CHEMISTRY MATERIAL

1. SOLUTIONS

Very Short Answer Questions [1 mark]

1. Define mole fraction.
Ans.
Mole fraction of a component in a solution may be defined as the ratio of moles of that component to the
total number of moles of all the components present in the solution.
2. How does the molarity of a solution change with temperature?
Ans.
Molarity decreases with increase in temperature as volume of solution increases with increase in
temperature.

3. 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.
NH 4Cl (aq)  NH 4 (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.

4. What is the similarity between Raoult’s law and Henry’s law?

Ans.
The similarity between Raoult’s law and Henry’s law is that in both the laws, the partial vapour pressure of
the volatile component or gas is directly proportional to its mole fraction in the solution.
5. What are maximum boiling azeotropes? Give one example.
Ans.
Maximum boiling azeotropes are those which boil at higher temperature than boiling point of each
component in pure state, e.g., 68% nitric acid and 32% water by mass.
6. Why is 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.
Otherwise, radiator will burst due to freezing of coolant (water).
7. What are isotonic solutions?
Ans:
The solutions of the same osmotic pressure at a given temperature are called isotonic solutions.
8. What is the van’t Hoff factor for a compound which undergo dimerisation in an organic solvent?
Ans.
2X  X 2
Number of moles of particles after association 1
i 
Number of moles of particles before association 2
9. Why is osmotic pressure of 1 M KCl higher than 1 M urea solution?
Ans.
This is because KCl dissociates to give K+ and Cl – ions while urea being a molecular solid does not
dissociate into ions in the solution.
10. Two liquids A and B boil at 145oC and 190oC respectively. Which of them has higher vapour pressure
at 80oC?
Ans:
Liquid A with lower boiling point is more volatile and hence will have higher vapour pressure.
11. What happens when blood cells are placed in pure water?
Ans:
Due to osmosis, water molecules move into the blood cells through the cell walls. As a result, blood cells
swell up and may even burst.
12. Why is osmotic pressure considered to be a colligative property?
Ans:
n
  CRT or   RT
V
It shows that osmotic pressure (  ) depends only on the number of moles ‘n’ of the solute present in a
definite volume of the solution (V) and there is no factor involving the nature of the solute. Hence, it is a
colligative property.
13. What are isotonic solutions?
Ans:
Isotonic solutions are those which have the same osmotic pressure at a given temperature.
14. Why is the elevation in b.p. of water different in the following tow solutions?
a) 0.1 molar NaCl solution . b) 0.1 molar sugar solution.
Ans:
NaCl is an electrolyte. It dissociates to give Na+ and Cl – ions in the solution. Sugar is a non – electrolyte. It
does not dissociate in the solution. Thus, the number of particles is greater in 0.1M NaCl solution than in
0.1 M sugar solution. Hence elevation in boiling point is greater is case of NaCl solution.
15. Give reason when 30 mL of ethyl alcohol and 30 mL of water are mixed, the volume of resulting
solution is more than 60 mL.
Ans:
Forces of attraction become less in ethyl alcohol and water as compared to ethanol and water molecule.
Short Answer Questions–I [2 marks]
1. 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.
2. State the following:
(i) Raoult’s law in its general form in reference to solutions.
(ii) Henry’s law about partial pressure of a gas in a mixture.
Ans.
(i) Raoult’s law: It states that for any solution, the partial pressure of each volatile component in the
solution is directly proportional to its mole fraction.

(ii) Henry’s law: It states that the partial pressure of a gas in vapour phase (P) is proportional to its mole
fraction (x) in the solution.
3. State Raoult’s law for the solution containing volatile components. Write two differences between an
ideal solution and a non-ideal solution.
Ans.
Raoult’s law states that for a solution of volatile liquids the partial vapour pressure of each component is
directly proportional to its mole fraction.

Differences between Ideal and non-Ideal solutions

4. Write two differences between a solution showing positive deviation and a solution showing negative
deviation from Raoult’s law.
Ans.

5. 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
K  WB 1000
MB  b , we get
Tb  WA
2.52 1.5 1000
MB 
0.7  90
M B  60 g mol 1
6. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1) in 250 g
of water. (Kf of water = 1.86 K kg mol–1)
Ans. Here, WB = 60 g, MB = 180 g mol–1, WA = 250 g, Kf = 1.86 K kg mol–1
Substituting these values in the expression
K  WB 1000
T f  f , we get
WB  WA
1.86  60 1000
T f   2.48 K
180  250
Freezing point of solution, Tf  Tfo  Tf  273.15 K  2.48 K  270.67 K
7. Define the following terms:
(i) Abnormal molar mass
(ii) van’t Hoff factor (i)
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 (i) gives the extent of association or dissociation of the solute particles in the solution.
It may be defined as the ratio of observed colligative property to calculated colligative property.
Observed colligative property
i
Calculated colligative property

8. Calculate the freezing point of a solution containing 0.5 g KCl (Molar mass = 74.5 g/mol) dissolved in
100 g water, assuming KCl to be 92% ionized. Kf of water = 1.86 K kg / mol .
Ans:
KCl  K   Cl 
n=2
i  1    n
i  1 
T f  iK f m
0.5  1000
=(1+0.92) 1.86 
74.5  100
T f  0.24
Tf  Tf0  Tf'
Tf'  0.24o C

9. What role does the molecular interaction play in solution of alcohol and water?
Ans:
There is strong hydrogen bonding in alcohol molecules as well as water molecules. The intermolecular
forces both in alcohol and water are H – bonds. When alcohol and water are mixed they form solution
because of the formation of H – bonds between alcohol and H2O molecules but these interactions are
weaker and less extensive then those in between pure water molecules. Hence, they show positive deviation
from the ideal behaviour

10. If the density of some lake water is 1.25 g mL – 1 and contains 92 g of Na+ ions per kg of water,
calculate the molality of Na+ ions in the lake.
Ans:
Moles of Na  ions
Molality 
Mass of water (kg )
92 g
92 g of Na+ ions =  4 moles
23g mol 1
Therefore, molality = 4m.
Three Mark Questions.
1. Define the following terms:
(i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass percentage
Ans:
(i) Mole fraction: It is the ratio of number of moles of a particular component to the total number of moles
of all the components.
Example: Mole fraction of component A in a binany solutions:
nA
xA 
nA  nB
 Where nA is the number of moles of component ‘A’ and nB is the number of moles of component B.
(ii) Molality: Molality of a solution is defined as the number of moles of the solute dissolved in 1000 g
(1 kg) of the solvent. It is denoted by ‘m’.
Moles of solute
Molality (m) 
Mass of solvent (in kg )
For example, 1.00 mol kg 1 (or 1.00 m) solution of KCl means that 1 mole of KCl dissolved in 1 kg of
water.
(iii) Molarity: Molarity (M) is defined as number of moles of solute dissolved in one litre (or one cubic
decimeter) of solution.
Moles of solute
Molarity (m) 
Volume of solution (in litre)
(iv) Mass percentage: The mass percentage of a component of solution is defined as:
Mass of the component in the solution 100
Mass % of a component 
Total mass of the solution
2. A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction
of each component in the solution? If the density of the solution is 1.2 g mL1 then what shall be the
molarity of the solution?
Ans:
10 g glucose is present in 100 g solution, i.e. 90 g of water or 0.090 kg of water
10
10 g glucose  mol  0.0555 mol
180
90
90 gH 2O   5 moles
18
0.0555 mol
Molality   0.617 m
0.090 kg

0.0555
Mole fraction of Glucose, xB   0.01
5  0.0555
Mole fraction of water ( xA )  1  0.01  0.99
100
Vol. of 100 g of solution  mL  83.33 mL  0.08333 L
1.2
0.0555 mol
Molarity   0.67 M
0.08333L
3. A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by mass. Calculate
the mass percentage of the resulting solution.
Ans:
300 g of 25% solution contain solute = 75 g
400 g of 40% solution contains solute = 160 g
Total mass of solute = 160 + 75 = 235 g
Total mass of solution = 300 + 400 = 700 g
235
% of solute in the final solution   100  33.5%
700
% of water in the final solution  100  33.5  66.5%
4. State Henry’s law and mention some important applications.
Ans:
Henry’s law: The solubility of a gas in a liquid is directly proportional to the partial pressure of the gas.
Applications of Henry’s law:
 (i) In the production of carbonated beverages (as solubility of CO2 increases at high pressure).
(ii) In deep sea diving.
(iii) In functioning of lungs.
(iv) In breathing fir climbers or people living at higher altitudes.
5. The partial pressure of ethane over a solution containing 6.56 103 g of ethane is 1 bar. If the
solution contains 5.00 102 g of ethane, then what shall be the partial pressure of the gas?
Ans:
Applying the relationship: m  K H  P
In the first case,
6.56 103 g  K H 1 bar
K H  6.56 103 g bar 1
or
In the second case,
5.00 102 g  6.56 g 103 g bar 1  P
5.00 102 g
P  0.762 bar
6.56 103 g bar 1
6. The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 modal solution of
a non-volatile solute in it.
Ans:
1 molal soluiton means 1 mole of the solute is dissolved in 1 kg of the solvent (water).
1
Mole fraction of solute   0.0177
1  55.5
P 0  Ps
Now  x2
P0

12.3  Ps
i.e.  0.0177
12.3
Ps  12.08 kPa
7. Calculate the mass of a non-volatile solute (molar mass 40 g mol-1) which should be dissolved in 114 g
octane to reduce its vapour pressure to 80%.
Ans: Ps  80% of P 0  0.80 P 0
W
Mole of solute 
40 g mol 1
114 g
Moles of solvent (octane) 
114 g mol 1
(Molar mass of C8 H18  114 g mol 1 )
P 0  Ps
Now x2
P0

W
P  0.80 P
0 0
 0
 40
P W
1
40
0.8W
or  0.2
40
W = 10 g
8. Suggest the most important type of intermolecular attractive interaction in the following pairs:
(i) n – hexane and n-octane (ii) I2 and CCl4
(iii) NaClO4 and water (iv) Methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H6O).
Ans:
(i) Both are non-polar. Hence, there will be London dispersion forces
(ii) London dispersion forces.
(iii) NaClO4 and water
(iv) Methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H6O).
9. Amongst the following compounds, identify which are insoluble, partially soluble and highly soluble
in water?
(i) Phenol (ii) Toluene (iii) Formic acid (iv) ethylene glycol
(v) chloroform (vi) pentanol
Ans:
(i) Phenol – Partially soluble in water (ii) Toluene – Insoluble in water
(iii) Formic acid – Soluble in water (iv) Ethylene glycol – Soluble in water
(v) Chloroform – Insoluble in water (vi) Pentanol – Partially soluble in water
10. If the solubility product of CuS is 6 1016 , calculate the maximum molarity of CuS in aqueous
solution.
Ans:
Maximum molarity of CuS in aqueous solution = Solubility of CuS in mole L-1.
If s is the solubility of CuS in mol L-1, then
CuS  Cu 2  S 2
s s
K sp  Cu 2   S 2 
s s
 s  s  s2
s 2  6 1016
s  6 1016  2.45 108 mol L1 or 2.45 108 M
11. The depression in freezing point of water observed for the same amount of acetic acid, trichloroacetic
acid and trifluoroacetic acid increases in the order given above. Explain briefly.
Ans:
The depression in freezing points are in the order:
Acetic acid < trichloroacetic acid < trifluoroacetic acid
Fluorine, being the most electronegative, has the highest electron withdrawing tendency.
Consequently, trifluoroacetic acid is the strongest while acetic acid is the weakest acid. Hence
trifluoroacetic acid ionizes to the largest extent.
Thus depression in freezing point is maximum for the trifluoroacetic acid.
12. Determine the amount of CaCl2 (i  2.47) dissolved in 2.5 litre of water such that its osmotic pressure
is 0.75. atm at 270 C.
Ans:
  i CRT
n
  i RT
V
i nRT

V
 V

i RT
0.75 atm  2.5L
  0.0308 mole
2.47  0.0821 L atm K 1 mol 1  300 K

Molar mass of CaCl2  40  2  35.5  111 g mol 1

 Amount dissolved  0.0308 111 g  3.42 g.
13. (i) Explain why on addition of 1 mol glucose to 1 litre water the boiling point of water increases.
(ii) Henry’s law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate the number of moles of
CO2 in 500 ml of soda water when packed under 2.53 × 105 Pa at the same temperature.
Ans.
(i) On addition of glucose, a non-volatile solute to water (a volatile solvent) the vapour pressure of water
decreases. In order to make the solution boil, its vapour pressure must be increased by raising the
temperature above the boiling point of pure water. In other words, there is an increase in the boiling point of
water.
pCO2
(ii) According to Henry’s law, pCO2  K H  xCO2 or xCO2 
KH
2.53 105 Pa
 xCO2   1.51103
1.67 10 Pa
8

Mass of water = Density of water × volume of water

= 1 g mL–1 × 500 mL = 500 g
Mass of water 500 g
Moles of water, n =   27.78 mol
Molar mass 18 g mol 1
nCO2 nCO2
xCO2   or nCO2  xCO2  nH2O
nH2O  nCO2 nH2O
nCO2  1.51103  27.78 mol
 0.042mol
2. Electrochemistry
One mark questions:
1. An electro chemical cell can be have like an electrolytic cell when---------.
Ans: Eext > Ecell
2. The difference between the electrode potentials of two electrodes when no current is drawn
through the cell is called ---------------.
Ans: Cell emf
3. A hypothetical electro chemical cell is shown below : A|A+ (xM) || B+ (yM) | B
The emf measured is + 0.20V. The cell reaction is
Ans: A+B+ A+ + B
4. Which cell will measure standard electrode potential of copper electrode-------.
Ans: Pt(s)|H2(g,1bar)|H+(aq.,1M)||Cu2+(aq.,1M)|Cu

5. The positive value of the standard electrode potential of Cu2+ / Cu indicates that --------.
Ans: this redox couple is a stronger reducing agent than the H +/H2 couple,
Cu can not displace H2 from acid.
6. Standard electrode potential for Sn4+/Sn2+couple is +0.15V and that for the Cr3+/Cr couple is–
0.74V. The two couple in their standard states are connected to make cell. The cell potential will be:
 Ans: 0.89V
7. The electrode potential data are given below
Fe+e Fe,E=+0.77V
Al3++3e– Al, Eo=–1.66V
Br2+2e– 2Br–,Eo=+1.80V
Based on the data, the reducing power of Fe2+ ,Al, Br– will increase in the order.
Ans: Br–<Fe2+<Al
8. Which one is always true about the spontaneous cell reaction in a galvanic cell in case of E cell ,
Go , Q ------------.
Ans: Eell>0,ΔGo<0,Q<Kc
9. The standard emf of a galvanic cell involving 3moles of electrons in a redox reaction is 0.59 V.The
equilibrium constant for the reaction of the cell is:
Ans: 1030

10. The SI unit of conductivity is

Ans: Sm–1
11. On increasing temperature, ionic conductance , electronic conductance is--------.
Ans: ionic conductance increases and electronic conductance decreases.
12. Λ (NH4OH) is equal to------.
Ans: Λ (NH4Cl)+Λ(NaOH) –Λ (NaCl)
13. Charge carried by 1mole of electrons is-------.
Ans: 9.65×104coulomb
14. The quantity of charge required to obtain one mole of aluminium from Al2O3 is-----.
Ans: 3F
15. In the electrolysis of aqueous sodium chloride solution, which half cell reaction will occur at anode -
------------
Ans: 2H2O(l) O2(g)+4H+(aq)+4e–; Eell=1.23V
16. Eell for some half cell reactions are given below. On the basis of these mark the correct answer------
--------.
(i)H+(aq)+e– H2(g)Eell=0.00V

(ii)2H2O(l) O2(g)+ 4H+(aq)+ 4e–Eell=1.23V

(iii)2SO–(aq) S2O–(aq)+2e–;Eell=1.96V
Ans: (i)In dilute sulphuric acid solution, hydrogen will be reduced at cathode.
(ii) In dilute sulphuric acid solution, SO– ion will be oxidised to tetra thionate at anode.
17. The electrolyte used in the mercury cell is---------.
Ans: paste of KOH and ZnO
18. A device that converts energy of combustion of fuels like hydrogen and methane directly in to
electrical energy is known as---------.
Ans: fuelcell
19. Which metal is used as electrode which do not participate in the reaction but provides surface for
conduction of electrons ---------.
Ans: Pt
20) Can E or Δ rGo for cell reaction ever be equal to zero?------------.
Ans.No, Eell or Δ rGo for cell reaction can never be zero.
ΔGo=–nFEo
Eo is never zero hence Δ Go will also be not equal to zero.
21) What is the effect of decreasing concentration on the molar conductivity of a weak electrolyte? --
--------.
Ans.The molar conductivity of a weak electrolyte increases with decrease in concentration.
22) Which equation gives the relationship between equivalent or molar conductivity and concentration
of a strong electrolyte? -------------------- .
Ans.Debye – Huckel Onsagerequation
Λ=Λo-A√ c
23) What is SHE? What is its electrode potential? -----------.
Answer: SHE stands for standard Hydrogen electrode. By convention, its electrode potential is
taken as 0 (zero).
24) What is Nernst equation for single electrode potential----------.
M n aq  ne  M  s 
0.05291 1
Ans: EM n / M n : EoMn+/Mn+- log10
n M n 
25. the factors that influence the value of cell potential of the following cell:
Mg(s)|Mg2+(aq)||Ag+(aq)|Ag(s)--------------------.
Ans.The factors that influence the value of cell potential are concentration of Mg2+ and Ag+ ions
in the solution and temperature.
26) the term – standard electrode potential is ------------.
Ans:When the concentration of all the species involved in a half-cell is unity, then the electrode
potential is called standard electrode potential.
27) electromotive force of a cell ----------------.
Ans:Electromotive force of a cell is also called the cell potential. It is the difference between
the electrode potentials of the cathode and anode.
Ecell  ECathode  EAnode
28) the factors that affect the value of electrode potential? ------------.
Ans: Factors affecting electrode potential values are –
Concentration of electrolyte , Temperature
Short Answer type (2M & 3M)
1) Represent the cell in which following reaction takes place :
Mg(s) + 2Ag+ (0.0001M) Mg2+ (0.13M) + 2Ag (s)
Calculate Ecell = +3.17V.
Ans: The cell may be represented as
Mg(s) / Mg2+ (0.13M) // Ag+ (0.0001M) / Ag (s)
The cell reaction may be given as,
Mg(s) → Mg2+ (0.13M) + 2e-
 2Ag+ (10-4M) + 2e- → 2Ag (s)
----------------------------------------------------------


 Mg2+ (0.13M) + 2Ag (s)
Mg(s) + 2Ag+ (10-4M) 

--------------------------------------------------------------------------------------------
(n=2)

Q=
 Mg  = 0.131
2

= 0.13 x 108
 Ag  1 10 
2 2
 4

According to Nernst equation

0.0591
E= Eo – log10 Q
n
0.0591
= 3.17- log (0.13 x 108)
2
= 2.96V

2) The standard electrode potential for Daniel cell is 1.1V . Calculate the standard Gibbs free energy for
the reaction :
Zn(s) + Cu+2(aq) Zn+2(aq) + Cu(s)
Ans: We Know,
 Go = -nFEo
n=2 for the given reaction
F=96500C, Eo = +1.1V
 Go = -2 x 96500 x 1.1
= -212300J
3) Calculate the equilibrium constant for the reaction,
Cu(s) +2 Ag+(aq) Cu2+(aq) + Ag(s)
Eocell = + 0.46V
Ans: we Know,
 nE o 
K = Antilog  
 0.059 
 2  0.46 
= Antilog  = 3.92 x1015
 0.059 
4) Resistance of a conductivity cell filled with 0.1M KCl solotion is 100 ohm. If the resistance of the same
cell when filled with 0.02M KCl solution is 520 ohm, calculate conductivity and molar conductivity of
0.02M KCl solution . conductivity of o.1M KCl is 1.29 Sm-1.
Ans: conductivity = conductance x Cell constant
K = C x Cell constant
1
1.29 = x cell constant
100
Cell constant = 1.29 x 100m-1
=129 m-1 = 1.29 cm-1
For 0.02M KCl , R = 520 ohm
Conductivity = Conductance x Cell constant
1
K = x Cell constant
R
 1
= x 1.29 = 2.48 x 10-3 ohm-1 cm-1
520
k  1000
We know, M =
M
2.48 103 1000
=
0.02
= 124 S cm2 mol-1
5) The electrical resistance of a coloumn of 0.05 M NaOH solution of diameter 1 cm and length 50 cm is
5.55 x 103ohm. Calculate its resistivity, conductivity and molar conductivity
Ans: Area of cross section =  r 2 = 3.14 x (0.5)2 cm2 = 0.785 cm2
l
We Know, R =  
A
50
5.55 x 103 =  
0.785
Resistivity,  = 87.135 ohm cm
1 1
Conductivity , k = = = 0.01148 S cm-1
 87.135
Molar conductivity  M = can be calculated as,
k  1000
M =
M
0.01148
=
0.05
= 229.6 S cm2 mol-1
6) Calculate  o M for CaCl2 and MgSO4 using following data :
 o Mg 2 = 106 S cm2 mol-1 ;  o SO 2 = 160 S cm2 mol-1.
4

Ans;  o
CaCl2 = 
o
Ca2
+ 2 o
Cl 

= 119 + 2 x76.3 = 271.6 S cm2 mol-1

^oMgSO4 =  o Mg 2 + 2  o SO 2
4

= 106 + 160 = 266 S cm2 mol-1

7) The conductivity of 0.001028 M acetic acid is 4.95 x 10-5 S cm-1. Calculate its dissociation constant if
^o for acetic acid is 390.5 S cm2 mol-1 .
k  1000
Ans: We know ,  M = ------ (i)
M
Given : k = 4.95 x 10-5 S cm-1 ; M = 0.001028
4.95 105 1000
From equation (i)  M =
0.001028
= 48.15 ohm-1 cm2 mol-1
48.15
Degree of dissociation , α =  c M / oM = = 0.1233
390.5
CH3COOH CH3COO- + H+
t=0 C 0 0
teq C-Cα Cα Cα
 CH 3COO    H  
Dissociation constant , K    
CH 3COOH
C  C C 2
K =
C  C 1
Substituting the values of “ C “ and “α” in above equation , we get ,
0.001028   0.1233
2

K = 1.78 x 10-5
1  0.1233
8) A solution of copper sulphate is electrolyzed for 10 minute with a current of ampere . what is the
mass of copper deposited at the cathode ?
it
Ans: W = ; where i = 1.5 amp , t = 10 x 60 = 600 sec
96500
1.5  600  31.75 63.5
= E= = 31.75 ( equivalent mass )
96500 2
= 0.296g
Mass of copper deposited at cathode = 0.296 g
9) How would you determine the standard electrode potential of Mg+2 / Mg ?
Ans: Standard reduction potential of Mg+2 / Mg can be determined by forming a cell with standard
hydrogen electrode .
Mg(s) / Mg2+ (1M) (aq) // H+ (1M) / H2 (1atm) Pt
Ecell  ECathode  EAnode
= E o H  / H2 _ E o Mg 2 / Mg

= 0 - E o Mg 2 / Mg

E o Mg 2 / Mg = - E o cell
10) What is the cell potential for the cell at 25oc
Cr / Cr3+ (10.1M) // Fe2+ (0.01M) / Fe
EoCr3 / Cr = 0.74V , E o Fe3 / Fe = -0.44V
Answer:
The cell reaction is
2Cr  3Fe2  6e  2Cr 3  3Fe
Nernst Equation –
2
Cr 3 
Ecell  E o
Fe2 / Fe
E o
Cr 3 / Cr  
0.0591
log 3
6  Fe2 
= (-0.44v – (-0.74v)
0.0591
= 0.3V - 0.059-log 104
6
= 0.3V – 0.0394V
= +0.2606 V
11) State (a) Kohlraush law of independent migration of ions. (b) Faraday s first law of electrolysis.
Ans: (a) The kohlraush law of independent migration of ions state that “ limiting molar conductivity
of an electrode is the sum of the individual contribution of the cation and the anion of the
electrolyte .”
 (b) The faradays law states that “ the amount of chemical reaction occuring at any electrode by
passing current is directly proportional to the quantity of electricity passed through the electrolyte .
12) Define conductivity for the solution of an electrolyte . why does the conductivity of solution
decreases with dilution ?
Ans: Conductivity of a solution is the conductance of ions present in a unit volume of the solution
or in other words , it is defined as
The conductance of a solution of 1cm in length and area of cross - section 1 seq.cm. It is
reciprocal of resistance .
1 l l
G and G , therefore G 
R A RA
On dilution , the number of ions per unit volume decreases. Hence the conductivity
decreases.
13) Solutions of Two electrolytes” A” and “B” are diluted. The ^m of “B” increases 1.5 times while that of
A increases 25 times . Which of the two is a strong electrolyte ? Justify your answer . Graphically
show the behaviour of “A” and “B” .
Ans: The ^m of “B” increases 1.5 times while that of A increases 25 times . This shows that B is a
strong electrolyte . The molar conductivity increases slowly with dilution as there is no increase in
number of ions on dilution as strong electrolyte are completely dissociated.

14) Explain with graph , the variation of molar conductivity of a strong electrolyte with dilution.
Ans: Strong electrolytes are completely ionised in all concentrations. For strong electrolytes,
^m increases slowly with dilution.
It is found to vary with concentration according to the Debye - Huckel - Onsager equation.
^m = ^om-[ A + B^om] RootC
Where, A and B are called Debye - Huckel constants. Against C , we get a
staightline with slope as “-A” and intercept as ^om.

From the graph we can see, the molar conductivity increases slowly as
concentration decreases because there is no increase in number of ions on dilution as strong
electrolytes are completely dissociated.
15) Conductivity of 2.5 x 10-4 M methanoic acid is 5.25 x 10-5 S Cm2 mol-1 . Calculate its molar
conductivityand degree of dissociation.
Given: ^o(H+) = 349.5 S Cm2 mol-1 and ^o(HCOO-) = 50.5 S Cm2 mol-1.
Ans: Molar conductivity of 2.5 x 10-4 M solution is
k  1000 5.25 105 1000
C M  =
M 2.5 104
 C M = 210S Cm2 mol-1
 -
 (HCOO ) = ^o(HCOO-) + ^o(H+)
 m = 50.5 + 349 .5 = 400
 C M 210
Α= = = 0.525
  M  400
16) How much charge is required for the following reductions:
(i) 1 mol of to Al. (ii) 1 mol of to Cu. (iii) 1 mol of to .
Answer
(i)
Therefore, Required charge = 3 F
= 289461 C
(ii) Cu 2  2e  Cu
Therefore, Required charge = 2 F
2  96487C
= 192974 C
(iii) MnO4  Mn 2
i.e., Mn7  5e  Mn2
Therefore, Required charge = 5 F
 5  96487C
= 482435 C
17). How much electricity in terms of Faraday is required to produce
(i) 20.0 g of Ca from molten .(ii) 40.0 g of Al from molten
Answer:
(i) According to the question,
Electricity required to produce 40 g of calcium = 2 F Al =
Therefore, electricity required to produce 20 g of calcium =
=1F
(ii) According to the question,
Al 3  3e  
Al
27 g

Electricity required to produce 27 g of Al = 3 F

3  40
Therefore, electricity required to produce 40 g of Al = F
27
= 4.44 F
18). How much electricity is required in coulomb for the oxidation of
(i) 1 mol of H2O to O2 .
(ii) 1 mol of FeO toFe2O3
Answer:
(i) According to the question,
Now, we can write:
1
O 2  O2  2e 
2
Electricity required for the oxidation of 1 mol of H 2O to O2 = 2 F
2  96487C
= 192974 C
(ii) According to the question
Fe2  Fe3  e1
 Electricity required for the oxidation of 1 mol of FeO to Fe2O3 = 1 F
= 96487 C
19). A solution of is electrolysed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode?
Answer :
Given,
Current = 5A
Time = = 1200 s
Therefore,

= 6000C
According to the reaction,
Ni 2  aq   2e   Ni
58.7 g  s 

Nickel deposited by 2  96487C = 58.71 g

Therefore, nickel deposited by 6000 C

= 1.825 g
Hence, 1.825 g of nickel will be deposited at the cathode.
20). Depict the galvanic cell in which the reaction takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
Answer :
The galvanic cell in which the given reaction takes place is depicted as:

(i) Zn electrode (anode) is negatively charged.

(ii) Ions are carriers of current in the cell and in the external circuit, current will flow from silver to
zinc.
(iii) The reaction taking place at the anode is given by,

The reaction taking place at the cathode is given by,

21) The cell in which the following reaction occurs:
2Fe3+(aq)+2I–(aq) 2Fe2+(aq)+I2(s)
Has E =0.236V at298K.Calculate the standard Gibbs energy and the equilibrium constant of the
cellreaction.
ANS:
2Fe3++2e– 2Fe2+or2I– I2+2e–
Thus, for the given cell reaction, n=2.

ΔrG°=–nFE =–2×96500×0.236Jmol–1= –45548Jmol–1= –45.55kJmol–1

Δ rG°=–2.303RTlogKc
 Δ rG° =– 45. 55 kJmol–1
r Go
 log KC 
2.303RT

45.55kJmol 1

2.303  8.314 103 kJK 1mol 1  298K

=–7.983
`Kc=Antilog(7.983)=9.616×107

2 2 . Write electrode reaction staking place in (I )Ni–Cd cell, (ii) Lead Acid Accumulator .
Ans.(I) Cd(s)+2OH–(aq) Cd(OH)2(s)+2e– (at anode)
NiO2(s)+2H2O+2e– Ni(OH)2(s)+2OH–(aq) (at cathode)
2
(ii) Pb(s)+SO4–(aq) PbSO4(s)+2e–(atanode)
2
PbO2(s)+SO4–(aq)+4H+(aq)+2e– PbSO4(s)+2H2O(l)(at cathode)
23. A solution of Ni(NO3 )2 is electrolysed between platinum electrodes using acurrent of 5 amperes for
20minutes . What mass of Ni is deposited at the cathode?
Ans.Quantity of electricity passed = I×t = (5A) × (20×60s) = 6000 C
The electrode reaction is: Ni2++2e – Ni
2×96500C deposit Ni = 58.7g
6000C will deposit Ni = ( 5 8 . 7 / 2 × 9 6 5 0 0 ) × 6000g =1.825g
24. Suggest away to determine the Λ value of water.
Ans.Λ(H2O) = λ +)+λ OH–)
= λ +)+λ OH–) + λ Cl–)–λ Cl–) + λ +)–λ +)
Rearranging we get
Λ(H2O)= [ λ +)+λ Cl–) ] + [λ +)+ λ OH–) ] – [λ +)+λ Cl–)]
Λ(H 2O) =Λ (HCl)+Λ (NaOH)–Λ (NaCl)
25. If acurrent of 0.5 ampere flows through a metallic wire for 2 hours , then how many electrons would
flow through the wire ?
Ans.Q(coulomb) = I(ampere) × t(s) = (0.5ampere) (2×60×60s) = 3600C
A flow of 96500C Is equivalent to the flow of 1mole of electrons, i.e., 6.02×1023electrons
therefore, 3600C is equivalent to flow of electrons = (6.022×1023 / 96500 )×3600
=2.246×1022electrons
26. The resistance of a conductivity cell containing 0.001 M KCl solution at 298K is 1500Ω. What is the
cell constant if conductivity of 0.001M KCl solution at 298K is 0.146×10–3Scm–1?
Ans.Conductivity (k)= ×Cellconstant

k=0.146×10–3Scm–1,R=1500Ω
0.146×10–3Scm–1= ×Cellconstant

Cellconstant=0.146×10–3Scm–1×1500Ω=219×10–3cm–1=0.219cm–1
27) Can you store AgCl solution in Zinc pot?
Ans:No. We can’t store AgCl solution in Zinc pot because standard electrode potential of Zinc is
less than silver.
28) What is an electrochemical series? How does it predict the feasibility of a certain redox reaction?
Ans: The arrangement of metals and ions in increasing order of their electrode potential values is
known as electrochemical series.The reduction half reaction for which the reduction potential is
lower than the other will act as anode and one with greater value will act as cathode. Reverse
reaction will not occur.
29) Give some uses of electrochemical cells?
Ans:Electrochemical cells are used for determining the
 pH of solutions
 solubility product and equilibrium constant
 in potentiometric titrations
10) What is meant by limiting molar conductivity?
Ans.The molar conductivity of a solution at infinite dilution is called limiting molar conductivity.
deposited.
14) Is it safe to stir AgNO3 solution with a copper spoon? Why or why not?
Given:E+/Ag=0.80voltandE2+/Cu=0.34volt
Ans.No, it is not safe to stir AgNO3 solution with copper, because copper ismore reactive than Ag and
can displace Ag from AgNO3 solution.
11) Two half cell reactions of an electro chemical cell are given below:
MnO(aq)+8H+(aq)+5e– Mn2+(aq)+4H2O(l),Eo=+1.51V
Sn2+(aq) Sn4+(aq)+2e–,Eo=+0.15V
Construct the redox reaction from the two half cell reactions and predict if this reaction favours formation
of reactants or products shown in the equation.
Ans.The redox reaction will be
2MnO(aq) + 16H+(aq) + 5Sn2+(aq ) 2Mn2+(aq) + 5Sn4+(aq) + 8H2O(l)
E = E–E = 1.51V – 0.15V = 0.36V ,i.e.,it will be positive.
Hence, reaction will favour formation of products.
Long Answers:
Question 1. Explain construction and working of standard Hydrogen electrode? (b) Write any two
differences between amorphous solids and crystalline solids.
Answer:
Construction: SHE consists of a platinum electrode coated with platinum black. The electrode is dipped in
an acidic solution and pure Hydrogen gas is bubbled through it. The concentration of both the
reduced and oxidized. Forms of Hydrogen is maintained at unity i.e) pressure of gas is 1 bar and
concentration of Hydrogen ions in the solution is 1 molar.
Working – The reaction taking place in SHE is At 298 K , the emf of the cell constructed by taking SHE as
anode and other half-cell as cathode, gives the reduction potential of the other half cell whereas for
a cell constructed by taking SHE as anode gives the oxidation potential of other half cell as
conventionally the electrode potential of SHE is zero.
Question 2.
The molar conductivity of 0.025 mol L-1 methanoic acid is 46.1 S . Calculate its degree of
dissociation and dissociation constant. Given = 349.6 S

and
2. Answer:

= 349.6 + 54.6 =
Now, degree of dissociation:

= 0.114 (approximately)
Thus, dissociation constant:

Question 3.Explain how rusting of iron is envisaged as setting up of an electrochemical cell.

Answer:
In the process of corrosion, due to the presence of air and moisture, oxidation takes place at a particular
spot of an object made of iron. That spot behaves as the anode. The reaction at the anode is given
by,
Electrons released at the anodic spot move through the metallic object and go to another spot of the
object.
There, in the presence of ions, the electrons reduce oxygen. This spot behaves as the cathode. These H+
ions come either from , which are formed due to the dissolution of carbon dioxide from air into
water or from the dissolution of other acidic oxides from the atmosphere in water.
The reaction corresponding at the cathode is given

The overall reaction is:

Also, ferrous ions are further oxidized by atmospheric oxygen to ferric ions. These ferric ions combine

with moisture, present in the surroundings, to form hydrated ferric oxide i.e., rust.
Hence, the rusting of iron is envisaged as the setting up of an electrochemical cell.
Q.4.For the given cells:
Lead storage cell , Mercury cell , Fuel cell and Dry cell
Answer the following:
(i )Which cell is used in hearing aids?
(ii )Which cell was used in Apollo space programme?
(iii)Which cell is used in auto mobiles and inverters?
(iv)Which cell does not have long life?
Ans.(i) Mercury cell (ii) Fuelcell
(iii) Lead storage cell (iv)Drycell
Q.5.A zinc rod is dipped in 0.1 M solution of ZnSO4 . The salt is 95% dissociated at this dilution at 298K.
o
Calculate the electrode potential (EZn2+Zn=–0.76V).
Ans.The electrode reaction written as reduction reaction is
Zn2++2e– Zn(n=2)
Applying Nernst equation , we get
o
EZn2+ Zn= EZn2+ Zn– log

As 0.1M ZnSO4 solution is 95% dissociated , this means that in the solution,

[Zn2+]= ×0.1M=0.095M

EZn2+ Zn=–0.76– log

=–0.76 –0.02955(log1000–log95)
=–0.76–0.02955(3–1.9777)=–0.76–0.03021=–0.7902V
Q.6.A strip of nickel metal is placed in a 1 molar solution of Ni(NO3)2 and a strip of silver metal is placed
in a 1 molar solution of AgNO3 . An electro chemical cell is created when the two solutions are
connected by a salt bridge and the two strips are connected by wires to a voltmeter.
(i )Write the balanced equation for the overall reaction occurring in the cell and calculate the cell
potential.
(ii )Calculate the cell potential , E, at 25°C for the cell if the initial concentration of Ni(NO3)2 is
0.100molar and the initial concentration of AgNO 3 is 1.00 molar.
o o
[ENi2+Ni=–0.25 V; EAg+Ag=0.80 V,log10–1=–1]

Ans.(i) Atanode:Ni Ni2++2e–

Atcathode:[Ag++e– Ag]×2
Cellreaction:Ni+2Ag+ Ni2++2Ag
E =E –E
o o
= EAg+ Ag– ENi2+ Ni
=0.80V–(–0.25V)
E =1.05V
o
(ii)Ecell=Ecell– log

Here,n=2,E =1.05V,[Ni2+]=0.1M,[Ag+]=1.0M

Ecell=1.05V– log

Ecell=1.05V –0.0295log10–1
=1.05+0.0295V=1.0795V

Q.7.(i) Calculate the standard free energy change for the following reaction at 25°C.
Au(s )+Ca2+(1M) Au3+ (1M)+Ca(s )
o o
EAu3+ Au=+1.50V, ECa2+ Ca=–2.87V

Predict whether the reaction will be spontaneous or not at 25oC . Which of the above two half cells
will act as an oxidising agent and which one will be a reucing agent?
(ii )Tarnishd silver contains Ag 2S. Can this tarnish be removed by placing tarnished silver ware in
an aluminium pan containing an inert electrolytic solution such as NaCl? The
Standard electrode potential for half reaction:
Ag2S(s)+2e– 2Ag(s)+S2–is–0.71V
And for Al3++3e– 2Al(s)is –1.66V
Ans.(i)E =EoCa2+ Ca–EoAu3+ Au
=(–2.87V)–(1.50V)
=–4.37V
ΔrG =–nFEocell
=–6×96500×(–4.37V)
=+2530.230kJ/mol
Since Δ rGo is positive, therefore, reactionisn on-spontaneous.
Au3+ /An half cell will be an oxidising agent while Ca2+ /Ca half cell will be ar educing agent. (ii)E for
reaction of tarnished silver ware with aluminium pan is
(–0.71V) –(–1.66V) i.e.,+0.95V
Tarnished silver ware, therefore, can be cleaned by placing it in an aluminium pan as Eocell is positive.
Q.8.A strip of nickel metal is placed in a 1molar solution of Ni(NO3)2 and as trip of silver metal is placed in
a 1molar solution of AgNO3. An electrochemical cell is created when the two solutions are connected
by a salt bridge and the two strips are connected by wires to a voltmeter.
(i )Write the balanced equation for the overall reaction occurring in th e cell and calculate the cell
potential.
(ii )Calculate the cell potential , E, at 25°C for the cell if the initial concentration of Ni(NO 3)2 is
0.100 molar and the initial concentration of AgNO 3 is 1.00 molar.
o o
[ENi2+Ni=–0.25 V; EAg+Ag=0.80 V,log10–1=–1]

Ans.(i) At anode:Ni Ni2++2e–

At cathode:[Ag++e– Ag]×2
Cell reaction:Ni+2Ag+ Ni2++2Ag
E =E –E
o o
= EAg+ Ag– ENi2+ Ni
=0.80V–(–0.25V)
E =1.05V
o
(ii)Ecell=Ecell– log

Here, n=2, E = 1.05V, [Ni2+]=0.1M, [Ag+]=1.0M

Ecell = 1.05V– log

Ecell = 1.05V –0.0295 log10–1

= 1.05+0.0295V =1.0795V

Q.9.(i ) State Kohlrausch law of independent migration of ions. Write an expression for the molar
conductivity of acetic acid at infinite dilution according to Kohlrausch law.
o
(ii Calculate Λm for acetic acid.
o o
Given that Λ m (HCl) = 426Scm2 mol–1 , Λ m(NaCl) = 126 Scm2 mol–1
o
Λ m(CH3 COONa) = 91Scm2 mol–1
Ans.(i)For definition refer to Basic Concepts Point 12.
Expression for the molar conductivity of acetic acid:
o o o
Λ m(CH3 COOH) = Λ CH 3 COO–+Λ H+
o o o
(ii) Λm(CH3COOH) =ΛCH3COO–+ ΛH+
o o o o o o
=ΛCH3COO–+ΛNa++ ΛH++ ΛCl––(ΛNa++ ΛCl–)
=Λ (CH3COONa)+Λ (HCl) –Λ (NaCl)

=(91+426 –126)Scm2mol–1
=391Scm2mol–1
Q.10.( i )State two advantages of H2 —O 2 fuel cell over ordinary cell.
(ii )Silver is electrode posited on a metallic vessel of total surface area 500 cm2 by passing a
curren to 0.5 amp for two hours . Calculate the thickness of silver deposited.
[Given:Density of silver = 10.5gcm -3 , Atomic mass of silver = 108 amu , F =96,500 C mol–1 ]
Ans.(i )Advantages of fuel cell:
( a )It is a pollution-free devices inceno harmful products are formed.
( b )Its efficiency is about 75% which is considerably higher than conventional cells.
( c )It is a continuous source of energy if the supply of gases is maintained . ( AnyTwo)
(ii) m = ZI t= (1 0 6 / 9 6 5 0 ) × 0.5 × 2×3600=4.029g
d= & V
V=4.029g / 10.5g cm-1=0.3837cm3
Let the thickness of silver deposited be x cm.
V = A × x or x = V/ A x= 0 . 3 8 8 7 / 5 0 0 c m 2 = 7.67×10–4cm.
Q.1 1 .(i )A current of 1.50A was passed through an electrolytic cell containing AgNO 3 solution
With inert electrodes. The weight of Ag deposited was 1.50g . How long did the current flow?
(ii)Write the reaction staking place at the anode and cathode in the above cell.
(iii)Give reactions taking place at the two electrodes if these are made up of Ag.
Ans.(i) Ag+ + e– Ag
Quantity of charge required to deposit 108g of silver = 96500 C
Quantity of charge required to deposit 1.50g of silver = 96500/ 108 × 1.50 =1340.28Ct=
Time taken = 1340.28/ 1.50=893.52s
( ii)Inert electrodes
Anode : 2H2O(l) O2(g)+4H+(aq)+4e–

Cathode: Ag+(aq)+e– Ag(s)

( iii)Agelectrodes
Anode:Ag(s) Ag+(aq)+e–
Cathode: Ag+(aq)+e– Ag(s)

Q. 12.Write the Nernst equation and emf of the following cells at 298 K:
( i ) Mg( s ) | Mg2+ (0.001M) || Cu2+ (0.0001M) | Cu(s )
(ii) Fe(s) | Fe2+ (0.001M) || H+ (1M) | H2(g) (1bar) | Pt(s)
( iii)Sn(s )|Sn2+ (0.050M)||H + (0.020M)|H 2 (g )(1bar)|Pt(s )
(iv)Pt(s)|Br– (0.010M)|Br2(l)||H+(0.030)|H2(g)(1bar)|Pt(s)
Given,Eg2+/Mg= –2.37V,Eu2+/Cu= +0.34V,Ee2+/Fe=–0.44V,
En2+/Sn=–0.14V,E2Br2/Br–=+1.08V.
Ans.(i)Cell reaction: Mg+Cu2+ Mg2++Cu;n=2

Nernst equation: Ecell= Eell– log

–
Ecell=0.34–(–2.37) –0.091log– =2.71–0.02955=2.68V

(ii)Cell reaction:Fe+2H+ Fe2++H2; n=2

Nernst equation:
Ecell= Eell– log [Fe2+] / [H+]

=0.44一 x(一3)=0.44+0.0887= 0.529V

(iii)Cell reaction: Sn+2H+ Sn2++H2;n=2

Nernst equation: Ecell= Eell– log

= 0–(–0.14)– log 0.05/(0.02)2

=0.14– log125=0.14– (2.0969)=0.078V

(iv)Cell reaction:2Br–+2H+ Br2+H2;n=2

Nernst equation: Ecell= Eell– log

\Ecell=(0–1.08)– log

=–1.08– log (1.111 x 107)

=–1.08– (7.0457)
=–1.08 –0.208
=–1.288V
Q.13. Predict the products of electrolysis in each of the following
(i )An aqueous solution of AgNO 3 with silver electrodes.
(ii )An aqueous solution of AgNO 3 with platinum electrodes.
(iii )AdilutesolutionofH 2SO4withplatinumelectrodes.
(iv)An aqueous solution of CuCl 2 with platinum electrodes.
Ans.( i )Electrolysis of aqueous solution of AgNO3 with silver electrodes:
AgNO3(s) Ag+(aq)+NO (aq)
H2OH+ +OH–

At cathode : Since, the reduction potential of Ag+ (+0.80V) is greater than that of water, (–0.83V), Ag+
will get reduced preferentially and silver metal will get deposited at the cathode. Will be
deposited as Ag in preference to H+ ions.
Ag+(aq)+e– Ag(s)
Atanode : Following reactions maytake place
H2O(l) O2(g)+2H+(aq)+2e–

NO( aq) NO3 + e –

Ag(s) Ag+(aq)+e–
Among these reactions, the reduction potential of silver is minimum. Therefore, the silver anode will
Itself undergo oxidation to form Ag+ ions which will pass into the solution.
(ii) At cathode : As given inpart (i).
At anode: Since the reduction potential of water is less than that of NO ions, water will get
Preferentially oxidised and oxygen will be evolved.
H2O(l) O2(g)+2H+(aq)+2e–
(iii)At cathode:
2H+(aq) + 2e– H2(g); Eo = 0.00V
2H2O(l) + 2e– H2(g) + 2 OH–(aq);Eo= –0.83V
Since, H + ions possess a higher reduction potential as compared to that of water, H + will get
preferentially reduced and H 2 gas is obtained at the cathode.
2H+(aq)+2e– H2(g)

At anode:H2O(l) O2(g)+2H+(aq)+2e–;Eo=+1.23V

SO–(aq) SO4+2e–;Eo=2.0 V
 Since, the reduction potential of H 2O is lessthan that of SO– ions, water will get preferentially
Oxidised and oxygen will be evolved attheanode.
(iv) At cathode : 2H2O(l)+2e– H2(g)+2OH–(aq);Eo=–0.83V
Cu2+(aq)+2e– Cu(s);Eo=+0.34V
As E ofor Cu2+ is greater than H2 O. So,copper metal is deposited at the anode.

Atanode: H2O(l) O2(g) + 2H+(aq) + 2e–; Eo = + 1.23V

2Cl–(aq) Cl2(g)+2e–(aq);Eo=+1.36V
Since E ovalue of H2O is less than Cl–, water will get preferentially oxidised at anode and O 2 gas will be
evolved.
Q.14.Using the standard electrode potentials given below, predict if there action between the following is
feasible:
( i ) Fe3+ ( aq) and I–( aq) (ii) Ag+ ( aq) and Cu(s )
( iii)Fe3+ ( aq) and Br– ( aq) ( iv) Ag( s ) and Fe3+ ( aq)
( v) Br2 ( aq) and Fe2+( aq)
Given standard electrode potentials:
E/2I2/I–=0.541V,Eu2+/Cu=+0.34V,
E/2Br2/Br– =+1.090V,Eg+/Ag=+0.80V,Ee3+/Fe2+ =+0.77V.
Ans.A reaction is feasible if e.m.f.of the cell reaction is positive.
(i)Fe3+( aq)+I–( aq) Fe2+( aq)+ I2
` Eell= Ee3+ /Fe2+– E 2I 2 /I –
=0.77V–0.54V=0.23V(feasible).

(ii)Ag+(aq)+Cu Ag(s)+ Cu2+(aq)

Eell=Eg+/Ag–Eu2+/Cu=0.80 V–0.34 V=0.46V(feasible).
( iii)Fe3+( aq)+Br–( aq) Fe2+ ( aq)+ Br2
Eell=0.77V–1.09 V=–0.32V(notfeasible).
(iv)Ag(s)+Fe3+(aq) Ag+(aq)+Fe2+(aq),
Eell=0.77V–0.80V=–0.03V(notfeasible).
3. CHEMICAL KINETICS
One mark questions:
1. For the assumed reaction X 2  3Y2  2 XY3 , write the rate of equation in terms of rate of
disappearance of Y2.
2. Why does the rate of a reaction increase with rise in temperature?
Ans. At higher temperatures, larger fraction of colliding particles can cross the energy barrier (i.e., the
activation energy), which leads to faster rate.
3. Define ‘order of a reaction’.
Ans. Order of a reaction may be defined as the sum of the powers of the concentration terms of the reactants
in the rate law expression.
4.
Identify the order of reaction from the following unit for its rate constant: L mol–1s –1
Ans. Second order.
5. For the reaction A  B , the rate of reaction becomes three times when the concentration of A is
increased by nine times. What is the order of reaction?

6. For which type of reactions, order and molecularity have the same value?
Ans. If the reaction is an elementary reaction, order is same as molecularity.
7. Why is the probability of reaction with molecularity higher than three very rare?
Ans. The probability of more than three molecules colliding simultaneously is very small. Hence,
possibility of molecularity being three is very low.
8. For a reaction, A  B  Products,the rate law is Rate = k[A][B] 3/2. Can the reaction be an
elementary reaction? Explain.
Ans. During an elementary reaction, the number of atoms or ions colliding to react is referred to as
molecularity. Had this been an elementary reaction the order of reaction with respect to B would have been
3
1, but in the given rate law it is . This indicates that the reaction is not an elementary reaction.
2
9. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of the
reaction?
Ans.
As t75% = 2t50%
Therefore, it is a first order reaction.
10. What is the effect of adding a catalyst on
(i) Activation energy (Ea), and
(ii) Gibbs energy (DG) of a reaction?
Ans.
(i) Decreases
(ii) No effect
11. Define threshold energy of a reaction.
Ans. Threshold energy is the minimum energy which must be possessed by reacting molecules in order to
undergo effective collision which leads to formation of product molecules.
12. Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain with
the help of one example.
Ans. Thermodynamically the conversion of diamond to graphite is highly feasible but this reaction is very
slow because its activation energy is high.
13. In some cases, it is found that a large number of colliding molecules have energy more than threshold
value, yet the reaction is slow. Why?
Ans. This is due to improper orientation of the colliding molecules at the time of collision.
Two Marks Questions
1. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? What is the unit of rate constant for such a reaction?

2. What do you understand by the rate law and rate constant of a reaction? Identify the order of a
reaction if the units of its rate constant are:
(i) L–1 mol s–1 (ii) L mol–1 s–1.

3. Calculate the overall order of a reaction which has the rate expression,
(i) Rate = k[A] 1/2 [B] 3/2 (ii) Rate = k[A] 3/2 [B] –
4. Write two differences between ‘order of reaction’ and ‘molecularity of reaction’.

5. Why is molecularity applicable only for elementary reactions and order is applicable for elementary
as well as complex reactions?
Ans. A complex reaction proceeds through several elementary reactions. Number of molecules involved in
each elementary reaction may be different, i.e., the molecularity of each step may be different. Therefore,
discussion of molecularity of overall complex reaction is meaningless. On the other hand, order of a
complex reaction is determined by the slowest step in its mechanism and is not meaningless even in the case
of complex reactions
6. For a chemical reaction R → P, the variation in the concentration (R) vs. time (t) plot is given
alongside. (i) Predict the order of the reaction. (ii) What is the slope of the curve?

7. The rate constant for a reaction of zero order in A is 0.0030 mol L–1 s–1. How long will it take for the
initial concentration of A to fall from 0.10 M to 0.075 M?

8. The rate constant for a first order reaction is 60 s –1. How much time will it take to reduce the initial
1
concentration of the reactant to th of its initial value?
10
9. Show that in a first order reaction, time required for completion of 99.9% is 10 times that of half-life
(t1/2) of the reaction

10. After 24 hrs, only 0.125 gm out of the initial quantity of 1 gm of a radioactive isotope remains behind.
What is its half life period?

Three Mark Questions

1. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:

Calculate the rate constant.

(Given: log 4 = 0.6021, log 2 = 0.3010)
2. A first order reaction is 50% complete in 25 minutes. Calculate the time for 80% completion of the
reaction.

3. The following data were obtained during the first order thermal decomposition of N2O5(g) at a
constant volume:

4. The rate constant for the first order decomposition of H2O2 is given by the following equation:
1.0 104
log k  14.2  K
T
Calculate Ea for this reaction and rate constant k if its half-life period be 200 minutes.
(Given: R = 8.314 JK–1 mol–1)
5. The rate constant of a first order reaction increases from 2 × 10–2 to 4 × 10–2 when the temperature
changes from 300 K to 310 K. Calculate the energy of activation (Ea).
(log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)

6. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K. Calculate
the activation energy of the reaction.
(Given: log 2 = 0.3010, log 4 = 0.6021, R = 8.314 J K–1 mol–1)

7. For a certain chemical reaction variation in the concentration In [R] vs. time plot is given alongside
For this reaction
(i) what is the order of the reaction?
(ii) what are the units of rate constant k?
(iii) give the relationship between k and t1/2 (half-life period).
(iv) what is the slope of the curve?
(v) draw the plot log [R]0 /[R] vs time t(s).
 4. d and f- BLOCK ELEMENTS
VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)
1. Explain CuSO4 .5H2 O is blue while CuSO4 is colourless?
Ans. Because water molecules act as ligands and results in crystal field splitting of d-orbitals of
Cu2+ ion.
2. Which element among 3d series exhibit highest oxidation state ?
Ans. Mn
3. In 3d series (Sc to Zn), the enthalpy of atomization of Zn is low. Why ?
Ans. Due to absence of unpaired electrons.
4. Which element among 3d series exhibit only one oxidation state ?
Ans. Sc
5. Why is the 3rd ionization energy of Mn (Z = 25) is unexpectedly high ?
Ans. Due to half-filled electronic configuration.
6. Define alloy.
Ans. Alloys are homogeneous solid solutions of two or more metals.
7. Transition metals show zero oxidation state with ligands like CO. Explain.
Ans. Co form synergic bonding with metal ion.
8. Why can’t HCl acid be used to acidify KMnO4 solution ?
Ans. Because KMnO4 oxidize HCl into Cl2.
9. Name one ore of Mn and Cr.
Ans. Mn : MnO2 Cr : FeCr2O4
10. Why Mn2+ compounds are more stable than Fe2+ compounds towards oxidation to
their + 3 state ?
Ans. Mn+2 has half-filled electronic configuration.
11. Why do transition metal (elements) show variable oxidation states ?
Ans. Due to presence of vacant d-orbitals.
12. Write any uses of pyrophoric alloy.
Ans. Making bullets, shells and ligher flints.
13. Which is more basic – La(OH)3 or Lu(OH)3 Why ?
Ans. La(OH)3 , due to lanthanide contraction, lower size, more covalent character, least basic.
14. Find out number of Cr – O – Cr bond/bonds in Cr2 O7 2− ion.
Ans. 1
15. What is effect of increasing pH on K2 Cr2 O7 solution ?
Ans. It changes into K2CrO4 solution/orange colour change into yellow colour.
16. Why is Ce4+ in aqueous solution a good oxidizing agent ?
Ans. Because Ce4+ is most stable in Ce+3 state in aqueous solution.
17. Why do Zr and Hf exhibit similar properties ?
Ans. Due to lanthanide contraction.
18. What is lanthanoid contraction ?
Ans. The regular slow decrease in the atomic or ionic radii of lanthanoids with increasing
atomic number.
19. Why is Cu (Z = 29) considered a transition metal ?
Ans. Due to its partially filled d-orbital in Cu2+ state.
20. Arrange the given in increasing order of acidic character : CrO3 , CrO, Cr2O3 .
Ans. CrO < Cr2O3 < CrO3.
21. Why KMnO4 or MnO4 − ion is coloured ?
Ans. Due to charge transfer complex formation.
SHORT ANSWER-I TYPE QUESTIONS (2 Marks)
1. Chromium is typical hard metal while mercury is a liquid. Explain why?
Ans. Cr has five unpaired d-electrons. Hence metallic bonds are strong. In Hg, there is absence
of unpaired electrons and size is larger.
2. Why KMnO4 is used in cleaning surgical instruments in hospitals?
Ans. This is because KMnO4 has a germicidal action.
3. Most of the transition metals do not displace hydrogen from dilute acids, why?
Ans. Due to their –ve reduction potential.
4. Explain why Cu+ is not stable in aqueous solution ?
Ans. Due to less –ve ∆hydH of Cu+ /it cannot compensate 2nd ionization potential of Cu
5. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Oxygen and fluoride have small size and high electronegativity. They can oxidise the metal.

6. Write electronic configuration of Cu+2 and Co+2.

Ans. Cu+2 = [Ar] 3d9 4s0 Co+2 = [Ar] 3d7
7. Balance the following equations :
(a) MnO4 − + Fe2+ + H+ →
(b) Cr2 O7 2− + Sn2+ + H+ →
Ans. (a) MnO4 − + Fe2+ + H+ → Mn+2 + Fe+3
(b) Cr2 O7 2− + Sn2+ + H+ → Cr+3 + Sn+4
8. Briefly explain why electronic configuration of lanthanoids are not known with certainty ?
Ans. 4f/5d subshells are very close in energy. +ve electrons can jump from 4f to 5d or vice-versa.
9. Why Zn, Cd, Hg are soft and have low melting point?
Ans. Due to weak interatomic attraction/absence of unpaired electrons.
10. What is the effect of pH on the solution of K2 Cr2 O4 solution ?
Ans. K2 Cr2 O4 solution changes into K2 Cr2 O7 /yellow colour changes into orange colour.
11. Which of the following is/are transition element and why ? Zn, Cd, Ag, Fe, Ni
Ans. Fe, Ni, Ag
12. What are interstitial compounds ? Give example.
Ans. When small atoms like C, H, B and N occupy interstitial site in their lattice. Example, TiC, Fe3 H,
13. Why are Zn, Cd, Hg volatile metals ? Explain.
Ans. Due to weak interatomic attraction/low boiling point.
14. Explain ‘Misch metal’ and write its use.
Ans. It is an alloy of 95% lanthanoid and 5% iron and traces of S, C, Ca and Al. Used in lighter
flint, bullet tips etc.
15. The following two reactions of HNO3 with Zn are given :
(a) Zn + conc. HNO3 → Zn(NO3 )2 + X + H2 O
(b) Zn + dil. HNO3 → Zn(NO3 )2 + Y + H2 O Identify X and Y.
Ans. X = NO2 Y = N2O
16. Complete the equations:
∆
(a) KMnO4 →
(b) 3K2 MnO4 →
Ans. (a) 2KMnO4 → K2MnO4 + MnO2 + O2
(b) 3K2MnO4 → MnO4 − + MnO2 + 2H2O
17. Out of Fe and Cu, which one would exhibit higher melting point ?
Ans. Fe, due to large number of unpaired d-electrons/more interatomic attraction.
18. Sc, the first member of first transition series does not exhibit variable oxidation state. Why?
Ans. Due to noble gas electronic configuration in + 3 oxidation state no other oxidation state
is stable.
SHORT ANSWER-II TYPE QUESTIONS (3 Marks)
1. (a) Deduce the number of 3d electrons in the following ions : Cu2+, Sc+3
(b) Why do transition metals form alloy?
(c) Why Zn+2 salts are white?
Ans. (a) Cu+2: 9 electrons Sc+3: 0 electron
(b) Transition metals have similar atomic radii.
(c) Absence of unpaired electron.

3. Describe the oxidizing action of K2Cr2O7 with the following. Write ionic equations for its
reaction (acidic medium) with :(a) I− (b) Iron(II) (c) H2S

4. Write any four differences between lanthanoids and actinoids.

Ans.
Lanthanoids Actinoids
(a) They are generally non- They are radioactive.
radioactive.
(b) Most of their ions are colourless. Coloured ions
(c) Show + 3, + 4 and + 2 oxidation Beside + 3, show higher oxidation state.
state.
(d) Less tendency of complex Higher tendency
formation.
5. (a) Why is separation of lanthanoid elements difficult?
(b) Transition metal exhibit higher enthalpies of atomization. Explain why?
(c) Why have the transition metal high enthalpy of hydration?
Ans. (a) Due to lanthanide contraction, the size of these elements is nearly same.
(b) Transition metal contain large number of unpaired electrons, and they have strong
interatomic attractions.
(c) Due to their small size and large nuclear charge.
6. (a) Use Hund’s rule to derive the electronic configuration of Ce+3 ions and calculate its
magnitude moment.
(b) Is lanthanum a f-block element ?
Ans. (a) 58Ce = [Xe] 4f 1 5d1 6s2 Ce+3 = 4f1 one unpaired electron
= √ ( + 2) = .73 BM
(b) No, it is a d-block element.
7. Account for the following :
(a) Silver chloride dissolves in excess of NH3.
(b) Cuprous chloride is diamagnetic while cupric chloride is paramagnetic.
(c) In CrO42− ion, all the Cr – O bond length are equal.
Ans. (a) AgCl forms a soluble complex with NH3 . AgCl + 2NH3 → [Ag(NH3)2 ]Cl
(b) Cu+ : 3d10 4s0 – All electrons are paired.
Cu+2 : 3d9 – Here, one unpaired electron is present.
(c) Due to resonance.
8. The Eº values in respect of electrodes of Cr, Mn and iron are :
Cr+3/Cr+2 = − 0.4 V Mn+3/Mn+2 = + 1.5 V Fe+3/Fe+2 = + 0.8 V
Compare the feasibilities of further oxidation of these ions.
Ans. Cr+3 is more stable than Cr2+.
Mn+2 is more stable than Mn+3.
Fe3+ is more stable than Fe2+.
Order of feasibility of +2 oxidation state is: Mn+2 > Fe+2 > Cr+2
9. Write any three properties of interstitial compounds.
Ans. (a) They are chemically inert.
(b) They retain metallic conductivity.
(c) They have high melting point than their pure metals.
(d) These are harder and more corrosion resistant.
10. Account for the following :
(a) All Scandium salts are white.
(b) The Ist ionization energy of the 5d series are higher than 3d and 4d transition elements in
respective groups.
(c) Ce+3 can be easily oxidized to Ce+4.
Ans. (a) Sc has only +3 oxidation state, there is no unpaired electron.
(b) Due to lanthanide contraction, effective nuclear charge increase.
(c) Due to gain noble gas electron configuration.
11. A green chromium compound (A) on fusion with alkali gives a yellow compound (B) which
On acidification gives a orange coloured compound (C). Identify A, B, C. Write equations
for reactions.
12. When an oxide of Mn (A) is fused with KOH in the presence of an oxidizing agent and dissolved
in water, it gives a dark solution of compound (B). Compound (B) disproportionate in neutral
or acidic solution to give purple compound (C). Identify A, B, C.
Ans. A : MnO2 B : K2 MnO4 C : KMnO4
13. A violet compound of manganes (A) decomposes on heating to liberate oxygen and compounds
(B) and (C) of manganese are formed. Compound (C) reacts with KOH in the presence of KNO3 to
give compound (B). On heating compound (C) with conc. H2SO4 and NaCl, Cl2 gas is liberated
and compound (D) of manganese is formed. Identify A, B, C, D along with reactions involved.

14. (a) What is meant by disproportionation of an oxidation state? Give one example.
(b) Draw the structures of Cr2O7 2− , CrO4 −2, MnO4 −.
(c) What is the effect of lanthoids contraction beyond lanthanoid?

Ans. (a) When any atom or ion undergo oxidation and reduction simultaneously it is
called disproportionation.
2Cu+ → Cu+2 + Cu

(c) Size of respective 4d and 5d series elements becomes comparable from fourth group
onwards (e.g., Zr and Hf).
15.
16.

17.
 5. COORDINATION COMPOUNDS
One mark questions:
1. What is the oxidation state of Ni in [Ni(CO)4]?
Ans. Zero
2. One mole of CrCl3. 6H2O reacts with excess of AgNO3 to yield 2 mole of AgCl
Write formula of complex. Write IUPAC name also.
Ans. [Cr(H2O)5Cl]Cl2 . H2O, Penta aqua chloride chromium (III) chlorido
3. Name the hexadentate ligand used for treatment of lead poisoning.
Ans. EDTA4– (ethylene diamine tetra acetate)
4. What is hybridization of [CoF6]3– ? [Co = 27] . Give its shape and magnetic properties.
Ans. sp3 d2, octahedral, paramagnetic. It is outer orbital complex.
5. Out of [Fe(CO)5], [Fe(C2O4)3] 3– , [Fe(H2O)6] 3+,[Fe(CN)6] 3– which is most stable?
Ans. [Fe(CO)5] is most stable because CO is strongest ligand.
6. What is crystal field splitting energy?
Ans : The energy difference between the two sets of d-orbitals is called crystal field splitting energy
denoted by ▲0
7. Why dx2 –y2 , dz2 have higher energy than dxy, dyz, dzx orbitals in octahedral crystal field?
Ans. The orbitals dx2 y2 , dz2 lying in the direction of ligands, will experience greater repulsion and their
energies will be raised relative to their positions in symmetrical field as compared to orbitals dxy, dyz, dzx
lying in between the axis away from the approach of ligand.

8. What is spectrochemical series?

Ans. The series in which ligands are arranged in increasing order of magnitude of crystal field splitting
energy (Δ0) is called spectrochemical series.
9. The correct IUPAC name of [Pt(NH3)2 Cl2] is ____________( Diammine dichlorido platinum (II))
10. The donor atoms in ethylene diamine tetra acetate ion is _____________ (two N and four O)
11. The shape and magnetic behaviour complex ion [Cu(NH3)4] +2 is____________( square planar and
paramagnetic)
12. The hybrid state of Co in high spin complex, K3[CoF6] is __________(sp3 d2 )
13. The primary and secondary valency of copper in the complex [Cu(NH3)4]SO4 are _______ (2, 4)
14. The hybridization state of the Cu in the compound [Cu(NH3)4]SO4 is _________(dsp2 )
15. What IUPAC names of following complexes?
1. [Co(NH3)6]3+ 2. [Fe (C2O4)3]3-
3. [Ni (CN)4]2- 4. [Pt(NH3)4 Cl2] 2+
2-
5. [NiCl4 ] 6. [Co(NH3)5 ONO]2+
7. [Co (NH3)5Cl]Cl2 8. [Cr (CN) (H2O)5]2+
9. [Co (NO2)6]3- 10. [Co (en)3 ]Cl3
Ans1. Hexamminecobalt (III)ion
Ans 2. Trioxalatoferrate (III) ion
Ans 3. Tetracyanonickelate (II) ion
Ans 4. Tetraamminedichloridoplatinum (IV) ion
 Ans 5.Tetrachloridonickelate (II) ion
Ans 6.Pentamminenitrito –O-cobalt (III) ion
Ans 7.Pentamminechlorido cobalt (III) Chloride
Ans 8.Pentaquacyanido chromium (III) ion
Ans 9. Hexanitrito –N-cobaltate (III) ion
Ans 10.Tris (ethylenediamine) Cobalt (III) Chloride
16. Write formula for the following compounds.
1. Hexammineplatinum (VI) Chloride
2. Potassium hexacyanoferrate (III)
3. diamminedichloridoplatinum (III) ion
4. Tetramminedichloridocobalt (III) ion
5. Amine chlorobis (ethylenediamine) cobalt (III) ion.
6. Hexaamminechromium (III) hexacyanocobaltate (III)
7. Pentramminenitro –N- Cobalt (III) Chloride.
8. Pentramminebromidoocobalt (III) sulphate
9. triamminediaquachlorocobalt (III) Chloride
10. Tetramminedichloridooplatinum (IV) Bromide
Ans 1.  Pt ( NH3 )6  Cl6
Ans 2. K3  Fe(CN )6 
Ans 3.  Pt (Cl2 )( NH3 )2 


Ans 4. Co( NH3 )4 Cl2 



Ans 5. CoC1(en)2 ( NH3 )

2

Ans 6. Cr ( NH3 )6 CO(CN )6 

Ans 7. Co( NH3 )5 NO2  Cl2
Ans 8. Co( NH3 )5 Br  SO4
Ans 9. Co( NH3 )3 ( H2O)2 Cl  Cl2
Ans 10.  Pt Cl2 ( NH3 )4  Br2

TWO MARKS QUESTION

1. Explain that the complex [Co (NH3)6 ]3+ is diamagnetic on the basis of valence bond theory.
Ans. In [Co (NH3)6 ]3+ as all the electrons are paired so it is diamagnetic

2. What are homoleptic and heteroleptic complex explain with suitable example?
Ans. Complexes in which the Central metal ion is bonded to only one kind of donor atom or group.
Example- [Co(NH3)6]3+ only ammonia is the ligand.
Complexes in which the Central metal ion is bound to more than one kind of donor group.
Example- [Co(NH3)4Cl2]+
3. [Ni(CN)4]2- is square planar whereas [NiCl4] 2- is tetrahedral . Explain.
Ans. In [Ni(CN)4]2- hybridization is dsp2 so square planar geometry

In [NiCl4]2- hybridisation is sp3 so tetrahedral geometryOrbitals of Ni2+ion

4. Write the postulates of crystal field theory

Ans According to crystal field theory
(a). The metal ligand bond is ionic.
(b). Ligands are point charges in case of anions or dipoles in case of neutral molecules
(c). When the asymmetrical negative field of ligands surrounds the metal atom or ion, the degeneracy of its
d- orbitals is lifted and they split into two sets.
(d). The pattern of splitting depends on the nature of crystal field.
(e). In general ligands can be arranged in a series in the order of increasing field strength
called spectrochemical series-
I − < Br− < SCN − < Cl − < S 2 − < F− < OH − < C 2 O 4 2− < H 2O < NCS− < EDTA4− < NH3 <en< CN− < CO
5. Why are complexes coloured? When is a coordination compound colourless?
Ans. The colour of complexes is due to d – d transitions of unpaired electron in d-orbitals
The complexes will be colourless if the configuration of metal ion or atom is d10 or d0
6. What is meant by unidentate, bidentate and ambidentate ligands? Give two examples for each.
Ans. A molecule or an ion which has only one donor atom to form one coordinate bond with the central
metal atom is called unidentate ligand, e.g,, Cl-and NH3.
A molecule or ion which contains two donor atoms and hence forms two coordinate bonds with the central
metal atom is called a bidentate

A molecule or an ion which contains two donor atoms but only one of them forms a coordinate bond at a
time with the central metal atom is called
7. Draw figure to show the splitting of d orbitals in an octahedral crystal field.

THREE MARKS QUESTION

1. What is crystal field splitting energy? How does the magnitude of Δo decide the actual configuration
of d orbitals in a coordination entity?
Ans-
When the ligands approach a transition metal ion, the d-orbitals split into two sets, one with lower energy
and the other with higher energy. The difference of energy between the two sets of orbitals is called crystal
field splitting energy (Δ0 for octahedral field). If Δ0 < P (pairing energy), the fourth electron enters one of
the e°g, orbitals giving the configuration t3 2ge1g, thus forming high spin complexes. Such ligands for which
Δ0 < P are called weak field ligands. If Δ0 > P, the fourth electron pairs up in one of the t2g orbitals giving
the configuration t42ge1g thereby forming low spin complexes. Such ligands for which Δ0> P are called
strong field ligands.
2. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why?
Ans:

3. A solution of [Ni(H2O)6] 2+ is green but a solution of [Ni(CN)4] 2– is colourless. Explain.

Ans- In [Ni(H2O)6] 2+, Ni is in + 2 oxidation state and having 3d8 electronic configuration, in which there
are two unpaired electrons which do not pair in the presence of the weak H2O ligand. Hence, it is coloured.
The d-d transition absorbs red light and the complementary light emitted is green. In [Ni(CN)4] 2- Ni is also
in + 2 oxidation state and having 3d8 electronic configuration. But in presence of strong ligand CN– the two
unpaired electrons in the 3d orbitals pair up. Thus, there is no unpaired electron present. Hence, it is
colourless.
4. [Fe(CN)6] 4– and [Fe(H2O)6] 2+ are of different colours in dilute solutions. Why?
Ans-In both the complexes, Fe is in + 2 oxidation state with d6 configuration. This means that it has four
unpaired electrons. Both CN– ion and H2O molecules which act as ligands occupy different relative
positions in the spectrochemical series. They differ in crystal field splitting energy (∆0). Quite obviously,
they absorb radiations corresponding to different wavelengths/frequencies from the visible region of light.
(VIBGYOR) and the transmitted colours are also different. This means that the complexes have different
colours in solutions.
5. Explain the following:
(i) The coordination-complexes are known for transition elements only.
(ii) Nickel (II) does not form low spin octahedral complexes.
(iii) [Fe(CN)6] 4- and [Fe(H20)6] 2 + are of different colours in dilute solutions.
Answer:
(i) Transition metals have vacant d-orbitals which accept lone pair from ligands to form a bond and give
pair of electron to molecular orbital of ligand forming d π -p π -bond.
(ii) 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.
(iii) They absorb different wavelengths from visible light, undergo d-d transitions and radiate
complementary colour. CN- is stronger ligand than H2O.
6. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the
following complexes:
(i) K3[Co(C2O4)3] (ii) (NH4)2[CoF4] (iii) cis-[Cr(en)2Cl2]Cl
Ans: (i) K3[Co(C2O4)3] =>[Co(C204)3] 3- . x + 3 (-2) = -3 . Oxidation state, x=+3
Coordination number is also 6 as C204 2- is bidentate.
Co+3 is a d6 case in which all electrons are paired
(ii) (NH4)2[COF4] = (NH4)2 2+[COF4] 2-
x - 4 = -2.
Oxidation state, x = + 2
Coordination number = 4.
Co2+ is a d5 case, paramagnetic
(iii) cis – [Cr(en)2Cl2] + Cl–
x + 0-2 = +1
Oxidation state, x = +3
Coordination number is 6 as ‘en’ is bidentate. Cr3+ is a d3 case, paramagnetic.
7. Discuss briefly giving an example in each case the role of coordination compounds in:
(i) biological systems
(ii) medicinal chemistry
(iii) analytical chemistry
(iv) extraction/metallurgy of metals
Ans:
(i) 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 1 of
blood which acts as oxygen carrier is a coordination compound of iron. Vitamin B12, cyanocobalamine, the
anti- pernicious anaemia factor, is a coordination compound of cobalt. Among the other compounds of
biological importance with coordinated metal ions are the enzymes like, carboxypeptidase A and carbonic
anhydrase (catalysts of biological systems).
(ii) There is growing Interest in the use of chelate therapy in medicinal chemistry. An example is the
treatment of problems caused by the presence of metals in toxic proportions in plant/animal systems. Thus,
excess of copper and iron are removed by the chelating ligands D-penicillamine and desferrioxime B via the
formation of coordination compounds.
EDTA is used in the treatment of lead poisoning. Some coordination compounds of platinum effectively
inhibit the growth of tumours. Examples are: ds-platin and related compounds.
(iii) Coordination compounds find use in many qualitative and quantitative chemical analysis. The familiar
colour reactions given by metal ions with a number of ligands (especially chelating ligands), as a result of
formation of coordination entities, form the basis for their detection and estimation by classical and
instrumental methods of analysis. Examples of such reagents include EDTA, DMG (dimethylglyoxime), a-
nitroso- β-naphthol, cupron, etc.
(iv) 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 and water to form the
 coordination entity [Au(CN)2]- in aqueous solution. Gold can be separated in metallic form from this
solution by the addition of zinc.
8. Compare the following complexes with respect to structural shapes of units, magnetic behaviour and
hybrid orbitals involved in units:
(i) [Ni(CN)4] 2- (ii) [NiCl4] 2- (iii) [CoF6] 3- [At. nos. : Ni = 28; Co = 27]
Answer (i)

9. Compare the following complexes with respect to their molecular shape and magnetic behaviour :
(i) [Cr(NH3)6] 3+ (ii) [Fe(CN)6] 4- (iii) [NiCl4] 2- (At. No. : Cr = 24, Fe = 26, Ni = 28)

Ans:
 6. HALOALKANES AND HALOARENES

Very short answer questions (1mark)

1. Write the IUPAC name of the following compound:

Ans. 2, 5-Dichlorotoluene/1,4-Dichloro-3-methylbenzene.
2. Draw the structure of the compound, 4-tert-butyl-3-iodoheptane.

3.

4. which is an example of a benzylic halide?

5. Wurtz reaction fails in case of tert-alkyl halides. Why?
Ans. This is because tert-alkyl halides prefer to undergo dehydrohalogenation in the presence of sodium
metal instead of undergoing Wurtz reaction.

6. What happens when bromine attacks CH2=CH—CH2—C  CH?

Ans. The reddish brown colour of bromine is discharged.
7. Identify the chiral molecule in the following pair:

8. Out of chlorobenzene and cyclohexyl chloride, which one is more reactive towards nucleophilic
substitution reaction and why?
Ans.
Cyclohexyl chloride is more reactive than chlorobenzene towards nucleophilic substitution reactions. Due
to resonance the C–Cl bond in chlorobenzene acquires partial double bond character which makes the
substitution of chlorine more difficult in chlorobenzene than in cyclohexyl chloride where the C–Cl bond
has pure single bond character.
9. Why is t-butyl bromide more reactive towards SN1 reaction as compared to n-butyl bromide?
Ans.
Due to higher stability of tertiary carbocation than primary carbocation.
10. Give one chemical test to distinguish between C2H5Br and C6H5Br.
Ans.
Hydrolysis of C2H5Br with aqueous KOH followed by acidification with dil. HNO3 and subsequent
treatment with AgNO3 gives light yellow ppt. of AgBr whereas C6H5Br does not give this test.
11. Give reason: Chloroform is stored in closed dark coloured bottles completely filled so that air is kept
out.
Ans.
This is because chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas
phosgene.
 Short answer questions (2M)
1. Draw the structure of major monohalo product in each of the following reactions:

2. Which one of the following compounds is more easily hydrolysed by KOH and why?
CH3CHClCH2CH3 or CH3CH2CH2Cl
Ans.

Due to +I effect of alkyl groups, the 2° carbonium ion CH 3  C H   CH 2  CH 3 derived from sec. butyl

chloride is more stable than the 1° carbonium ion CH 3  CH 2  C H 2 derived from n-propyl chloride.
Therefore sec. butyl chloride gets hydrolysed more easily than n-propyl chloride under SN1 conditions.
3. How the following conversion can be carried out? Ethanol to But-2-yne
Ans.

4. Give reasons for the following:

(i) Chloroethane is insoluble in water.
(ii) Thionyl chloride method is preferred for preparing alkyl chlorides from alcohols.
Ans.
(i) Chloroethane is unable to form hydrogen bonds with water. Hence, it is insoluble in water.
(ii) The byproducts of the reaction, i.e., SO2 and HCl being gases escape into the atmosphere leaving
behind alkyl
chlorides in almost pure state.
5. Differentiate between retention and inversion.
Ans.
If the relative configuration of the atoms/groups around a chiral centre in an optically active molecule
remains the same before and after the reaction, the reaction is said to proceed with retention of
configuration. On the other hand, if the relative configuration of the atoms/groups around a stereocentre in
the product is opposite to that in the reactant, the reaction is said to proceed with inversion of configuration.
For example,
6. Give reasons:
(i) C—Cl bond length in chlorobenzene is shorter than C—Cl bond length in CH3—Cl.
(ii) SN1 reactions are accompanied by racemisation in optically active alkyl halides.
Ans.
(i) In chlorobenzene, C—Cl bond acquires partial double bond character while in methyl chloride, C—Cl
bond has pure single bond character. As a result C—Cl bond in chlorobenzene is shorter than methyl
chloride.

(ii) Carbocations are intermediate in SN1 reactions. Carbocations being sp 2 hybridised are planar species,
therefore, attack of nucleophile on it can occur from both front and rear with almost equal ease giving a
racemic mixture.
7. (i) Which alkyl halide from the following pair is chiral and undergoes faster SN2 reaction?

(ii) Out of SN1 and SN2, which reaction occurs with

(a) Inversion of configuration (b) Racemisation

Ans: 2-bromobutane is a chiral molecule.

primary halides undergo faster SN2 reactions than secondary halides

due to less steric hinderance.

(ii) (a) SN2 reaction occurs with inversion of configuration.

(b) SN1 reaction occurs with racemisation.

8. Predict the order of reactivity of the following compounds in SN1 and SN2 reactions: C6H5CH2Br,
C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br
Ans.
C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br (SN1). C6H5C(CH3)(C6H5)Br
< C6H5CH(C6H5)Br < C6H5CH(CH3)Br < C6H5CH2Br (SN2).
Of the two secondary bromides, the carbocation intermediate obtained from C6H5CH(C6H5)Br is more
stable than that obtained from C6H5CH(CH3)Br because it is stabilised by two phenyl groups due to
resonance. Hence, the former bromide is more reactive than the latter in SN1 reaction. Phenyl group is
bulkier than a methyl group. Thus, C6H5CH(C6H5)Br is less reactive than C6H5CH(CH3)Br in SN2 reactions.
9. Give reasons for the following:
 (i) p-nitrochlorobenzene undergoes nucleophilic substitution faster than chlorobenzene. Explain
giving the resonating structures as well.
(ii) Iodoform is obtained by reaction of acetone with hypoiodite ion but not iodide ion.
Ans.
(i) In p-nitrochlorobenzene a carbanion intermediate is formed. This is stabilised by resonance as shown
below.

The –I effect of nitro group further stabilises the intermediate. Hence, p-nitrochlorobenzene reacts faster
than chlorobenzene.
(ii) Hypoiodite ion can act as an oxidising agent while iodide ion does not.
10. How will you distinguish between the following pairs of compounds:
(i) Chloroform and carbon tetrachloride. (ii) Benzyl chloride and chlorobenzene.
Ans.
(i) On heating chloroform and carbon tetrachloride with aniline and ethanolic potassium hydroxide
separately chloroform forms pungent smelling isocyanide but carbon tetrachloride does not form this
compound.

(ii) On adding sodium hydroxide and silver nitrate to both the compounds benzyl chloride forms white
precipitate but chlorobenzene does not form white precipitate.

11. Give the structural formula and IUPAC name of the following compounds:
(i) BHC (ii) DDT

Short answer questions (3M)

1. Draw the structures of the major monohalo product for each of the following reactions:
2. Write the major product(s) in the following reactions:

3. How do you convert the following:

(i) Prop-1-ene to 1-fluoropropane
(ii) Chlorobenzene to 2-chlorotoluene
(iii) Ethanol to propanenitrile
4. Write IUPAC names of the following:

Ans.
(i) 4-Bromopent-2-ene
(ii) 3-Bromo-2-methylbut-1-ene
(iii) 4-Bromo-3-methylpent-2-ene

5. (i) Explain why the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(ii) An optically active compound having molecular formula C7H15Br reacts with aqueous KOH to
give a racemic mixture of products. Write the mechanism involved in this reaction.
Ans. (i) In chlorobenzene, chlorine is attached to sp2 carbon where bond length of C – Cl is less where as in
cyclohexyl chloride , chlorine is attached to sp3 carbon where bond length C – Cl is more and dipole
moment depends on bond length of two atoms
(ii) Since the optically active compound, C7H15Br reacts with KOH forms a racemic mixture, therefore
it must be tertiary alkyl halide and the reaction will follow SN1 mechanism.

6. Compound ‘A’ with 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.
(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?
7. Predict the major product formed when HCl is added to isobutylene. Explain the mechanism
involved.

8. Consider the three types of replacement of group X by group Y as shown here.

This can result in giving compound (A) or (B) or both. What is the process called if (i) (A) is the only
compound obtained? (ii) (B) is the only compound obtained? (iii) (A) and (B) are formed in equal
proportions?
Ans.
(i) Retention
(ii) Inversion
(iii) Racemisation
9. 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.
 Ans.
(i) 1-Bromopentane, it is primary halide therefore undergoes SN2 reaction faster.
(ii) 2-Bromopentane as carbon number two is symmetric carbon.
(iii) 2-Bromo-2-methyl butane, because tertiary alkyl halides on dehydrogenation form most substituted
alkene which is more stable.
10. Give reasons for the following:
(i) Benzyl chloride is highly reactive towards the SN1 reaction.
(ii) 2-bromobutane is optically active but 1-bromobutane is optically inactive.
(iii) Electrophilic reactions in haloarenes occur slowly.
Ans.
(i) Benzyl chloride is highly reactive towards the SN1 reaction because the intermediate benzyl carbocation
formed in slowest step is stabilized through resonance.

(ii) 2-bromobutane is a chiral molecule as it contains an asymmetric carbon atom therefore, it is optically
active whereas 1-bromobutane is an achiral molecule as it does not contain asymmetric carbon atom
therefore it is optically inactive.

(iii) Halogen in haloarenes withdraws electrons through –I effect and release electrons through +R effect.
The inductive effect is stronger than resonance effect and causes net electron withdrawal. As a result, the
electrophilic substitution reactions in haloarenes occur slowly.

11. Give reasons for the following observations:

(i) p-dichlorobenzene has higher melting point than those of o– and m– isomers.
(ii) Haloarenes are less reactive than haloalkanes towards nucleophilic substitution reaction.
(iii) The treatment of alkyl chloride with aqueous KOH leads to the formation of alcohol but in the
presence of alcoholic KOH, alkene is the major product.
Ans.

(i) It is due to the greater symmetry of para-isomer that fits in the crystal better as compared to ortho and
meta-isomers.
(ii) As C–X bond in aryl halide acquires a partial double bond character due to resonance while the C–X
bond in alkyl halide is a pure single bond.
(iii) Alkoxide ion present in alcoholic KOH, is not only a strong nucleophile but also a strong base so
preferentially eliminate a molecule of HCl from alkyl halide to form alkenes.
12.(i) Why are alkyl halides insoluble in water? (ii) Why is butan-1-ol optically inactive but butan-2-ol is
optically active? (iii) Although chlorine is an electron withdrawing group, yet it is ortho, para
directing in electrophilic aromatic substitution reactions. Why?
 Ans.
(i) This is due to the inability of alkyl halide molecule to form intermolecular hydrogen bonds with water
molecules.

due to presence of a chiral carbon butan-2-ol is an optically active

compound.

(iii) As the weaker resonance (+ R) effect of Cl which stabilise the carbocation formed tends to oppose the
stronger inductive (– I) effect of Cl which destabilise the carbocation at ortho and para positions and makes
deactivation less for ortho and para position.

13.Give reasons:
(i) n-Butyl bromide has higher boiling point than t-butyl bromide.
(ii) Racemic mixture is optically inactive.
(iii) The presence of nitro group (—NO2) at o/p positions increases the reactivity of haloarenes
towards nucleophilic substitution reactions.
Ans.
(i) n-Butyl bromide being a straight chain alkyl halide has larger surface area than tert.butyl bromide.
Larger the surface area, larger the magnitude of the van der Waal’s forces and hence higher is the boiling
point.
(ii) A racemic mixture contains the two enantiomers d and l in equal proportions. As the rotation due to one
enantiomer is cancelled by equal and opposite rotation of another enantiomer, therefore, it is optically
inactive.
(iii) The presence of NO2 group at o/p position in haloarenes helps in the stabilisation of resulting carbanion
by –R and –I effects and hence increases the reactivity of haloarenes towards nucleophilic substitution
reactions.

7. Alcohols, Phenols and Ethers

Alcohols
One mark/Two marks:
1) Why propanol has higher boiling point than that of the hydrocarbon, butane?
Butane molecules are held together by weak van der Waals forces of attraction whereas propanol
molecules are held together by strong intermolecular hydrogen bonding
2) Why ethanol has higher boiling point in comparison to methoxymethane?
Ethanol has intermolecular H-bonding and has higher boiling point whereas methoxymethane does not.
3) Why alcohols are more soluble in water than hydrocarbons of comparable molecular masses? Alcohols
can form H-bonds with water so soluble whereas hydrocarbons does not form H-bonds with water and
are insoluble.
4) Arrange the following sets of compounds in order of their increasing boiling points.
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol
Ans: Methanol, ethanol, propan-1-ol, butan-2-ol, butnal-1-ol, pentan-1-ol
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane
Ans: n-Butane, ethoxyethane, pentanal and pentan-1-ol
5) Name the reagents used in the following reactions:
(i) oxidation of primary alcohol to carboxylic acid
Ans: K2Cr2O7/H+ (or) KMnO4/OH- followed by hydrolysis in presence of dil H2SO4
(ii) Oxidation of primary alcohol to aldehyde
Ans: Pyridinium chlorochromate (PCC)
(iii) Benzyl alcohol to benzoic acid
Ans: Acidified KMnO4 or alkaline KMnO4 followed by hydrolysis in presence of dil H2SO4
(iv) Dehydration of propan-2-ol to propene
Ans: Conc. H2SO4 at 433-443K
(v) Butan-2-one to butan-2-ol
Ans: LiAlH4 (or) NaBH4
6) Name the alcohol which is resistant to oxidation and why?
Tertiary alcohol because they do not have α-hydrogen
7) Hydroboration-oxidation:
Alkene react with diborane to form trialkyl borane .This is oxidized to primary alcohol by hydrogen
peroxide in presence of aqueous sodium hydroxide.

,
3CH3CH=CH2 + B2H6 → (CH3CH2CH2)3B → 3CH3CH2CH2OH + H3BO3
Three marks
1. Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent on
methanal?

Ans:

2. Write the structures of the products of the following reactions.

Ans:
3. Write the products of each of the following alcohol react with (i) HCl-ZnCl2 (ii) HBr (iii) SOCl2
(i) Butan-1-ol
CH3CH2CH2CH2OH → no reaction at room temperature
,∆
CH3CH2CH2CH2OH → CH3CH2CH2CH2Cl
CH3CH2CH2CH2OH → CH3CH2CH2CH2Br
CH3CH2CH2CH2OH → CH3CH2CH2CH2OH

(ii) 2-methyl-2-butan-2-ol

4. Lucas Test: (Test to distinguish 1◦,2◦ and 3◦ alcohols)

Alcohols reacts with Lucas reagent ( Conc. HCl & ZnCl2) to form immiscible alkyl halide
ROH + HX → RX + H2O
If turbidity appears immediately, tertiary alcohol is indicated
If turbidity appears within five minutes, secondary alcohol is indicated
If turbidity appears only upon heating, primary alcohol is indicated
5. Give the expected products from the following reactions:
( a) Catalytic reduction of butanal
,
Ans: CH3CH2CH2CHO → CH3CH2CH2CH2OH
(b) Hydration of propene in presence of dil. H2SO4
,
CH3CH=CH2 → CH3CH(OH)CH3
(c ) Reaction of propanone with methyl magnesium bromide followed by hydrolysis

CH3COCH3 + CH3MgBr →

6. Predict the major product of acid catalysed dehydration of

(i) 1-methylcyclohexanol
(ii) butan-1-ol
CH3CH2CH2CH2OH → CH3CH=CHCH3 + CH3CH2CH=CH2
But-2-ene (major) But-1-ene (Minor)

(iii) 4-methylheptan-4-ol

(iv) Pentan -2-ol

(v) 2-cyclohexylbutan-2-ol

Phenols
One mark/Two marks:
1) Why Phenol is more acidic than ethanol?
Phenol is more acidic than ethanol because phenoxide ion is stabilized by resonance while ethoxide ion
does not.
2) Give two reactions to show the acidity of phenol.
(i) Pheonl reacts with active metals like sodium to liberate H2 gas
(ii) Phenol reacts with NaOH, to form sodium phenoxide and water
3) Give a test for Phenol (or) Distinguish phenol and ethanol
Phenol reacts with neutral ferric chloride to form violet colour compound due to the formation of
[Fe(OC6H5)6]3- Whereas ethanol does not
4) Why is the C-O bond length in phenols less than that in methanol?
The lone pairs on oxygen is involved in delocalization with benzene ring. Therefore C-O bond has partial
double bond character and has shorter bond length
5) Phenol is more reactive than benzene towards aromatic electrophilic substitution reaction. Why?
Electron donating –OH group activates the benzene ring and the intermediate carbocation is more
resonance stabilized
6) p-nitrophenol is a stronger acid than phenol while p-cresol is a weaker acid. Why?
NO2 group is electron withdrawing group, it increases stability of phenoxide ion whereas –OCH3 group is
electron releasing group and it decreases the stability of phenoxide ion.
7) Arrange the following compounds in increasing order of their acidic strength.
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol
Ans: Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5-dinitrophenol, 2,4,6-trinitro phenol
8) While separating a mixture of ortho- and para- nitrophenols by steam distillation, name the isomer
which will be steam volatile. Give reasons.
ortho-nitrophenol is steam volatile due to intra molecular H-bonding and can be separated by steam
distillation. Whereas para nitrophenols is not steam volatile due to inter molecular H-bonding
9) Write the chemical reaction for the preparation of phenol from chlorobenzene.

10) Write the chemical reaction for the preparation of phenol from cumene.

11) Write the chemical reaction for the preparation of phenol from aniline

12) Write the chemical reaction for the preparation of phenol from benzene

13) What is Aspirin? How to prepare it?

Acetylsalicylic acid is called as Aspirin.
Acetylation of salicylic acid gives aspirin

14) Reimer –Tiemann reaction

The electrophile in Reimer Tiemann reaction is :CCl2 (Dichloro carbene)

15) Kolbe’s reaction

16) Nitration of Phenol:

(i) With dil HNO3

(ii) With Conc. HNO3

17) Bromination of Phenol
(i) In non polar solvents like CS2

(ii) In polar solvents like H2O

18) How to convert phenol to benzene?

19) What happens when phenol is treated with Na2Cr2O7/H+ ?

Phenol is oxidised with Na2Cr2O7/H+ and form benzoquinone.

Ethers
Two marks:
1) Williamson’s ether synthesis:
Primary alkylhalide reacts with sodium alkoxide (1◦ / 2◦ / 3◦) to form ether and it proceeds by SN2
reaction
CH3CH2I + CH3CH2ONa → CH3CH2OCH2CH3
2) Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-
nitrobenzene. Why?

Ans: Chemically both sets are equally possible

In set (i), due to the presence of electronwithdrawing group –NO2 , activates the ether formation
In set (ii), Due to the presence of primary halide desired ether will be formed
3) Why is Williamson’s synthesis not applicable when the alkyl halide used is tertiary?
Because tertiary alkyl halide preferably undergoes elimination rather than substitution. Therefore the
resultant product is alkene not an ether.

Ex.
Three marks:
1. Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol and 3-
methylpentan-2-ol.
,∆
CH3CH2OH → CH3CH2Br

2. Write the name of reagents and equations for the preparation of the following ethers by Williamson’s
synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene (iii)2-methoxy-2-methylpropane (iv) 1-methoxyethane

3. Predict the products of the following reactions:

Ans:
4. Write the equation for the reaction of HI with
(i) 1-propoxypropane (ii) methoxybenzene (iii) benzylethylether

5) Give the major products that formed by heating each of the following with HI

Ans:

6) Write equations of the following:

(i) Brominaton of anisole:

(ii) Nitration of anisole:

(iii) Friedel crafts reaction – alkylation of anisole

(iv) Friedel crafts reaction –acetylation of anisole

8. Aldehydes, Ketones and Carboxylic Acids

Very Short Answer Questions [1 mark]

1. Give IUPAC name of the following compound:
(CH3)2C=CHCOCH3
Ans. 4-Methyl-pent-3-en-2-one
2. Write the structure of the following compound : 3-oxopentanal.

3. Write the IUPAC name of the following compound:

4. Write the IUPAC name of the following compound:

5. Give the name of the reagent that bring the following transformation: But-2-ene to ethanal.
Ans. O3/H2O—Zn dust
6. Arrange the following in increasing order of their boiling point:
CH3CH2OH, CH3CHO, CH3—O—CH3

7. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions: ethanal, propanal, propanone, butanone.
Ans. Butanone < Propanone < Propanal < Ethanal
8. What is Tollens’ reagent? Write one usefulness of this reagent.
Ans. Ammonical silver nitrate (AgNO3 + NH4OH) solution is known as Tollens’ reagent. It is used to detect
the presence of —CHO group in an organic compound.
9. What do you mean by Schiff’s base? Give an example.
Ans. Aldehydes and ketones react with primary aliphatic or aromatic amines to form azomethines or
Schiff’s bases.

10. Name the aldehyde which does not give Fehling’s solution test.
Ans. Benzaldehyde
11. How will you prepare benzyl alcohol from benzaldehyde without using a reducing agent?

12. Write two important uses of formalin.

Ans. Formalin is used in the
(i) preservation of biological specimens.
(ii) manufacture of bakelite.
13. Write the structural formula and IUPAC name of terephthalic acid.

Short Answer Questions–I [2 marks]

1. Propose the mechanism for the following reaction:

2. Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition reactions
than propanal? Explain your answer.
Ans. The carbon atom of the carbonyl group of benzaldehyde is less electrophilic than carbon atom of the
carbonyl group present in propanal. The polarity of the carbonyl group is reduced in benzaldehyde due to
resonance as shown below and hence it is less reactive than propanal.

3. Complete the following reaction sequence:

4. Write the equations involved in the following reactions:
(i) Wolff-Kishner reduction
(ii) Etard reaction

5. Write structures of main compounds A and B in each of the following reactions.

6. Oxidation of ketones involves carbon–carbon bond cleavage. Name the products formed on oxidation
of 2, 5-dimethylhexan-3-one.

7. An organic compound ‘A’ with molecular formula C5H8O2 is reduced to n-pentane on treatment with
Zn–Hg/HCl. ‘A’ forms a dioxime with hydroxylamine and gives a positive lodoform test and Tollens’
test. Identify the compound A and deduce its structure.
8. What product will be formed on reaction of propanal with 2-methylpropanal in the presence of
NaOH? Write the name of the reaction also.

9. Name the reagents used in the following reactions:

10. Do the following conversions in not more than two steps:

(i) Propene to Acetone (ii) Propanoic acid to 2-hydroxypropanoic acid

11. An aromatic compound ‘A’ on treatment with CHCl3 and KOH gives two compounds, both of which
give same product ‘B’ when distilled with zinc dust. Oxidation of ‘B’ gives ‘C’ with molecular
formula C7H6O2. Sodium salt of ‘C’ on heating with soda lime gives ‘D’ which may also be obtained
by distilling ‘A’ with zinc dust. Identify ‘A’, ‘B’, ‘C’ and ‘D’.

12. Identify the compounds A, B and C in the following reaction:

13. Arrange the following compounds in increasing order of their property as indicated:

14. Arrange the following in the decreasing order of their acidic character.
(i) C6H5COOH, FCH2COOH, NO2CH2COOH
(ii) CH3CH2OH, CH3COOH, ClCH2COOH, FCH2COOH, C6H5CH2COOH

Short Answer Questions–II [3 marks]

1. (A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H8O. 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).
(i) Write the structures of (A), (B), (C) and (D).
(ii) Out of (A), (B) and (C) isomers, which one is least reactive towards addition of HCN?

2. (i) Account for the following:

(a) Cl—CH2COOH is a stronger acid than CH3COOH.
(b) Carboxylic acids do not give reactions of carbonyl group.
(ii) Out of CH3CH2—CO—CH2—CH3 and CH3CH2—CH2—CO—CH3, which gives iodoform test?
Ans.
(i) (a) Because of –I effect of Cl atom in ClCH2COOH and +I effect of CH3 group in CH3COOH the
electron density in the O—H bond in ClCH2COOH is much lower than CH3COOH. As a result O—H bond
in ClCH2COOH is much weaker than in CH3COOH therefore loses a proton more easily than CH3COOH.
Hence ClCH2COOH acid is stronger acid than CH3COOH.
 (b) Carboxylic acids are resonance hybrid of the following structures:

Because of contribution of structure (IV), the carbonyl carbon in aldehydes and ketones is electrophilic.
On the other hand, electrophilic character of carboxyl carbon is reduced due to contribution of structure
(II). As carbonyl carbon of carboxyl group is less electropositive than carbonyl carbon in aldehydes and
ketones, therefore, carboxylic acids do not give nucleophilic addition reactions of aldehydes and
ketones.
(ii) CH3—CH2—CH2—COCH3
3. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) Benzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid strength)
(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acid strength)
Ans.
(i) Methyl tert-butyl ketone < Acetone < Acetaldehyde
(ii) 4-Methoxy benzoic acid < Benzoic acid < 3,4-Dinitrobenzoic acid
(iii) (CH3)2CHCOOH < CH3CH(Br)CH2COOH < CH3CH2CH(Br)COOH
4. Complete each synthesis by giving missing reagents or products in the following:

5. Write structures of compounds A, B and C in each of the following reactions:

6. Do the following conversions in not more than two steps:
(i) Benzoic acid to Benzaldehyde
(ii) Ethyl benzene to Benzoic acid
(iii) Propanone to Propene

7. Predict the products of the following reactions:

8. Give reasons:
(i) The a-hydrogen of aldehydes and ketones are acidic in nature.
(ii) Propanone is less reactive than ethanal towards addition of HCN.
(iii) Benzoic acid does not give Friedel-Crafts reaction.
Ans.
(i) The acidity of a-hydrogen atom of carbonyl carbon is due to the strong withdrawing effect of the
carbonyl group and resonance stabilisation of the conjugate base.
(ii) This is due to steric and electronic reasons. Sterically, the presence of two methyl groups in propanone
hinders more the approach of nucleophile to carbonyl carbon than in ethanal having one methyl group.
Electronically two methyl groups reduce the positivity of the carbonyl carbon more effectively in propanone
than in ethanal.
(iii) Benzoic acid does not give Friedel Craft reaction because:
(a) the carboxyl group is strongly deactivating.
(b)the catalyst AlCl3 which is a lewis acid gets bonded to the carboxyl group strongly.
 9. AMINES
One mark questions:
1. The correct IUPAC name for CH2  CHCH2 NHCH3 is
Ans: N-methylprop-2-en-1-amine
2. In order to prepare a 1° amine from an alkyl halide with simultaneous addition of one CH2 group in
the carbon chain, the reagent used as source of nitrogen is ___________.
Ans: Potassium cyanide, KCN
3. The best reagent for converting 2-phenylpropanamide into 2-phenylpropanamine is ___________.
Ans: LiAlH4 in ether
4. Which reagent would not be a good choice for reducing an aryl nitro compound to an amine?
Ans: LiAlH4 in ether
5. The best reagent for converting, 2-phenylpropanamide into 1-phenylethanamine is ____________.
Ans: NaOH/Br2
6. An organic compound ‘A’ on treatment with NH3 gives ‘B’ which on heating gives ‘C’. ‘C’ when
treated with Br2 in the presence of KOH produces ethylamine. Compound ‘A’ is
Ans: CH3—CH2—COOH
7. The source of nitrogen in Gabriel synthesis of amines is ___________.
Ans: Potassium phthalimide, C6H4(CO)2N– K+
8. Among 1o, 2o, 3o and methyl amines the strongest base in aqueous medium is ___________.
Ans: (CH3)2NH
9. Among methyl amine, dimethyl amine, ammonia, aniline which is the weakest Brönsted base?

Ans:

10. The most reactive amine towards dilute hydrochloric acid among methyl amine, dimethyl amine,
trimethyl amine is ____________.

Ans:

11. The order of reactivity of halides with amines is ___________.

Ans: RI > RBr > RCl
12. Benzylamine may be alkylated as shown in the following equation:
C6 H5 CH 2 NH 2 R + X  C6 H5 CH2 NHR
Which of the following alkylhalides is best suited for this reaction through S N1 mechanism?
Ans: C6H5CH2Br
13. Carbylamine reaction is used as a test for _____________.
Ans: primary amines
14. Among methyl amine, dimethyl amine, trimethyl amine which dissolve in an alkali solution after it
undergoes reaction with Hinsberg’s reagent?
Ans: CH3NH2
15. Methylamine reacts with HNO2 to form ____________.
Ans: CH3OH + N2
16. In the nitration of benzene using a mixture of conc. H2SO4 and conc. HNO3, the species which
initiates the reaction is ____________.
Ans: NO2
17. Reduction of nitrobenzene by which reagent gives aniline?
Ans: Sn/HCl , Fe/HCl , H2-Pd
18. Which halo benzene cannot be prepared by Sandmeyer's reaction?
Ans: Iodobenzene , Fluorobenzene
19. Write the IUPAC name of the given compound:

Ans: N, N – Dimethylbutanamide
20. Write the IUPAC name of the given compound:

Ans. N- Phenylethanamide
21. Write the IUPAC name of the given compound:

Ans. 2,4-Dibromobenzenamine or 2,4-Dibromoaniline

22. Why do amines behave as nucleophiles?
Ans:
Due to the presence of a lone pair of electrons on nitrogen atom, amines behave as nucleophiles.
23. What is the role of pyridine in the acylation reaction of amines?
Ans. Pyridine and other bases are used to remove the side product, i.e., HCl from the reaction mixture.

24. What is the role of HNO3 in the nitrating mixture used for nitration of benzene?
Ans. HNO3 acts as a base in the nitrating mixture and provides the electrophile NO2 .
25. The conversion of primary aromatic amines into diazonium salts is known as __________ .
Ans. Diazotisation.
26. Write a chemical reaction in which the iodide ion replaces the diazonium group in a diazonium salt.
Ans:

27. Give reasons:

Acetylation of aniline reduces its activation effect.
Ans:
Due to the resonance, the electron pair of nitrogen atom gets delocalized towards carbonyl group /
resonating structures.
28. Give reasons:
Although – NH2 is o/p direction group, yet aniline on nitration gives a significant amount of m-
nitroaniline.
Ans:
Due to protonation of aniline / formation of anilinium ion.
29. Give reasons:
(CH3)2NH is more basic than (CH3)3 N in an aqueous solution.
Ans:
 Because of the combined factor of inductive effect and solvation or hydration effect.
30. Give reasons:
Aromatic diazonium salts are more stable than aliphatic diazonium salts.
Ans:
Due to resonance stabilization or structural representation/ resonating structures.
31. Give a simple chemical test to distinguish between Aniline and N, N – dimethylaniline.
Ans:
Add chloroform in the presence of KOH and heat, aniline gives a offensive smell while N, N –
dimethylaniline does not. (or any other correct test)
32. Arrange the following in the increasing order of their pKb values:
C6H5NH2, C2H5NH2, C6H5NHCH3
Ans:
C2H5NH2<C6H5NHCH3<C6H5NH2
33. Give reasons:
N, N – Diethylbenzene sulphonamide is insoluble in alkali.
Ans:
It has no acidic hydrogen.
34. Give reasons:
Only a small amount of HCl is required in the reduction of nitro compounds with iron scrap and HCl
in the presence of steam.
Ans:
FeCl2 formed gets hydrolysed to release HCl during the reaction.
35. Give reasons:
Acetanilide is less basic than aniline.
Ans:
Acetylation of aniline results in decrease of electron density on nitrogen

36. Give reasons:

Aromatic 1o amines can’t be prepared by Gabriel Phthalimide synthesis.
Ans:
Aryl halides do not undergo nucleophilic substitution with anion formed by phthalimide.
Two Marks Questions
1. Suggest a route by which the following conversion can be accomplished.

Ans.

2. What are the reactions involved in the reductive removal of nitro group from an aromatic
compound?
Ans.

3. Identify A and B in each of the following processes:

(i) CH3CH 2Cl 
NaCN
 A 
Re duction
Ni / H2
B
(ii) C6 H5 NH2  
NaNO2 / HCl
 A 
C6 H5 NH2
OH 
B
Ans:
4. Arrange the following:
(i) In increasing order of their basic strength
C6H5—NH2, CH3—CH2—NH2, CH3—NH—CH3
(ii) In increasing order of solubility in water
CH3—NH2, (CH3)3N, CH3—NH—CH3
Ans.
(i) C6H5NH2 < CH3—CH2—NH2 < CH3NHCH3
(ii) (CH3)3N < (CH3)2NH < CH3NH2
5. Account for the following:
(i) Aniline gets coloured on standing in air for a long time.
(ii) MeNH2 is stronger base than MeOH.
Ans.
(i) Due to electron-donating effect (+R-effect) of —NH2 group, the electron density on the benzene ring
increases. As a result, aniline is easily oxidised on standing in air for a long time to form coloured products.
(ii) Nitrogen is less electronegative than oxygen therefore lone pair of electrons on nitrogen is readily
available for donation. Hence, MeNH2 is more basic than MeOH.

6. Account for the following:

(i)Although trimethylamine and n-propylamine have the same molecular weight, but the former boils
at a lower temperature (276 K) than the latter (322 K). Explain.
Ans:
(i) n-Propylamine has two H-atoms on the N-atom and hence undergoes intermolecular H-bonding, thereby
raising its boiling point. Trimethylamine, (CH3)3N, being a tertiary amine does not have any H-atom on the
N-atom. As a result, it does not undergo H-bonding and hence its boiling point is low.
7. Write structures of compounds A and B in each of the following reactions:

Ans. (i)
8. How will you carry out the following conversions?
(i) toluene toluidine p - (ii) p p - - toluidine diazonium chloride toluic acid
Ans:

9. Write the following conversions:

(i) nitrobenzene acetanilide
(ii) acetanilide p-nitroaniline
Ans:

10. Arrange the following:

(i) In decreasing order of the pKb values:
C2H5NH2 , C6H5NHCH3 , (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:
C6H5NH2 , C6H5N(CH3)2, (C2H5)2 NH and CH3NH2
Ans:
(i) C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2NH
(ii) C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
11. Arrange the following:
(i) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2 , C6H5NHCH3 , C6H5CH2NH2
 (ii) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
Ans:
(i) (a) p-nitroaniline < aniline < p-toluidine.
(b) C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
(ii) (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
12. Arrange the following:
(i) In increasing order of boiling point:
C2H5OH, (CH3)2 NH, C2H5NH2
(ii) In increasing order of solubility in water:
C6H5NH2, (C2H5)2NH, C2H5NH2
Ans:
(i) (CH3)2NH < C2H5NH2 < C2H5OH
(ii) C6H5NH2 < (C2H5)2NH < C2H5NH2
13. Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water, whereas aniline is not.
Ans:
(i) In aniline due to resonance, the lone pair of electrons on the N-atom are delocalised over the benzene
ring. Due to this, electron density on the nitrogen decreases. On the other hand, in CH3NH2, +I-effect of
CH3 increases the electron density on the N-atom. Consequently aniline is a weaker base than methylamine
and hence its pKb value is higher than that of methylamine.
(ii) Ethylamine dissolves in water because it forms H-bonds with water molecules as shown below: In
aniline, due to the large hydrocarbon part the extent of H-bonding decreases considerably and hence aniline
is insoluble in water
14. Account for the following:
(i) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(ii) Although amino group is o- and p-directing in aromatic electrophilic substitution reactions,
aniline on nitration gives a substantial amount of m-nitroaniline.
Ans:
(i) Methylamine being more basic than water, accepts a proton from water, liberating OH– ions.
These OH– ions combine with Fe3+ ions present in H2O to form brown precipitate of hydrated ferric
oxide.
(ii) Nitration is usually carried out with a mixture of conc. HNO3 and conc. H2SO4. In presence of these
acids, most of aniline gets protonated to form anilinium ion. Thus, in presence of acids, the reaction mixture
consists of aniline and anilinium ion. The —NH2 group in aniline is o, p-directing and activating while the

— N H 3 group in anilinium ion is m-directing and deactivating. Nitration of aniline mainly gives p-
nitroaniline. On the other hand, the nitration of anilinium ion gives m-nitroaniline.
Thus, nitration of aniline gives a substantial amount of m-nitroaniline due to protonation of the amino
group.
15. Account for the following:
(i) Aniline does not undergo Friedel–Crafts reaction.
(ii) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(iii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Ans:
(i) Aniline being a Lewis base, reacts with Lewis acid AlCl3 to form a salt.
 As a result, N of aniline acquires positive charge and hence it acts as a strong deactivating group for
electrophilic substitution reaction. Consequently, aniline does not undergo Friedel–Crafts reaction.

(ii) The diazonium salts of aromatic amines are more stable than those of aliphatic amines due to dispersal
of the positive charge on the benzene ring as shown below:

(iii) Gabriel phthalimide reaction gives pure primary amines without any contamination of secondary and
tertiary amines. Therefore, it is preferred for synthesising primary amines.
16. Give one chemical test to distinguish between the following pairs of compounds:
(i) Methylamine and dimethylamine (ii) Secondary and tertiary amines
Ans:
(i) Methylamine is 1° amine, therefore, it gives carbylamine test, i.e., when heated with an alcoholic
solution of KOH and CHCl3 it gives an offensive smell of methyl carbylamine. In contrast, dimethylamine
is a secondary amine and hence does not give this test.
(ii) By Hinsberg’s reagent (benzenesulphonyl chloride). The amine is treated with benzenesulphonyl
chloride and shaken with alkali solution when the two amines behave in different ways: (a) Secondary
amines form dialkyl benzenesulphonamide which does not react with alkali and hence it remains insoluble.
(b) Tertiary amines do not react with benzenesulphonyl chloride at all.
17. Give one chemical test to distinguish between the following pairs of compounds:
(ii) Ethylamine and aniline (ii) Aniline and benzylamine (iii) Aniline and N-methylaniline
Ans:
(i) Ethylamine is primary aliphatic amine while aniline is a primary aromatic amine. These may be
distinguished by the azo dye test: Refer to Basic Concepts Point 12(c).
(ii) Benzylamine reacts with nitrous acid to form a diazonium salt which being unstable even at low
temperature, decomposes with evolution of N2 gas. Aniline reacts with HNO2 to form benzene diazonium
chloride which is stable at 273-278 K and hence does not decompose to evolve N2 gas.
(iii) Aniline being a primary amine gives carbylamine test, i.e., when heated with an alcoholic solution of
KOH and CHCl3, it gives an offensive smell of phenyl isocyanide. In contrast, N-methylaniline, being
secondary amine does not give this test.
Three Mark Questions
1. (i) Arrange the following compounds in increasing order of dipole moment.
CH3CH2CH3, CH3CH2NH2, CH3CH2OH
(ii) Give possible explanation for each of the following:
(a) The presence of a base is needed in the ammonolysis of alkyl halides.
(b) Amides are more acidic than amines.
Ans:
(i) CH3CH2CH3 < CH3CH2NH2 < CH3CH2OH
(ii) (a) To remove HX formed so that the reaction shifts in the forward direction.

Due to +R effect, availability of lone pair of electron on N of —NH2 group decreases. As a result, acid
amide is much weaker base than amines. Because of the positive charge on N, as a result of resonance, N
can easily lose a proton and behaves, as a weak acid.
2. Write the structures of A, B and C in the following:
NaNO2  HCl
(i) C6 H 5  CONH 2 
Br2 / aq . KOH
A 
0 5 o C
 B 
KI
C
 CHCl3  alc. KOH
(ii) CH 3Cl 
KCN
 A 
LiAlH 4
 B  
C

Ans.

3. Complete the following reactions:

(i) C6 H 5  COOH 
NH 3
A
 Heat
 B Br2 / KOH
C
NaNO2  HCl
(ii) C6 H5 NO2  A 
Fe / HCl
273278 K
B

CuCN
C

Ans:

4. Complete the following chemical equations:


(i) C6 H5 N2Cl  C6 H5 NH 2 
OH

(ii) C6 H 5 N 2Cl  CH 3CH 2OH 
(iii) RNH 2  CHCl3  KOH 
Ans:

5. How are the following conversions carried out:

(i) Aniline to fluorobenzene
(ii) Benzene diazonium chloride to benzene
(iii) Methyl chloride to ethylamine
 Ans:
(i) Aniline to fluorobenzene

(ii) Benzene diazonium chloride to benzene

(iii) Methyl chloride to ethylamine

6. How will you convert the following:

(i) Aniline to chlorobenzene
(ii) Ethanoic acid to methanamine
(iii) Benzene diazonium chloride to phenol
Ans.
(i) Aniline to chlorobenzene

(ii) Ethanoic acid to methanamine

(iii) Benzene diazonium chloride to phenol

7. Complete the following reactions:

Ans:

8. How do you convert the following:

(i) N-phenylethanamide to p-bromoaniline
(ii) Benzene diazonium chloride to nitrobenzene
(iii) Benzoic acid to aniline
Ans:
9. Give the structures of A, B and C in the following reactions:

(i) CH 3CH 2 I 
NaCN
 A  OH
Partial hydrolysis
 B 
NaOH  Br2
C

(ii) C6 H5 N2Cl 
CuCN
 A 
H 2O / H
 B 
NH 3

C
(iii) CH 3CH 2 Br 
KCN
 A 
LiAlH 4
 B 
HNO2
0o C
C
Ans:

10. Give the structures of A, B and C in the following reactions:


NaNO2  HCl
(i) C6 H5 NO2 
Fe / HCl
A 273 K
  B 
H 2O / H

C
(ii) CH3COOH 
NH3
Heat
 A 
NaOBr
 B  
NaNO2 / HCl
C
(iii) C6 H5 NO2 
Fe / HCl
A 
HNO2
273 K
 B 
C6 H5OH
C
Ans:

(i)

(ii)

(iii)
11. Complete the following reactions:
(i) C6 H 5 NH 2  CHCl3  alc. KOH 
(ii) C6 H 5 NH 2  H 2 SO4 (conc.) 
(iii) C6 H 5 NH 2  Br2 (aq) 
Ans:

(i)

(ii)

(iii)

12. Complete the following reactions:

(i) C6 H 5 N 2Cl  C2 H 5OH 
(ii) C6 H 5 NH 2  Br2 (aq) 
(iii) C6 H 5 NH 2  (CH 3CO)2 O 
Ans:

(i)

(ii)

(iii)

13. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.
Ans. Aromatic primary amines react with HNO2 at 273-278 K to form aromatic diazonium salts.

Aliphatic primary amines also react with HNO2 at 273–278 K to form aliphatic diazonium salts. But these
are unstable even at this low temperature and thus decompose readily to form a mixture of compounds
consisting of alkyl chlorides, alkenes and alcohols, out of which alcohols generally predominate.
14. Give plausible explanation for each of the following: (i) Why are amines less acidic than alcohols of
comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Ans. (i) Loss of a proton from an amine gives amide ion while loss of a proton from alcohol gives an
alkoxide ion as shown below:

As O is more electronegative than N, RO– can accommodate the negative charge more easily than the RNH–
can accommodate the negative charge. RO– is more stable than RNH– . Therefore, amines are less acidic
than alcohols.
(ii) In primary amines, two hydrogen atoms are present on N-atom and they undergo extensive
intermolecular hydrogen bonding which results in association of molecules while in tertiary amines, no
hydrogen atom is present on N-atom. Hence there is no hydrogen bonding in tertiary amines. As a result of
this primary amines have higher boiling point than tertiary amines.
(iii) Aliphatic amines are stronger bases than aromatic amines because:
(a) due to resonance in aromatic amines, the lone pair of electrons on the nitrogen atom gets delocalised
over the benzene ring and thus is less easily available for protonation.
(b) the aryl amine ions have lower stability than the corresponding alkyl amines, i.e., protonation of
aromatic amines is not favoured.
15. Write the structures of different isomeric amines corresponding to the molecular formula, C 4H11N.
(i) Write the IUPAC names of all the isomers
(ii) What type of isomerism is exhibited by different types of amines?
Ans: Eight isomeric amines are possible

Isomerism exhibited by different amines

 Chain isomers: (i) and (ii) ; (iii) and (iv) ; (i) and (iv)
 Position isomers: (ii) and (iii) ; (ii) and (iv)
 Metamers: (v) and (vi) ; (vii) and (viii)
 Functional isomers: All the three types of amines are the functional isomers of each other.
16. Write short notes on the following:
(i) Carbylamine reaction
(ii) Diazotisation
(iii) ‘Hofmann’s bromamide reaction
Ans:
(i) Carbylamine reaction: Both aliphatic and aromatic primary amines when warmed with chloroform and
an alcoholic solution of KOH, produces isocyanides or carbylamines which have very unpleasant odours.
This reaction is called carbylamine reaction.

(ii) Diazotisation: The process of conversion of a primary aromatic amino compound into a diazonium salt,
is known as diazotisation. This process is carried out by adding an aqueous solution of sodium nitrite to a
solution of primary aromatic amine (e.g., aniline) in excess of HCl at a temperature below 5°C.

(iii) Hoffmann’s bromamide reaction: When an amide is treated with bromine in alkali solution, it is
converted to a primary amine that has one carbon atom less than the starting amide. This reaction is known
as Hoffinann’s bromamide degradation reaction.

17. Write short notes on the following:

(i) Coupling reaction
(ii) Ammonolysis
(iii) Acetylation

Ans:
(i) Coupling reaction: In this reaction, arene diazonium salt reacts with aromatic amino compound (in acidic
medium) or a phenol (in alkaline medium) to form brightly coloured azo compounds. The reaction generally
takes place at para position to the hydroxy or amino group. If para position is blocked, it occurs at ortho
position and if both ortho and para positions are occupied, than no coupling takes place.

(or)

(ii) Ammonolysis: It is a process of replacement of either halogen atom in alkyl halides (or aryl halides) or
hydroxyl group in alcohols (or phenols) by amino group. The reagent used for ammonolysis is alcoholic
ammonia. Generally, a mixture of primary, secondary and tertiary amine is formed.
 (iii) Acetylation: The process of introducing an acetyl (CH3CO-) group into molecule using acetyl chloride
or acetic anhydride is called acetylation.

10. BIOMOLECULES
Very short answer questions (1mark)

1. Why are carbohydrates generally optically active?

Ans. Carbohydrates have chiral or asymmetric carbon atom.
2. What happens when glucose is treated with bromine water?
Ans. When glucose is treated with bromine water it forms gluconic acid.

3. What happens when glucose reacts with nitric acid?

Ans. Glucose gets oxidised to succinic acid

4. Write a reaction which shows that all the carbon atoms in glucose are linked in a straight chain.
Ans. On prolonged heating with HI, glucose gives n-hexane.

5. Which component of starch is a branched polymer of a-glucose and insoluble in water?

Ans. Amylopectin
6. Which of the two components of starch is water soluble?
Ans. Amylose is water soluble whereas amylopectin is water insoluble component.
7. Name two   amino acids which form a dipeptide which is 100 times more sweet than cane sugar.
Ans. Aspartic acid and phenylalanine.
8. What type of bonding helps in stabilising the   helix structure of proteins?
Ans. The   helix structure of proteins is stabilised by intramolecular H-bonding between C—O of one
amino acid residue and the N—H of the fourth amino acid residue in the chain.
9. How do you explain the presence of five —OH groupsin glucose molecule?
Ans. Glucose gives pentaacetate derivative on acetylation with acetic anhydride. This confirms the presence
of five —OH groups.
10. What are biocatalysts? Give an example.
Ans. Enzymes are termed as biocatalysts as they catalyse numerous reactions that occur in the bodies of
animals and plants to maintain life process e.g., invertase, pepsin, urease.
11. What are three types of RNA molecules which perform different functions?
Ans. There are three types of RNAs:
(i) Ribosomal RNA (rRNA) (ii) Messenger RNA (mRNA) (iii) Transfer RNA (tRNA)
Short answer questions (2M)
1. Write the reactions involved when D-glucose is treated with the following reagents:
(i) HCN (ii) Br2 water

2. How do you explain the presence of an aldehydic group in a glucose molecule?

Ans.
Glucose reacts with hydroxylamine to form a monoxime and adds one molecule of hydrogen cyanide to
give cyanohydrin so it contains a carbonyl group which can be an aldehyde or a ketone. On mild oxidation
with bromine water, glucose gives gluconic acid which is a six carbon carboxylic acid. This indicates that
carbonyl group present in glucose is an aldehydic group.
3. Label the glucose and fructose units in the following disaccharide and identify anomeric carbon
atoms in these units. Is the sugar reducing in nature? Explain.

Ans.
C-l of glucose unit and C-2 of fructose unit are anomeric carbon atoms in the given disaccharide. The
disaccharide is non-reducing sugar because —OH groups attached to anomeric carbon atoms are involved
in the formation of glycosidic bond.

4. Amino acids behave like salts rather than simple amines or carboxylic acids. Explain.
 Ans.
In aqueous solution, the carboxyl group loses a proton and amino group accepts a proton to form a zwitter
ion.

5. Explain what is meant by the following: (i) peptide linkage (ii) pyranose structure of glucose.
Ans.
(i) Refer to NCERT Textbook Exercises, Q. 12(i).
(ii) The six-membered cyclic structure of glucose is called pyranose structure (  - or  -), in analogy with
heterocylic compound pyran.

6. Describe what you understand by primary structure and secondary structure of proteins.
Ans.
Primary structure: The specific sequence in which the various  -amino acids present in a protein are
linked to one another is called its primary structure. Any change in the primary structure creates a different
protein.
Secondary structure: The conformation which the polypeptide chain assumes as a result of hydrogen
bonding is known as secondary structure. The two types of secondary structures are  -helix and  -pleated
sheet structures.
In  -helix structure, the polypeptide chain forms all the possible hydrogen bonds by twisting into a
righthanded screw (helix) with the —NH group of each amino acid residue hydrogen bonded to the

groups of an adjacent turn of the helix. In  -pleated structure, all peptide chains are stretched
out to nearly maximum extension and then laid side by side and are held together by hydrogen bonds.
7. (i) What type of linkage is present in nucleic acids?
(ii) Give one example each for fibrous protein and globular protein.
Ans.
(i) Phosphodiester linkage.
(ii) Fibrous protein: Myosin, keratin, collagen, etc. Globular protein: Insulin, haemoglobin, etc.
8. Name the bases present in RNA. Which one of these is not present in DNA?
Ans.
The bases present in RNA are adenine (A), guanine (G), cytosine (C) and uracil (U). Uracil is not present in
DNA.
9. If one strand of a DNA has the sequence —ATGCTTCA—, what is the sequence of the bases in the
complementary strand?
Ans.
As we know that in DNA molecule, adenine (A) always pairs with thymine (T) and cytosine (C) always
pairs with guanine (G). Thus,
Sequence of bases in one strand : ATGCTTCA
Sequence of bases in the complementary strand : TACGAAGT
 Short answer questions (3M)
1. Define the following terms:
(i) Glycosidic linkage (ii) Invert sugar (iii) Oligosaccharides
Ans:
(i) The linkage between two monosaccharides through oxygen atom in an oligosaccharide or a
polysaccharide is known as glycosidic linkage.
(ii) Sucrose is dextrorotatory (+ 66.5°) but after hydrolysis it gives an equimolar mixture of D-(+)-glucose
and D-(–)-fructose, which is laevorotatory. This change of specific rotation from dextrorotation to
laevorotation is called inversion of sugar and the mixture obtained is called invert sugar.
(iii) Carbohydrates which on hydrolysis give two to ten molecules of monosaccharides are called
oligosaccharides e.g., sucrose.
2. (i) Which of the following biomolecules is insoluble in water? Justify. Insulin, Haemoglobin, Keratin.
(ii) Draw the Haworth structure for a-D-Glucopyranose.
(iii) Write chemical reaction to show that glucose contains aldehyde as carbonyl group.
Ans.
(i) Keratin being a fibrous protein insoluble in water.

(ii)

(iii) Glucose reduces Tollens’ reagent to metallic silver.

3. (i) Give one structural difference between amylose and amylopectin

(ii) Name the protein and its shape present in oxygen carrier in human body.
(iii) Name two fat storing tissues in human body.
Ans.
(i) Amylose is a long unbranched chain polymer of   D(+) glucose. Amylopectin is a branched chain
polymer of   D glucose.
(ii) Globular protein and its shape is spherical.
(iii) Liver and adipose tissue.
4. (i) A non-reducing disaccharide ‘A’ on hydrolysis with dilute acid gives an equimolar mixture of D-
(+)-glucose and D-(–)-fructose.

Identify A. What isthe mixture of D-(+)-glucose and D-(–)-fructose known as? Name the linkage that
holds the two units in the disaccharide.

(ii)   amino acids have relatively higher melting points than the corresponding halo acids. Explain.

Ans.

(i) l A = C12H22O11 (sucrose). l Invert sugar. l Glycosidic linkage.

 (ii) a-Amino acids act as zwitter ions, (H3N + —CHR—COO– ) or dipolar ions. Due to this dipolar salt-like
structure, they have strong dipole-dipole interactions. Therefore, their melting points are higher than the
corresponding halo acids which do not exist as zwitter ions.

5. (i) Draw the pyranose structure of glucose. (ii) What type of linkage is present in proteins? (iii) Give
one example each for water-soluble vitamins and fat-soluble vitamins.

6. (i) Write the product obtained when D-glucose reacts with H2N—OH.
(ii) Amino acids show amphoteric behaviour. Why?
(iii) Why cannot vitamin C be stored in our body?