phenylacetic acid 2- phenyl ethanoic acid

Structure of Carboxyl Group

In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by about 120°. The
carboxylic carbon is less electrophilic than carbonyl carbon because of the possible resonance structure.

Preparation of Carboxylic Acids

Carboxylic acids can be prepared by
(i) oxidationof1° alcohols and aldehydes.
(ii) oxidation of alkyl benzenes.
(iii) hydrolysis of alkyl cyanides and amides. (iv) carbonation of Grignard's reagent.
(v) hydrolysis of acyl halides and anhydrides.
(vi) Aromatic carboxylic acids are prepared by side chain oxidation of alkyl benzenes .

Reactions of Carboxylic Acids

Reactions Involving Cleavage of O- H Bond
(i) Carboxylic acids react with active metals like Na, K, Ca, Mg, Zn, etc, to form respective salts with evolution of
H2 gas.
(ii) They neutralise alkalies forming salts.
(iii) They react with weaker bases such as carbonates and bicarbonates producing CO2 gas.
Reactions Involving Cleavage of C -OH Bond
(i) Formation of anhydrides When carboxylic acids are heated in presence of strong dehydrating agent such as
P203 Or conc. H2SO4 acid anhydrides are formed.

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(ii) Formation of ester When carboxylic acids are heated with alcohols or phenols in presence of a mineral acid
such as conc. H2SO4 or HCI gas, esters are formed. This reaction is known as esterification.
(iii) Formation of acid chlorides They react with SOCI2 , PCI5 or PCI3 to form acid chlorides by replacement of -O H
group by Cl atom.
(iv) Formation of amides They react with NH3 to give ammonium salt which on further heating at high
temperature give amides.
Reactions Involving - COOH Group
(i)Carboxylic acids are reduced to 1° alcohols by LiAlH4 or withB2H6
(ii) They lose CO2 to form hydrocarbons when their sodium salts are heated with soda lime
(NaOH + CaO) in the ratio (3 : 1). This is known as decarboxylation.
(iii) Alkali metal salts of carboxylic acid also undergo decarboxylation on electrolysis of their aqueous solutions
and form hydrocarbons having twice the number of carbon atoms present in the alkyl group of the acid. The
reaction is known as Kolbe electrolysis.

(iv) Carboxylic acid having an -hydrogen are halogenated at the -position with Cl2 or Br in presence of small
amount of red phosphorous to give -halocarboxylic acids. The reaction is known as Hell- Volhard Zelinsky
reaction.
Test to Distinguish between a Phenol and a Carboxylic acid
(i) Sodium bicarbonate test Carboxylic acids when treated with NaHCO3 solution gives brisk effervescence due to
evolution of CO2 gas whereas phenol doesn't give this test.
CH3COOH+ NaHCO3. -------› CH3COONa + H2O+ CO3
(ii) Ferric chloride test Carboxylic acids give coloured ppt. when treated with neutral FeCl3 solution whereas
phenol give a violet coloured complex with FeCI3 solution.

3CH3 COOH + FeCl3 . -------› (CH3COO) 3 Fe+ 3HCI (Buff coloured ppt.)
6 C6H5-OH + FeCl3 . -------› [Fe(O C6H5 )6]3- + 6H+ + 3Cl-

Uses
(i) The main use of carboxylic acids are in industries, in the manufacture of soaps.
(ii) Esters are used in perfumery industries and sodium benzoate is used as a preservative

MULTIPLE CHOICE QUESTIONS (1 MARK)

1. Which of the following reactions convert acetone into hydrocarbon having same number of
carbon atoms?
(a) Wolff-Kishner reaction (b) Hofmann reaction
(c) Grignard reaction (d) Reduction with LiAIH4
2. Identify the reaction which is used to obtain B-hydroxy ketone.
(a) Condensation reaction (b) Aldol condensation
(c) Cross aldol condensation (d) Cannizaro reaction

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3. The reagent which can be used to distinguish acetophenone from benzophenone is
(a) 2,4-dinitrophenylhydrazine (b) aqueous solution of NaHSO3
(c) benedict reagent (d) I2 and Na2CO3
4. The most appropriate reagent to distinguish between acetaldehyde and formaldehyde is:
(a) Fehling’s solution (b) Tollens’ reagent
(c) Schiff’s reagent (d) Iodine in presence of base
5. Which of the following compound is most acidic?
(a) BrCH2COOH (b) ClCH2COOH
(c) FCH2COOH (d) ICH2COOH
6. Give IUPAC name of the product, when acetamide is heated with anhydrous phosphorus
Pentoxide.
(a) Ethylamine (b) Propane nitrile
(c) Cyano methane (d) Ethane nitrile
7. Which acid is present in vinegar?
(a) CH3COOH (b) H2SO4
(c) HCl (d) HNO3
8. Chlorination of toluene in the presence of light and heat followed by treatment with
aqueous NaOH gives-
(a) o-Cresol (b) p-Cresol
(c) 2,4-Dihydroxidytoulene (d) Benzoic acid
9. Benzaldehyde can be prepared by oxidation of toluene by
(a) Acidic KMnO4 (b) K2Cr2O7/H+
(b) CrO2Cl2 (d) all of these
10. Which of the following compound will give butanone on oxidation with alkaline KMnO4
Solution?
(a) Butan-1-ol (b) Butan-2-ol
(c) Both (a) and (b) (d) None of these
Ans 1-a, 2-b, 3-d, 4-d, 5-c, 6-d, 7-a, 8-d, 9-c , 10-b
ASSERTION REASON TYPE QUESTIONS (1 MARK)
Note: In the following questions (1-5) a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is the correct explanation
for assertion.
(b) Assertion and reason both are correct statements but the reason is not a correct
explanation for assertion.
(c) Assertion is a correct statement but the reason is the wrong statement.
(d) Assertion is a wrong statement but the reason is a correct statement.

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1. Assertion: Carbonyl compounds when react with NaHSO3 form white crystalline solid.
Reason: Aldehydes are used in the blending of perfumes and flavouring agents.
2. Assertion: Benzaldehyde gives silver mirror test.
Reason: Benzaldehyde gives Fehling's solution test.
3. Assertion: Aldehydes are more reactive than ketones in nucleophilic addition reaction.
Reason: This is due to steric and electronic reasons
4. Assertion: p-Chlorobenzoic acid is a stronger acid than m-chlorobenzoic acid.
Reason: In meta position, only inductive effect is considered.
5. Assertion: Carboxylic acids when reacts with NaHCO3 the C02 evolved comes from
carboxylic acid and not from NaHCO3
Reason: RCOOH is a stronger acid than H2CO3
ANS. 1. – (b), 2. – (c), 3. -(a), 4. -(d), 5.-(d)

VERY SHORT ANSWER QUESTIONS (2 MARKS)

1. Write the IUPAC name of the following:
CH3 — CH2— CHO
Ans Propanal
2. Draw the structure of 3-methylpentanal.
Ans CH3 — CH2— CH(CH3) — CH2— CHO
3. Give chemical test to distinguish between benzophenone and acetophenone.
Ans Benzophenone (C6H5COC6H5) and acetophenone (C6H5COCH3) can be distinguished by iodoform
test. Acetophenone, being a methyl ketone on treatment with I2 / NaOH [or NaOI] undergoes
iodoform reaction to give a yellow ppt. of iodoform. On the other hand, benzophenone does not
give this test.
4. Arrange the following compounds in an increasing order of their reactivity in nucleophilic addition
reactions: Ethanal, Propanal, propanone, butanone.
Ans On moving from ethanal to butanone, + 1-effect and steric hindrance of alkyl group increases due
to which the electron density on the carbon atom of the carbonyl group progressively increases
and hence, attack by nucleophile becomes slower and slower. Thus, the reactivity increases in the
order as:
Butanone < propanone < propanal < ethanal
5. Illustrate the Cross-aldol condensation reaction:
Ans 'Aldol' is an abbreviation of aldehyde and alcohol. When the enolate of an aldehyde or a ketone
reacts at the α-carbon with the carbonyl of another molecule under basic or acidic conditions to
obtain β-hydroxy aldehyde or ketone, this reaction is called Aldol Reaction.
6. Write the IUPAC name of the compound CH3 —CH(OH) — CH2—COOH.
Ans 3-hydroxybutanoic acid
7. Write the structure of 2-hydroxybenzoic acid.

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Ans

COOH
OH

8. Write IUPAC name of

OCOCH3

H3C CH3
Ans 3, 5-dimethylphenylethanoate
9. Illustrate the following reaction giving a suitable example: Decarboxylation
Ans Decarboxylation refers to the reaction in which carboxylic acids lose carbon dioxide to form
hydrocarbons when their sodium salt are heated with soda lime. e.g.
Soda lime (mixture Of NaOH and
CaO in3: ratio)
CH3COONa+ + Na2C03
Sodium ethanoate Methane

10. Draw the structure of the compound named 4-methylpent-3-en-2-one.

Ans

SHORT ANSWER TYPE QUESTIONS (3 MARKS)

1. Write the equations involved in the following reactions:
(i) Wolff-Kishner reduction. (ii) Étard reaction.
Ans (i) The Wolff-Kishner reduction process starts with the formation of a hydrazone anion, which
then releases the nitrogen atom, resulting in the formation of a carbanion. After reacting with the
water in the environment, the carbanion forms a hydrocarbon. Diethylene glycol is commonly used
as a solvent in this form.

(ii) Etard Reaction Toluene reacts with chromyl chloride in presence of CS, followed by hydrolysis

produces benzaldehyde.
2. Write the reactions involved in the following reactions:
(i) Clemmensen reduction
(ii) Cannizzaro reaction

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Ans (i) Clemmensen reduction The carbonyl group of aldehydes and ketones is reduced to -CH, group
on treatment with zinc-amalgam and concentrated hydrochloric acid. This reaction is known as
Clemmensen reduction.

(ii) Cannizzaro reaction Aldehydes which do not have - H atoms undergo self-oxidation and
reduction reaction on treatment with conc. alkali. This reaction is known as Cannizzaro reaction. In
this reaction, one molecule of aldehyde is reduced to alcohol while another molecule is oxidised to
salt of carboxylic acid.

3. How are the following conversions carried out?

(i) Propene topropan-2-ol.
(ii) Ethyl chloride to ethanal.
Ans (i) CH3CH=CH2 + H2SO4/H2O ⟶ CH3CH(OH)CH3
(ii) CH3CHCl + KOH ⟶ CH3CH2OH + Cu/573K ⟶ CH3CHO
4. Give a possible explanation of the following:
There are two -NH2 groups in semicarbazide. However, only one such group is involved in the
formation of semicarbazones.
Ans However, only one is involved in the formation of semicarbazones. Solution: Only one of the
two −NH2 groups, which is connected directly to the carbonyl-carbon atom, undergoes
resonance in semicarbazide. As a result, the electron density on the −NH2group in the resonance
falls.
5. Write the equations involved in the following reactions:
(i) Stephen reaction.
(ji) Wolff-Kishner reaction.
Ans (i) Stephen reaction.

(ji) Wolff-Kishner reaction.

6. Although phenoxide ion has more number of resonating structures than carboxylate ion,
carboxylic acid is a stronger acid than phenol. Give two reasons.

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Ans (i) Phenoxide ion has non-equivalent resonance structures in which the negative charge is at the less
electronegative carbon atom whereas in case of carboxylate ion, the ion is stabilised by equivalent
resonance structures, in which negative charge is on more electronegative atom.
(ii) In carboxylate ion, the negative charge is delocalised over two electronegative oxygen atoms,
whereas in phenoxide ion the negative charge is less effectively delocalised over one oxygen atom
and less electronegative carbon atoms. Thus, the carboxylate is more stabilised than phenoxide ion.
Hence, carboxylic acids are more acidic than phenols.
7. How will you carry out the following conversions?
(i ) Acetylene to acetic acid
(ii) Toluene to m-nitrobenzoic acid
Ans (i) Acetylene to Acetic acid :-

(ii) Toluene to m-nitrobenzoic acid :-

8. How do you convert the following?

(a) Ethanal to propanone
(b) Toluene to benzoic acid
Ans

9. Arrange the following compounds in the increasing order of their property as indicated.
(i) CH3COCH3, C6H5COCH3,CH3CHO
(reactivity towards nucleophilic addition reaction)
(ii) CI-CH2-COOH, F-CH2-COOH, CH3 -COOH (acidic character)
Ans (i), C6H5COCH3  CH3COCH3  CH3CHO

(ii) CH3 -COOH  CI-CH2-COOH  F-CH2-COOH,

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 10. Arrange the following compounds in an increasing order of their property as indicated:
(i) Benzoic acid, 3,4-dinitrobenzoic acid, 4-methoxybenzoic acid (acidic strength)
(iì) CH3CH2,CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acidic strength)
Ans (i) 4-methoxybenzoic acid  Benzoic acid  3,4-dinitrobenzoic acid

(ii) (CH3)2CHCOOH  CH3CH(Br)CH2COOH  CH3CH2,CH(Br)COOH

LONG ANSWER TYPE QUESTIONS (5 MARKS)
1. (i) describe
(a) Aldol condensation (b) Cannizzaro reaction
(ii) Describe a chemical test to distinguish between
(a) ethanal and propanal (b) benzaldehyde and acetophenone
(c) propan-2-one and pentan-3-one
Ans (a) Aldol condensation -Aldol Condensation can be defined as an organic reaction in which
enolate ion reacts with a carbonyl compound to form β-hydroxy ketone or β-hydroxy aldehyde,
followed by dehydration to give a conjugated enone. Aldol Condensation plays a vital role in
organic synthesis, creating a path to form carbon-carbon bonds.
(b) Cannizzaro reaction- Cannizzaro reaction is a chemical reaction named after Stanislao
Cannizzaro that involves the base-induced disproportionation of two molecules of a non-ionizable
aldehyde to yield a carboxylic acid and a primary alcohol.
(a) Ethanal and Propanal : Ethanal gives iodoform test but propanal does not give such test.
(b) Benzaldehyde and Acetophenone : Benzaldehyde forms silver mirror with ammoniacal
silver nitrate solution (Tollens reagent) and Acetophenone does not give this test. Acetophenone
gives iodoform test. Benzaldehyde does not react.
(c) propan-2-one and pentan-3-one - Pentan-2-one gives iodoform test and Pentan-3-one does
not gives iodoform test Pentan-2-one gives white ppt with sodium bisulphite whereas pentan-3-
one does not give ppt.
2. (a) Carry out the following conversions: (i) p-nitrotoluene to 2-bromobenzoic acid
(ii) Propanoic acid to acetic acid (b)An alkene with molecular formula C5H10 on ozonolysis gives a
mixture of two compounds, B and C. Compound B gives positive Fehling test and also reacts with
iodine and NaOH solution. Compound C does not give Fehling solution test but forms iodoform.
Identify the compounds A, B and C.

Ans (i)

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 (ii) Propanoic acid to acetic acid

Since ,compound B gives Fehling's test therefore ,it must be aldehyde .Further since aldehyde 'B'
gives iodoform on treatment with 𝑙2 and NaOH therefore ,it must be aldehyde .Further since
aldehyde 'B' must be acetaldehyde (𝐶𝐻3𝐶𝐻𝑂)(CH3CHO) Since 'C' does not give Fehling test it must
be a ketone further Since ketone 'C' contain three carbon atoms and gives iodoform on treatment
with 𝐼2 and NaOH
CASE BASED QUESTIONS (4 MARKS)
1. Ketones may be prepared by the oxidation of secondary alcohols in the presence of acid dichromate.
The reaction probably proceeds via the rate limiting formation of a chromate ester followed by
decomposition of the ester to give the products. In case of primary alcohol, this process may lead to
oxidation of the alcohol to carboxylic acid. This problem is overcome by attenuating the oxidizing
power of chromic acid based reagents to generate a milder oxidizing agent. The two most popular
oxidizing agents for oxidizing primary alcohols to aldehydes are pyridinium chlorochromate (PCC)
and pyridinium dichromate (PDC).These reagents are prepared by the treatment of chromic acid
with pyridine. The ketones may also be generated from the secondary alcohols using aluminium t-
butoxide in the presence of acetone. The secondary alcohol is refluxed with the reagent in an excess
of acetone. This reagent is particularly helpful in oxidation of Unsaturated alcohol as only the
alcoholic OH is oxidized.
1a Which of the following statements) is/are true regarding preparation of aldehydes and ketones?
(i) Both can be prepared by the oxidation of the concerned alcohol with copper at about 250°C
(ii) Both can be prepared by the oxidation of the concerned alcohol by Oppenauer oxidation
(iii) Both can be prepared by the oxidation of respective alcohol with acidic dichromate.
(a) (i) only (b) (ii)a n d (iii)
(c) (i) and(iii) (d) All the three
1b 2-Pentanone and 3-pentanone can be distinguished by :
(a) Cannizzaro's reaction (b) Aldol condensation
(c) Iodoform reaction (d) Clemmensen's reduction
1c Phenylmethyl ketone can be converted into ethylbenzene in one step by which of the following
reagents?
(a) LiAIH4 (b) Zn-Hg/HCI
(c) NaBH4 (d) CH3Mgl
1d Which of the following compounds will give butanone on oxidation with alkaline KMnO4 solution?
(a) Butan-1-ol (b) Butan-2-01
(c) Both of these (d) None of these
Ans 1a- (a), 1b- (c), 1c- (b), 1d- (b)

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 Unit 9- AMINES
IMPORTANT CONCEPTS OF THE CHAPTER:
Classification: Amines are classified according to the number of carbon atoms bonded directly to the
nitrogen atom. A primary (1°) amine has one alkyl (or aryl) group on the nitrogen atom, a secondary
(2°) amine has two, and a tertiary (3°) amine has three.

Physical Properties of Amines

1. The lower aliphatic amines are gases with fishy smell. Primary amines with three or more
carbon atoms are liquid and higher members are all solids.
2. Lower aliphatic amines are water soluble because they can form hydrogen bonds with
water molecules, however the solubility decreases with increase in hydrophobic alkyl
group.
3. Boiling points order: primary amine > secondary amine > tertiary amine

Preparation:
HOFFMANN BROMAMIDE REACTION:-

GABREIL PHTHALIMIDE SYNTHESIS:

Chemical Properties Basic Strength of Amines

Amines act as Lewis bases due to the presence of lone pair of electrons on the nitrogen
atom. More the Kb (dissociation constant of base), higher is the basicity of amines.
Lesser the pKb higher is the basicity of amines. Aliphatic amines (R-NH2) are stronger
bases than NH3due to the electron releasing +I effect of the alkyl group. Among
aliphatic methyl amines, the order of basic strength in aqueous solution is as follows:
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 (C2H5)2NH > (C2H5)3N > C2H5NH2> NH3 (CH3)2NH > CH3NH2> (CH3)3N > NH3
Aromatic amines are weaker bases than aliphatic amines and NH3, due to the fact that
the electron pair on the nitrogen atom is involved in resonance with the π-electron
pairs of the ring.

BENZOYLATION:

CARBYLAMINE REACTION:

HINSBERG'S TEST:

N.N-Diethylbenzenesulphonamide (Insoluble in KOH)

Tertiary amines do not react with benzene sulphonyl chloride.

ELECTROPHILIC SUBSTITUTION REACTIONS:-

BROMINATION:-

To prepare monosubstituted derivative, activating effect of –NH2 group must be controlled

byprotecting–NH2 by acetylation with acetic anhydride.

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 NITRATION: Direct nitration of aniline is not possible as it is susceptible to oxidation, thus
amino group is first protected by acetylation.

In strongly acidic medium, aniline is protonated to form anilinium ion which is meta
directing so it gives meta product also

SULPHONATION:

Aniline does not undergo Friedel Craft reaction due to salt formation with
aluminium chloride, the Lewis acid, which is used as a catalyst.

Properties of benzene diazonium chloride

DIAZOTISATION:

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 SECTION –A MULTIPLE CHOICE QUESTIONS ( 1 MARK EACH)

1.Hoffmann Bromamide Degradation reaction is shown by

(A) ArNH2 (B) ArCONH2
(C) ArNO2 (D) ArCH2NH2

2.Carbylamine test is used to distinguish between

(A) Primary and secondary amine (B) Secondary and tertiary amine
(C) Aldehydes and ketones (D) Primary ,secondary and tertiary amine

3. The IUPAC name of the following compound is

(A) N,N-Dimethyl butan-1-amine (B) N,N-Diethyl butan-1-amine

(C) N-ethyl-N-butyl ethanamine (D) N-butyl-N-ethyl ethanamines

4.Which of the following name reaction is used to convert amides into amines?
(A) Carbylamine reaction (B) Gabriel Phthalimide Reaction
(C ) Sandmeyer reaction (D) Hoffmann bromamide degradation reaction

5. The correct decreasing order of basic strength for the following amines….
I. C6H5-NH2 II. O2N-C6H4-NH2 III. H3C-C6H4-NH2

(A) I > II > III (B) II > I > III

(C) III > I > II (D) III > II > I

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 6. The order of reactivity of ALKYL halides with amines is……
(A) RI > RBr > RCl (B) RBr > RI > RCl
(C) RCl > RBr > RI (D) RBr > RCl > RI

7 Which of the following given reagent is also called Hinsberg”s reagent?

(A) Lithium aluminium hydride (B) Alkyl magnesium bromide
(C) Benzenesulphonyl chloride (D) None of the above

8. An organic compound ‘A’ reacts with NH3 gives ‘B’. on heating , ‘B’ gives ‘C’. ‘C’ in presence of
KOH and Br2 gives CH3CH2-NH2. What is ‘A’?
(A) CH3COOH (B) CH3CH2COOH
(C) CH3CH2CH2COOH (D) CH3CH2CH2CH2COOH

9.When methanamine is treated with benzoyl chloride, the major product is

(A) N-phenylethanamide (B) N-methylbenzamide
(C) Acetophenone (D) N-ethylethanamide

10. Benzoic acid is treated with SOCl2 and the product (X) formed is reacted with ammonia to
give (Y). (Y) on reaction with Br2 and KOH gives (Z). (Z) in the reaction is
(A) aniline (B) chlorobenzene
(C) benzamide (D) benzoyl chloride

ANSWER KEY SECTION-A (MULTIPLE CHOICE QUESTION)

1. (A) 2.(D) 3.(B) 4.(D) 5.(C) 6.(A) 7.(C) 8.(B) 9.(B) 10.(A)

SECTION –B ASSERTION AND REASONING QUESTIONS ( 1 MARK EACH)

These questions consist of two statements, each printed as Assertion and Reason. While answering
these questions, you are required to choose any one of the following four responses.
(A) If both Assertion & Reason are correct and the Reason is a correct explanation of Assertion.
(B) If both Assertion & Reason are correct but Reason is not correct explanation of Assertion.
(C) If the Assertion is true but Reason is false.
(D) Assertion is false and Reason is true.

1.Assertion: Tertiary amines are less basic than secondary amines in aqueous solution.
Reason: Overcrowding due to three alkyl groups hinders the attack of the acid on the tertiary amines .

2.Assertion: Anilinium chloride is more acidic than ammonium chloride.

Reason: Anilinium ion is resonance stabilized.

3. Assertion: (CH3)3N is less basic than (CF3)3N.

Reason: F is highly electronegative in nature, so –CF3 group is an electron withdrawing group

4. Assertion: Aniline does not undergo Friedel-Crafts reaction.

Reason: –NH2 group of aniline reacts with AlCl3 (Lewis acid) to give acid-base reaction.

5. Assertion: Only a small amount of HCl is required in the reduction of nitro compounds
with iron scrap and HCl in the presence of steam.
Reason: FeCl2 formed gets hydrolysed to release HCl during the reaction.
ANSWER KEY for SECTION-B (ASSERTION AND REASON QUESTION)
1. (A) 2.(C) 3.(D) 4.(A) 5.(D)

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 SECTION –C VERY SHORT ANSWER QUESTIONS ( 2 MARK EACH)

Q1. Write IUPAC names of the following compounds and classify them into primary, secondary and
tertiary amines.
(i) C6H5NHCH3
N-Methyl aniline ( 20 )
(ii)(CH3CH2)2NCH3
N-Ethyl-N-methylethanamine (30)
Q2. Give reason for the following:
(i)Why do primary amines have higher boiling point than tertiary amines?
(ii) Why are aliphatic amines stronger base than aromatic amines ?
Answer:(i) Due to strong intermolecular H-bonding in primary amines.
(ii)In aromatic amines lone pair is engaged with benzene in resonance.

Q3. Arrange the following:

i) C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2 (In decreasing order of the pKbvalues)
ii) Aniline, p-nitroaniline and p-toluidine( In increasing order of basic strength)
Answer: (i) C6H5NH2, C6H5NHCH3, C2H5NH2, (C2H5)2NH
(ii) p-Nitroaniline , aniline, p-toluidine
Q4. Explain why?
A. Ethylamine is soluble in water but aniline is not, why?
B. Nitrobenzene does not undergo Friedal Craft reaction.
Answer:
A. Ethylamine forms intermolecular H-bond with water, but aniline does not form H-bond to a very
large extent due to the presence of large hydrophobic –C6H5 group
B. Due to deactivating nature of nitro group

Q5. Give reasons for the following-

a. Aniline is acetylated before nitration reaction.
b. pKb of aniline is lower than the m-nitroaniline.
Answer:
a. Aniline is acetylated, before nitration reaction in order to avoid formation of tarry oxidation products
and protecting the amino group, so that p -nitro derivative can be obtained as major product.
b. pKb of aniline is lower than the m-nitro aniline.The basic strength of aniline is more that m-
nitroaniline . pkb value is inversely proportional to basic strength. Presence of Electron withdrawing
group decrease basic strength.

Q6. Write short notes on the following:

(i)Hofmann's reaction
(ii)Coupling Reaction

Answer:
i) Hoffmann developed a method for preparation of primary amines bytreating an amide with bromine
in an aqueous or ethanolic solutionof sodium hydroxide. In this degradation reaction, migration of
analkyl or aryl group takes place from carbonyl carbon of the amideto the nitrogen atom. The amine so
formed contains one carbon lessthan that present in the amide

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ii) Benzene diazonium chloride reacts with phenol in which the phenol molecule at its para position is
coupled with the diazonium salt to form p-hydroxyazobenzene. This type of reaction is known as
coupling reaction.

Q7.Complete the following reactions:

(i) C6H5NH2 + CHCl3 + alc.KOH →
(ii)C6H5N2Cl + H3PO2 + H2O →
Answer i)
(i)

ii)

Q8. Give chemical test to distinguish between:

(a) C6H5NH2 & CH3NH2
(b) CH3NHCH3 & (CH3)3N
Answer:
a) Carbylamine test
b) Hinsbergs test
Q9. Write structures and IUPAC names of
(i) The amide which gives propanamine by Hoffmann bromamide reaction.
(ii)The amine produced by the Hoffmann degradation of benzamide.

Answer:
(i) Butanamide:
ii) Aniline.

Q10.Arrange the following amines in decreasing order of basic strength

i) (C2H5)2NH , C2H5NH2 , NH3 , (C2H5)3N
ii) (CH3)2NH, (CH3)3N , NH3 , CH3N

Answer:
(C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
(CH3)2NH > CH3NH2 > (CH3)3N >

SECTION –D SHORT ANSWER QUESTIONS ( 3 MARK EACH)

Q1. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Ethylamine and aniline
(iii) Aniline and benzylamine
Ans: (i) Carbylamine reaction
(ii) Azo dye Test
(iii) Azo dye Test

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Q2. Give reasons for the following:
(i)Although amino group is o, p− directing in aromatic electrophilic substitution reactions,aniline on
nitration gives a substantial amount of m-nitroaniline.
(ii)Aniline does not undergo Friedel-Crafts reaction.
(iii)Gabriel phthalimide synthesis is preferred for synthesizing primary amines.
Answer:
(i) Because nitration is carried out in an acidic medium. In an acidic medium, aniline is protonated
to give anilinium ion which is meta-directing
(ii) Friedel-Craft reaction is carried out in the presence of AlCl3. But AlCl3 acts as a Lewis acid, while
aniline acts as a Lewis base. Thus, aniline reacts with AlCl3 to form a salt.
(iii)Gabriel phthalimide synthesis results in the formation of primary amines only.
Secondary and tertiary amines are not formed in this synthesis. Thus, a pure primary amine can
be obtained.
Q3. How will you convert:
(i) Benzyl chloride to 2-phenylethanamine
(ii) Benzene to Aniline
(iii) Aniline to p-bromoaniline
Answer:
i) C6H5CH2Cl + (Ethanolic) NaCN --------- C6H5CH2CN + H2/Ni ------- C6H5CH2CH2NH

ii)
iii)

Q4. An organic compound [A] C3H6O2 on reaction with ammonia followed by heating yield B. Compound
B on reaction with Br2 and alc. NaOH gives compound C (C2H7N). Compound C forms a foul smelling
compound D on reaction with chloroform and NaOH. Identify A, B, C, D
Answer:
(A) CH3CH2COOH
(B) CH2CH2CONH2
(C) CH3CH2NH2
(D) CH3CH2NC

Q5. Give reasons for the following

a. Primary amine on treatment with benzenesulphonyl chloride forms a product which is soluble in
NaOH however secondary amine gives product which is insoluble in NaOH.
b. Aniline does not react with methyl chloride in the presence of anhydrous AlCl3 catalyst.
c. Alkyl amines are found to be stronger bases than ammonia.
Answer:
a. Due to the presence of acidic hydrogen in the N-alkylbenzenesulphonamide formed by the treatment
of primary amines.
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b. Aniline does not react with methylchloride in the presence of AlCl3 catalyst , because aniline is a base
and AlCl3 is Lewis acid which lead to formation of salt.
c. Due to presence of electron releasing group in alkyl amines

Q6. Account for the following:

a. Aniline cannot be prepared by the ammonolysis of chlorobenzene under normal conditions.
b. N-ethylethanamine boils at 329.3K and butanamine boils at 350.8K, although both are isomeric in
nature.
c. Acylation of aniline is carried out in the presence of pyridine.

Answer:
a) In case of chlorobenzene, the C—Cl bond is quite difficult to break as it acquires a partial double
bond character due to conjugation. So Under the normal conditions, ammonolysis of chlorobenzene
does not yield aniline.
b) Primary and secondary amines are engaged in intermolecular association due to hydrogen bonding .
Due to the presence of three hydrogen atoms, the intermolecular association is more in primary amines
than in secondary amines as there are two hydrogen atoms available for hydrogen bond formation in it.
c) During the acylation of aniline, stronger base pyridine is added. This done in order to remove the HCl
so formed during the reaction and to shift the equilibrium to the right hand side.

Q7. What happens when reactions:

a. N-ethylethanamine reacts with benzenesulphonyl chloride.
b. Benzylchloride is treated with ammonia followed by the reaction with Chloromethane.
c. Aniline reacts with chloroform in the presence of alcoholic potassium hydroxide.

Answer:
(a) N,N-diethyl benzene sulphonamide is formed.
b) When benzylchloride is treated with ammonia , Benzylamine is formed which on reation with
Chloromethane yields a secondary amine ,N-methylbenzylamine .
c) When aniline reacts with chloroform in the presence of alcoholic potassium hydroxide ,phenyl
isocyanides or phenyl isonitrile is formed .

Q8. Convert the following:

a. Phenol to N-phenylethanamide. b. Chloroethane to methanamine. C. Propanenitrile to ethanol.
c.

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Q9.Give one chemical test to distinguish between the following pairs of compounds.
(i) Secondary and tertiary amines
(ii) Ethylamine and aniline
(iv) Aniline and benzylamine
Answer:
i) Hinsbergs reagent
ii) Azo dye test
iii) with nitrous acid

Q10. Give the structure of the A ,B and C in the following reaction

Answer:

SECTION –E CASE BASED STUDY ( 4 MARK EACH)

Read the passage given below and answer the following questions:
A mixture of two aromatic compounds (A) and (B) was separated by dissolving in chloroform followed
by extraction with aqueous KOH solution. The organic layer containing compound (A), when heated
with alcoholic solution of KOH produce C7H5N (C) associated with unpleasant odour.
The following questions are multiple choice question. Choose the most appropriate answer:
1. What is A?
(a) C6H5NH2 (b) C6H5CH3 (c) C6H5CHO (d) None of these
OR
The reaction of (A) with alcoholic solution of KOH to produce (C) of unpleasant odour is called
(a) Sandmeyer reaction (b) Carbylamine reaction (c) Ullmann reaction (d) Reimer-Tiemann reaction

2. The alkaline aqueous layer (B) when heated with chloroform and then acidified give a mixture
of isomeric compounds of molecular formula C7H6O2. (B) is
(a) C6H5CHO (b) C6H5COOH (c) C6H5CH3 (d) C6H5OH

3.In the chemical reaction,

CH3CH2NH2 + CHCl3 +3KOH → (A) + (B) + 3H2O,
the compounds (A) and (B) are respectively
(a) C2H5NC and KCl (b) C2H5CN and KCl (c) CH3CH2CONH2 and KCl (d) C2H5NC and K2CO3
4. Direct nitration of an aromatic compounds (A) is not feasible because
(a) The reaction cannot be stopped at the mononitration stage
(b) A mixture of o, m and p-nitroaniline is always obtained
(c) nitric acid oxidises most of the aromatic compounds to give oxidation products along with only a
small amount of nitrated products
(d) all of the above
ANSWER KEY for SECTION-E (case based study question)
1. (A) OR (B) 2.(D) 3.(A) 4.(C)

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 Unit 10- Biomolecules
BIOMOLECULES

MACROMOLECULES MICROMOLECULES
- Large sized,high mol wt.
- Above 1000 daltons - Small sized, high mol wt
- Found in the insoluble pool - Between 18 and 800 daltons
- Found in the acid soluble pool
Carbohydrates
Proteins sugars
Nucleic acids aminoacids Nucleotides
Lipids Minerals Gases
Water

 CARBOHYDRATES
 Optically active polyhydroxy aldehydes or ketones

Sugars Non- sugars

Oligo
Monosaccharides Polysaccharides
saccharides

Cannot hydrolyse in to smaller molecules Yields 2-10 Yields a large number of

monosaccharides monosaccharides on
on hydrolysis hydrolysis

No of Types of Aldoses Ketoses e.g.: Gen formula- e.g. Starch,

Carbons Sugar (C6H10O5)n Cellulose,
Sucrose, Lactose,
Glycogen
3 Trioses Glyceraldehyde Erythrulose Maltose

4 Tetroses Erythrose Dihydroxy

acetone

5 Pentoses Ribose, Ribulose,

Deoxyribose Xylulose

6 Hexoses Glucose, Fructose

Galactose,
Mannose

7 Heptoses Glucoheptose Sedo

heptulose

*D & L sugars
The series of Aldoses or Ketoses in which the configuration of the penultimate C-atom (C-next to CH2-OH group)
is described as D-sugars if-OH is towards RHS & L- sugars if -OH is towards LHS.

*Epimers
A pair of Diastereomers
that differ only in the
configuration about a single Carbon
atom only.

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*Anomers
The two sugars that
differs in configuration
only on the Carbon that
was the Carbonyl Carbon
in the open chain form

*Mutarotation
The change in specific rotation
of an optically active compound
in solution with time, to an
equilibrium value, is called
mutarotation.
*Cyclic structure of glucose is PYRANOSE structure whereas that of Fructose is FURANOSE structure

*Important Reactions of glucose

*Diasaccharides:
 On hydrolysis
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose(Invert Sugar or Invertose) α-D-Glucose β-D-Fructose
(α1- β2 glycosidic bond) It is a non- reducing sugar
C12H22O11 + H2O C6H12O6 + C6H12O6
Maltose α-D-Glucose α-D-Glucose
(α1- α4 glycosidic bond) It is a reducing sugar
C12H22O11 + H2O C6H12O6 + C6H12O6
Lactose β-D-Galactose β-D-Glucose
(β1- β4 glycosidic bond) It is a reducing sugar

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*Polysaccarides
i) Starch (C6H10O5)n Amylose + Amylopectin

(α-D-Glucose) (α-D-Glucose)
(α1- α4 glycosidic bond) chain(α1- α4 glycosidic bond
& branching(α1- α6 glycosidic bond)
Water soluble Water insoluble
(15-20% starch) (80-85% starch)

Starch (C6H10O5)n + H2O Maltose (C12H22O11 ) + H2O α-D-Glucose

ii) Cellulose(C6H10O5)n + H2O β-D-Glucose

 (β1- 4 glycosidic bond)

 Most abundant organic substance in plant (Cell Wall) kingdom.
 Straight chain polysaccharide.
iii) Glycogen (C6H10O5)n
 Known as animal starch because its structure is similar to amylopectin and is rather more highly
branched.
 Present in liver, muscles and brain.
 When the body needs glucose, enzymes break the glycogen down to glucose.
 Also found in yeast and fungi.

 PROTEINS
 Condensation polymer of α-amino acids.
 Helps as transport agent, as enzyme, as metabolic regulator, as antibodies and as structural materials.
Amino acids

NEUTRAL
ACIDIC AMIDE SULPHUR AROMATIC CYCLIC BASIC
ALIPHATIC ALCOHOLIC

Aspartic Phenyl
Glycine** Serine Asparagine Cysteine Proline Arginine*
Acid Alanine*

Glutamic
Alanine Threonine* Glutamine Methionine* Tyrosine Lysine*
Acid

Valine* Tryptophan* Histidine*

Leucine*

Isoleucine*

Extra Extra Extra Extra Extra

(-NH or -
(-COOH (-CONH2 imine
(-OH group) (-S) NH2
group) group) (-NH)
group)

*essential amino acids : VIP HALL Me TT

**Glycine is simplest & only optically inactive α-amino acids.

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*PEPTIDE BOND :

An amide formed between

–COOH group and –NH2 group.
The bond formed between
two amino acids by the
elimination of a water molecule
is called a peptide linkage
or bond(–CO– NH–)

 When the number of such amino acids is more than ten, then the products are called polypeptides. A
polypeptide with more than hundred amino acid residues, having molecular mass higher than 10,000u is
called a protein.

*ZWITTER ION:
In aqueous solution, the carboxyl group
can lose a proton and amino group can
accept a proton, giving rise to
a dipolar ion known as zwitter ion.
This is neutral but contains both
positive and negative charges.

In zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids and bases.
ISOELECTRIC POINT: The pH at which the amino acid molecule has no net charge & do not migrate towards any
electrode is called its Isoelectric point.
*Structure of proteins can be studied at 4 levels. Primary, secondary, tertiary and quaternary.
(i) The sequence in which the various amino acids are linked to one another in a protein molecule is called its
primary structure.
(ii) Secondary structure refers to the shape in which a long polypeptide chain exist. They are found to exist in two
different types of structures which are α-helix and β-pleated sheet.
(iii) The tertiary structure of proteins represents overall folding of the polypeptide chains. The main forces which
stabilises 2° and 3° structure of proteins are hydrogen bonds, disulphide linkages, van der Waals' forces and
electrostatic forces of attraction.
(iv) Although many proteins exist as a single polypeptide chain, but some of the proteins are composed of two or
more polypeptide chains called subunits. The spatial arrangement of these subunits with respect to each other is
known as quaternary structure.
On the basis of molecular structure, proteins are classified as fibrous and globular proteins.
(a) Fibrous proteins When the polypeptide chains run parallel and are held together by hydrogen and disulphide
bonds, a fibre like structure is formed. Such proteins are insoluble in water. e.g. keratin, myosin.

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(b) Globular proteins When the chains of polypeptides coil around to give a spherical shape. the protein is called
a globular protein. Such proteins are usually soluble in water. e.g. albumin, insulin.
*Denaturation of Proteins
Due to temperature or pH change, secondary and tertiary structures are destroyed but primary structure
remains intact. This process is called denaturation of proteins.

*Enzymes
The biocatalysts which are needed to catalyse biochemical reactions. Almost all the enzymes are globular
proteins. Enzymes are very specific for a particular substrate and reaction.

*Vitamins
 required in small amounts for the growth, life and health of human beings and animals.
 can be water soluble (vitamin B and C) or fat soluble (Vitamin A, D, E and K).
 Water soluble vitamins must be supplied regularly in diet because they are readily excreted in urine
and cannot be stored (except B) in our body.
 Deficiency of vitamins in diet may cause various types of deficiency diseases.

Name of
Sources Deficiency diseases
vitamins

Vitamin A1 Fish liver oil, carrots, butter and milk Xerophthalmia, night blindness

Vitamin B1 Milk, yeast, green vegetables and Beri-Beri (loss of appetite)

cereals

Vitamin B2 Milk, egg white, liver Cheilosis, digestive disorders

Vitamin B6 Yeast, milk, cereals Convulsions

Vitamin B12 Meat, fish, egg and curd Pernicious anaemia

Vitamin C Citrus fruits, amla and green leafy Scurvy

vegetables

Vitamin D Exposure to sunlight, fish Rickets and osteomalacia

Vitamin E Vegetable oils Muscular weakness and increased fragility

of RBCS

Vitamin K Green leafy vegetables Delayed blood clotting

*Hormones
The chemical substances, produced by endocrine glands in the body and are released directly in blood stream. On
the basis of chemical constitution hormones can be divided into two classes: steroid and non-steroid
hormones.

*Nucleic Acids

 Constituents of nucleus of a cell and are responsible for heredity or inherent characters. DNA
(Deoxyribonucleic acid) and RNA (Ribonucleic acid) are two main types of nucleic acids. These are
polynucleotides as they are long chain polymers of nucleotides.
 Complete hydrolysis of DNA (or RNA) yields a pentose sugar, phosphoric acid and nitrogen containing
heterocyclic compounds called bases.
 DNA has four bases: adenine (A), guanine (G), cytosine (C) and thymine (T). RNA has adenine guanine,
cytosine and uracil (U).

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  A unit formed by the attachment of a base to 1' position of sugar is called nucleoside. When nucleoside is
linked to phosphoric acid at 5' position of sugar moiety, we get a nucleotide Thus, nucleotide is made up
of a pentose sugar, a heterocyclic base and phosphoric acid unit.
 James Watson and Francis Crick gave a double strand helix structure of DNA. Two nucleic acids chains are
bound about each other and held together by hydrogen bonds between pair of base The two strands are
complementary to each other. types and they perform
 RNA has a single stranded helical structure. RNA molecules are of three different functions. They are named
as messenger RNA (m-RNA), ribosomal RNA (rRNA) and transfer RNA (t-RNA). RNA (Ribonucleic acid)
synthesises protein in the cell.
 VERY IMPORTANT QUESTIONS

Q. No. MULTIPLE CHOICE QUESTIONS (1 MARK)

1 α-D-Glucose and β-D-Glucose are

(a) Geometrical isomers (b) enantiomers
(c) anomers (d) optical isomers
2 Glucose reacts with acetic anhydride to form
(a) Monoacetate (b) Tetraacetate
(c) Penta-acetate (d) Hexa-acetate
3 Which of the following statements is not true about glucose?
(a) It is an aldohexose (b) On heating with HI it forms n-hexane
(c) It is present in furanose form (d) It does not give 2,4-DNP test
4 Which of the following polymer is stored in the liver of animals?
(a) Amylose (b) Cellulose
(c) Amylopectin (d) Glycogen
5 The functional unit that is repeated in a protein molecule is
(a) An ester linkage (b) a glycosidic linkage
(c) a peptide linkage (d) an ether linkage
6 Which of the following is an essential amino acid
(a) Methionine (b) Tyrosine
(c) Proline (d) Glycine
7 Proteins are found to have two different types of secondary structures viz. α-helix and β-
pleated sheet structure. α-helix structure of protein is stabilised by :
(a) Peptide bonds (b) van der Waals forces
(c) Hydrogen bonds (d) Dipole-dipole interactions
8 Which of the following B group vitamins can be stored in our body?
(a) Vitamin B1 (b) Vitamin B2
(c) Vitamin B6 (d) Vitamin B12

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 9 Which of the following acids is a vitamin?
(a) Aspartic acid (b) Ascorbic acid
(c) Adipic acid (d) Saccharic acid
10 DNA and RNA contain four bases each. Which of the following bases is not present in
RNA?
(a) Adenine (b) Uracil
(c) Thymine (d) Cytosine

Answers
1. (c) 2. (c) 3.(c) 4.(d) 5.(c) 6.(a) 7.(c) 8.(d) 9.(b) 10.(c)

ASSERTION REASON TYPE QUESTIONS (1 MARK)

Note : In the following questions (1-5) a statement of assertion followed by a statement

of reason is given. Choose the correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason explains the
assertion.
(b) Assertion and reason both are correct statements but reason does not explain
assertion.
(c) Assertion is correct statement and reason is wrong statement.
(d) Assertion is wrong statement and reason is correct statement.

1 Assertion : D (+) – Glucose is dextrorotatory in nature.

Reason : ‘D’ represents its dextrorotatory nature.
2 Assertion : Vitamin D can be stored in our body.
Reason : Vitamin D is fat soluble vitamin.
3 Assertion : Maltose is a reducing sugar, which gives two moles of D-glucose on hydrolysis
Reason : Maltose has a 1,4-β glycosidic linkage.
4 Assertion : Disruption of the natural structure of a protein is called denaturation.
Reason : The change in colour and appearance of egg during cooking is due to denaturation
5 Assertion : Sucrose is a non-reducing sugar.
Reason : It has glycosidic linkage

Answer 1. (c) 2. (a) 3. (c) 4. (b) 5. (b)

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 VERY SHORT ANSWER QUESTIONS ( 2 MARKS)
1 Explain what is meant by
(a) pyranose structure of glucose?
(b) glycosidic linkage?
Answer (a) The six membered cyclic structure of glucose is called pyranose structure (α or β),
in analogy with pyran.

Pyran Glucose
(b) The two monosaccharide units are joined together by an oxide linkage formed by
the loss of a water molecule is called glycosidic linkage.

2 Write such reactions and facts about glucose which cannot be explained by its open chain
structure.
Answer Despite having the aldehyde group, glucose does not react with Schiff’s reagent and does
not form the hydrogen sulphite addition product with sodium bisulphite.
3 What is essentially the difference between the α-form of glucose and β-form of glucose?
Explain.
Answer (1) The two forms differs from each other in orientation of -OH group at C-1.
(2) α -form is obtained by crystallisation from concentrated solution of glucose at
303 K, while β -form is obtained by crystallisation from hot and saturated solution
at 371 K.
4 How will you obtain the following from glucose?
(a) n-hexane
(b) Gluconic acid

Answer (a) (b)

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 5 Answer the following questions:
(a) Why are vitamin B and vitamin C essential for us?
(b) What is the difference between a nucleoside and a nucleotide?
Answer (a) Because these cannot be stored in our body as are soluble in water and are
excreted in urine.(except vitamin B12)
(b) Nucleoside: A unit formed by the attachment of a base to
6 Explain the meaning of the following terms:
(a) Polypeptide
(b) Enzymes
Answer (a) When more than ten α-amino acids are joined together by peptide bonds, then the
products are called polypeptides
(b) The biocatalysts(proteins) which are needed to catalyse biochemical reactions are
called enzymes.
7 Give the chemical name of the following:
(a) Vitamin E
(b) Vitamin C

Answer (a) Tocopherol

(b) Ascorbic acid

8 Describe what do you understand by primary and secondary structure of proteins?

Answer (i) The sequence in which the various amino acids are linked to one another in a protein
molecule is called its primary structure.
(ii) Secondary structure refers to the shape in which a long polypeptide chain exist.
They are found to exist in two different types of structures which are α-helix and β-
pleated sheet.
9 What are vitamins? Deficiency of which vitamins cause convulsions and pernicious
anaemia?
Answer The organic compounds which cannot be produced by the body and must be supplied in small
amounts in diet to perform specific biological functions for the normal health, growth and
maintenance of body are called vitamins.

Convulsions are caused by the deficiency of vitamin B and pernicious anaemia is

caused by the deficiency of vitamin B12
10 What is meant by denaturation of proteins?
Answer When proteins are subjected to a change in pH, temperature, etc, the hydrogen bonds are
disturbed due to which the secondary and tertiary structures breakdown but primary
structure remains the same and hence protein loses its biological activity. This is known
as denaturation, e.g. coagulation of egg white on boiling, curdling of milk, etc.

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 SHORT ANSWER QUESTIONS ( 3 MARKS)

1 What happens when D-glucose is treated with the following reagents

(a) Br₂ water
(b) HCN
(c) (CH3CO)2O
Answer (a)

(b)

(c)

2 What is glycogen? How is it different from starch? How is starch structurally different
from cellulose?
Answer Glycogen is a polysaccharide carbohydrate which is stored in animal body. It is also
known as animal starch.
Starch is a polymer of a-glucose and consists of two components amylose and
amylopectin.
Amylose is a linear polymer of a-D-glucose. Both glycogen and amylopectin are branched
polymers of a-D-glucose but glycogen is more highly branched than amylopectin. Amylopectin
consists of 20-25 glucose units, while glycogen chain consists of 10-14 glucose units.

Starch is a branched chain polymer of a-D-glucose, while cellulose is a linear polymer of

B-D-glucose. Cellulose is present in the cell wall of plants, while starch is the storage
material of plants.
3 How can reducing and non-reducing sugars be distinguished? Mention the structural
features characterising reducing sugars.

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Answer Reducing sugars: The sugars which reduce Fehling solution and Tollen's reagent are called
reducing sugars, e.g. all monosaccharides containing free -CHO or -C=O groups are reducing
sugars. Thus, the presence of free aldehydic or ketonic group is main feature of reducing sugars.

Non-reducing sugars: The sugars which do not reduce Fehling solution or Tollen's
reagent are called non-reducing sugars, e.g. sucrose. In non-reducing sugars, reducing
groups of monosaccharides, i.e. aldehydic or ketonic groups are bonded.
4 Define the following as related to proteins:
(a) Peptide linkage
(b) Zwitter ion
(c) Biocatalysts
Answer (a) Peptide linkage :
An amide formed between
–COOH group and –NH2 group.
The bond formed between
two amino acids by the
elimination of a water molecule
is called a peptide linkage
or bond(–CO– NH–)

(b) Zwitter ion:

In aqueous solution, the carboxyl
group can lose a proton and
amino group can accept a proton,
giving rise to a dipolar ion known
as zwitter ion.
This is neutral but contains both
positive and negative charges.

(c) Enzymes are biological catalysts that catalyses the biochemical reactions
occurring in living organism. They are made up of proteins. e.g. invertase, zymase,
5 How are vitamins classified? Name the vitamin responsible for the coagulation of blood.
Answer Classification of vitamins: Vitamins are classified into two groups depending upon their
solubility in water or fat :
(i) Fat soluble vitamins
(ii) Water soluble vitamins

Vitamin K is responsible for coagulation of blood.

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 6 (a) Except for vitamin B12, all other vitamins of a group B, should be supplied
regularly in the diet. Why?
(b) Name the vitamin responsible for the coagulation of blood.
Answer (a) B vitamins are necessary for the correct functioning of the body's cells. They aid in
the conversion of food into energy (metabolism), the formation of new blood cells,
and the maintenance of healthy skin, brain, and other bodily structures.
(b) Vitamin K is important for blood clotting and avoiding excessive bleeding
7 Write the main structural difference between DNA and RNA. Out of the four bases name
those which are common to both DNA and RNA.
Answer The structural differences between DNA and RNA
(i) The sugar in DNA is deoxyribose lacking oxygen atom at 2'C, while that in RNA is ribose
having oxygen atom at 2'C.

(ii) DNA has a double-stranded α-helical structure, while RNA has a single-stranded α-
helical structure.
Adenine, Guanine and Cytosine are the bases which are common to both DNA and RNA.
8 (a) What type of bonding helps in stabilising the a-helix structure of proteins?
(b) Differentiate between globular and fibrous proteins.
Answer (a) α-helix is one of the most common ways in which a polypeptide chain is formed. It
is stabilised by hydrogen bonds.

(b)
Sr.
Globular Proteins Fibrous Proteins
No.

1 The chains of polypeptides coil around to They have fibre like structure
give a spherical shape

2 The interaction present in these are H- The molecules are held together by H-
bonds, ionic or sulphur bridges. bonds and disulphide bonds.

3 these are usually water soluble, e.g. insulin, These are water insoluble e.g. keratin,
fibrinogen, haemoglobin etc. myosin, fiboin etc.

9 (a) What type of linkage is present in nucleic acid?

(b) The two strands of DNA are not identical but are complementary. Explain.
Answer (a) The constituents of nucleic acids (ribose or deoxyribose, sugar, purine or
pyrimidine base and phosphoric acid) are joined through covalent linkage. DNA
consists of two strands and RNA has a single strand. The two strands of DNA are
linked together through hydrogen bonds.
(b) The two strands are internally connected by hydrogen bonding between complementary
bases.
The two strands of DNA are not identical because their sequence of bases has to
be complementary to each other. e.g. if one sequence is ATCG, then the other has
to be TAGC.

10 Amino acids may be acidic, alkaline or neutral. How does this happen? What are essential
and non-essential amino acids? Name one of each type.

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Answer Amino acids may be acidic, basic or neutral depending upon the relative number of amino and
carboxyl group present in the molecule.

Equal number of amino and carboxyl groups makes it neutral, more number of amino
than carboxyl groups makes it basic and more carboxyl group as compared to amino
groups makes it acidic.
Essential amino acids are the a-amino acids which are needed for health and growth of human
beings but are not synthesised by the human body, e.g. valine.

Non-essential amino acids are the a-amino acids which are needed for health and
growth of human beings and are synthesised by the human body, e.g. glycine.
CASE BASED QUESTIONS ( 4 MARKS)
1 Read the given passage and answer the questions that follow:
Carbohydrates are polyhydroxy aldehydes and ketones and those compounds which on hydrolysis
give such compounds are also carbohydrates. The carbohydrates which are not hydrolysed are
called monosaccharides. Other carbohydrates are oligosaccharides and polysaccharides.
Monosaccharides with aldehydic group are called aldose and those with free ketonic groups are
called ketose. Carbohydrates are optically active. Number of optical isomers = 2"
where, n = number of asymmetric carbons. Carbohydrates are mainly synthesised by plants during
photosynthesis.

(a) Write the name of two compounds which are not carbohydrates but have the
formula
CX(H2O)y.
(b) Write the name of two compounds which are carbohydrates but have the formula
CX(H2O)y.
(c) Which of the following cannot be hydrolysed further?
Glucose, fructose, sucrose, ribose.
(d) What do you mean by a disaccharide?
OR
What are the functional groups that can be present in monosaccharides?
Answer (a) Formaldehyde (CH₂O) and acetic acid (C2H4O2)
(b) Rhamnose (C6H12O5) and deoxyribose (C5H10O4)
(c) Glucose, fructose and ribose.
(d) The carbohydrate which on hydrolysis gives two units of monosaccharides is known as a
disaccharide. For example, sucrose is a disaccharide because on hydrolysis it gives one unit
of a-glucose and ẞ-fructose each.
OR

Monosaccharides have alcoholic groups (primary and secondary) and aldehydic or

ketonic group.

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SESSION 2022-23
BLUE PRINT
SAMPLE QUESTION PAPER SET – 1
CLASS – XII, SUBJECT – CHEMISTRY
Sl Chapter MCQ VSA SA CASED LA (5 TOT

No. (1marks) (2marks) (3marks) BASED marks) AL

QUESTION

(4 marks)

1. Solutions 3(1) 4(1) 7

2. Electrochemistry 1(1) 2(1) 5(1) 8

3. Chemical Kinetics 1(3) 2(2) 7

4. d- and f- Block 1(2) 5(1) 7

Elements

5. Co-ordination 1(2) 2(1) 3(1) 7

Compounds

6. Haloalkanes and 1(1) 2(1) 3(1) 6

Haloarenes

7. Alcohols, Phenols and 1(3) 2(1) 3(1) 8

Ethers

8. Aldehydes, Ketones 1(2) 5(1) 7

and Carboxylic acids

9. Amines 1(3) 3(1) 6

10. Biomolecules 1(1) 2(1) 4(1) 7

Total 18 14 15 8 15 70

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -1
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70

a) There are 35 questions in this question paper with internal choice.

b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks each.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed
SECTION - A
1. Which among the following molecules does not give haloform test: 1
a) Ethanol b) acetaldehyde c) butanone, d) acetic acid
2. Which one is the correct order of basicity: 1
a) CH3NH2>( CH3)2NH> (CH3)3N b) (CH3)2NH> (CH3)3N > CH3NH2
c) Aniline> NH3> Cyclohexanamine d) Cyclohexanamine> NH3 > aniline
3. Which of the following represents a gem dihalide? 1
a ) Ethylene dichloride b) 2,2-dichloropropane
c) 1,3-dichloropropane d) 1,2-dichloropropane
4. 2- methoxy-2-methyl propane on heating with HI would produce 1
a) methyl alcohol and sec-propyl iodide. b) methyl iodide and tert-butyl alcohol
c) methyl iodide and isobutene d) methyl alcohol and tert-butyl iodide
5. Which of the following reaction is used to differentiate between CH3CHO & PhCHO. 1
a) Cannizzaro reaction b) Rossenmund reduction
c) Fehling’s test d) Tollen’s test
6. The SI unit of molar conductance is 1
a) Sm2/mol b) Sm2 c) S/mol d) Scm2/mol
7. Mol Ls is the unit of rate constant when the order of reaction
-1 -1 1
a) 1st order b) zero order c) 3rd order d) 2nd order
8. Which among those a transition element but forms colourless salts. 1
a) Zn2+ b) Pb2+ c) Mn2+ d) Sc3+
9. In dichromate dianion, 1
a) 4 Cr-O bonds are equivalent b) 6 Cr-O bonds are equivalent
c) all Cr-O bonds are equivalent d) all Cr-O bonds are non-equivalent
10. The following graph represents 1

a) First order reaction b) second order reaction

c) Zero oder reaction d) pseudounimolecular reaction
11. Compare the acidity of Phenol (I), p-methoxyphenol (II), p-nitrophenol (III), m- 1
nitrophenol (IV).
a) IV>III>I>II b) III>IV>I>II c) II>I>IV>III d) III>IV>I>II
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12. Magnetic moment of [Fe(H2O)6]2+ is 1
a) 0 b) √24 B.M. c) √35 B.M. d)√20 B.M.
13. Which of the following amines cannot be acylated? 1
a) Trimethylamine b) sec. Butylamine
c) N,N-dimethylaniline d) N-ethylethanamine
14. The complex salt having the molecular composition, [Co(NO2)(SCN)(en)2]Br exhibits 1
a) geometrical isomerism b) linkage isomerism
c) ionization isomerism d) all the above
15. Given below are two statements labelled as Assertion (A) and Reason (R) 1
A: Phenol is more reactive than benzene towards electrophilic substitution reaction.
R: In case of phenols, intermediate carbocation is more stabilized by resonance.
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
16. Given below are two statements labelled as Assertion (A) and Reason (R) 1
A: Acitanilide is less basic than aniline.
R: Acetylation of aniline results in decreasing electron density of N.
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
17. Given below are two statements labelled as Assertion (A) and Reason (R) 1
A: Sucrose is called inverted sugar.
R: Configuration of stereocentres in sucrose gets inverted after hydrolysis.
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A 1
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
18. Given below are two statements labelled as Assertion (A) and Reason (R) 1
A: A rate of reaction can also increase with its product if one of the product act as
catalyst.
R: A catalyst lowers the activation energy fo reactions.
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
SECTION – B
19. Two half-reactions of an electrochemical cell are given below : 2
MnO–4 (aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = 1.51 V
Sn2+ (aq) → Sn4+ (aq) + 2e–, E° = + 0.15 V.
Construct the redox reaction equation from the two half-reactions and calculate the cell
potential from the standard potentials and predict if the reaction is reactant or product
favoured.
20. A reaction is of second order with respect to a reactant. How will the rate of reaction be 2
affected if the concentration of this reactant is
(i) doubled, (ii) reduced to half?

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21. The rate constant of a reaction at 500 K and 700 K are 0.02 s-1 and 0.07 s-1 respectively. 2
Calculate the value of activation energy, En (R = 8.314 J K-1 mol-1)
22. What are reducing and non-reducing sugars? 2
What is the structural feature characterizing reducing sugars?
23. In the complex, [Cr(H20)4(CN)2]Cl 2
a) the charge on central metal is _____________________.
b) the IUPAC name of the complex .
OR,
When a co-ordination compound CrCl3.6H2O is mixed with AgNO3, 2 moles of AgCl are
precipitated per mole of the compound. Write
(i) Structural formula of the complex. (ii) IUPAC name of the complex.
24. Haloarenes are not susceptible towards nucleophilic substitution. Explain the reason. 2
OR,
How would you convert the following:
(a) Prop-1-ene to 1-fluoropropane (b) Chlorobenzene to 2-chlorotoluene
25. Explain the following reactions with an example for each : 2
(i) Reimer-Tiemann reaction
(ii) Friedel-Crafts reaction.
SECTION – C

26. The vapour pressures of pure liquids A and B are 450 mm and 700 mm of Hg 3
respectively at 350 K. Calculate the composition of the liquid mixture if total vapour
pressure is 600 mm of Hg. Also find the composition in the vapour phase.
OR,
Vapour pressure of pure water at 298 K is 23.8 m m Hg. 50 g of urea (NH2CONH2) is
dissolved in 850 g of water. Calculate the vapour pressure of water for this solution and
its relative lowering.
27. a) Write down the IUPAC name of [Co(NH3)4(H20)Cl]Cl2. 3
b) Which of the following is more stable and why?
[Co(NH3)6]3+ & [Co(en)3]3+.
calculate the magnetic moment of Co in both cases.
OR,
Name the following coordination entities and draw the structures of their
stereoisomers :
(i) [Co(en)2Cl2]+ (ii) [Cr(C2O4)3]3- (iii) [Co(NH3)3 Cl3]
28. a) SN1 reactions are accompanied by racemisation in optically active alkyl halides. 3
Explain.
b) Compare the reactivity of the following compounds towards nucleophilic
substitution with explanation.
Isopropyl iodide, methyl iodide, tert-butyl iodide, benzyl iodide.
29. How do you convert the following: 3
(i) Phenol to anisole
(ii) Propan-2-ol to 2-methylpropan-2-ol
(iii) Aniline to phenol?
30. Account for the following: 3
(a) Gabriel phthalimide synthesis is not preferred for preparing aromatic primary
amines.
(b) On reaction with benzene sulphonyl chloride, primary amine yields product soluble
in alkali whereas secondary amine yields product insoluble in alkali.

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 SECTION – D
31. Read the passage given below and answer the following questions: 4
Glucose is known as dextrose because it occurs in nature as the optically active dextrorotatory
isomer. It is essential constituent of human blood. The blood normally contains 65 to 110 mg of
glucose per 100 mL (hence named Blood sugar). The level may be much higher in diabetic
persons. The urine of diabetic persons also contain considerable amount of glucose. In combined
form, it occurs in cane sugar and polysaccharides such as starch and cellulose.
Glucose has an aldehyde group (-CHO), one primary alcoholic group (-CH2OH) and four secondary
alcoholic groups (-CHOH) in their structure. Due to the presence five hydroxyl groups (-OH),
glucose gives acetylation reaction. Glucose also undergoes oxidation with mild oxidising agents
like bromine water as well as with strong oxidising agents like nitric acid. Since glucose is readily
oxidised, it acts as a strong reducing agent and reduces Tollen's reagent and Fehling solution.
Glucose exists in two crystalline forms:α -D-glucose and β-D-glucose undergoes If either of the
two forms is dissolved in water and allowed to stand, the specific rotation of the solution changes
gradually, until a constant value is obtained. This change is called mutarotation.
a) Why do diabetic persons carry a packet of glucose with them?
b) Write down the structure of gluconic acid.
c) Name the carbohydrate which is most abundant in the plant kingdom.
d) Which test confirms presence of five hydroxyl group in glucose?
32. Read the passage given below and answer the following questions: 4
An ideal solution may be defined as the solution which obeys Raoult's law exactly over
the entire range of concentration. The solutions for which vapour pressure is either
higher or lower than that predicted by Raoult's law are called non-ideal solutions.
Non-ideal solutions can show either positive or negative deviations from Raoult's law
depending on whether the A-B interactions in solution are stronger or weaker than A - A
and B - B interactions.
The following questions are multiple choice questions. Choose the most appropriate
answer:
(i) Which of the following solutions is/are ideal solution(s)?
(I) Bromoethane and iodoethane (II) Acetone and chloroform
(III) Benzene and acetone (IV)n-heptane and n-hexane
(a) only I (b) I and II (c) II and III (d) I and IV
(ii) For which solution ΔHmix and ΔVmix are negative?
a) acetone and aniline b) ethanol and cyclohexane
c) acetone and CS2 d) benzene and toluene

(iii) For water and nitric acid mixture which of the given graph is correct?

(A) graph A (c) Graph B

(C) Both of these (d) None of these

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 (iv) Water- HCl mixture
I. shows positive deviations II. forms minimum boiling azeotrope
III. shows negative deviations IV. forms maximum boiling azeotrope
(a) I and II (b) II and III
(c) I and IV (d) III and IV
SECTION – E
33. a) Write anode and cathode reactions that occur in dry cell. How does a dry cell differ 2
from a mercury cell?
b) The molar conductivities at infinite dilution for sodium acetate, hydrochloric acid 3
and sodium chloride are 91.0, 425.9 and 126.4 S cm2 mol-1 respectively at 298 K.
Calculate the molar conductivity of acetic acid at infinite dilution.
OR,
a) Write the Nernst equation and calculate the e.m.f. of the following cell at 298 K:
Cu(s) | Cu2+ (0.130 M) | | Ag+ (1.0 × 10-4 M)) | Ag (s) 3
Given: E⊖(Cu2+/Cu) = + 0.34V and E⊖(Ag2+/Ag) = + 0.80V 2
b) Write the name of two fuels other than hydrogen used in fuel cell. Write two
advantages of fuel cell over an ordinary cell.
34. a) Based on the data, arrange Fe2+, Mn2+ and Cr2+ in the increasing order of stability of 1
+2 oxidation state:
E°Cr3+/Cr2+ = – 0.4 V, E°Mn3+/Mn2+ = 1.5 V, E°Fe3+/Fe2+ = 0.8 V
b) When MnO2 is fused with KOH in the presence of KNO3 as an oxidizing agent, it gives
4
a dark green compound (A). Compound (A) disproportionates in an acidic solution to
give a purple compound (B). An alkaline solution of compound (B) oxidizes Kl to
compound (C), whereas an acidified solution of compound (B) oxidizes Kl to (D).
Identify (A), (B), (C), and (D).
35. a) A compound ‘X’ (C2H4O) on oxidation gives ‘Y’ (C2H4O2). ‘X’ undergoes haloform 3
reaction. On treatment with HCN ‘X’ forms a product ‘Y’ which on hydrolysis gives 2-
hydroxy propanoic acid.
(i) Write down structures of ‘X’ and ‘Y’. (ii) Name the product when ‘X’ reacts with dil 1*2
NaOH. (iii) Write down the equations for the reactions involved.
b) (i) How do you convert the following?
(a) Ethanal to propanone (b) Toluene to benzoic acid
OR,
(i) An organic compound (A) has a characteristic odor. On treatment with NaOH, it
forms two compounds (B) and (C). Compound (B) has molecular formula C7H80 which 5
on oxidation gives back (A). The compound (C) is a sodium salt of an acid. When (C) is
treated with soda lime it yields an aromatic hydrocarbon (D). Deduce the structures of
(A), (B), (C) and (D). Write the sequence of reactions involved.
MARKING SCHEME
SECTION – A
1. d 1
2. d 1
3. b 1
4. d 1
5. c 1
6. a 1
7. d 1
8. d 1
9. a&c 1

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 10. a 1
11. b 1
12. b 1
13. c 1
14. d 1
15. a 1
16. a 1
17. c 1
18. a 1
SECTION – B
19. The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn2+ → Sn4+ (aq) + 2e– ] × 5 E° = + 0.15 V ½
Af cathode (reduction) :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I)] × 2 E° = + 1.51 V ½
The Net R × M = 2MnO–4(aq) + 16H+ + 5Sn2+ → 2Mn2+ + 5Sn4+ + 8H2O
Now E°cell = E°cathode – E°anode
= 1.51 – 0.15 = + 1.36 V 1
∴ Positive value of E°cell favours formation of product.
20. Since Rate = K[A]2 1
For second order reaction Let [A] = a then Rate = Ka2
(i) If [A] = 2a then Rate = K (2a)2 = 4 Ka2
∴Rate of reaction becomes 4 times
(ii) If [A] = a/2 then Rate = K (a/2)2=Ka2/4 1
∴ Rate of reaction will be ¼ th.
21. Given : k2 = 0.07 s-1, k1, = 0.02 s-1, T1 = 500 K, T2 = 700 K, ½

22. The sugars those can reduce Fehling’s solution and Tollen’s reagent are called reducing ½
sugars. Ex- glucose, maltose, lactose etc.
The sugars those can’t reduce Fehling’s solution and Tollen’s reagent are called non- ½
reducing sugars. Ex: sucrose, raffinose etc.
When aldehyde and ketone group of carbohydrate is free, they can react with Fehling’s 1
solution and Tollen’s reagent, then they act as reducing sugars.
23. a) +3 1
b) Tetraaquadicyanidochromium(III) chloride 1
OR,
(i) The complex formed on mixing a coordination compound CrCl3.6H2O with AgNO3 is as 1
follows
CrCl3.6H2O + AgNO3 → [Cr(H2O5)Cl]Cl2. H2O 1
(ii) Pentaaquachloridochromium (III) chloride monohydrate
24. C-X bond get partial double bond character due to resonance, hence difficult to break. 2
halogen bearing C is sp2 hybridized, hence C-X bond is shorter and stronger.
Aryl cation is highly unstable, so SN1 can’t occur

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 Aryl group has high electron density, so backside attack of Nucleophile is not possible and
SN2 is not feasible.
OR,
a)

b)
1

25. (i) Reimer-Tiemann reaction : Treatment of phenol with CHCl3 in presence of aqueous 1
NaOH at 340K followed by hydrolysis gives salicylaldehyde.

(ii) Friedel-Crafts reaction : This reaction is used for introducing an alkyl or an acyl group
into an aromatic compound in presence of Lewis acid catalyst (AlCl3)
1
Example:

SECTION – C

26. Vapour pressure of pure liquid A (P∘A) = 450 mm

Vapour pressure of pure liquid B (P∘B) = 700 mm 1
Total vapour pressure of the solution (P) = 600 mm

½
½

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 OR,

27. a) Tetraammineaquachloridocobalt(III) chloride 1

b) Since ethylenediaamine(en) is a chelating ligand, [Co(en)3]3+ is more stable. ½
For both cases magnetic moment is zero as both are L.S. complex. *2
OR,
(i) [Co(en)2Cl2]+
Name : Dichloridobis(ethan-1,2-diamine)Cobalt (III) ion
1

The geometrical isomers of [CoCl2(en)2]+ (2 isomers) ½

(ii) [Cr(C2O4)3]3-
Name : Trisoxalatochromate (III) ion
½

½
(iii) [Co(NH3)3 Cl3]
Name : Triamminetrichlorido cobalt (III)
Structure : The geometrical isomers of [Co(NH3)3Cl3] (2 isomers) :
½

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28. a) The SN1 reactions proceed through the formation of carbocations. In the case of optically 2
active alkyl halides, the product formed is a racemic mixture. This is because the
intermediate carbocation is planar species, therefore, the attack of the nucleophile, OFT ion
can take place from both the faces (front and rear) with equal ease. As a result, a 50: 50
mixture of the two enantiomers (laevo and dextro) is formed. Thus, the product formed is
a racemic mixture (±) which is optically inactive.

b) As we know rate of SN1 is proportional with the stability of carbocations, here the
stability of carbocations is as follows:
PhCH2+ > (CH3)3C+ > (CH3)2CH+ > CH3+
hence, the rate of SN1 will be as follows:
1
benzyl iodide>tertiary butyl iodide>isopropyl iodide>methyl iodide.
29. (i) Phenol to anisole 1

(iii) Aniline to phenol

30. a) Gabriel phthalimide synthesis is not preferred for preparing aryl amines because aryl 1
halides do not undergo nucleophilic substitution reaction with phthalimide.
b) The sulphonamide formed by the reaction of secondary amine and benzene sulphonyl
chloride does not contain any hydrogen atom attached to the N atom, so it is not acidic.
Therefore, it is insoluble in alkali.

30.
Due to the presence of ‘H’ on nitrogen, it is soluble in alkali.
2

Since there is no ‘H’ on nitrogen, it is insoluble in alkali.

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 SECTION – D
31. i) The sugar level of a diabetic person sometimes suddenly falls. So immediate intake of 1
glucose increases the sugar level to normal.
ii)

gluconic acid structure 1

iii) Cellulose 1
iv) Reaction with Acetic anhydride, which produces pentaacetate of glucose.
32. i) d 1
ii) a 1
iii) b 1
iv) d 1
SECTION – E

33. a) Anode: Zn → Zn2+ + 2e– ½

Cathode: ½
NH4+(aq) + MnO2(s) + e– → MnO(OH) + NH3
The potential of a dry cell decreases slowly but continuously, while the potential of 1
mercury cell remains constant throughout its life.
b) Molar conductivity at infinite dilution for acetic acid can be calculated as:
∧° (CH3COOH ) = λ°H+ + ∧°CH3COO– 3
= λCH3COO– + λ°Na+ + λ°H+ + λ°cl– – λ°Na+ – λ°cl–
∧°(CH3COOH+) = ∧°(CH3COONa) + ∧° (H+Cl) – ∧° (NaCl)
∧°(CH3COONa) = 91.0 S cm2 mol-1
∧°(H+Cl) = 425.9 S cm2 mol-1
∧°(NaCl) = 126.4 S cm2 mol-1
∴ ∧°(CH3COOH+) = 91.0 + 425.9 – 126.4 = 390.5 S cm2 mol-1.
OR,
a) The electrode reactions and cell reaction are:
½
½

b) Methane, oxygen
Advantages of fuel cells: 1
(i) Fuel cells have greater efficiency than ordinary cells.
(ii) These do not produce any harmful by-product and therefore, do not cause any ½
pollution. *2

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34. a) As the value of reduction potential increases, the stability of +2 oxidation state 1
increases. Therefore, correct order of stability is Cr3+ | Cr2+ < Fe3+ | Fe2+ < Mn3+ | Mn2+.
b) When MnO2 is fused with KOH in the presence of KNO3, as an oxidizing agent, it gives a
dark green compound (A).
1*4

35. a) Compound ‘X’ (C2H4O) is oxidized to ‘Y’ (C2H4O2). Since it undergoes a haloform reaction,
it must be acetaldehyde.
(i) X = CHCHO Y = CH3COOH 1
On treatment with HCN, X gives cyanohydrin which on hydrolysis gives 2-
hydroxypropanoic acid.

(ii) When ‘X’ reacts with dil. NaOH, undergoes an aldol condensation reaction forming aldol
which on heating gives but-2-enal. 1

(iii) Equations for reactions 1

b)

OR,
The compound A is C6H5CHO, benzaldehyde having a characteristic odor. The reactions
are:
5

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SESSION 2022-23
BLUE PRINT
SAMPLE QUESTION PAPER SET – 2
CLASS – XII, SUBJECT – CHEMISTRY
Sr. Chapter MCQ A/R VSA 1 SA 1 Case LA TOTAL
No. Based
1 1 mark 2 marks 3 marks 4 5
mark marks marks
1 Solutions 2 (2) 2 (1) 3(1) 7 (4)

2 Electrochemistry 1(1) 1(1) 2 (1) 5(1) 9(4)

3 Chemical 1(1) 2 (1) 4 (1) 7 (3)

Kinetics
4 d and f Block 2 (2) 5(1) 7 (3)
Elements
5 Coordination 1(1) 1(1) 2 (1) 3(1) 7 (4)
compounds
6 Haloalkanes and 2 (2) 1(1) 3(1) 6 (4)
Haloarenes
7 Alcohols, 1(1) 2 (1) 3(1) 6 (3)
Phenols and
Ethers
8 Aldehydes, 2 (2) 1(1) 5(1) 8 (4)
Ketones and
Carboxylic acids
9 Amines 1(1) 2 (1) 3(1) 6 (3)

10 Biomolecules 1(1) 2 (1) 4 (1) 7 (3)

TOTAL 14 4 (4) 14 (7) 15 (5) 8 (2) 15(3) 70 (35)

(14)

Note: Marks outside the bracket and number of questions inside the bracket

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -2
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70

General Instructions:
Read the following instructions carefully.
a) There are 35 questions in this question paper with internal choice.
b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks each.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed.
SECTION-A
The following questions are multiple-choice questions with one correct answer. Each question carries 1
mark. There is no internal choice in this section

Sr.No. MCQs Mark

s
1. In equimolar solution of glucose, NaCl , and BaCl2 , the order of osmotic pressure is 1
as follow
(a) Glucose > NaCl> BaCl2 (b) NaCl>BaCl2> Glucose
(c) BaCl2> NaCl> Glucose (d) Glucose>BaCl2> NaCl
2. The value of Henry’s Constant KH is 1
(a) Greater for gases with higher solubility
(b) Greater for gases with lower solubility
(c) Constant for all gases
(d) Not related to the solubility of gases.
3 An ether is more volatile than an alcohol having the same molecular formula. The 1
reason for this difference is
(a) Dipolar character of ethers
(b) Alcohols having resonance structures
(c) Intermolecular hydrogen bonding in ethers
(d) Intermolecular hydrogen bonding in alcohols.
4 The variation of molar conductivity with concentration of an electrolyte (X) in 1
aqueous solution is shown in the figure.
The electrolyte X is

(а) HCl (b) CH3COOH

(c) NaCl (d) KNO3

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5. In the Dichromate anion (Cr2O72- ) 1
(a) 4 Cr-O bonds are equivalent (b) 6 Cr-O bonds are equivalent
(c) All Cr-O bonds are equivalent (d) All Cr-O bonds are not equivalent
6. For a second order reaction, what is the unit of the rate of the reaction? 1
(a) s -1 (b) mol L -1 s-1 (c) mol-1 L s-1 (d) mol -2 L2 s-1
7. The formula of the complex Triamminetri(nitrito-O) cobalt (III) is. 1
(a) [Co(NH3)3(ONO)3] (b) [Co(NH3)3 (NO2)3]
(c) [Co(NH3)3 (ONO2)3] (d) [Co(NH3)3 (NO2)]
8. The correct order of increasing acidic strength is: 1
(a) Phenol< Ethanol< Chloroacetic acid < Acetic Acid
(b) Ethanol <Phenol< Chloroacetic acid < Acetic Acid
(c) Ethanol <Phenol< Acetic Acid < Chloroacetic acid
(d) Chloroacetic acid < Acetic Acid< Phenol< Ethanol
9. The reagent which does not react with both , acetone & Benzaldehyde 1
a) Sodium hydrogensulphite b)Phenyl hydrazine
c) Fehling’s Solution d) Grignard Reagent
10. Arrange the following compounds in increasing order of their reactivity towards SN2 1
nucleophilic substitution reaction:
(I) 1-bromobutane (II) 1-bromo-2,2 dimethylpropane , (III) 1-bromo-2-
methylbutane , (IV) 1-bromo-3-methylbutane.
a) I <II<III<IV b) II<III<IV<I
c ) II<III<IV<I d) III<IV<II<I

11. Molecules whose mirror image is non superimposable over them are known as 1
chiral. Which of the following molecule is chiral in nature?
(a) 2-Bromobutane (b) 1-Bromobutane
(c) 2-Bromopropane (d) 2-Bromopropan-2-ol
12. In acidic medium , equivalent weight of K2Cr2O7 is ( M= molecular Weight) 1
(a) M (b) M/2
(c) M/3 (d) M/6

13. Which one is the complementary base of cytosine in one strand to that in other 1
strand of DNA?
(a) Adenine (b) Guanine
(c) Thymine (d) Uracil.
14. On heating an aliphatic primary amine with chloroform and ethanolic 1
potassium hydroxide , the organic compound formed is:
(a) an aniline (b) an alkyl isocyanide (c) an alkanol (d) an alkyl cyanide
15. Given below are two statements labelled as Assertion (A) and Reason (R) 1
Assertion (A): Galvanised iron does not rust.
Reason (R): zinc has a more negative electrode potential than iron.

Select the most appropriate answer from the options given below:
a) Both A and R are true and R is the correct explanation of A
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
16. Given below are two statements labelled as Assertion (A) and Reason (R) 1
Assertion (A): Assertion: KCN reacts with methyl chloride to methyl isocyanide.
Reason: CN- is an ambident nucleophile.
Select the most appropriate answer from the options given below:
a) Both A and R are true and R is the correct explanation of A
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false. d) A is false but R is true.
122 | P a g e
17. Given below are two statements labelled as Assertion (A) and Reason (R) 1
Assertion: Butan-1-ol on reaction with alkaline KMnO4 will give butanone.
Reason: Alkaline KMnO4 oxidises secondary alcohol to ketone.

Select the most appropriate answer from the options given below:
a) Both A and R are true and R is the correct explanation of A
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
18. Given below are two statements labelled as Assertion (A) and Reason (R) 1
Assertion (A): [CoCl2(en)2]+ exists in three isomers.
Reason: [CoCl2(en)2]+ shows two geometrical isomers cis & trans. Trans has two
optical isomers but cis has no optical isomers.

Select the most appropriate answer from the options given below:
a) Both A and R are true and R is the correct explanation of A
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
SECTION : B
This section contains 7 questions with internal choice in two questions. The
following questions are very short answer type and carry 2 marks each.

19. Explain why on addition of 1 mol of NaCl to 1 Litre of water , the boiling point of 2
water increases , while addition of 1 mol of methyl alcohol to one litre of water
decreases its boiling point.
20. Predict if the reaction between the Ag(s) and Fe3+ (aq.) is feasible: 2
(Given E0 Ag+/ Ag = 0.80 V , E0 Fe3+ / Fe2+ = 0.77V)
Explain it by calculating E0cell.
21. A + 2B 3C + 2D . The rate of disappearance of B is 1 x 10-2 mol/L/s. 2
What will be (i) rate of reaction (ii) rate of change in concentration of C ?
OR
A reaction is of second order with respect to a reactant. How will the rate of reaction
be affected if the concentration of this reactant is
(i) Doubled, (ii) reduced to half?

22. Write the mechanism of hydration of ethane to yield ethanol. 2

OR
Give the structure of A & B also name the reaction involved.

(i) NaOH/CO2, 410K

(i) CHCl3 + NaOH, 340 K

A (ii) H+ / H2O (ii) H+ / H2O

23. a) Draw the geometrical isomers of complex [Pt (NH3)2Cl2]. 2

b) On the basis of CFT ,write the electronic configuration for d4 ion if
∆0 < P .
24. a) Arrange the following compounds in an increasing order of their basic strength: 2
C2H5NH2 , C6H5NH2 , (C2H5 )2NH , C6H5CH2NH2 , NH3.

123 | P a g e
 b) What happens when Benzene diazoniumchloride treated with Phenol.
25. What is meant by: 2
a ) Peptide Bond b) Phosphodiester linkage

OR
Name two fat soluble vitamins and the diseases caused due to their deficiency in diet.

SECTION : C
This section contains 5 questions with internal choice in two questions. The
following questions are short answer type and carry 3 marks each.
26. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing 3
point of water observed is 1.0 0C. Calculate the Van’t Hoff factor and degree of
dissociation of Fluoroacetic Acid. Kf of water = 1.86 K Kg Mol-1
27. a) For the complex [Fe (en)2 Cl2] Cl , identify the following:
(i) Name of the complex. 1
(ii) Primary & Secondary Valency of Central atom on the basis of Werner’s Theory. ½+
b) Square planer complexes with coordination number of four exhibit geometrical ½
isomerism whereas tetrahedral complexes do not .Why? 1
OR
a) Explain on the basis of Valence Bond theory that [Ni(CN)4]2- ion with square 2
planer structure is diamagnetic and [Ni(Cl)4]2- ion with tetrahedral geometry is
paramagnetic. ½+
b) What is meant by : ½
(i) Ambidentate Ligand.
(ii) Homoleptic Complexes.
28. a)How will you distinguish between the following pairs of compounds by giving 3
chemical reaction:
(i) Primary alcohol & Secondary alcohol.
(ii) Phenol & Ethanol.
b) Write short note on Williamson’s Synthesis for the preparation of ether.
.29. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms 3
compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of molecular
formula C6H7N. Write the structures and IUPAC names of compounds A, B, C.
OR
Answer the following:
(i) Ethylamine is soluble in water whereas aniline is not.
(ii) Aniline does not undergoes Friedal-Craft Reaction.
(iii) Although amino group is o,p-directing in aromatic substitution reactions, aniline
on nitration gives a substantial amount of m-nitroaniline.

30. Draw the structure of major products in the following reactions: 3

(i)

(ii)

(iii)

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 SECTION : D
The following questions are case-based questions. Each question has an internal
choice and carries 4 marks each. Read the passage carefully and answer the
questions that follow:
31. Chemical kinetics deals with rate of chemical reactions, how fast reactants get used
up or how fast products are formed in the reaction. Differed chemical reactions have
different speed. Rate of reaction depends upon concentration of reactants,
temperature, pressure especially in gaseous reactions and presence of catalyst.
Chemical reaction takes place as a results of collision between reacting molecules.
The rate of reaction does not depend upon total number of collisions rather it
depends upon number of effective collisions. In a redox reaction, if E°cell is +ve, ∆G° 2
will be –ve and ‘K’ equilibrium constant will be high i.e. products formed will be 1
more than the reactants.
a) What type of molecules undergo effective collisions?
1
b) ‘k’ (The rate constant), ‘Ea’ (Activation Energy) and ‘A’ (Arrhenius constant) are 3
× 10-4 Sec-1, 104.4 kJ mol-1 and 6.0 × 1014 S-1 respectively. What is value of ‘k’ when T
→ ∞? 1
c) What is meant by activation energy?
OR
What does e–Ea/RT represent?
32. Biomolecules are complex molecules which build up living organisms and required
for their growth, maintenance and ability to reproduce. Carbohydrates are
polyhydroxy aldehydes and ketones which are major sources of energy.
Monosaccharides are simple sugars which cannot be hydrolysed. Oligosaccharide, on
hydrolysis give 2 to 10 molecules of monosaccharides. Polysaccharides like starch and
cellulose on hydrolysis give large number of molecules of glucose a-glucose and b-
glucose (Anomers). Proteins are complex nitrogenous polymers of amino acids
connected through peptide bonds. The sequence in which amino acids are linked is
called Primary structure. Secondary structures are of 2 types a-helix in globular
proteins and b-pleated structure in fibrous proteins involving H-bonds. Tertiary
structure has H-bonds, disulphide linkage, ionic bonding and van der Waals’ forces.
Insulin is hormone for metabolism of glucose, has quaternary structure. Denaturation
of protein destroys secondary and tertiary structure, loss of biological activity but
primary structure remaining the same.
Enzymes are highly specific, work at specific pH, moderate temperature and
catalyse biochemical reactions. Hormones perform specific functions and secreted by 1
endocrine glands. Vitamins are essential for healthy body. A, D, E, K are fat soluble 2
vitamins. Vitamin C and B1, B2, B6 are water soluble. B12 is neither water, nor fat 1
soluble. Nucleic acids are polymer of nucleotides. RNA consist of m-RNA, t-RNA, r-
RNA. RNA has Adenine, Cytosine, Uracil and Guanine. It helps in protein synthesis. It 1
cannot replicate. DNA contains deoxyribose, A, C, G and Thymine. It transfers genetic
characteristics. DNA has double helix structure and undergoes replication.
a) Sucrose cannot reduce the Tollen’s reagent .why ?
b) What is denaturation of protein and which structure of protein remains intact
during denaturation?
c) Name a disaccharide which on hydrolysis give glucose and galactose.
OR
What type of protein is albumin?
SECTION :E
The following questions are long answer type and carry 5 marks each. Two
questions have an internal choice.

125 | P a g e
33. (a) Calculate EMF of the following cell at 298 K: 3
Zn(s) / Zn2+ (0.1 M) // Ag+ (0.01M) / Ag (s)
[ Given E0 Zn2+/ Zn = - 0.76 V , E0 Ag+/Ag = + 0.80 V , log 10 = 1 ) 2
b) What is the free energy change for (a) Galvanic Cell (b) Electrolytic Cell
3
OR
a) Resistance of a conductivity cell filled with 0.1 M KCl solution is 100 Ω. If the
resistance of the same cell when filled with 0.02 M KCl is 520 Ω , Calculate the 2
conductivity and molar conductivity of 0.02 M KCl solution. The Conductivity of 0.1
M KCl solution is 1.29 S/m.

b) Write the chemical reactions taking place at the electrodes during discharging of
lead storage battery.
34. a) Assign reasons for the following :
(i) Mn2O3 is basic whereas Mn2O7 is acidic. 1
(ii) Eu2+ is a strong reducing agent. 1
(iii) Actinoids contraction is greater than Lanthanoids. 1
b) Complete the following chemical equations : 2
(i) 2 MnO4- (aq) + 5 C2O42- (aq) + 16 H+→
(ii) 2 CrO42- + 2 H+ →
OR
a) Give reasons: 1
(i) Iron has higher enthalpy of atomization than that of copper. 1
(ii) E0 value for Mn3+ / Mn2+ couple is much more positive than that for Fe3+/Fe2+. 1
(iii) Ce4+ is a strong oxidising agent.
b) How do you prepare: 2
(i) K2MnO4 from MnO2.
(ii) Na2Cr2O7 from Na2CrO4.
35. a) Write the structures of A, B, C, D , E and F in the following reactions: ½*
6=3
C6H6 CH3COCl / Anhyd.AlCl3 A Zn-Hg / Conc. HCl B KMnO4/KOH C

H3O3+
NaOH/Br2
1+1=
E+
2
F
D
b) Do the following conversions:
(i) Benzaldehyde to α-hydroxyphenylacetic Acid
(ii) Ethanal to But-2enal

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 KENDRIYA VIDYALAYA SANGTHAN, GUWAHATI REGION
SET-2 CHEMISTRY
MARKING SCHEME

1. ( c) 1
2. (b) 1
3. (d) 1
4. (b) 1
5. (b) 1
6. (c) 1
7. (a) 1
8. (c) 1
9. (c) 1
10. (c) 1
11. (a) 1
12. (d) 1
13. (b) 1

14. (b) 1
15. (a) 1
16. (d) 1
17. (d) 1
18. (c) 1

19. 1+1=2
Methyl alcohol is more volatile than water. But NaCl is non-volatile solute. On
addition of NaCl in water , vapour pressure is lowered and as a result boiling point of
water increased. But on addition of methyl alcohol, vapour pressure is more than
that of water. Hence boiling point decreases.

20. 1+1=2

21

1
1

OR
Since Rate = K[A]2 1
For second order reaction Let [A] = a, then Rate = Ka2
(i) If [A] = 2a then Rate = K (2a)2 = 4 Ka2 1
∴Rate of reaction becomes 4 times

127 | P a g e
 (ii) If [A] = a/2 then Rate = K (a/2)2=Ka2/4
∴ Rate of reaction will be 1/4 th

22 ½

OR
A B

23 .

½
½

OR
Electronic Configuration: t2g3 eg1 1
1
24 a) C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 <(C2H5 )2NH 1
b)
1

(Any other correct coupling reaction)

25. a) Peptide Bond :- The amide linkage formed between –COOH group of one-α Amino 1
acid & -NH2 group of the other α Amino acid by loss of a water molecule.
b) The Phosphodiester bond is a covalent bond which is generally formed between 1
the phosphate group of 5′ carbon of one of the nucleotides and 3′ carbon of another
nucleotide through the formation of ester linkage.
OR ½+
Vitamin A:- Night blindness and Xerophthalmia. ½
Vitamin D :- Rickets and osteomalacis.( Or Any Other types & example) ½+
½

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26 ½ for
formula
writing

1 for
calculating
‘i’

½ for
writing
relation
between α
&i

( Any other correct Method can be used to calculate Vant’s Hoff Factor & degree
of dissociation) 1 for
calculating
‘α’
27 a) 1
. (i) dichloridobis(ethane-1,2 –diamine)iron( III) chloride.
(ii) Primary Valency=+3 ; Secondary Valency = 6. ½+½
b) Because the relative position of the ligands attached to the central atom are
same with respect to each other. 1
OR
a)
Outer electronic configuration of nickel (Z = 28) in ground state is 3d84s2. Nickel
in this complex is in + 2 oxidation state. It achieves + 2 oxidation state by the loss
of the two 4s-electrons. The resulting Ni2+ ion has outer electronic configuration
of 3d8. Since CN– ion is a strong field, under its attacking influence, two unpaired
electrons in the 3d orbitals pair up.

Outer electronic configuration of nickel (Z = 28) in ground state is 3d84s2 Nickel

in this complex is in + 2 oxidation state. Nickel achieves + 2 oxidation state by the
loss of two 4s-electrons. The resulting Ni2+ ion has outer electronic configuration
of 3d8. Since Cl- ion is a weak field ligand, it is not in a position to cause electron
pairing

b) (i) Ambidentate Ligand.:- Monodentate ligands having more than one

coordinating atoms are called Ambidentate ligand.
129 | P a g e
 (ii) Homoleptic Complexes:- Complexes in which the metal atom or ion is linked
to only one type of ligands are called Homoleptic complexes.
1
28. a)
(i) Lucas Test & Correct chemical reaction ½+½
(ii) Litmus Test ( or any other suitable test) & correct chemical reaction ½+½
b)
Correct chemical reaction. 1
A= C6H5COOH ; Benzoic Acid ½+½
29.. B= C6H5CONH2 ; Benzamide ½+½
C= C6H5NH2 ; Aniline ½+½
OR
(i) Ethylamine dissolves in water due to intermolecular H-Bonding however due 1
to large hydrophobic part in aniline extent of H-bonding is very less and hence
insoluble in water.
(ii) Aniline being a Lewis base reacts with Lewis Acid AlCl3 to form salt , which is 1
strongly deactivating group.
C6H5NH2 + AlCl3 C6H5NH2+AlCl3- .
(iii) In presence of too much acidic medium, most of the aniline gets protonated 1
to from Anilinium ion which is meta directing. ( Or Correct chemical reaction)

30. (i) 1 mark for correct product/Major Product 1

(ii) 1 mark for correct product/ Major Product 1
(iii) 1 mark for correct products/ Major Product 1
31. a) Those molecules which possess activation energy and collide in proper ½+½
orientation undergo effective collisions.
b) Arrhenius constant k = Ae-Ea/RT 2
⇒ k = Ae–Ea/∞ = Ae° = A = 6.0 × 10 14 s–1.
c) The extra energy which must be supplied to reactants in order to undergo 1
effective collision to form products.
OR
It represents fraction of molecules possessing activation energy (Ea) or more 1
than Ea.
32 a) Sucrose do not have free aldehyde group. 1
b) When a protein in its native form, is subjected to physical change like change 1+1
in temperature or chemical change like change in pH, the hydrogen bonds are
disturbed. Due to this, globules unfold and helix get uncoiled and protein loses its
biological activity. This is called denaturation of protein.
c) Lactose 1
OR

Globular protein. 1
33. a) ½ mark for correct overall chemical reaction
½ mark for E0cell = 1.56 V 3
½ marks for the value of ‘n’
½ marks for Nernst Equation
1 mark for calculating Ecell = 1.47 V

b) – ve for Galvanic Cell & + ve for electrolytic Cell 1+1

OR
a) 1 Mark for correct value of Cell Constant = 1.29 cm-1
1 Mark for correct value of conductivity = 0.00248 S cm-1
1 mark for correct value of molar conductivity = 124 S cm2 mol-1 3

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 b) Anode: Pb(s) + SO4 2–(aq) → PbSO4 (s) + 2e–
Cathode: PbO2 (s) + SO4 2–(aq) + 4H+ (aq) + 2e– → PbSO4 (s) + 2H2O (l )
Overall reaction 1
Pb(s) + PbO2 (s) + 2H2SO4 (aq) → 2PbSO4 (s) + 2H2O(l) 1

34 a)
(i) In transition metal oxides, Transition metal in lower oxidation state are basic 1
and in higher oxidation state acidic. As the oxidation state increases non-metallic
character increases.
(ii) Most common oxidation state of Lanthanoids is +3. So Eu2+ lose one electron 1
to Eu3+.
(iii)In actinoids, 5f orbitals are filled. These 5f orbital have a poorer shielding 1
effect than 4f orbitals in Lanthanoids.
b)
(i) 2 MnO4- (aq) + 5 C2O42- (aq) + 16 H+→ 2Mn2+ + 10 CO2 + 8H2O 1
(ii) 2 CrO42- + 2 H+ → Cr2O72- + H2O 1

OR
a)
(i) Due to higher number of unpaired electrons in iron. 1
(ii)Because Mn2+ is more stable than Mn3+ due to half-filled d5 configuration. 1
(iii) Most common oxidation state of Lanthanoids is +3.So Ce4+ gain one electron
and reduced to Ce3+. 1
b)
(i) 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2 H2O ( Or any other correct method)
(ii) 2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O ½+½

Note:- ( In both reaction ½ mark for completion of reaction & ½ mark for ½+½
balancing)
35. a) A = C6H5COCH3 ; B = C6H5CH2CH3 ; C = C6H5COOK ; (½ *6)=3
D = C6H5COOH ; E = CHI3 or C6H5COONa ; F = C6H5COONa or CHI3
b) (i) 1 mark for correct chemical reaction. 1
(ii) 1 mark for correct chemical reaction 1

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -3
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70

S.No. Chapter MCQ A/R VSA I SA I

Case LA Total wt
Based
1 1 2 3 4 5
Marks Marks Marks Marks Marks Marks

1 Solutions 2(2) 2(1) 3(1)

2 Electrochemistry 1(1) 3(1) 5(1)

3 Chemical Kinetics 1(1) 2(1) 4(1)

4 d-and f-Block Elements 2(2) 5(1)

5 Coordination Compounds 1(1) 1(1) 2(1) 3(1)

6 Haloalkanes and 3(3) 1(1) 2(1)

Haloarenes
7 Alcohols, Phenols and 1(1) 5(1)
Ethers
8 Aldehydes, Ketones and 1(1) 3(1) 4(1)
Carboxylic Acids
9 Amines 1(1) 1(1) 4(2)

10 Biomolecules 1(1) 1(1) 2(1) 3(1)

Total 14(14) 4(4) 14(7) 15(5) 8(2) 15(3)

Note:- Marks are Outside of bracket and number of questions in bracket

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -3
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70
General Instructions:
Read the following instructions carefully.
a) There are 35 questions in this question paper with internal choice.
b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries 1
mark. There is no internal choice in this section.
1. KH value for Ar(g), CO2(g), HCHO(g) and CH4(g) are 4.039, 1.67, 1.83 × 10–5, and 0.143, respectively.
Arrange these gases in the order of their increasing solubility
(a) HCHO < CH4 < CO2 < Ar (b) HCHO < CO2 < CH4 < Ar
(c) Ar < CO2 < CH4 < HCHO (d) Ar < CH4 < CO2 < HCHO
2. On mixing 20 mL of acetone with 30 mL of chloroform, the total volume of the solution is:
(a) > 50 mL (b) < 50 mL (c) = 10 mL (d) = 50 mL
3. Λ𝑚 (NH4OH) is equal to-
(a) Λ𝑚 (NH4OH) + Λ𝑚 (NH4Cl) - Λ𝑚 (HCl) (b) Λ𝑚 (NH4Cl) + Λ𝑚 (NaOH) - Λ𝑚 (NaCl)
(c) Λ𝑚 (NH4Cl) + Λ𝑚 (NaCl) - Λ𝑚 (NaOH) (d) Λ𝑚 (NaOH) + Λ𝑚 (NaCl) - Λ𝑚 (NH4Cl)
4. Which set of ions exhibit specific colours? (Atomic number of Sc = 21, Ti = 22, V=23, Mn = 25, Fe = 26,
Ni = 28 Cu = 29 and Zn =30)
(a) Sc3+, Ti4+, Mn3+ (b) Sc3+, Zn2+, Ni2+ (c) V 3+, V2+, Fe3+ (d) Ti3+, Ti4+, Ni2+
5. For a certain chemical reaction variation in the concentration ln [R] vs time plot is given alongside.

133 | P a g e
what is the order of the reaction?
(a) Zero Order (b) First Order (c) Second Order (d) Third Order
6. In which of the following ions, number of unpaired electron is zero?
(a) Fe2+ (Z=26) (b) Cr2+ (Z=24) (c) Zn2+ (Z=30) (d) Cu2+ (Z=29)
7. The conversion of an alkyl halide into an alcohol by aqueous NaOH is classified as:
(a) a dehydrohalogenation reaction (b) a substitution reaction
(c) an addition reaction (d) a dehydration reaction
8. Chlorobenzene is formed by the reaction of chlorine with benzene in the presence of AlCl3. Which of
the following species attacks the benzene ring in this reaction?
(a) Cl- (b) Cl+ (c) AlCl3 (d) [AlCl4] –
9. Which reagent will you use for the following reaction?
CH3CH2CH2CH3 → CH3CH2CH2CH2Cl + CH3CH2CHClCH3
(a) Cl2/UV light (b) NaCl + H2SO4
(c) Cl2 gas in presence of Fe in dark (d) Cl2 gas in dark
10. Which of the following statements are not true about glucose?
(a) It is an aldohexose (b) On heating with HI, it forms n-hexane
(c) It is present in furanose form (d) It does not give 2,4-DNP test
11. Hoffmann Bromamide Degradation reaction is shown by
(a) ArNH2 (b) ArCONH2 (c) ArNO2 (d) ArCH2NH2
12. The compounds [Co(SO4)(NH3)5]Br and [Co(SO4)(NH3)5]Cl represents
(a) Linkage isomerism (b) no isomerism
(c) Ionisation isomerism (d) Coordination isomerism
13. Which of the following compounds will react with NaOH solution in water
(a) C6H5OH (b) C6H5CH2OH (c) (CH3)3COH (d) C2H5OH
14. KMnO4 acts as an oxidising agent in alkaline medium. When alkaline KMnO4 is treated with KI,
iodide ion is oxidised to:
(a) I2 (b) IO– (c) IO3 – (d) IO4 –
15. Given below are two statements labelled as Assertion (A) and Reason (R)
Assertion : Only α -amino acids are obtained on hydrolysis of proteins.
Reason : In zwitter ionic form, amino acids show amphoteric behaviour.
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
16. Given below are two statements labelled as Assertion (A) and Reason (R)
Assertion : Low spin tetrahedral complexes are rarely observed.
134 | P a g e
Reason : Crystal field splitting is less than pairing energy for tetrahedral complexes
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
17. Given below are two statements labelled as Assertion (A) and Reason (R)
Assertion (A) : It is difficult to replace chlorine by –OH in chlorobenzene in comparison to that in
chloroethane.
Reason (R) : Carbon-chlorine (C—Cl) bond in chlorobenzene has a partial double bond character due
to resonance.
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
18. Given below are two statements labelled as Assertion (A) and Reason (R)
Assertion: (CH3)2NH > CH3NH2 > (CH3)3N > NH3 is the order of basic strength in case of methyl
substituted amines.
Reason: The inductive effect, solvation effect and steric hindrance of the alkyl group decides the basic
strength of alkyl amines in the aqueous state.
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
19. Calculate the mass of ascorbic acid (vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to lower
its melting point by 1·5°C. (Kf for CH3COOH) = 3·9 K kg mol-1 )
20. (a) Write the two conditions for collisions to be effective collisions.
(b) How order of reaction and molecularity differ towards a complex reaction?
21. When a coordination compound CoCl3.6NH3 is mixed with AgNO3, 3 moles of AgCl are precipitated
per mole of the compound. Write
(i) Structural formula of the complex,
(ii) IUPAC name of the complex.
22. (a) Define ambident nucleophile with an example.
(b) Among the isomers of pentane (C5H12), write the one which on photochemical chlorination yields a
single monochloride.
23. (a) Write an isomer of C3H9N which gives foul smell of isocyanide when treated with chloroform and
ethanolic NaOH.
(b) Out of (CH3)3N and (CH3)2NH, which one is more basic in aqueous solution?

135 | P a g e
24. Give reasons :
(i) Aniline is a weaker base than cyclohexylamine.
(ii) It is difficult to prepare pure amines by ammonolysis of alkyl halide.
25. Define the following terms :
(i) Glycosidic linkage (ii) Invert sugar
26. Give reasons for the following :
(a) Measurement of osmotic pressure method is preferred for the determination of molar masses of
macromolecules such as proteins and polymers.
(b) Aquatic animals are more comfortable in cold water than in warm water.
(c) Elevation of boiling point of 1 M KCl solution is nearly double than that of 1 M sugar solution.
27. The following curve is obtained when molar conductivity (Λm) is plotted against the square root of
concentration, C½ for two electrolytes A and B:

(i) How do you account for the increase in the molar conductivity of the electrolyte A on dilution ?
(ii) As seen from the graph, the value of limiting molar conductivity (Λ°m) for electrolyte B cannot be
obtained graphically. How can this value be obtained ?
(iii) Define limiting molar conductivity.
28. (i) What type of isomerism is shown by the complex [Co(en)3] Cl3 ?
(ii) Write the hybridisation and magnetic character of [Co(C2O4)3] 3–. (At. no. of Co = 27)
(iii) Why a solution of [Ni(H2O)6] 2+ is green while a solution of [Ni(CN)4] 2– is colourless ? (At. no. of Ni =
28).
29. . Give reasons :
(a) HCHO is more reactive than CH3 – CHO towards addition of HCN.
(b) pKa of O2N – CH2 – COOH is lower than that of CH3 – COOH.
(c) Alpha hydrogen of aldehydes and ketones is acidic in nature.
30. Write the reactions involved when D-glucose is treated with the following reagents : (i) Br2 water
(ii) H2N-OH (iii) (CH3CO)2O
31. Observe the table given showing volume of CO2 obtained by reaction of CaCO3 and dilute HCl after
every minute. Answer the questions that follow:
Time/minute Volume of CO2/cm3 Time/minute Volume of CO2/cm3
0 0 cm3 4 40 cm3
1 24 cm3 5 40 cm3
2 34 cm3 6 40 cm3
3 38 cm3
136 | P a g e
(a) What happens to the rate of reaction with time for the above reaction?
(b) How the rate of reaction is affected when powdered CaCO3 is used instead of marble chips?
(c) What happens to the rate of reaction when conc. HCl is used instead of dil. HCl?
(d) Write two important factors necessary for fruitful collisions.
32. Study the table in which pka of various is given. Answer the questions based on table and related
studied concepts.
Compounds pka Compounds pka
1. Acetic acid 4.76 8. p-Toluic Acid 4.38
2. HCOOH 3.75 9. Salicylic Acid 2.98
3. CH3CH2COOH 4.38 10. p-nitro benzoic acid 3.44
4. ClCH2COOH 2.87 11. p-methoxy benzoic acid 4.88
5. FCH2COOH 2.59 12. p-chloro benzoic acid 3.99
6. CH2=CH-COOH 4.30 13. p-hydroxy benzoic acid 4.58
7. Benzoic Acid 4.19

(a) Why is HCOOH stronger than CH3COOH?

(b) Why is p-hydroxy benzoic acid more acidic than p-methoxy benzoic acid?
(c) Why is salicylic acid stronger than benzoic acid?
(d) Give one use of salicylic acid.
33. Answer the following questions based on Electrochemistry:
a. Why on dilution the ∧m of CH3COOH increases drastically while that of CH3COONa increases
gradually?
b. Solutions of two electrolytes ‘A’ and ‘B’ are diluted. The limiting molar conductivity of ‘B’ increases
1.5 times while that of ‘A’ increases 25 times. Which of the two is a strong electrolyte? Justify your
answer.
c. The products of electrolysis of aqueous NaCl at the respective electrodes are:
Cathode: H2 and Anode: Cl2 and not O2. Explain.
d. Why is alternating current used for measuring resistance of an electrolytic
solution?
e. What is the necessity to use a salt bridge in a Galvanic cell?
OR
Define the terms specific conductance, molar conductance and equivalent conductance. Derive the
relationship between molar conductance and equivalent conductance.
34. Account for the following: [3+2]
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the highest
oxidation state of +4.
(ii) Cr2+ is a strong reducing agent.
(iii) Cu2+ salts are coloured while Zn 2+ salts are white.
(b) Complete the following equations:
137 | P a g e
 ∆ ∆
(i) 2MnO2 +4 KOH + O2 → (ii) Cr2O7 2- + 14 H+ + 6I- →
OR
a. Define Lanthanoid Contraction. [3+2]
b. Give its two consequences.
c. Tabulate the similarities and differences between actinoids and lanthanoids.

35.Explain the following observations: [3+2]

(i) The boiling point of ethanol is higher than that of methoxymethane.
(ii) Phenol is more acidic than ethanol.
(iii) o- and p-nitrophenols are more acidic than phenol.
(iv)Give one chemical test each to distinguish between the following pairs of compounds:
(a) Phenol and Benzoic acid
(b) 1-Propanol and 2-Propanol
OR
(i) Name the starting material used in the industrial preparation of phenol. [2+3]
(ii) Write complete reaction for the bromination of phenol in aqueous and
non aqueous medium.
(iii) . (A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H80. Isomers (A) and (C) give positive Tollens’ test whereas isomer (B) does not give Tollens’
test but gives positive Iodoform test. Isomers (A) and (B) on reduction with Zn (Hg)/conc. HCl, give the
same product (D). Write the structures of (A), (B), (C) and (D).

138 | P a g e
 Marking-Scheme
1.(C) According to Henry’s law, P = KH C
Hence, higher the KH value, lower is the solubility of gas.
2. (b) A mixture of chloroform and acetone forms a solution with negative deviation from Raoult’s law.
This is because chloroform molecule is able to form hydrogen bond with acetone molecule. That’s why
volume of resulting solution decreases.
3. (b) Λ𝑚 (NH4Cl) + Λ𝑚 (NaOH) - Λ𝑚 (NaCl)
4. (c) V 3+, V2+, Fe3+ ions exhibit specific colours. Atomic number of V = 23, Electronic configuration of V
- [Ar]3d3 4s2 Electronic configuration of V2+ - [Ar]3d3 Electronic configuration of V3+ - [Ar] 3d2 Atomic
number of Fe = 26 Electronic configuration of Fe - [Ar]3d6 4s2 Electronic configuration of Fe3+ - [Ar]3d5
Since these ions have partially filled d- subshells, they exhibit colour.
5. (b) First Order
6. (c) Zn2+ (Z=30), [Ar]=4S0 3d10
7. (b) a substitution reaction R − X + NaOH  R − OH + NaX
8. (b) Electrophilic Substitution reaction :AlCl3 + Cl2  [AlCl4] - + Cl+
9. (a) Free radical chlorination of Butane gives a complex mixture of isomeric mono- and
polychlorobutanes. So correct answer is Cl2/UV light.
10. (c) It is present in furanose form
Actually Glucose is present in Pyranose form.
11. (b) ArCONH2

12. (c) The compounds [Co(SO4)(NH3)5]Br and [Co(SO4)(NH3)5]Cl represents Ionisation isomerism,
because they give different ion in aqueous solution i.e Br- and Cl- ion.
13. (a) C6H5OH will react with NaOH solution in water to form C6H5ONa + H2 gas.
14. (c) 2KMnO4 + KI + H2O → 2KOH + 2MnO2 + KIO3
15. (b) Only α-amino acids are obtained on hydrolysis of proteins. They may contain other functional
groups also.
In aqueous solution, the carboxyl group can lose a proton and amino group can accept a proton, giving
rise to a dipolar ion known as zwitter ion. This is neutral but contains both positive and negative
charges.
16. (a) In tetrahedral complexes, the splitting of the d-orbitals is inverted and is smaller in comparison
to octahedral complexes. The Crystal field splitting energy is not large enough to force pairing and
hence, low spin complexes are rarely observed.
17. (a) Chlorobenzene is very less reactive to nucleophilic substitution reaction by –OH group as
Carbon-chlorine (C—Cl) bond in chlorobenzene has a partial double bond character due to resonance.
18. (a) (CH3)2NH > CH3NH2 > (CH3)3N > NH3 is the order of basic strength in case of methyl substituted
amines as the inductive effect, solvation effect and steric hinderance of the alkyl group decides the basic
strength of alkyl amines in the aqueous state.

139 | P a g e
19.

20. (a) Two

conditions for collisions to be effective collision are : (i) The reactant molecules must have attained
sufficient energy to break chemical bonds (ii) The reactant molecules must have the proper orientation.
(b) The number of the reacting species that collide simultaneously in a chemical reaction is called as
molecularity of a reaction. The sum of the coefficients of the reacting species is the order of reaction.
For complex reactions, molecularity has no significance while the order of reaction is applicable.
21. (i) [Co(NH3)6]Cl3
(ii) Hexamminecobalt (III) chloride
22. (a) Nucleophiles having two nucleophilic centres. CN−/SCN−/NO2 −.
(b) Neopentane / C(CH3)4
23. (a) Isomer of C3H9N is CH3CH2CH2NH2 (Propan-1-amine), gives foul smell of isocyanides. (because
primary amine gives carbylamine reaction.)
(b) Secondary amines are more basic than tertiary amines in aqueous solution due to steric factor. So,
(CH3)2NH is more basic in aqueous solution.
24. (i) Cyclohexylamine is more basic than aniline because aniline is a resonance hybrid of various
resonance structures. As a result, in aniline the electron donating capacity of nitrogen for protonation is
considerably decreased.
(ii) Ammonolysis of alkyl halides does not give single amine but gives a mixture of primary, secondary
and tertiary amines.

25. (i) Glycosidic linkage : The two monosaccharides units are joined together through an oxide linkage
formed by loss of a molecule of H2O.
(ii) Invert sugar : Hydrolysis of sucrose brings about a change in sign of rotation from dextro (+) to
laevo (–) and the product is known as invert sugar.
26. (a) As compared to other colligative properties, its magnitude is large even for very dilute solutions
/ macromolecules are generally not stable at higher temperatures and polymers have poor solubility /
pressure measurement is around the room temperature and the molarity of the solution is used instead
of molality.
(b) Because oxygen is more soluble in cold water or at low temperature.
(c) Due to dissociation of KCl / KCl (aq) K+ + Cl- , which is nearly equal to 2.

140 | P a g e
27. (i) As seen from the graph, electrolyte A is a strong electrolyte which is completely ionised in
solution. With dilution, the ions are far apart from each other and hence the molar conductivity
increases.
(ii) To determine the value of limiting molar conductivity for electrolyte B, indirect method based upon
Kohlrausch law of independent migration of ions is used.
(iii) When concentration approaches zero, the molar conductivity is known as limiting molar
conductivity.
28. (i) Optical isomerism
(ii) d2sp3, diamagnetic
(iii) Unpaired electrons in [Ni(H2O)6] 2+/d-d transition.
29. (a) Due to +I effect of methyl group in CH3CHO.
(b) due to –I effect of nitro group in nitro acetic acid.
(c) Due to the strong electron withdrawing effect of the carbonyl group and resonance stabilisation of
the conjugate base.
30.

31. (a) The rate of the reaction first decreases and then becomes constant with time.
(b) The rate of reaction increases as the surface area of the reactant increases.
(c) The rate of reaction increases with increasing the concentration of the reactant.
(d) Two Factors responsible for Effective Collisions are proper orientation of reactant molecules and
activation energy.
32. (a) It is because HCOO–is more stable than CH3COO–.
(b) It is because —OH has more —I effect than —OCH3 group.
(c) It is because salicylate is more stable than benzoate ion due to intra molecular H-bonding.
(d) It is used for preparation of Aspirin which is an important Analgesics, Antipyretic and prevents
heart attack.
33. a. In the case of CH3COOH, which is a weak electrolyte, the number of ions
increases on dilution due to an increase in degree of dissociation.
CH3COOH + H2O → CH3COO– + H3O+
b. ‘B’ is a strong electrolyte because a strong electrolyte is already dissociated into
ions, but on dilution inter ionic forces are overcome, ions are free to move. So,
there is a slight increase in molar conductivity on dilution.
c. On anode water should get oxidized to produce O2 in preference to Cl– but due to
overvoltage/over potential Cl is oxidized to Cl2 in preference to water.
d. Alternating current is used to prevent electrolysis so that concentration of ions in
the solution remains constant.

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e. To complete the inner circuit and to maintain the electrical neutrality of the
electrolytic solutions of the half-cells we use a salt bridge in a Galvanic cell.
OR
(a) Specific conductance: The reciprocal of specific resistance is termed as specific conductance or it is
the conductance of one-centimetre cube of a conductor.
It is denoted by the symbol 🇰 (kappa)
🇰 = 1/ρ or 🇰 = (l/a) x C
Specific conductance is also called conductivity.
(b) Molar conductance: Molar conductance is defined as the conductance of all the ions produced by
ionisation of 1 g- mole of an electrolyte when present in per litre of solution. It is denoted by Λm.
Molar conductance Λm = k x 1000/M
(c) Equivalent conductance: Equivalent conductance is defined as the conductance of all ions produced
by one gram-equivalent of an electrolyte present per litre of solution. It is denoted by Λeq.
Equivalent conductance Λeq = k x 1000/N.
Relationship between molar conductance and equivalent conductance.
Λm = k x 1000/M, Λeq = k x 1000/N ∴ Λm / Λeq = n Where n= valence factor
34. : a) (i) Because oxygen stabilizes the highest oxidation state (+7 of Mn) even more than fluorine i.e.,
+4 since oxygen has the ability to form multiple bonds with metal atoms.
(ii) Cr2+ exists in the d4 system and is easily oxidized to Cr3+ by losing one electron which has the stable
d3/t2g orbital configuration. So, Cr2+ is a strong reducing agent.
(iii) Cu2+ has the configuration 3d9 with one unpaired electron which gets excited in the visible region to
impart its colour while Zn2+ has 3d10 configuration without any unpaired electron so no d – d transition
possible and hence colourless.
(b) (i) 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
Potassium manganate
(ii)Cr2O72- + 14 H+ + 6I- → 2Cr3+ + 7H2O + 3I2

OR
a. Lanthanide contraction:
The steady decrease in atomic and ionic sizes of lanthanide elements with increasing atomic number is
called Lanthanide contraction.
Cause of Lanthanide contraction:
In the lanthanide series, as we move from one element to another, the nuclear charge increases by one
unit and one electron is added. The new electrons are added to the same inner 4f- subshells. However,
the shielding of one 4 f electron by another is less than one d electron by another with the increase in
nuclear charge along the series. There is a regular decrease in the sizes with increasing atomic
numbers.
b. Consequences of Lanthanide contraction:
1. Resemblance of second and third transition series: As a result of Lanthanide contraction, the
elements of second and third transition series resemble each other
much more than the elements of first and second transition series.
2. Similarities among lanthanoids: Because of very small change in radii of
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lanthanoids, their chemical properties are quite similar. Thus, it is very difficult
to separate the elements in a pure state.
c. Similarities between lanthanoids and actinoids:
1. Both exhibits +3 oxidation state. 2. Both involve the filling of f-orbitals.
3. Both having same number of unpaired electrons have quite similar spectra. In the
absorption spectra of the elements of both the series, sharp lines like bands
appear due to f-f transition.
Differences between lanthanoids and actinoids:

35. (i) It is because ethanol is associated with intermolecular H-bonding, therefore, ethanol has higher
boiling point than that of methoxymethane which is not associated with intermolecular H-bonding.
(ii) Phenol is more acidic than ethanol because phenoxide ion is more stable due to resonance as
compared to ethoxide ion which is unstable due to positive inductive effect of ethyl group.
(iii) It is because —NO2 group is electron withdrawing (- R effect), it increases the stability of o- and p-
nitro phenoxide ion (phenolate ion) as compared to phenoxide ion
(iv)(a) Add NaHCO3 to each. Phenol will not react, whereas benzoic acid will give brisk effervescence
due to CO2.
(b) Add I2 and NaOH. 2-Propanol will give yellow ppt. of iodoform, whereas 1-propanol will not give
yellow ppt.
OR
i) Cumene also known as Isopropyl benzene is the starting material.
ii)

iii) A = CH3CH2CH2CHO B = CH3COCH2CH3

C = (CH3)2CHCHO D = CH3CH2CH2CH3

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SESSION 2022-23
BLUE PRINT
SAMPLE QUESTION PAPER SET – 4
CLASS – XII, SUBJECT – CHEMISTRY
S.NO Name of Chapter MCQ A/R VSA-I SA-I CASE STUDY LA (5M) TOTAL
(1M) (1M) (2 M) (3 M) (4M)
1. Solutions 2(2) 2(1) 3(1) 7(4)
2. Electrochemistry 1(1) 3(1) 5(1) 9(3)

3. Chemical Kinetics 1(1) 2(1) 4(1) 7(3)

4. d and f block 2(2) 5(1) 7(3)

elements

5. Coordination 1(1) 1(1) 2(1) 3(1) 7(4)

compounds

6. Haloalkanes and 3(3) 1(1) 2(1) 6(5)

haloarenes

7. Alcohols, Phenols 1(1) 5(1) 6(2)

and ethers

8. Aldehydes, ketones 1(1) 3(1) 4(1) 8(3)

and carboxylic acids

9. Amines 1(1) 1(1) 4(2) 6(4)

10. Biomolecules 1(1) 1(1) 2(1) 3(1) 7(4)

TOTAL 14(14) 4(4) 14(7) 15(5) 8(2) 15(3) 70(35)

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -4
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70
General Instructions:
Read the following instructions carefully.
a) There are 35 questions in this question paper with internal choice.
b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks each.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed
Q QUESTIONS
NO.
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries
1 mark. There is no internal choice in this section.
1 In which of the following conversions, phosphorus pentachloride is used as the reagent?
(a) H2C = CH2 → CH3CH2Cl (b) CH3CH2OH → CH3CH2Cl
(c) H3C-O-CH3 → CH3Cl (d) CH ≡ CH → CH2 = CHCl
2 Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of
a)Inductive effect b) Steric Hindrance c) Insolubility d) Instability
3 Generally, transition elements form coloured salts due to the presence of unpaired electrons.
Which of the following compound will be coloured in solid state?
(a) Ag2SO4 (b) CuF2 (c) ZnF2 (d) Cu2Cl2
4 The value of Henry’s constant KH is
(a) greater for gases with higher solubility (b) greater for gases with lower solubility
(c) constant for all gases (d) not related to the solubility of gases.
5 The amount of electricity required to deposit 1 mol of aluminium from a solution of AlCl3 will
be
(a) 0.33 F (b) 1 F
(c) 3 F (d) 1 ampere
6 For a chemical reaction R → P, the variation in the concentration (R) vs. time (t)
plot is given as

The slope of curve is

(a) -k (b) ln[R0]
(c) log [R] (d) k
7 Arrange the following in the order of basic strength
A) C6H5NH2 B) p-NO2-C6H4-NH2 C) p-CH3O-C6H4-NH2 D) C6H5CH2NH2
(a) B < A < C <D (b) B>A>C>D (c) A<B<C<D (d) A>B>C>D
8 When 1 mol CoCl3.6H2O is treated with excess of AgNO3, 3 mol of AgCl are obtained. The
formula of the complex is
(a) [Cr(H2O)6].Cl3 (b) [CrCl2(H2O)4]Cl.2H2O
(c) [CrCl3(H2O)3].3H2O (d) [CrCl(H2O)5]Cl2.H2O
9 What would be the major product of the following reaction?
C6H5-CH2-OC6H5 + HI A + B
a) A=C6H5CH2OH B=C6H6 b)A=C6H5CH2OH B=C6H5I
c)A=C6H5CH3 B=C6H5I d) A=C6H5CH2I B=C6H5OH
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10 The reaction of toluene with chlorine in presence of FeCl3 gives predominantly.
(a) a mixture of o-and p-chlorotoluene (b) benzyl chloride
(c) m-chlorotoluene (d) benzoyl chloride
11 Which reagent can be suitably used for the following conversion?

(a)KMnO4 (b)LiAlH4 (c)H2O/H+ (d)PCC

12 Which of the following statements is correct regarding a solution of two components A and B
exhibiting positive deviation from ideal behaviour?
(a) Intermolecular attractive forces between A-A and B-B are stronger than those between A-B.
(b) Δmix H = 0 at constant T and P.
(c) Δmix V = 0 at constant T and P.
(d) Intermolecular attractive forces between A-A and B-B are equal to those between A-B.
13 Which ion is a strong oxidising agent?
(a)Ti4+ (b) V2+ (c) Mn3+ (d) Cr3+
14 Sucrose is a _____ chemical, and the hydrolysis product combination is ______in nature.
(a) dextrorotatory; dextrorotatory (b) laevorotatory; laevorotatory
(c) laevorotatory; dextrorotatory (d) dextrorotatory; laevorotatory
15 Given below are two statements as assertion (A) and reason(R)
Assertion: CHCl3 is stored in dark bottles.
Reason: CHCl3 is oxidised in dark.
Select the most appropriate answer from the options given below:
(a) Both A and R are true and R is the correct explanation of A
(b) Both A and R are true but R is not the correct explanation of A.
(c)A is true but R is false
(d)A is false but R is true.
16 Given below are two statements as assertion (A) and reason(R)
Assertion: Haemoglobin is a globular protein
Reason: Globular proteins are insoluble in water
Select the most appropriate answer from the options given below:
(a) Both A and R are true and R is the correct explanation of A
(b) Both A and R are true but R is not the correct explanation of A.
(c)A is true but R is false
(d)A is false but R is true.
17 Given below are two statements as assertion (A) and reason(R)
Assertion: Toxic metal ions are removed by chelating ligands.
Reason: Chelate complexes tend to be more stable.
Select the most appropriate answer from the options given below:
(a) Both A and R are true and R is the correct explanation of A
(b) Both A and R are true but R is not the correct explanation of A.
(c)A is true but R is false
(d)A is false but R is true.
18 Given below are two statements as assertion (A) and reason(R)
Assertion: N-ethyl benzene sulphonamide is soluble in alkali
Reason: The hydrogen attached to nitrogen in sulphonamide is strongly acidic
Select the most appropriate answer from the options given below:
(a) Both A and R are true and R is the correct explanation of A
(b) Both A and R are true but R is not the correct explanation of A.
(c)A is true but R is false
(d)A is false but R is true.

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 SECTION B
This section contains 7 questions with internal choice in two questions. The following questions are
very short answer type and carry 2 marks each.
19 The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of
production of N2 and H2 if k=2.5 x 10-4 mol-1 Ls-1.
20 Define the following-
i)Peptide linkage ii) Glycosidic linkage
OR
Write the products formed when D-glucose is treated with the following reagents:
a) HNO3 b) HI
21 Of the two bromo derivatives, C6H5CH(CH3) Br and C6H5CH(C6H5) Br, which one is more
reactive in SN1 substitution reaction and why?
OR
Give reason for the following:
a) Haloarenes easily dissolve in organic solvents.
b) Racemic mixture is optically active
22 Draw all the isomers (geometrical and optical) of [Co(NH3)Cl(en)2]2+
23 Define Azeotropes. What type of azeotrope is formed by negative deviation from Raoult’s law?
Give an example.
24 Give the chemical tests to distinguish between the following pairs of compounds:
a) Ethyl amine and Aniline
b) Aniline and Benzylamine
25 Account for the following:
a) Aniline does not undergo Friedel crafts reaction.
b) Aromatic amines cannot be prepared by Gabriel Phthalimide synthesis.

SECTION C
This section contains 5 questions with internal choice in two questions. The following questions are
short answer type and carry 3 marks each.
26 Predict the products of the following reactions:

27 (a)Explain the hybridization, shape and magnetic behaviour of the complex [CoF6]3- on the
basis of Valence bond theory.
(b) On the basis of crystal field theory, write the electronic configuration for d4 ion if Δ0 < P.
28 Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 litre
of water at 25°C, assuming that it is completely dissociated.
OR
Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50g of urea (NH2CONH2) is dissolved in
850 g of water. Calculate the vapour pressure of water for this solution and its relative
lowering.
29 Differentiate between the following:
a) Amylose and amylopectin b)Fibrous and globular proteins
OR
Explain primary and secondary structure of proteins.
30 What is molar conductivity and explain how does it vary with concentration for strong and
weak electrolyte?

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 SECTION D
The following questions are case-based questions. Each question has an internal choice and carries 4
(1+1+2) marks each. Read the passage carefully and answer the questions that follow.
31 Carboxylic acids are distinctly acidic and ionise in water to give H3O+ ions. In general electron
withdrawing groups increase the acidity of carboxylic acids while the electron donating groups
decrease the acidity of carboxylic acids. The EDG such as -CH3, -OH, -NH2 and -OCH3 make
benzoic acid weaker while EWG such as -Cl, -NO2 etc make benzoic acid stronger. The ortho
isomer of every substituted benzoic acid is the strongest among the three isomers due to the
effect called ortho effect. Carboxylic acids neutralise alkalis, decompose carbonates and
bicarbonates evolving CO2 with brisk effervescence.
Answer the following questions:
a) Cl—CH2COOH is a stronger acid than CH3COOH.Why?
b) Give one test to distinguish between phenols and benzoic acid.
c) Why are carboxylic acids more acidic than alcohols or phenols although all of them
have hydrogen atom attached to an oxygen atom (-O-H)?
OR
Why carboxylic acids do not give reactions of carbonyl group?
32 The half-life of a reaction is the time required for the concentration of reactant to decrease by
half, i.e.,

[A]t = [A]/2
For first order reaction, t1/2=0.693/k,
This means t1/2 is independent of initial concentration. Figure shows that typical variation of
concentration of reactant exhibiting first order kinetics. It may be noted that though the major
portion of the first order kinetics may be over in a finite time, but the reaction will never cease
as the concentration of reactant will be zero only at infinite time.
(a) Draw graph of t1/2 v/s initial concentration for the first order reaction.
(b) What is the order of reaction if the unit of rate constant is L mol-1 s-1
(c) If the half-life period of a first order reaction in A is 2 minutes, how long will it take [A] to
reach 25% of its initial concentration?
OR
The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing
wood had only 80% of the 14C found in a living tree. Estimate the age of the sample.
SECTION E
The following questions are long answer type and carry 5 marks each. Two questions have an internal
choice.
33 (a) Write the anode and the cathode reactions and the overall reaction occurring in a lead
storage battery when current is drawn from it.
(b) Predict the products of electrolysis in the following case:
(i) An aqueous solution of AgNO3 with platinum electrodes.
(c) Calculate emf of the following cell at 25 °C:
Fe/Fe2+(0.001 M)// H+(0.01 M)/H2(g) (1 bar)/Pt(s)
E°(Fe2+/Fe) = -0.44V, E°(H+/H2) = 0.00 V
34 i) Write the steps involved in the mechanism for the conversion of ethanol to diethyl ether.
ii) Convert the following
a) Propene to propan-2-ol
b) Phenol to picric acid

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 OR
i)Write the steps involved in the mechanism of preparation of ethene from ethanol.
ii)Write the chemical equations involved in:
a) Kolbe’s reaction
b) Reimer Tiemann reaction
35 (a) Describe the preparation of potassium dichromate from iron chromite ore.
(b) Account for the following:
(i) Transition metals show variable oxidation states.
(ii) Zn, Cd and Hg are not considered as transition elements.
(iii) Actinoid contraction is greater from element to element than lanthanoid contraction.
OR
(a) Describe the preparation of potassium permanganate.
(b) How does the acidified permanganate solution react with (i) iron(II) ions (ii) SO2 and (iii)
oxalic acid? Write the ionic equations for the reactions.

MARKING SCHEME
CHEMISTRY (CLASS XII)
SAMPLE TEST PAPER-4 (2022-23)
TOTAL MARKS = 70 MAX. TIME: 3Hrs
Q NO. ANSWERS
SECTION A
1 (b)
2 (b)
3 (b) Cu2+ has 1 unpaired electron in CuF2, hence, it is coloured in solid state.
4 (b) greater for gases with lower solubility
5 (c) 3F
6 (a) -k
7 (a)
8 (a)
9 (d)
10 (a)
11 (b)
12 (a) Intermolecular attractive forces between A-A and B-B are stronger than those
between A-B.
13 (c) Mn3+ is a strong oxidising agent because after gaining one electron it is converted into
Mn2+ which has stable d5 configuration.
14 (d)
15 (c)
16 (c)
17 (a)
18 (a)
SECTION B
19

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20 a) Peptide linkage-The amide linkage formed between two amino acids molecules by the
loss of water
b) Glycosidic linkage-The oxide linkage formed between two monosaccharides by the
loss of water molecule to form a disaccharide
OR
a) Saccharic acid b) n-hexane
21 C6H5CH(C6H5)Br as the mechanism is SN1 and the carbocation formed here is more stable.
OR
a) As the new intermolecular forces of attraction between haloalkanes and organic
solvent molecules have same strength as the ones being broken in the separate
haloalkanes and solvent molecules.
b) Because it has equimolar mixture of both dextro and laevo forms, so rotation of plane
polarised light is compensated.
22

=
23 Azeotropes are binary liquid mixtures having the same composition in liquid and vapour
phase and boil at constant temperature.
Maximum boiling azeotrope
e.g 68% nitric acid and 32% water by mass.
24 (a) Ethyl amine and Aniline-Azo dye test
(b) Aniline and Benzylamine-carbylamine test
25 (a) Aniline does not undergo Friedel Craft reaction as it reacts with AlCl3 forming salt as
it is a lewis base.
b) Because one of the steps is nucleophilic substitution reaction which haloarenes do not
undergo readily.
SECTION C
26

27 (a)

(b) t32g e1g

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28 Calculation of Van’t Hoff factor
K2SO4 dissociates in water as :

OR

29

(b)

OR

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 a) The primary structure of proteins is comprised of a linear chain of amino acids.
The secondary structure contains regions of amino acid chains that are stabilized by
hydrogen bonds from the polypeptide backbone. These hydrogen bonds create alpha-
helix and beta-pleated sheets of the secondary structure. Alpha helix is a right handed-
coiled or spiral conformation of polypeptide chains. In alpha helix, every backbone N-H
group donates a hydrogen bond to the backbone C=O group, which is placed in four
residues prior.
Beta sheets consist of beta strands connected laterally by at least two or three backbone
hydrogen bonds; they form a generally twisted, pleated sheet. In contrast to the alpha
helix, hydrogen bonds in beta sheets form in between N-H groups in the backbone of one
strand and C=O groups in the backbone of the adjacent strands.
30 Molar conductivity of a solution at a given concentration is the conductance of the
volume ‘V’ of a solution containing one mole of electrolyte kept between two electrodes
with area of cross section ‘A’ and distance of unit length.
FOR STRONG ELECTROLYTES, molar conductivity increases slowly with dilution because
in strong electrolytes the dissociation of the electrolyte into ions is almost complete.
However, upon dilution interionic attractions are reduced.
This leads to increase in ionic mobility thus molar conductivity increases with dilution
(or decrease in concentration)
FOR WEAK ELECTROLYTES
molar conductivity increases steeply with dilution because in weak electrolytes the
dissociation of electrolyte into ions is comparatively less. Dilution helps in dissociation of
electrolyte. As a result, more ions are formed and corresponding value of conductivity
also increases. This increase quite large.

SECTION D
31

b)Reaction with NaHCO3-Brisk effervescence in carboxylic acid

c) The aliphatic carboxylic acids are stronger acids than alcohols and phenols. The
difference in the relative acidic strengths can be understood if we compare the resonance
hybrids of carboxylate ion, alkoxide and phenoxide ion.

The resonance hybrids may be represented as:

Carboxylate ion and Phenoxide ion
The electron charge on the carboxylate ion is more dispersed in comparison to the
phenoxide ion since there are two electronegative oxygen atoms in carboxylate ion as
compared to only one oxygen atom in phenoxide ion. In other words, the carboxylate ion
152 | P a g e
 is relatively more stable as compared to phenate ion. Thus, the release of H+ ion from
carboxylic acid is comparatively easier or it behaves as a stronger acid than phenol.
OR
This is due to the lone pairs on oxygen atom attached to hydrogen atom in the -COOH
group are involved in resonance and hence making the carbon atom less electrophilic.
Hence, carboxylic acids do not give the reaction of carbonyl groups.
32 (a)

(b) Second order reaction

(c) t1/2=0.693/k
=> k=0.693/2= 0.3465 min-1

t= (2.303/0.3465) log 100/25

= 0.798 log 4
= 0.798 x 2x0.3010
= 0.4804 min
OR
Radioactive decay follows first order kinetics.

SECTION E
33 (a)

(b)

(c)

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34

a) i)CH3CH=CH2 + H2O/dil. H2SO4CH3CH(OH)CH3

ii)By treating phenol with conc. HNO3
OR
a)

b) i) Kolbe’s reaction-

ii)Riemer Tiemann reaction:

35 (a) 4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2

2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O

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Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
(b) (i) Due to incompletely filled d-orbitals and involvement of (n – 1) d electrons in
addition to ns electrons in chemical bonding.
(ii) Because they have completely filled d-orbitals (nd10) in their ground state as well as
in their common oxidation state.
(iii) Because 5f orbitals have poor shielding effect than 4f.
OR
(a) Potassium permanganate (KMn04) is prepared by the fusion of a mixture of
pyrolusite (Mn02), potassium hydroxide and oxygen, first green coloured potassium
manganate is formed. 2MnO2 + 4KOH + 02 —> 2K2Mn04+2H20 The potassium manganate
is extracted by water, which then undergoes disproportionation in neutral or acidic
solution to give potassium permanganate.
(b)

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SESSION 2022-23
BLUE PRINT
SAMPLE QUESTION PAPER SET – 5
CLASS – XII, SUBJECT – CHEMISTRY

S. Chapter MCQ A/R VSA1 SA1 Case LA Total

No Based Wt
1 Mark 1 Mark 2 Mark 3 Mark 4 Mark 5 Mark
1 Solutions 1(1) 3(1) 4(1) 8(3)

2 Electrochemistry 1(1) 2(1) 5(1) 8(3)

3 Chemical kinetics 2(2) 4(2) 6(4)

4 d – and f – block 2(2) 1(1) 5(1) 8(4)

elements
5 Coordination 1(1) 2(1) 3(1) 6(3)
compounds
6 Haloalkanes and 2(2) 1(1) 2(1) 3(1) 8(5)
haloarenes
7 Alcohols, Phenols 1(1) 1(1) 2(1) 3(1) 7(4)
and Ethers
8 Aldehydes, ketones 2(2) 5(1) 7(3)
and Carboxylic
acids
9 Amines 1(1) 1(1) 3(1) 5(3)

10 Biomolecules 1(1) 2(1) 4(1) 7(3)

Tot 14(14) 4(4) 14(7) 15(5) 8(2) 15(3) 70(35)

al

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 KENDRIYA VIDYALAYA SANGATHAN GUWAHATI REGION
SAMPLE QUESTION PAPER SET -1
CLASS – XII SUB – CHEMISTRY
Time : 3hrs M.M. - 70

General Instructions:

Read the following instructions carefully.

a) There are 35 questions in this question paper with internal choice.

b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks each.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed

SECTION –A
The following questions are multiple-choice questions with one correct answer.
Each question carries 1 mark. There is no internal choice in this section.

1 Molecules whose mirror image is non superimposable over them are known as chiral. 1
Which of the following molecules is chiral in nature?
a) 2-Bromobutanee b) 1-Bromobutane c) 2-Bromopropane
d) 2-Bromopropane-2-ol

2 Which one of the following alkyl halides will undergo 𝑆 1 reaction most readily? 1
a) (𝐶𝐻 ) 𝐶 − 𝐹 b) (𝐶𝐻 ) − 𝐶𝑙 c) (𝐶𝐻 ) 𝐶 − 𝐵𝑟 d) (𝐶𝐻 ) 𝐶 − 𝐼

3 The maximum oxidation state shown by Mn in its compounds is 1

a) +4 b) +5 c) +6 d) +7

4 Unit of rate constant for zero order is? 1

a) Mol/sec b) sec -1 c) mol.lit-1s-1 d) mol -1

5 Which of the following statements is not correct for amines? 1

a) Amines can be prepared by reduction of amides.
b) Aromatic primary amines can be prepared from Gabriel phthalimide synthesis.
c) Aryl nitro compound cannot be converted into amine using 𝐿𝑖𝐴𝑙𝐻 in ether.
d) In the Hoffmann bromamide degradation, amine is formed with side products.

6 Which of the following does not give Fehling solution test? 1

a) 𝑃ℎ𝐶𝐻𝑂 b) 𝐴𝑐𝑒𝑡𝑜𝑛𝑒 c) 𝐶𝐻 𝐶𝐻𝑂 d) both a & b

7 A magnetic moment of 1.73 BM will be shown by which among the following. 1

a) [𝐶𝑢(𝑁𝐻 ) ] b) [𝑁𝑖(𝐶𝑁) ] c) [𝐶𝑜𝐶𝑙 ] d) 𝑇𝑖𝐶𝑙

8 A solution has higher osmotic pressure than its standard solution. Which of the 1
following term will be used for this solution?
a) Isotonic b) Hypertonic c) Dilute d) Hypotonic
9 What is/are the number(s) of unpaired electrons in the square planar 1
[𝑁𝑖(𝐶𝑁) ] ion?
a) Zero b) one c) Two d) Three
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10 The reaction by which benzaldehyde is converted to benzyl alcohol, is 1
a) Fittig reaction
b) Cannizzaro reaction
c) Wurtz reaction
d) Aldol condensation

11 The electrolytic purification of copper can be carried out in an apparatus similar to the 1
one shown below

The half - cell equation for the reaction at the anode is

a) 𝐶𝑢(𝑠) + 2𝑒 → 𝐶𝑢
b) 𝐶𝑢(𝑠) → 𝐶𝑢 + 2𝑒
c) 𝐶𝑢 + 2𝑒 → 𝐶𝑢
d) 𝐶𝑢 → 𝐶𝑢 + 2𝑒
12 In clemmensen reduction, carbonyl compound is treated with 1
a) Zinc amalgam + HCl
b) Sodium amalgam + HCl
c) Zinc amalgam + nitric acid
d) Sodium amalgam + 𝐻𝑁𝑂

13 Which of the following reactions of glucose can be explained only by its cyclic 1
structure?
a) Glucose forms penta acetate.
b) Glucose reacts with hydroxylamine to form an oxime.
c) Pentaacetate of glucose does not react with hydroxylamine.
d) Glucose is oxidised by nitric acid to gluconic acid.

14 For the reaction, 𝐴 → 𝑃 , the rate of reaction increases sixteen times when the 1
concentration of the reactant increases four times. The order of the reaction is
a) 2.5 b) 0.5 c) 1.5 d) 2.0

15 Assertion(A): In alcohols, boiling point decreases with decrease in the branching of 1

the carbon chain.
Reason (R): There is the decrease in vander Waal’s forces between the number of
carbon atoms with decrease in the surface area.

Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A
c. A is true but R is false.
d. A is false but R is true.

16 Assertion(A): tert – butyl bromide undergoes Wurtz reaction to give 2,2,3,3 – 1

tetramethylbutane.
Reason (R): In wurtz reaction, alkyl halides react with sodium in dry ether to give
hydrocarbon containing double the number of carbon atoms present in the alkyl halide.

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 Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A
c. A is true but R is false.
d. A is false but R is true.
17 Assertion(A): Iron has higher enthalpy of atomisation than that of copper. 1
Reason (R): Lower the number of unpaired electrons, higher will be the enthalpy of
atomisation.

Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A
c. A is true but R is false.
d. A is false but R is true.
18 Assertion(A): N – methyl acetamide undergoes Hoffmann bromamide reaction. 1
Reason (R): In Hoffmann bromamide reaction, the amine formed has one carbon atom
less than the parent 1 amide.

Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A
c. A is true but R is false.
d. A is false but R is true.
SECTION B
This section contains 7 questions with internal choice in two questions. The
following questions are very short answer type and carry 2 marks each.
19 For a first order reaction, show that time required for 99.9% completion is thrice the 2
time required for completion of 90% of reaction.

20 Give reason 2
(A) All the carbon atoms are linked in straight chain in D-glucose.
(B) Glucose is soluble in water but cyclohexane is insoluble in water.
OR
(A) Why cannot vitamin C be stored in our body?
(B) Sucrose is dextrorotatory but the mixture obtained after hydrolysis is
laevorotatory. Why?

21 Why are aryl halides less reactive towards nucleophilic substitution reaction? How can 2
we enhance the reactivity of aryl halide?
OR
Give Reason
(A) Although chlorine is electron withdrawing group, yet it is ortho-para directing
in electrophilic substitution reaction.
(B) P-dichlorobenzene has higher melting point than those of o and m isomer.

22 (A) [ NiCl4]2- is paramagnetic, while [Ni(CO)4] is diamagnetic though both are 2

tetrahedral. Why?
(B) Write difference between homoleptic and heteroleptic complex with one
example of each.

23 Name the cell used for low current devices like hearing aids, watches etc. Also give the 2
half cell reaction and overall reaction for such cell.

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24 (A) Why does a rate of reaction increase with rise in temperature? 2
(B) Can concentration of catalyst determine the rate. If yes, give example with
reason.

25 How will you bring following conversions? 2

(A) Propan-2-one to tert-butyl alcohol
(B) Aniline to Phenol

SECTION C
This section contains 5 questions with internal choice in two questions. The
following questions are short answer type and carry 3 marks each.
26 Write equations for the following reactions. 3
a) Ethyl magnesium chloride is treated with formaldehyde followed by addition of
water.
b) Chlorobenzene is reacted with acetyl chloride in presence of anhydrous AlCl3
c) Phenol is heated with zinc.

27 Using valence bond theory, explain the following in relation to complex [𝐶𝑜𝐶𝑙 ] 3
a) Type of hybridisation.
b) Type of complex – inner or outer orbital complex.
c) Magnetic behaviour.

28 Answer the following questions. 3

a) On mixing two liquids X and Y, volume of resulting solution decreases. What
type of deviation from Raoult’s law is shown by the resulting solution? What
change in temperature would you observe after mixing liquids X and Y?
b) What is anoxia?

29 Give reasons for any three of the following observations. 3

a) Primary amines are higher boiling than tertiary amines.
b) Aliphatic amines are stronger bases than aromatic amines.
c) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric
oxide.
d) 𝑝 of aniline is more than that of methylamine.

30 a) Compound ‘A’ with molecular formula C4H9Br is treated with aq. KOH solution. 3
The rate of this reaction depends upon the concentration of the compound ‘A’
only. When another optically active isomer ‘B’ of this compound was treated
with aq. KOH solution, the rate of reaction was found to be dependent on
concentration of compound and KOH both.
i) Write down the structural formula of both compounds ‘A’ and ‘B’.
ii) Out of these two compounds, which one will be converted to the product
with inverted configuration.
b) Write Swart reaction.
OR

(a) Name the possible haloalkane which will yield n-butane on their reaction with
sodium in presence of ether. Write the reaction involved.
(b) The treatment of alkyl chlorides with aqueous KOH leads to the formation of
alcohols but in presence of alcoholic KOH, alkenes are major product. Why?

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 SECTION D
The following questions are case-based questions. Each question has an internal
choice and carries 4 (1+1+2) marks each. Read the passage carefully and answer
the questions that follow.
31 Polysaccharides may be very large molecules. Starch, Glycogen, Cellulose, and chitin 4
are examples of polysaccharides.
Starch is the stored form of sugars in plants and is made up of amylose and
amylopectin ( Both polymers of glucose). Amylose is soluble in water and can be
hydrolysed into glucose units breaking glycosidic bonds, by the enzymes α amylase and
β-amylase. It is straight chain polymer. Amylopectin is a branched chain polymer of
several D-glucose molecules. 80% of amylopectin is present in starch. Plants are able to
synthesise glucose and the excess glucose is stored as starch in different plant parts,
including roots and seeds. The starch that is consumed by animals is broken down into
smaller molecules, such as glucose.
Glycogen is the storage form of glucose in human and other vertebrates, and is made
up of monomers of glucose. Magnitude of branching in glycogen is greater than
amylopectin.
Like amylose, cellulose is linear polymer of glucose. Cellulose is linear polymer of
glucose.
Answer the following questions
(a) Why glycogen is known as animal starch?
(b) What type of linkage is present between monosaccharides to form
polysaccharides?
(c) Write two differences between amylose and amylopectin.\
OR
Write one similarity and one difference between amylose and cellulose.

32 The colligative properties of electrolytes require a slightly different approach than the 4
one used for the colligative properties of non-electrolytes. The electrolytes dissociate
into ions in a solution. It is the number of solute particles that determines the
colligative properties of solution. The electrolyte solution therefore, show abnormal
colligative properties. To account for this effect, we define a quantity called Van’t Hoff
factor, given by
No. of particles in solution after dissociation or association
i = ____________________________________________________________________
Actual no. of particles dissolved in solution
i=1 ( For non-electrolytes)
i>1 (For electrolytes, undergoing dissociation)
i<1 (For solutes undergoing association)
Van’t Hoff factor depends on degree of dissociation or degree of association as the case
may be.
Answer the following questions
(a) Give example of a solution in which solute molecules undergo association in
solution.
(b) A substance trimerises when dissolved in water. What will be its Van’t Hoff
factor?
(c) 0.1M K4[Fe (CN)6] is 60% dissociated. Calculate its Van’t Hoff factor?
OR
Arrange the following compound in order of increasing Van’t Hoff factor
C6H12O6, NaCl, CaCl2, Ca3(PO4)2

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 SECTION E
The following questions are long answer type and carry 5 marks each. Two
questions have an internal choice
33 a) Why does the conductivity of a solution decreases with dilution? 5
b) Write the reaction involved in the working of 𝐻 − 𝑂 fuel cell.
c) What is the potential of hydrogen electrode which is in contact of a solution
whose 𝑝 is 10?

OR

a) If the 𝐸 for a given reaction has a negative value, then what would be the
relationship between ∆𝐺 and Keq?
b) How many electrons flow through a metallic wire, if a current of 0.5 A is passed
for 2 hours?
c) For a cell, 𝐴𝑔(𝑠)|𝐴𝑔𝑁𝑂 (0.01𝑀)||𝐴𝑔𝑁𝑂 (1.0𝑀)|𝐴𝑔(𝑠).
What is the emf of the cell at 25oC

34 An alkene ‘A’ (molecular formula 𝐶 𝐻 ) on ozonolysis gives a mixture of two 5

compounds B and C. Compound B gives positive Fehlings’s test and also forms
iodoform on treatment with 𝐹 and NaOH. Compound C does not give Fehling’s test but
forms iodoform.
a) Identify A, B and C
b) Write the reaction of ozonolysis of A.
c) Write the equation of Fehling’s test of B.
d) Write the equation of iodoform test for B and C.

OR

An aromatic compound A (molecular formula 𝐶 𝐻 𝑂) gives 2, 4- DNP test. It gives a

yellow precipitate of compound B on treatment with iodine and NaOH. Compound A
does not give Tollen’s test. On drastic oxidation with chromic acid, it gives a carboxylic
acid C having molecular formula 𝐶 𝐻 𝑂 ) .
a) Identify A, B and C
b) Write the equation involved in 2, 4 – DNP test of A.
c) Write equation of iodoform test of A.
d) Write equation of A with 𝐾𝑀𝑛𝑂 .

35 Answer the following. 5

a) Which element of transition series has highest second ionisation enthalpy?
b) Why does copper not replace hydrogen form acids?
c) Draw the structure of
i) Dichromate ion
ii) Permanganate ion.
d) How will you obtain?
𝑁𝑎 𝐶𝑟 𝑂 from 𝑁𝑎 𝐶𝑟𝑂 ?

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 KENDRIYA VIDYALAYA SANGATHAN, GUWAHATI REGION
MARKING SCHEME OF MODEL SAMPLE PAPER – 5 (2022-23)
CHEMISTRY THEORY (043)
Q. N Answers
1 a
2 d
3 d
4 c
5 b
6 d
7 a
8 b
9 a
10 b
11 b
12 a
13 c
14 d
15 d-A is false but R is true
16 a-Both A and R are true and R is the correct explanation of A
17 c-A is true but R is false
18 d-A is false but R is true
19 For 90 % completion (t90%),
Initial Concentration of reactant = Ri = 100
Final concentration of reactant = Rf = 10
t90% = 2.303log (Ri/Rf)/k = 2.303/K (Eqn1)
For 99.9 % Completion
Initial Concentration of reactant = Ri = 100
Final concentration of reactant = Rf = 0.1
t99.9% = 2.303log (Ri/Rf)/k = (2.303X3)/K (Eqn-2)
Dividing Eqn by Eqn 1
t99.9%/ t90% = 3
Therefore, t99.9% = 3 X t90%

20 (C) On reduction with HI, glucose gives n-hexane which verify that in glucose all the C atoms
are linked in straight chain
C6H12O6 CH3CH2 CH2 CH2 CH2 CH3
(D) Glucose forms hydroge bond with water due to presence of O-H bond but cyclohexane can’t
form hydrogen bond.
OR
(C) Vitamin C is water soluble vitamin they are readily excreted by urine and can’t be stored.
(D) Sucrose is dextrorotatory but hydrolysis gives dextrorotatory glucose and laevorotatory
fructose. Since the laevorotation of fructose (-92.4o) is more than dextrorotation of glucose
(+52.5o) hence the mixure is laevorotatory.
21 Due to +R effect partial double bond developed between C & X, greater s character in C of aryl
halide, instability of phenyl carbocation, presence of pie electron density.
By adding electron withdrawing group at o and p.
OR
Give Reason
(C) Inductive effect destabilises the intermediate carbocation and resonance effect stabilises
the intermediate carbocation ( Reference NCERT Page No.315)
(D) P-dichlorobenzene has greater symmetry than m-dichlorobenzene. Therefore close
packing of p-dichlorobenzene is more efficient and has higher m.p.

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22 (C) Cl- is weak field ligand hence unpaired electron do not pair up in [ NiCl4]2- & it has two
unpaired electrons and paramagnetic while CO is strong field ligand & all unpaired
electrons paired up and hence [Ni(CO)4] is diamagnetic
(D) Homoleptic : Same ligands are present. Ex [Ni(CO)4]
Heteroleptic : Different types of ligands present. Ex. [ Pt (NH3)4Cl2]SO4
23 Mercury cell
At Anode: Zn(Hg) + 2OH- Zn2+ + H2O + 2e
At Cathode: HgO + H2O + 2e Hg + 2OH-
Overall reaction -Zn(Hg) + HgO ZnO + Hg
24 (C) Increase in temperature increases the fraction of reactant having sufficient activation
energy and hence rate increases.
(D) Yes Concentration of catalyst can determine the rate if catalyst involved in rate
determining step
Ex. 2H2O2 + I- 2H2O + O2
Step1 H2O2 + I- H2O + IO- ( Slow Step-Rate determining)
Step2 H2O2 + IO - H2O + O2 + I- ( Fast step

25

26 𝑎) 𝐶 𝐻 𝑀𝑔𝐶𝑙 + 𝐻𝐶𝐻𝑂 + 𝐻 𝑂 → 𝐶𝐻 𝐶𝐻 𝐶𝐻 𝑂𝐻
b)

c)

27 a) 𝑠𝑝 𝑑
b) 𝑜𝑢𝑡𝑒𝑟 𝑜𝑟𝑏𝑖𝑡𝑎𝑙
c) Paramagnetic
28 a) Negative deviation and temperature decreases.
b) Low blood oxygen causes climbers to become weak and unable to think clearly, this
condition is known as anoxia
29 a) Primary amines form hydrogen bonding. Tertiary amines do not form hydrogen bonding.
b) In aromatic amines, lone pair on N atom involves in delocalisation, so pair of electrons less
available for protonation.
c) Methylamine is more basic than water. So it accepts a proton from water forming OH- ions.
𝐹𝑒𝐶𝑙 → 𝐹𝑒 + 3 𝐶𝑙
2𝐹𝑒 + 6 𝑂𝐻 → 2 𝐹𝑒(𝑂𝐻) 𝐵𝑟𝑜𝑤𝑛 𝑝𝑝𝑡.
d) In aniline, lone pair of electrons on N atom is delocalised over benzene ring. So electron
density on N decreases.
30 a) i) A is (𝐶𝐻 ) 𝐶 − 𝐵𝑟 undergoes 𝑆 mechanism
B is 𝐶𝐻 𝐶𝐻 𝐶𝐻(𝐵𝑟)𝐶𝐻 undergoes 𝑆 mecanism
ii) compound B will give product with inverted configuration
b) 𝐶𝐻 𝐵𝑟 + 𝐴𝑔𝐹 → 𝐶𝐻 𝐹 + 𝐴𝑔𝐵𝑟
OR
a) 2 𝐶𝐻 𝐶𝐻 𝐶𝑙 + 𝑁𝑎 + 𝑒𝑡ℎ𝑒𝑟 → 𝐶𝐻 𝐶𝐻 𝐶𝐻 𝐶𝐻 + 𝑁𝑎𝐶𝑙
b) aq. KOH gives OH- ions which are strong nucleophile. Leads to undergo a substitution
reaction to form alcohol.

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 Alc.KOH contains alkoxide (RO-) ion, which is a strong base. Leads to elimination by
abstracting 𝛽 − ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
31 (d) Glycogen is stored as reserved food material like starch in plant that is why it is called
animal starch.
(e) Glycosidic linkage
(f) Amylose – Water soluble component of starch
- Linear chain polymer of α-D-Glucose
Amylopectin- Water insoluble component
- Branched chain polymer of α-D-Glucose
OR
Similarity : Both are linear chain polymer i.e branching absent
Difference : amylose is polymer of α-D-Glucose, While cellulose is polymer of β-D-Glucose

32 (d) Urea solution /glucose solution/ any other solution in which neither association or
dissociation take place
(e) For complete association
i = 1/n = 1/3 = 0.33
(f) Degree of dissociation = α = 0.6 and No. of ions produced by 1 mole = n= 5
α = i-1/ n-1 = i-1 /5-1
i-1 = 0.6 X 4 = 2.4
Therefore, i = 3.4
OR
order of increasing Van’t Hoff factor
C6H12O6 < NaCl < CaCl2 < Ca3(PO4)2

33 a) No of ions per unit volume decreases with dilution.

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34 a) A – 2-methyl but – 2-ene, B – Acetaldehyde , C – Acetone
b) 2 − 𝑚𝑒𝑡ℎ𝑦𝑙𝑏𝑢𝑡 − 2 − 𝑒𝑛𝑒 + 𝑂 → 𝐶𝐻 𝐶𝐻𝑂 + 𝐶𝐻 𝐶𝑂𝐶𝐻
c) 𝐶𝐻 𝐶𝐻𝑂 + 2𝐶𝑢 + 5𝑂𝐻 → 𝐶𝐻 𝐶𝑂𝑂 + 3𝐻 𝑂 + 𝐶𝑢 𝑂
d) 𝐶𝐻 𝐶𝐻𝑂 + 𝑁𝑎𝑂𝐻 + 𝐼 → 𝐻𝐶𝑂𝑂𝑁𝑎 + 𝐶𝐻𝐼
𝐶𝐻 𝐶𝑂𝐶𝐻 + 𝑁𝑎𝑂𝐻 + 𝐼 → 𝐶𝐻 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝐻𝐼

OR

a) A – Acetophenone B – iodoform C -benzoic acid

b)

c) 𝐶 𝐻 𝐶𝑂𝐶𝐻 + 𝑁𝑎𝑂𝐻 + 𝐼 → 𝐶 𝐻 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝐻𝐼

d) 𝐶 𝐻 𝐶𝑂𝐶𝐻 + 𝐾𝑀𝑛𝑂 → 𝐶 𝐻 𝐶𝑂𝑂𝐻

35 a) Copper has highest second IE because second electron is to be removed from fully filled
d – subshell.
b) Cu is less reactive than hydrogen.
c) i) ii)

iii) 2𝑁𝑎 𝐶𝑟𝑂 + 𝐻 𝑆𝑂 → 𝑁𝑎 𝐶𝑟 𝑂 + 𝑁𝑎 𝑆𝑂 + 𝐻 𝑂

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