CHAPTER 1 (SOLUTIONS)

1. Solubility of gases decreases with increase in temperature because solubility of gas in liquid is
a reversible and exothermic process. So as temperature is increased, according to Le
Chatelier’s principle equilibrium will shift in backward direction.
2. Aquatic animals feel more comfortable in cold water than in hot water because solubility of
gases is more in cold water than in hot water.
3. Henry’s law- It states that the partial pressure of the gas in vapour phase (p) is proportional to
the mole fraction of the gas (x) in the solution.
P = KH x, where KH is Henry’s constant
4. Higher the value of KH at a given pressure, the lower is the solubility of the gas in the liquid.
5. Applications of Henry’s Law- i) To increase the solubility of CO2 in soft drinks and soda water,
the bottle is sealed under high pressure.
ii) At high altitudes, people suffer from anoxia because of low concentrations of oxygen in
blood due to less partial pressure of oxygen at higher altitudes.
iii) To avoid bends, tanks used by scuba divers are filled with air diluted with helium.
6. Solution of ethylene glycol known as an antifreeze, is used in cars for cooling the engine
because it lowers the freezing point of water.
7. Raoult’s law- It states that for any solution the partial vapour pressure of each volatile
component in the solution is directly proportional to its mole fraction.
PA = P Aͦ xA, where PA is partial vapour pressure of volatile component A, P Aͦ is vapour
pressure of pure component A, xA is the mole fraction of A
8. Raoult’s law becomes a special case of Henry’s law in which KH becomes equal to P Aͦ .
9. Vapour pressure of the solvent decreases when non volatile solute is added to it or vapour
pressure of solution is less than that of solvent as solute particles decrease the escaping
tendency of the solvent molecules.
10. Difference between ideal and non-ideal solutions-

Ideal Solution Non Ideal Solution

Follows Raoult’s law at all temperature and Does not follow Raoult’s law at all temperature
concentrations. P = PA + PB and pressure. P ≠ PA + PB
Intermolecular forces in resulting solution are Intermolecular forces in resulting solution are
same as in pure components. A – B = A – A = B – different from that of pure components. A – B ≠
B A – A, B – B
No change in volume while mixing Change in volume while mixing components.
components. Δ V mix ≠ 0
Δ V mix = 0
No heat change take place while mixing the Heat changes take place while mixing the
components. Δ H mix = 0 components. Δ H mix ≠ 0
Eg: n – hexane + n – heptane, benzene + Eg: Acetone + Water &Acetone + CHCl3
toluene, bromoethane + chloroethane
11. Non-ideal solutions are of two types- Non-ideal solution showing positive deviation and non-
ideal solution showing negative deviation.
 12. Difference between Non-ideal solution showing positive deviation and negative deviation-
Showing positive deviation Showing negative deviation

Vapour pressure of resulting solution is greater Vapour pressure of resulting solution is less than
than sum of partial pressure of components. P sum of the partial pressure of pure
> PA + PB components. P < PA + PB

Resulting intermolecular force is weaker than Resulting intermolecular force is stronger than
pure components. pure components.

Δ V mix = +ve Δ V mix = –ve

Volume of solution > Sum of volume of pure Volume of solution < Sum of volume of pure
components components
Δ H mix = +ve , Endothermic mixing process, Δ H mix = –ve ,Exothermic process,
Temperature decreases Temperature increases

Acetone +H2O, Ethanol + Water, Carboxylic Acetone + CHCl3, HNO3 + H2O, Phenol + Aniline
Acid + H2O

13. Two components form non ideal solution forming positive deviation because new
intermolecular forces are weaker than pure components.
14. Two components form non ideal solution forming negative deviation because new
intermolecular forces are stronger than pure components
15. Azeotropes – These are the binary mixtures having the same composition in liquid and
16. vapour phase and boil at a constant temperature.
17. Minimum boiling azeotropes are formed by solutions showing positive deviation from Raoult’s
law. Eg, A mixture of ethanol and acetone
18. Maximum boiling azeotropes are formed by solutions showing negative deviation from
Raoult’s law. Eg, A mixture of HNO3 and water.
19. We can get only 95% of ethanol solution not 100% because it forms azeotropic mixture so
cannot be further separated.
20. We can get only 68% of nitric acid (HNO3) solution not 100% because it forms azeotropic
mixture so cannot be further separated.
21. Colligative Properties – These are the properties which depend on the number of solute
particles irrespective of their nature.
22. Liquid which boils at lower temperature has higher vapour pressure.
23. A solution boils at higher temperature than pure solvent because its vapour pressure is less
than pure solvent.
24. A solution freezes at lower temperature than pure solvent because its vapour pressure is less
than pure solvent.
25. Osmosis- It is the process of movement of solvent from solvent side to solution side through
semi-permeable membrane.
26. Osmotic pressure (Π)- It is the pressure applied on solution side to prevent the process of
osmosis. Π = CRT = nRT/V (C = n/V) n= Number of moles of solute , V is volume of soluiton, R=
gas constant, T = Temperature(in Kelvin)
27. Reverse Osmosis- It is the phenomenon in which solvent starts moving from solution side to
solvent side when pressure greater than osmotic pressure is applied on the solution side. For
reversed osmosis, P (external pressure) > Π.
28. Application of reverse osmosis – Desalination of sea water.
29. Isotonic solution- Solutions having same osmotic pressure having same concentration. When
two such solutions are separated by semi-permeable membrane, no osmosis takes place.
30. Hypertonic solution- Solution having more osmotic pressure or high concentration than the
other solution. Exosmosis or shrinkage takes place in such case.
31. Hypotonic solution- Solution having less osmotic pressure or less concentration than the other
solution. Endosmosis or swelling takes place in such case.
32. Raisins placed in water – endo-osmosis takes place or raisins swelled.
33. Raisins placed in salt solution – exo-osmosis takes place or shrinkage of raisins takes place.
34. When blood cells are placed in solution containing more than 0.9% NaCl solution, blood cells
will shrink.
35. When blood cells are placed in solution containing less than 0.9% NaCl solution, blood cells will
swell.
36. Osmotic pressure is best method used to determine molar masses of proteins, polymers and
other macromolecules because – i) It is measured at room temperature. ii) Molarity is used
instead of molality. iii) Its magnitude is large even for very dilute solutions.
37. Molal elevation constant or Ebullioscopic Constant (Kb)- It is defined as the elevation in boiling
point when one mole of solute is dissolved in 1000 g of solvent.
38. Molal Depression Constant or Cryoscopic Constant (Kf)- It is defined as the depression in
freezing point when one mole of solute is dissolved in 1000 g of solvent.
39. Van’t Hoff Factor(i) –

40. When i < 1, it means association takes place.

41. When i > 1, it means dissociation takes place.
42. Van’t Hoff factor and association and dissociation-
Association Dimerisation Trimerisation Tetramerisation Pentamerisation

i= 1/2 1/3 1/4 1/5

Dissociation NaCl K2SO4, MgCl2 AlCl3 K4 [Fe (CN)6]

i= 2 3 4 5

43. Urea, Glucose, Sugar (non- electrolyte) has small value of colligative properties as they do not
dissociate into ions than the solutions of NaCl, KCl, K2SO4, MgCl2 etc of same concentration
as they dissociate into ions.
44. Mass %, ppm, mole fraction and molality are independent of temperature as mass does not
changes with temperature whereas molarity depends on temperature because volume
depends on temperature.
45.
Number of moles = Given mass / Molar mass

46.

47.

48.
 CHAPTER 2 (ELECTROCHEMISTRY)

1. Resistance, R = ρ l/A where ρ= resisitivity, l=length of conductor, A = area of cross section

2. Conductance, , κ is conductivity or specific conductance

3. Relation between conductivity, conductance and cell constant-
Conductivity, κ = G l/A = G G* where l/A = G* (cell constant)
4. Relation between conductivity, resistance and cell constant-
Conductivity, κ = l/R A = G* /R where l/A = G* (cell constant)
5. Unit of conductivity is S/cm
6. Ionic conductance or electrolytic conductance increases with the increase of temperature.
7. Electric conductance or metallic conductance decreases with increase of temperature.
8. Molar conductivity- It is the conducting power of all the ions produced by dissolving one gram
mole of an electrolyte in total volume V of the solution.
Λm = κ * 1000/ M where M = Molar concentration
9. Unit of molar conductivity is Scm2/mol
10. Conductivity always decreases with decrease in concentration or on dilution both, for weak
and strong electrolytes because the number of ions per unit volume decreases on dilution.
11. Molar conductivity increases with decrease in concentration or on dilution both, for weak and
strong electrolytes because total volume of solution increases.
12. In case of strong electrolytes, increase in molar conductivity with decrease in concentration or
dilution is small as number of ions remains same but solute- solute interaction decreases.
13. In case of weak electrolytes, increase in molar conductivity with decrease in concentration or
dilution is large as number of ions increases due to increase in dissociation of electrolyte.
14. Graph between molar conductivity and square root of concentration:
KCl in this graph is strong electrolyte as small increase in molar
conductivity
CH3COOH in this graph is weak electrolyte as there is sharp increase
in molar conductivity.
Limiting molar conductivity of strong electrolyte can be found
through this graph but Limiting molar conductivity of strong
electrolyte can be found using Kohlrausch law

15. Kohlrausch law : Limiting molar conductivity of an electrolyte can be represented as the sum
of the individual contributions of the anion and cation of the electrolyte.

16. Limiting Molar Conductivity It is Molar Conductivity at Infinite dilution (Λ ° m

17. Degree of dissociation, α = Λm/ Λ ° m
18. Dissociation constant, Ka

19. Products of electrolysis-

Compound undergoing Substance liberated at Substance liberated at
elctrolysis cathode anode

NaCl (Molten) Sodium (Na) Chlorine (Cl2)

NaCl (aqueous) Hydrogen (H2) Chlorine (Cl2)

 Dilute Sulphuric acid Hydrogen (H2) Oxygen (O2)
(H2SO4)
Conc Sulphuric acid Hydrogen (H2) S2O82-
(H2SO4)
Aqueous Copper Copper (Cu) Oxygen (O2)
sulphate (CuSO4 ) using
Pt electrodes
Aqueous Copper Copper (Cu) Copper oxidised to
sulphate (CuSO4) using Cu2+
Cu electrodes
Aqueous Copper Copper (Cu) Oxygen (O2)
chloride (CuCl) using Pt
electrodes
Aqueous silver nitrate Silver (Ag) Silver oxidised to Ag+
(AgNO3) using Ag
electrodes
Aqueous silver nitrate Silver (Ag) Oxygen (O2)
(AgNO3) using Pt
electrodes

20. Materials that can be used as fuels in fuel cell – Hydrogen, Methanol, Methane
21. Advantages or benefits of fuel cell- i) Its efficiency is about 70% ii) It is pollution free device.
22. Functions of salt bridge- i) It completes the circuit. ii) It maintains the electrical neutrality of the
solutions.
23. Mercury cell has constant cell potential throughout its useful life because ions are not involved
in the overall cell reaction.
24. Dry cell become dead after a long time even if it has not been used because acidic
ammonium chloride (NH4Cl) corrodes the zinc container.
25. Primary cell – Which cannot be used again. Eg Mercury cell, Dry cell
26. Secondary cell or battery- which can be used again or recharged. eg Lead storage battery,
Nickel cadmium cell

27. Lead Storage battery: Anode : Pb Cathode : Pb packed with PbO2

 Electrolyte : 38% H2SO4
During discharging
2– –
Anode: Pb(s) + SO4 (aq) → PbSO4(s) + 2e
2– + –
Cathode: PbO2(s) + SO4 (aq) + 4H (aq) + 2e → PbSO4 (s) + 2H2O (l )
overall cell reaction consisting of cathode and anode reactions is:
Pb(s) + PbO2 (s) + 2H2 SO4 (aq) → 2PbSO4 (s) + 2H2O(l)
On charging the battery the reaction is reversed, Anode becomes cathode and cathode
becomes anode.
28. Cell used in Apollo space programme- Fuel cell
29. Fuel cell- It is a cell which converts energy produced during combustion of fuels into electrical
energy.
30. Fuel Cell : Anode&Cathode : Porous C Electrolyte : Aq NaOH
–
Cathode: O2(g) + 2H2O(l ) + 4e- --------→ 4OH (aq)
– –
Anode: 2H2 (g) + 4OH (aq) --------→ 4H2O(l) + 4e
31. Cell used in hearing aids, watches – Mercury cell
32. Mercury Cell:
– –
Anode(Zn-Hg) : Zn(Hg) + 2OH → ZnO(s) + H2O + 2e
– –
Cathode(HgO-C) : HgO + H2O + 2e → Hg(l ) + 2OH
33. Cell does not have long life- Dry Cell
34. Dry Cell:
2+ –
Anode(Zn) : Zn(s) → Zn + 2e
–
Cathode(Graphite) : MnO2 + NH4 + + e → MnO(OH) + NH3
35. Cell used in automobiles and inverters – Lead storage cell
36. Standard cell potential, E ͦcell = E ͦcathode – E ͦanode (Electrode with lower reduction potential
acts as anode and Electrode with higher reduction potential acts as cathode.)
37. Element with lower standard reduction potential(E ͦ) value is more reactive and get oxidised
easily and act as reducing agent where as element with higher standard reduction potential
value is less reactive and get easily reduced and act as oxidising agent
38. We can’t store solution of less reactive metal(higher E ͦ) in a container made of more reactive
metal( Lower E ͦ )
39. Corrosion of Iron :
2+ –
Oxidation: Fe (s)→ Fe (aq) +2e
+ –
Reduction: O2 (g) + 4H (aq) +4e → 2H2O(l)
2+ +
Atomospheric oxidation : 2Fe (aq) + 2H2O(l) + ½O2(g) → Fe2O3(s) + 4H (aq)
40. More reactive metal (having E ͦ more than iron) will be used to coat iron (Fe) to prevent Fe
from corrosion.

41. Standard Gibbs energy, , N is number of electrons, F is faraday’s constant =

96500 C, E ͦcell is Standard cell potential
42. ∆rG ͦ = –2.303 RT log Kc, Kc is equilibrium constant, R = 8.314 J/K/mol, T is temperature in Kelvin
43. E ͦcell = 0.0591log Kc
n

44. Difference between electrochemical and electrolytic cell

Electrochemical cell Electrolytic cell

It is a device to convert chemical energy It is a device to convert electrical energy
to electrical energy. to chemical energy.
 It is based on redox reaction which is The redox reaction is non spontaneous
spontaneous
45.
 CHAPTER 3 (CHEMICAL KINETICS)
1. Rate of reaction- It is change in concentration of any one of reactant or product with time.
2. Average rate:

3. Units of rate of reaction is always mol/L/sec or bar/sec or atm/sec. Does not depend on order of
reaction.
4. Order of reaction- It is the sum of power of concentration of reactants in the rate law expression.
5. Molecularity - It is defined as the number of reacting particles which collides simultaneously to bring
about the chemical change.
6. Factors affecting rate of reaction-
i) Concentration of reactants- Rate of reaction increases with increase in concentration of
reactants.
ii) Surface area of reactants- More the surface area more is the rate of reaction. Powered
substances have more surface area.
iii) Temperature- Rate of reaction increases with increase in temperature. For every 10 ͦ rise in
temperature, rate of reaction gets doubled.
iv) Catalyst – Catalysts increases the rate of reaction by lowering the activation energy of the
reaction. It does not alter ΔG, Gibbs energy and equilibrium constant (K) of reaction
7. Rate constant(k) - It is defined as the specific rate of reaction when the molar concentrations of the
reactants is taken to be unity.
8. Units of rate constant for any order of reaction is given by formula (mol/L)1-n s-1 or (bar)1-n s-1 where n is
order of reaction.
9. Characteristics of rate constant-
i) Greater the value of rate constant, faster is the reaction.
ii) Each reaction has a particular value of rate constant at a particular temperature.
iii) The value of rate constant for the same reaction changes with temperature.
iv) The value of rate constant for a reaction doesn’t depend upon the concentration of the reactants.
10. Slowest step of the reaction is the rate determining step of the reaction.
11. Difference between order and molecularity-
Order of reaction Molecularity of reaction

It is the sum of power of concentration It is defined as the number of reacting

of reactants in the rate law expression. particles which collides simultaneously
to bring about the chemical change.

It can be fractional or zero It cannot be fractional or zero

It is determined experimentally It is determined theoretically

It is applicable for both elementary and It is applicable only for elementary

complex reactions reactions

Order is given by the slowest step Molecularity of the slowest step is same
as the order of the overall reaction.

12. Elementary Reactions- Single stepped reactions are called elementary reactions.
13. Complex reactions- Reactions taking place in more than one step.
14. Pseudo first order reactions- These are the reactions which appears to be higher order but actually
follows kinetics of first order. Examples- Hydrolysis of ester, Inversion of cane sugar. In both these
examples, water is present in excess.
15. Condition for a reaction to behave as pseudo first order reaction- One of the reactants is present in
excess.
16. Threshold energy- It is the Minimum energy which reactant molecules must possess in order to convert
to products.
17. Activation Energy – It the extra energy which is to be supplied to reactant molecules to make their
energy equal to or greater than threshold energy.
18. Collision Frequency- The number of collisions between the reacting molecules taking place per second
per unit volume is known as collision frequency(Z).
19. Zero Order reaction:

20. First order reaction:

For gaseous phase

21. Graphs –

22. For zero order reaction-

Order of reaction = Zero

Units of rate constant (k) = mol/L/s
Slope= -k
Intercept = [R0]
23. For First Order Reaction-
Order of reaction = First
Units of rate constant (k) = s-1
Slope= -k
Intercept =ln [R0]

Order of reaction = First

Units of rate constant (k) = s-1
Slope= -k/2.303
Intercept =log [R0]

24. .Arrhenius Equation –

-Ea /RT
25. Arrhenius equation: k = A e (exponential form)
ln k = – Ea/RT + ln A (logarithmic form), A is the Arrhenius factor or the frequency factor or pre-
exponential factor
-Ea /RT
26. The factor e corresponds to the fraction of molecules that have kinetic energy greater
than Ea
27. Half-life of a reaction(t1/2)- It is the time in which the concentration of a reactant is reduced to
one half of its initial concentration.

28. Half life for zero order:

29. Half life for first order:

30. A catalyst does not alter Gibbs energy, ΔG of a reaction. It catalyses the spontaneous reactions but
does not catalyse nonspontaneous reactions.
31. A catalyst does not change the equilibrium constant of a reaction
32.
33. Arrhenius equation at two different temperatures:
 CHAPTER- 4 (d and f Block Elements)
Give reason for the following:
1) Zn, Cd and Hg are not considered as transition metals.
And. Because they have completely filled d orbitals in the ground state as well as in their oxidation
state.
2) Cu and Ag has completely filled d orbitals in their ground state but still they are considered as
transition elements.
Ans. They have incompletely filled d orbitals in their oxidation state.
3) There is irregular variation in the ionisation enthalpies of elements of first transition series (3d
series).
Ans. Due to varying degree of stability of different 3d configuration.
4) Highest oxidation state of metal is exhibited in its oxide or fluoride only.
Ans. Because of the high electronegativity and small size of oxygen and fluorine.
5) Cu+ is not stable in aqueous solution.
Ans. Because it undergoes disproportionation to form Cu 2+ ion. The higher stability of Cu2+ is due to
its high negative hydration enthalpy which compensates 2nd ionisation enthalpy of Cu.
6) Actinoid contraction is greater from element to element than lanthanoid contraction.
Ans. Because of more poorer shielding effect of 5f electrons than 4f electrons.
7) Transition metals and many of their compounds show paramagnetic behaviour.
Ans. Because of presence of unpaired electrons.
8) The enthalpies of atomisation of transition metals are high.
Ans. Because of presence of large number of unpaired electrons resulting in stronger metallic bonds.
9) Transition metals form coloured complexes.
Ans. Because of unpaired electrons and d- d transition.
10) Transition metals and their compounds act as good catalyst.
Ans. Because they show variable oxidation states and provide large surface area.
11) Transition elements form interstitial compounds.
Ans. Because of the presence of voids in their crystal lattice in which small atoms can easily occupy
positions.
12) d1 configuration is very unstable in ions
Ans. Because these ions have tendency to lose the only electron present in d subshell to acquire d 0
configuration.
13) The highest oxidation state is exhibited in oxo- anions of a metal.
Ans. Because oxygen is highly electronegative and has tendency to form multiple bonds
14) The chemistry of actinoids is not so smooth as that of lanthanoids
Ans. Because actinoids are radioactive in nature and show large number of oxidation states because
of small energy difference between 5f, 6d and 7s.
 15) Zn2+ salts are white or colourless while Cu2+ salts are coloured.
Ans. Zn2+ has no unpaired electron while Cu2+ has unpaired electron which lead to d- d transition.
16) Zn is soft where as Cr is hard.
Ans. Zn has no unpaired electron resulting in weak metallic bonds while Cr has five unpaired
electrons resulting in stronger metallic bonds.
17) Mn(III) undergoes disproportionation reaction easily.
Ans. Mn 3+ is less stable and changes to Mn2+ which has stable half filled d configuration.
18) Actinoids exhibit much larger number of oxidation states than the lanthanoids.
Ans. Due to small energy gap between 5f, 6d and 7s.
19) Among lanthanoids Ln(III) compounds are predominant. However in solutions or in solid
compounds, +2 and +4 ions are also obtained.
Ans. They show +2 and +4 state to attain extra stable f0 & f7 configuration.
20) Mn2+ is much more resistant than Fe2+ towards oxidation.
Ans. Mn2+ has stable half filled d5 configuration so does not get oxidised to Mn3+ while Fe2+ has d4
configuration so gets easily oxidised to Fe3+ which has stable half filled d5 configuration.
21) There is hardly any increase in atomic size with increasing atomic numbers in series of
transition metals.
Ans. With increase in atomic number in a series , the increased nuclear charge is partly cancelled by
the increased shielding effect of electrons in the d orbitals.
22) Transition metals show variable oxidation states.
Ans. Because of almost similar energies of both (n-1) d and ns orbitals due to which electrons from
both participate in bonding.
23) The metallic radii, physical and chemical properties of third (5d) transition series are virtually
the same as those of corresponding members of second series(4d).
Ans due to lanthanoid contraction.
24) Zr and Hafnium have same atomic radii or have similar properties.
Ans. Due to lanthanoid contraction
25) Highest fluoride of Mn is MnF4 where as the highest oxide is Mn2O7.
Ans. Because of tendency of oxygen to form multiple bonds.
26) Eu2+ is a strong reducing agent
Ans. Because it changes to Eu3+ as +3 is the common oxidation state of lanthanoids
27) Orange colour of dichromate ion changes to yellow in alkaline medium.
Ans. Due to conversion of dichromate to chromate ion in alkaline medium.
28) E0 M2+/M values for transition metals show irregular variation.
Ans. Due to irregular variation of ionisation enthalpies .
29) Mn2O7 is acidic whereas MnO is basic
Ans. Higher the oxidation state more is the tendency to gain the electron and hence higher is acidic
character while lower oxidation state means tendency to donate electrons and hence basic character
30) Transition metals form large number of complex compounds
Ans. Due to small size and high nuclear charge of ion and availability of d orbitals
31) The higher oxidation states are usually exhibited by members in the middle of series of
transition metals.
Ans. Because of greater number of unpaired electrons
32) The metal- metal bonding is more frequently found with 2nd and 3rd series of transition metals.
Ans. Because of larger size of 4d and 5d elements, valence electrons are less tightly held.
33) Actinoids show irregularities in their electronic configuration
Ans. Due to extra stability of f0, f7 and f14 configuration.
34) Sc3+ is colourless in aqueous solution where as Ti3+ is coloured.
Ans. Sc 3+ has no unpaired electron while Ti3+ has one unpaired electron in d orbital
35) Actinoids show large number of oxidation states.
Ans. Because of comparable energies of 5f, 6d and 7s.
36) E0 value for Mn3+/Mn2+ couple is much more positive than that of Cr3+/Cr or Fe3+/Fe2+
Ans. Due to much larger third ionisation enthalpy of Mn as Mn2+ has highly stable d5 configuration.
37) Separation of lanthanoid elements is difficult.
Ans. Due to lanthanoid contraction.
38) d block elements exhibit more oxidation states than f block elements.
Ans. Because of less energy gap between d and s subshell in d block while f block elements have
large energy gap between f and d subshell.
39) Cr2+ is stronger reducing agent than Fe2+
Ans. Because after the loss of one electron Cr2+ becomes Cr3+ which has more stable half filled
configuration (t2g3) in a medium like water.
40) Of d4 species, Cr2+ is strongly reducing while manganese 3+ is strongly oxidising.
Ans. Because after loss of one electron Cr2+ becomes Cr3+ which has stable half filled configuration
(t2g3) while Mn3+ after loss of electron becomes Mn2+ which has stable half filled configuration (d5).
41) Transition metals form alloys.
Ans because they have similar atomic radii.
42) Name lanthanoid which exhibits +4 oxidation state.
Ans. Cerium.
43) Name element of 3d series which shows maximum number of oxidation states.
Ans. Mn because of maximum number of unpaired electrons in 3d and 4s orbitals.
44) Which element of 3d series having highest melting point and why
Ans. Chromium (Cr) because of large number of unpaired electrons resulting in strong metallic
bonds.
 45) Which element can stabilize the higher oxidation states like +6, +7 and +8 of transition metals
to the greatest extent and why?
Ans. Oxygen because of its tendency to form multiple bonds.
46) Which element of 3d series can show an oxidation state of +1 and why?
Ans. Copper (Cu) because after losing one electron it gets completely filled electronic configuration
(3d10)
47) Which element of 3d series is a strong oxidizing agent in the +3 oxidation state and why?
Ans. Mangenese (Mn) because Mn2+ has extra stability due to half-filled d-subshell so Mn3+ ion easily
gain one electron to attain stable Mn2+ configuration.
48) Ti4+ is colorless whereas V4+ is colored in an aqueous solution.
Ans. Ti4+ has no d electron so no d-d transition while V4+ has one electron in d so d-d transition
takes place.
49) Write one difference between transition elements and p-block elements with reference to
variability of oxidation states.
Ans. Transition elements, in general, show variable oxidation states which differ by 1 unit, whereas p-
block elements show variable oxidation states which differ by 2 units.
50) Name an element of the lanthanoid series which is well known to show a +4 oxidation state. Is
it a strong oxidizing agent or a reducing agent?
Ans. Cerium. It is a strong oxidizing agent
51) Name the element in 3d series (ist transition series) which shows only one (+3) oxidation state
and why?
Ans. Scandium because it achieves stable noble gas configuration after losing one electron.
52) Name an important alloy that contains some of the Ianthanoid metals
Ans. Misch metal
53) Write the formula of an oxo-anion of chromium (Cr) in which it shows the oxidation state equal
to its group number.
Ans. Cr2072-
54) Out of Fe and Cu, which has a higher melting point and why?
Ans. Fe because of strong metallic bond due to large number of unpaired electrons.
55) Cr2+ is reducing in nature while with the same d-orbital configuration (d4), Mn3+ is an oxidizing
agent.
Ans. Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t2g level.
On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which has
extra stability.
56) In a transition series of metals, the metal which exhibits the greatest number of oxidation
states occurs in the middle of the series.
Ans. because, in the middle of the transition series, the maximum number of electrons are available
for sharing with others.
57) What are the transition elements? Write two characteristics of the transition elements.
Ans. Transition elements are those elements that have incompletely filled (partly filled) d-subshell in
their ground state or in any one of their oxidation states.
Characteristics:

1. Transition elements show variable oxidation states.

2. They exhibit catalytic properties.

58) The E°M2+|M for copper is positive (0.34 V). Copper is the only metal in the first series of
transition elements showing this behavior. Why?

Ans. This is because copper has a high enthalpy of atomization and enthalpy of ionization. Therefore,
the high energy required to convert Cu(s) to Cu2+ (aq) is not balanced by its hydration enthalpy.

59) Chromium is a typical hard metal while mercury is a liquid.

Ans. Because of strong metallic bond in Cr due to large number of unpaired electrons while mercury
has weak metallic bond due to no unpaired electron.

60) In 3d series (Sc to Zn), which element has the lowest enthalpy of atomization and why?

Ans. Zn because it has no unpaired electrons and hence weak metallic bonding.

61) Metal-metal bonding is more frequent for the 4d and the 5d series of transition metals than that
for the 3d series.

Ans. The second and third transition series metals show a great tendency to form strong M-M bonds
than the first transition series elements.

62) E° value for (Mn2+|Mn) is negative whereas for (Cu2+| Cu) is positive.

Ans. The negative value of E° (Mn2+| Mn) is due to the stability of the half-filled d-subshell in
Mn2+(3d5). The positive E°(Cu2+|Cu) is due to the high ionization enthalpy and high enthalpy of
atomization of copper.

63) How does the colour of Cr2O72- change when treated with an alkali?

Ans. The orange color of Cr2O72- change to yellow due to the formation of chromate ion.
Cr2O72- + 2OH– → 2Cr2O72- + H2O (Yellow)

64) The metallic radii of the third (5d) series of transition metals are virtually the same as those of
the corresponding group members of the second (4d) series.

Ans. Due to lanthanoid contraction.

65) There is a general increase in density from titanium (Z = 22) to copper (Z = 29).

Ans. because as we move along a transition series from left to right, the atomic radii decrease due to
an increase in effective nuclear charge. Therefore, the atomic volume decreases but at the same
time atomic mass increases. Therefore, density (mass/volume) increases.

66) Following are the transition metal ions of 3d series.

Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers: Ti = 22, V = 23, Mn = 25, Cr = 24)
Answer the following:
(i) Which ion is most stable in an aqueous solution and why?
 (ii) Which ion is a strong oxidizing agent and why?
(iii) Which ion is colorless and why?

Ans. (i) Cr3+ because of the half-filled t2g3 configuration.

(ii) Mn3+ due to stable d5 configuration of Mn2+
(iii) Ti4+ because it has no unpaired electrons.

67) La(OH)3 is more basic than Lu(OH)3. Why?

Ans. Due to lanthanoid contraction

68) La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.

Ans. As they do not have unpaired electron and so no f-f transition takes place.

69) Among the divalent cations in the first series of transition elements, manganese exhibits the
maximum paramagnetism.

Ans. It has maximum number of unpaired electrons.

70) Mn3+ is a good oxidizing agent.

Ans. due to stable d5 configuration of Mn2+

71) E°M2+/M values are not regular for first-row transition metals (3d series).

Ans. because of irregular variation of ionization enthalpies (IE1 + IE2) and the sublimation energies.

72) Although ‘F’ is more electronegative than ‘O’, the highest Mn fluoride is MnF4, whereas the
highest oxide is Mn207.

Ans. Because of tendency of oxygen to form multiple bonds.

73) What is lanthanoid contraction? What is its cause and consequences?

Ans. The steady decrease in atomic or ionic radii of lanthanoids as we move from lanthanum to
lutetium is called lanthanoid contraction.

Cause: It is caused due to increased nuclear charge and poor shielding effect of 4f electrons.

Consequences: 1) Similarity in the atomic radii of 4d and 5d series elements.

2) Difficulty in the separation of lanthanoids.

3) Basic strength of hydroxides decreases from La(OH)3 to Lu(OH)3.

74) Name a member of the lanthanoid series which is well known to exhibit a +2 oxidation state.

Ans. Europium

75) HCl is not used to acidify KMnO4 solution. Why?

Ans. HCl is not used to the acidify KMnO4 solution because KMnO4 is a very strong oxidizing agent
and it can oxidize HCl to liberate chlorine gas.

76) Zn, Cd and Hg are soft metals. Why?

Ans. Because of weak metallic bond due to absence of unpaired electron.

77) E° value for the Mn3+/Mn2+ couple is highly positive (+1.57 V) as compared to Cr3+/Cr2+.

Ans. Mn2+ exists in half-filled d5 state which is very stable while Mn3+ is d4 which is not so stable.
Mn3+ can be easily reduced to Mn2+ . While Cr3+ is d3 is half-filled (t2g3) is stable in nature and Cr2+ is
d4, has one extra electron which it would like to donate to attain the stable half-filled (t2g3)
configuration.

78) When MnO2 is fused with KOH in the presence of KNO3 as an oxidizing agent, it gives a dark
green compound (A). Compound (A) disproportionates in an acidic solution to give a purple
compound (B). An alkaline solution of compound (B) oxidizes Kl to compound (C), whereas an
acidified solution of compound (B) oxidizes Kl to (D). Identify (A), (B), (C), and (D).
Ans When MnO2 is fused with KOH in the presence of KNO3, as an oxidizing agent, it gives a dark
green compound (A).

79) When chromite ore FeCr2O4 is fused, with NaOH in presence of air, a yellow-colored
compound (A) is obtained, which on acidification with dilute sulphuric acid gives a compound
(B). Compound (B) on reaction with KCI forms an orange colored crystalline compound (C).
(i) Write the formulae of the compounds (A), (B), and (C).
(ii) Write one use of the compound (C).
Ans.

(ii) Potassium dichromate (C) is used as a powerful oxidizing agent in redox titrations in the
laboratories
Important Points:
1. General electronic configuration of Lanthanoids: [Xe] 4f1-14 5d0-1 6s2.
2. Most common oxidation state of lanthanoids is +3, However, occasionally +2 (Eu+2 and Yb+2)
and +4 ions (Ce+4 and Tb+4) in solution or in solid compounds are also obtained.
3. Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions.
Colour of these ions may be attributed to the presence of unpaired electrons in f subshell.
4. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and
Lu3+) are all paramagnetic.
5. Alloy of lanthanoid: Mischmetal which consists of a lanthanoid metal (~ 95%) and iron (~5%)
and traces of S, C, Ca and Al. A good deal of mischmetall is used in Mg-based alloy to
produce bullets, shell and lighter flint.
6. General electronic configuration of Actinoids: [Rn] 5f1-14 6d0-1 7s2.
7. The actinoids show +3 oxidation state in common.
8. The magnetic properties of the actinoids are more complex than those of the lanthanoids.
 CHAPTER 5 (COORDINATION COMPOUNDS)

1. Difference between a double salt and a complex salt

2. In coordination compounds, metals show two types of linkages (valences)-primary and

secondary.
3. Primary valencies- Ionisable, tells Oxidation state, non-directional
4. Secondary Valencies – Non-ionisable, tells coordination number, tells geometry(directional)
5. Number of ions produced by a coordination compound like [Cu(NH3)4]Cl2 in solution =
Number of ions outside the coordination sphere ( in this example 2 Cl-) + One (Coordination
sphere written in square brackets)
6. In case of netural coordination compound (having no ions outside the coordination sphere and
no charge on the coordination sphere like [Ni(CO)4]) --------→Number of ions is equal to zero.
7. More the number of ions produced more is the conductivity.
8. Coordination number of metal when coordination compd contains
i) Only unidentate ligands = Number of unidentate ligands
ii) Only bidentate ligands = 2 X Number of bidentate ligands ( en, Ox or C2O4)
iii) Both unidentate and bidentate ligands = Number of unidentate ligands + 2 X number
of bidentate ligands
9. Ligands - -Ions or molecules bound to the central atom/ion in the coordination entity are called
ligands.
10. Types of ligands
Unidentate/ Monodentate Is bound to a metal ion through a single donor atom.
ligand e.g.,Cl−,H2O , NH3, I-, Br-, CO, OH-, NO2-, ONO-, CN-, SCN-,
CH3COO-
Bidentate ligand Is bound to a metal ion through two donor atoms. e.g.,en or
H2NCH2CH2NH2 (ethane 1,2-diamine) , Ox orC2O42− (oxalate
ion)
Polydentate ligand It is linked to a metal ion through several donor atoms. e.g.,
Ethylenediaminetetraacetate ion (EDTA ) is a hexadentate
ligand.
Chelate ligands When a di or polydentate ligand uses its two or more donor
atoms to bind to a single metal ion and form a ring structure it is
said to be a chelate ligand.
Coordination compounds with chelate ligands are more stable
than the compounds with monodentate ligands as the complex
has ring structure
Ambidentate ligands Can bind to the central metal atom through any of the two donor
atoms present in it. e.g., NO2−, ONO-SCN−,NCS-,CN-, NC-
11. Homoleptic and heteroleptic complexes
 12. Naming of Coordination Compounds-
i) In case of coordination compounds having counter ions, cation is written first and then
anion, simply means if counter ions are written first then their name is written first and
then name of coordination entity (written in square brackets) or vice versa.
ii) If counter ions of one kind are more than once, numerical prefixes should not be used.
iii) While naming coordination entity, ligands are named first and then the metal ( metal is
written first in the coordination entity and then the ligands).
Ligands Name Ligands Name

F- fluorido NCS- isothiocyanato

Cl- chlorido CO32- carbonato

Br- bromido NO3- nitrato

I- iodido CO carbonyl

NO2- nitrito-N CH3NH2 methyamine

ONO- nitrito-O NH2CH2CH2NH2 or Ethane-1,2-

en diamine

SO42- sulphato PH3 phosphine

Ox or C2O4- oxalato (C6H5)3P triphenylphosphine

CN- cyanido H2O aqua

CH3COO- acetato NH3 ammine

SCN- thicyanato NO nitrosyl

Py or C6H5N pyridine

These names to be used only when they act as ligand otherwise their normal names to be
used like if Cl is outside the coordination sphere, we use chloride instead of chloride.

iv) When the coordination centre is bound to more than one ligand, the names of the
ligands are written in an alphabetical order which is not affected by the numerical
prefixes that must be applied to the ligands.
v) When there are many monodentate ligands of one type are present in the coordination
compound, we use numerical prefixes like di-, tri-, tetra-, and so on.
vi) If ligands like ethane-1,2-diamine, triphenylphosphine are present more than once in
the coordination sphere, then we use numerical prefixes like bis, tris, tetrakis etc
vii) After the ligands are named, the name of the central metal atom is written. If the
coordination complex is anionic, then the name of central metal atom ends in -ate.
Like Fe-→ ferrate, Cu -→ Cuperate, Ag -→ Argentate, Au -→ Aurate, Sn → Stannate.
viii) Then the oxidation state of metal is written in Roman numerals in the bracket.
13. Isomerism –
Structural isomerism – 4 types
Ionisation Isomerism Arises when the counter ion in a complex salt is itself a potential
ligand and can displace a ligand [Co(NH3)5SO4]Br and
[Co(NH3)5Br]SO4.

Linkage Isomerism Seen in a coordination compound containing ambidentate ligand,

ie, NO2−, ONO-SCN−,NCS-,CN-, NC- [Co(NH3)5(NO2)]Cl2 and
[Co(NH3)5(ONO)]Cl2
Coordination See when both cation and anion are coordination entities
Isomerism Arises from the interchange of ligands between cationic and
anionic entities [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]

Solvate Isomerism Arises due to the presence of solvent molecules as a ligand or as

free solvent molecules in the crystal lattice. [Cr(H2O)6]Cl3 and
[Cr(H2O)5Cl]Cl2.H2O

Stereoisomerism –
a) Geometrical Isomerism-
COORDINATIO [Ma2b2]
N NO-4 (Square [Pt(NH3)2Cl2]
planar
complexes)
Tetrahedral complexes do not show geometrical isomerism.
Reason: The relative positions of the unidentate ligands attached to the central metal atom
are the same with respect to each other

COORDINATIO [Ma2b4 ]
N NO 6 [Co(NH3)4Cl2 ]+
(Octahedral
complexes)

[M(a-a)2b2]
[CoCl2(en)2]+

[Ma3b3]
[Co(NH3)3(NO2)3
]

b) Optical Isomerism: Optical isomers are mirror images that cannot be superimposed on
one another and are called as enantiomers.

Optical [M(a-a)3]
Isomerism [Co(en)3] +3
 [M(a-a)2b2]
[CoCl2(en)2] +
Only cis form is
optically active .
Trans is optically
inactive because
it has plane of
symmetry
14. Valence Bond Theory:
Coordination Hybridisation Geometry
Number
6 d2sp3( inner orbital complex or Octahedral
low spin)-
sp3d2 (outer orbital complex or
high spin)
4 dsp2 Square planar

sp3 Tetrahedral

5 sp3d Trigonal bipyramidal

Strong ligands cause pairing of electrons but no pairing occurs when number of orbitals
required for hybridisation are already available as strong and weak ligand is concept of
Crystal field theory .
Strong ligands: NCS – < edta4– < NH3 < en < CN – < CO
Weak Ligands: I – < Br– < SCN – < Cl – < S2– < F – < OH – < C2O4 2– < H2O
C2O42- acts as strong ligand with Co
Magnetic behaviour- Paramagnetic (if unpaired electron is there)
Diamagnetic (if no unpaired electron is there)
15. Crystal Field Theory-
Octahedral complex –

The splitting of degenerate levels due to the presence of ligands in a definite geometry is
termed as crystal field splitting
 Tetrahedral Complexes-

For the same metal, the same ligands and metal-ligand distances
∆t = (4/9) ∆0
Low spin complexes are rarely observed in tetrahedral complexes as pairing energy is always
greater than the crystal field splitting energy in case of tetrahedral complexes.
16. Colour of the coordination compoundsis due to d-d transition of the electron.
In the absence of a ligand, crystal field splitting does not occur and hence the substance is
colourless. For example, the removal of water from [Ti(H2O)6 ]Cl3 on heating renders it
colourless.
 CHAPTER- 10 (BIOMOLECULES)
KEY POINTS EXPLANATIONS
Monosaccharides Cannot be hydrolysed further. eg- glucose, fructose,
ribose
Disaccharides Sucrose (α-D- glucose(C1) + β-D-fructose(C2)),
Maltose(α-D- glucose(C1) + α- D- glucose(C4))
Lactose (β-D-galactose(C1) + β-D-glucose(C4))
Polysaccharides Starch (two components—Amylose and Amylopectin) polymer
of α-D- glucose
Amylose- Water soluble,15-20% of starch, unbranched
chain, C1– C4 glycosidic linkage.
Amylopectin- Water insoluble, 80-85% of starch, branched
chain polymer, C1–C4 & C1–C6 glycosidic linkage
Cellulose- Straight chain polymer of β -D-glucose
C1-C4glycosidic linkage (β-link),
not digestible by human
constituent of cell wall of plant cells
Glycogen- Highly branched polymer of α-D- glucose
.found in liver, muscles and brain.
Reducing sugars Aldehydic/ ketonic groups free so reduce Fehling’s/
Tollens solution and. Eg- All monosaccharides, maltose
and lactose
Non- Aldehydic/ ketonic groups are bonded so cannot reduce
reducing Fehling’s solution and Tollens’ reagent. Eg- Sucrose, All
sugars polysaccharides
Anomers. The two cyclic hemiacetal forms of glucose differ only in
the configuration of the hydroxyl group at C1, called
anomeric carbon Such isomers, i.e., α –form and β -form,
are called anomers.
Reactions of Rection with HI – n-hexane is formed
glucose

Indicates six carbon atoms are linked in a straight chain.

Reaction with hydroxylamine(NH2OH)- Glucose Oxime is
formed

Reaction with hydrogen cyanide (HCN)- Cyanohydrin is

formed

Both the reactions indicate the presence of a carbonyl

group (>C = O) in glucose.
 Reaction with bromine water – Gluconic acid is formed

Reaction indicates that the carbonyl group is present as an

aldehydic group.
Reaction with acetic anhydride – pentaacetate of glucose
is formed

It indicates the presence of five –OH groups.

Reaction with nitric acid- Saccharic acid is formed

It indicates the presence of a primary alcoholic (–OH)

group in glucose.
Reactions not Despite having the aldehyde group, glucose does not give
explained by open Schiff’s test and it does not form the hydrogensulphite
chain structure of
addition product with NaHSO3 .
glucose Or
Evidence of cyclic The pentaacetate of glucose does not react with
structure of glucose hydroxylamine indicating the absence of free —CHO group.
Glucose is found to exist in two different crystalline forms
ie, α –form and β -form.
Invert sugar Sucrose is dextrorotatory but after hydrolysis gives
dextrorotatory glucose and laevorotatory fructose. Since the
laevorotation of fructose (–92.4°) is more than dextrorotation
of glucose (+ 52.5°), the mixture is laevorotatory. Thus,
hydrolysis of sucrose brings about a change in the sign of
rotation, from dextro (+) to laevo (–) and the product is named
as invert sugar
Glycosidic linkage Linkage between two monosaccharide through O
(Found in
Disaccharides(oligo
saccharides),
Polysaccharides)
Importance Major portion of our food. / used as storage molecules as
of starch in plants and glycogen in animals/.
Carbohydrate Cell wall of bacteria and plants is made up of
s cellulose./wood and cloth are cellulose /
provide raw materials for many important industries like
textiles, paper, lacquers and breweries.
essential amino which cannot be synthesised in the body and must be
acids obtained through diet, eg- Valine, Leucine
Nonessential amino which can be synthesised in the body eg - Glycine,
acids Alanine
Amino Acids All other naturally occurring a-amino acids and have L
configuration.
All are optically active(except glycine)
Zwitter ion. In aqueous solution, amino acids exist as a dipolar ion
known as Zwitter ion.
Peptide linkage peptide linkage is an amide formed between –COOH group
(Present in and –NH2 group of two successive amino acids in peptide
chain.
dipeptide, tri or
soon, polypeptide)
10- str. of sequence of amino acids that is said to be the primary
proteins: structure of protein
20- str. of secondary structure of protein refers to the shape in which
proteins: a long polypeptide chain can exist.
They are found to exist in two types of structures viz. α -
helix and β -pleated sheet structure.
Both stabilized by H-bonding
Tertiary structure Further folding of the secondary structure. It gives rise to
of proteins: two major molecular shapes viz. fibrous and globular.
Satbilised by hydrogen bonds, disulphide linkages, van der
Waals and electrostatic forces of attraction
Fibrous proteins Polypeptide chains run parallel, held together by hydrogen
and disulphide bonds,
fibre– like structure.
Water insoluble.
Eg- are keratin(in hair, wool, silk) and myosin (present in
muscles).
Globular proteins chains of polypeptides coil around to give a spherical shape.
water soluble.
Eg-Insulin and albumins
Native Protein Protein found in a biological system with a unique three-
dimensional structure and biological activity
Denaturation of When a protein is subjected to physical change like change
Proteins in temperature or chemical change like change in pH, the
hydrogen bonds are disturbed. Due to this, globules unfold
and helix get uncoiled and protein loses its biological
activity. This is called denaturation of protein.
During denaturation, 2° and 3° structures are destroyed
but 1º structure remains intact.
eg- The coagulation of egg white on boiling, curdling of milk
Enzymes Enzymes are essential biological catalysts which are
required to catalyse biological reactions, e.g., maltase,
lactase, invertase, etc. Almost all the enzymes are globular
proteins
Fat soluble vit Vitamins A, D, E and K.
Stored in liver and adipose (fat storing) tissues
Water soluble vit Vitamin B, C.
these vitamins must be supplied regularly in diet because
they are readily excreted in urine cannot be stored (except
 vitamin B12) in our body

Vitamins –sources- Vit- A (Fish liver oil, carrots)- Night blindness

Deficiency diseases
Vitamin B1 (Yeast, milk,)- Beri beri
Vit-B2 (Milk, egg white)- Cheilosis
Vit- B6 (Yeast, milk,)- Convulsions
Vit- B12 (Meat, fish,)- Pernicious anaemia
Vit C(Citrus fruits)- Scurvy,
Vit D(Exposure to sunlight, fish and egg yolk)- Rickets,
osteomalacia
Vit E(wheat oil, sunflower oil)- fragility of RBCs

Vit K(leafy vegetables)- Increased blood clotting time

DNA pentose sugar (D-2-deoxyribose) +phosphoric acid

+nitrogenous bases [Adenine(A),Guanine(G),Cytosine
(C),Thymine (T )]
Double stranded
Both strands are complementary to each other because the
hydrogen bonds are formed between specific pairs of
bases. (Aform 2 H bonds with T and C forms 3 H bonds with
G)- AT, CG
RNA pentose sugar (β D ribose) + phosphoric acid +
nitrogenous bases (A, G, C, U )
Instead of Thymine, uracil is present
Nucleoside sugar + base

Nucleotide sugar + base + phosphate

Polynucleotide Linkage is phosphodiester

 ORGANICS
REASONING QUESTIONS
HALOALKANES AND HALOARENES

1. Benzyl chloride is highly reactive towards the SN1 reaction.

Ans. Benzyl carbocation is stabilized by resonance.
2. 2-bromobutane is optically active but 1-bromobutane is optically inactive.
Ans. 2-Bromobutane is chiral, therefore, optically active, whereas 1-chlorobutane is not chiral, therefore optically
inactive.
3. The C-Cl bond in chlorobenzene is shorter than in CH3Cl.
Ans. Because of partial double bond character of C-Cl bond in chlorobenzene due to resonance.
4.Sulphuric acid not used during reaction of alcohols with KI.
Ans. Because it converts KI to HI and then oxidises it to I2.
5. Alkyl halides though polar are immiscible with water. Or Haloalkanes and haloarenes are insoluble in water.
Ans. Because they are unable to form hydrogen bond with water molecules as well as not able to break the bonds
already present between water molecules.
6. Grignard reagents should be prepared under anhydrous conditions.
Ans. Because they react with water or moisture to give hydrocarbons.
7. Dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
Ans. Because in chlorobenzene C-Cl bond is sp2 hybridised where as in cyclohexyl chloride the C−Cl bond is sp3
hybridised. As sp2 has more s character and more electronegative than sp3, chlorobenzene is less polar than
cyclohexyl chloride.
8. p-Chlorobenzene has higher melting point than those of o- and m-isomer.
Ans. because p- chlorobenzene being more symmetrical fits closely in the crystal lattice than o- and m- isomer.
9. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in presence of alcoholic
KOH, alkenes are major products.
Ans. Alkoxide ion (OR-) present in alcoholic KOH, is not only a strong nucleophile but also a strong base so
preferentially eliminate HCl from alkyl halide to form alkenes.
10. Out of chlorobenzene and cyclohexyl chloride, which is more reactive towards nucleophilic substitution reaction
and why?
Ans. Cyclohexyl chloride is more reactive because C-Cl bond has pure single bond character in cyclohexyl chloride
while in chlorobenzene, C-Cl has partial double bond character due to resonance.
11. t-butyl bromide is more reactive towards SN1 reaction as compared to n-butyl bromide.
Ans. due to higher stability of tertiary carbocation than primary carbocation.
12. Chloroform is stored in closed dark coloured bottles completely filled so that air is kept out.
Ans. Because chloroform is slowly oxidised by air in presence of light to poisonous gas called phosgene(COCl2)
13. Thionyl chloride method is preferred for preparing alkyl chlorides from alcohols.
Ans. Because the byproducts (SO2, HCl) formed in the reaction are gases in nature and pure alkyl chlorides are left
behind.
14. SN1 reactions are accompanied by racemisation in optically active alkyl halides.
Ans. In SN1 reaction, carbocations are formed which are planar so attack of nucleophile on it can occur from both
front and backside giving a racemic mixture.
15. Haloalkanes are more reactive than haloarenes.
Ans Because in haloalkanes C-Cl bond has pure single bond character while in haloarene, C-Cl has partial double
bond character due to resonance.
16. Electrophilic reactions in haloarenes occur slowly.
Ans. Because halogen in haloarenes withdraws electron through -I effect and releases electrons through +R effect.
The -I effect is stronger than +R effect and causes net electron withdrawal.
17. Although chlorine is an electron withdrawing group, yet it is ortho, para directing in electrophilic aromatic
substitution reactions.
Ans. As weaker +R effect of Cl which stabilise the carbocation formed tends to oppose stronger -I effect of Cl which
destabilise the carbocation at ortho and para positions and makes deactivation less for ortho and para position.
18. n-butyl bromide has higher boiling point than t-butyl bromide.
Ans. n-butyl bromide has larger surface area, larger Vander Waal’s forces and hence higher boiling point than t-
butyl bromide.
19. Racemic mixture is optically inactive.
Ans. Racemic mixture contains d and l enantiomers in equal proportions. As the rotation due to one enantiomer is
cancelled by equal and opposite rotation of another enantiomer so it is optically inactive.
20. The presence of nitro group (-NO2) at o/p positions increases the reactivity of haloarenes towards nucleophilic
substitution reactions.
Ans. The presence of nitro group (-NO2) at o/p positions in haloarenes helps in the stabilisation of resulting
carbanion by -R and -I effects.
21. n-Butyl bromide has higher boiling point than f-butyl bromide.
Ans. n-butyl bromide has more surface area than i-butyl bromide, therefore, more van der Waals’ forces of
attraction, hence higher boiling point.
22. Suggest a possible reason for the following observations:
(i) The order of reactivity of haloalkanes is RI > RCl > RBr.
(ii) Neopentyl chloride (CH3)3CCH2Cl does not follow SN2 mechanism.
Ans.

23.

24. Why is methyl chloride hydrolysed more easily than chlorobenzene?

Ans. It is due to double bond character in chlorobenzene due to resonance which is difficult to break as compared
to single bond (C—Cl) in CH3Cl.
25. SN1- Racemisation
26. SN2 – Inversion
27. Order of reactivity in SN1- Tertiary alkyl halides> Secondary alkyl halides> Primary alkyl halides
28. Order of reactivity in SN2- Primary alkyl halides> Secondary alkyl halides> Tertiary alkyl halides

ALCOHOLS, PHENOLS AND ETHERS

1. Alcohols have higher boiling points than hydrocarbons and ethers of comparable molecular masses.
Ans. Because of intermolecular hydrogen bonding in alcohols.
2. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses.
Ans. Alcohols form hydrogen bond with water molecules.
3. O-nitrophenol is steam volatile while p-nitrophenol is less volatile or o- nitrophenol has lower boiling
point than p-nitrophenol.
Ans. O-nitrophenol exists as discrete molecules due to intramolecular H- bonding while p-nitrophenol exists as
associated molecules because of intermolecular H- bonding.
4. O-nitrophenol is more acidic than o-methoxyphenol.
Ans. Due to –R and –I effect of the NO2 group, electron density in the O-H bond decreases and hence loss of a
proton becomes easywhile in o-methoxyphenol, due to +R effect of OCH3 , elctron density in the O-H bond
increases thereby making the loss of proton difficult.
5. Phenol is acidic but does not react with sodium bicarbonate solution.
Ans. Because phenol is weaker acid than carbonic acid and hence does not liberate CO2 from sodium
bicarbonate.
6. Ethers are insoluble in water.
Ans. They do not form H-bond with water.
7. Give reasons for the following:
(i) p-nitrophenol is more acidic than p-methylphenol.
(ii) Bond length of C—O bond in phenol is shorter than that in methanol.
(iii) (CH3)3C—Br on reaction with sodium methoxide (Na+ _OCH3) gives alkene as the main product
and not an ether.
Ans. (i) Due to -I and -R effect of NO2, p-nitrophenoxide ion is more stable than p-methyl phenoxide ions ( + I
and +R effect of—CH3 group)
(ii) It is due to partial double bond character of C-O bond in phenol due to resonance .
(iii) Tert. halide undergoes elimination reaction with strong nucleophile to form alkene and not ether.
8. Give reasons for the following:
(i) Phenol is more acidic than ethanol.
(ii) Boiling point of ethanol is higher in comparison to methoxymethane.
(iii) (CH3)3C—O—CH3 on reaction with HI gives CH3OH and (CH3)3C—I as the main products and not
(CH3)3 C—OH and CH3I
Ans. (i) It is because phenoxide ion is more stable than methoxide ion due to resonance
(ii) It is because ethanol is associated with intermolecular H-bonding, whereas methoxymethane is not.
(iii) It is because the reaction between (CH3)3C—O—CH3 and HI follows SN1 mechanism where product
formation is controlled by stability of carbocation. (CH3)3C+ (Tert. carbocation) is more stable than methyl
carbocation (CH3+) reacts with I- to form tert. butyl iodide and methanol.
9. The C—O—H bond angle in alcohols is slightly less than the tetrahedral angle (109°28).
Ans. It is due to repulsion between lone pair of electrons on oxygen with bonded pair of electrons.
10. Of the two alcohols (a) CH2=CH—CH2OH and (6) CH2=CH—CH2—CH2OH, which one will react more
easily with cone. HCl in the presence of ZnCl2?
Ans.

11. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method.
Ans. It is because secondary and tertiary alcohols, on dehydration lead to the formation of alkene and not
ethers due to the stability of 2° and 3° carbocation.
12. Account for the following:
(i) The boiling points of alcohols decrease with increase in branching of the alkyl chain.
(ii) Phenol does not give protonation reaction readily.
(iii) Phenylmethyl ether reacts with HI to give Phenol and Methyl iodide and not Iodobenzene and
Methyl alcohol.
Ans. (i) It is because branched chain alcohols have minimum surface area, therefore, minimum force of
attraction, hence, they have lower boiling point.
(ii) It is due to +ve charge on 3 out of 5 resonating structures of phenol. It cannot be protonated easily.
(iii) It is because of partial double bond character of C-O bond in phenol and phenoxide ion is stabilized by
resonance, whereas methoxide ion is not.
13. o- and p-nitrophenols are more acidic than phenol.
Ans. It is because —N02 group is electron withdrawing (- R effect), it increases the stability of o- and p-
nitrophenoxide ion (phenolate ion) as compared to phenoxide ion.
 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
1. Account for the following:
(i) CH3CHO is more reactive than CH3COCH3 towards reaction with HCN.
(ii) Carboxylic acid is a stronger acid than phenol.
Ans. (i) CH3CHO is more polar and has less stearic hindrance, therefore, more reactive with HCN than
CH3COCH3.
(ii) Carboxylate ions are more stable than phenoxide ions as negative charge is delocalised on two oxygen
atoms in carboxylate ions.
2. Account for the following:
(i) Cl—CH2COOH is a stronger acid than CH3COOH.
(it) Carboxylic acids do not give reactions of carbonyl group.
Ans.

3. There are two -NH2 groups in semicarbazide (H2NNHCONH2). However, only one is involved in the
formation of semicarbazone.
Ans. As lone pairs on the N of NH2 group attached to -CO- goes in resonance with carbonyl group and hence
not available for donation.
4. Ethanal is soluble in water.
Ans. It forms H-bond with water.
5. Although phenoxide ion has more number of resonating structures than Carboxylate ion, Carboxylic acid
is a stronger acid than phenol. Give two reasons.
Ans. In carboxylate ions, negative charge is delocalised over two oxygen atoms which is more stable.
Phenoxide is less stable as negative charge is delocalised over one oxygen atom and carbon atoms of benzene
ring.
6. Give reasons for the following:
(i) Ethanal is more reactive than acetone towards nucleophilic addition reaction.
(ii) (CH3)3C—CHO does not undergo aldol condensation.
(iii) Carboxylic acids are higher boiling liquids than alcohols.
Ans. (i) It is because ethanal is more polar than acetone due to only one methyl group, whereas in acetone,
there are two methyl groups which are electron releasing and reduce positive charge on carbonyl carbon and
also stearic hinderance is less in ethanal.
(ii) It is because (CH3)3C—CHO does not have alpha hydrogen.
(iii) It is due to greater intermolecular H-bonding in carboxylic acids than alcohols and they exist as dimers
7. Cyclohexanone forms cyanohydrin in good yield but 2, 4, 6-tri- methylcyclohexanone does not.
Ans.

8. Oxidation of aldehydes is easier than ketones.

 Ans. As aldehydes contain H atom on the carbonyl group but ketones do not. Cleavage of C-H bond in
aldehydes is easier than cleavage of C-C bond in ketones.
9. CH2=CHCOOH is more acidic than CH3CH2COOH
Ans. Because in CH2=CHCOOH, carbonyl group is attached to sp2 hybridised carbon atom which is more
electronegative and makes release of H+ ion easy.
10. Benzoic acid is stronger acid than acetic acid.
Ans. Because of greater electronegativity of sp2 hybridised carbon to which carboxyl carbon is attached in
benzoic acid.
11. Methanal is more reactive towards nucleophilic addition reaction than ethanal.
Ans. Methyl group due to its +I effect reduces the positive charge on carbonyl carbon atom and also hinderes
the approach of nucleophile. Since in ethanal, there is one methyl group while methanal has no methyl group,
so methanal is more reactive towards nucleophilic addition reaction.
12. The alph hydrogen of aldehydes and ketones are acidic in nature.
Ans. Due to strong withdrawing effect of carbonyl group and resonance stabilisation of the conjugate base.
13. Benzoic acid does not give Friedel Crafts reaction.
Ans. Because carboxyl group is strongly deactivating and catalyst AlCl3 which is a lewis acid gets bonded to the
carboxyl group strongly.
14. During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid
catalyst, the water or the ester should be removed as soon as it is formed.
Ans. Formation of ester from carboxylic acid and alcohol is a reversible reaction. So, in order to shift the
equilibrium in the forward direction, water or ester should be removed as soon as it is formed.

AMINES
1. Give Reasons for the following:
i) Aniline does not undergo Friedel-Crafts reaction.
ii) þ methylaniline is more basic than þ nitroaniline.
iii) Acetylation of —NH2 group is done in aniline before preparing its ortho and para
compounds.
Ans. I) It is because C6H5NH2 is basic, reacts with Lewis acid AlCl3 to form salt.
ii) It is because methyl group is electron releasing so increasing the electron density on nitrogen,
whereas nitro group is electron withdrawing.
iii) It is done so as to decrease the reactivity of Aniline towards electrophilic substitution reactions.
2. Which of the two is more basic and why?

Ans. CH3NH2 is more basic as CH3 group is electron releasing thereby increasing the electron density on N
while phenyl group is electron withdrawing thereby decreasing the electron density on N.
3. Primary amines have higher boiling points than tertiary amines.
Ans. Primary amines molecules are associated due to intermolecular H bonding which is absent in tertiary
amines.
4. Ethylamine is soluble in water, whereas aniline is almost insoluble, why?
Ans. It is because ethyl amine can form H-bonds with water whereas aniline cannot form H-bonds due to large
hydrophobic group.
5. Diazonium salts of aromatic amines more stable than those of aliphatic amines.
Ans. It is because benzene diazonium ion is stabilized by resonance.
6. Why is an alkylamine more basic than ammonia?
Ans. It is because alkyl groups are electron releasing. In alkyl amines, they will increase electron density on ‘N’,
therefore, they are more basic than NH3.
7. pKb value for aniline is more than that for methylamine.
Ans. It is because aniline is less basic than methyl amine due to presence of electron withdrawing
phenyl group, it has more pKb.
8. On reaction with benzene sulphonyl chloride, primary amines yield product soluble in alkali while
secondary amines yield product insoluble in alkali.
Ans. It is because sulphonamide formed by the reaction of primary amine and benzene sulphonyl chloride has
H attached to N (acidic H) while sulphonamide formed by the reaction of secondary amine and benzene
sulphonyl chloride does not has H attached to N.
9. Although NH2 group is o and p directing, yet aniline on nitration gives substantial amount of m-
nitroaniline.
Ans. Under strong acidic conditions of nitration, aniline form anilinium ion which is m directing group.
10. Aromatic amines cannot be prepared by Gabriel phthalimide synthesis.
Ans. It is because aryl halides donot undergo nucleophilic substitution reactions easily as C-X bond has partial
double bond character due to resonance.
11. Amines are less acidic than alcohols of comparable molecular masses.
Ans. Loss of proton from an amine gives amide ion while loss of proton from alcohol gives an alkoxide ion. As O
is more electronegative than N, RO- can accommodate negative charge easily than RNH- . SO, RO- is more
stable than RNH-.
12. Amines behave as nucleophiles or are basic in nature.
Ans. Due to the presence of a lone pair of electrons on nitrogen.
13. Methyl amine is stronger base than methanol.
Ans. Nitrogen is less electronegative than oxygen therefore lone pairs on N is readily available for donation.
14. Aniline gets coloured on standing in air for a long time
Ans. As it is easily oxidised on standing in air due to increase in electron density on benzene ring due to +R
effect of NH2 group.
15. The presence of base is needed in the ammonolysis of alkyl halides.
Ans. To remove HX formed so that reaction shifts in the forward direction.
16. Amides are more acidic than amines.
Ans. In amides lone pair on N goes in resonance with carbonyl group , availability of lone pair on N of NH2
group decreases in amide and also N acquires positive charge due to which NH2 group easily lose a proton and
behaves as acid.

NOTE:
1. Stronger acid higher Ka value and lower pKa value
2. Stronger base, higher Kb value and lower pKb value
3. Weaker acid, lower Ka value and higher pKa value.
4. Weaker base, lower Kb value and higher pKb value.
5. Electron withdrawing groups increases the acidic character and decreases the basic
character.
6. Electron releasing group increases the basic character and decreases the acidic character.
 REAGENTS USED FOR ORGANIC CHEMISTRY
TERMS EXPLANATIONS/ANSWER
OXIDISING AGENTS-
1. Acidified KMnO4 Alcohols to carboxylic acids
Alkyl benzene to Benzoic acid
2. CrO3/Pyridine Primary alcohol to Aldehyde
Secondary alcohol to Ketones
3. PCC Primary alcohol to Aldehyde
Secondary alcohol to Ketones
4. CrO3/H2SO4 Alcohols to Caboxylic acids
5. K2Cr2O7/H2SO4 Alcohols to carboxylic acids
6. CrO2Cl2, H3O+ Methyl benzene to Benzaldehyde
7. Fehling Solution Aliphatic Aldehyde to Carboxylate ion
8. Tollen’s Reagent Aldehyde to Carboxylate ion
9. Na2Cr2O7/H2SO4 Phenol to benzoquinone
10. Cu Primary alcohol to Aldehyde
Secondary alcohol to Ketone
Tertiary alcohol to alkene

REDUCING AGENTS

1. Zn-Hg,HCl Aldehydes and ketones to alkanes

2. NH2NH2,KOH,ethylene Aldehydes and ketones to alkanes
glycol
3. Zn Ozonide to aldehyde or ketone or both
Phenol to benzene
4. Sn,HCl Nitro to Amine
5. Fe,HCl Nitro to Amine
6. H3PO2 Diazonium salt to Benzene
7. C2H5OH Diazonium salt to Benzene
8. LiAlH4/H2O i)Aldehydes, Ketones, Esters, Carboxylic acids to
Primary Alcohol
ii) Acid amide and nitrile to Amines
9. DIBAL-H Nitrile and Carboxylic acid to Aldehyde
10. H2/Pd-BaSO4 Acid chloride to Aldehyde
11. NaBH4 Aldehydes and Ketones to Alcohols
12. H2/Pd i)Nitro to Amine
ii) Aldehydes and Ketones to Alcohols
13. SnCl2+HCl, H2O Nitrile to aldehyde
14. B2H6 Carboxylic acid to Primary Alcohol
15. H2/Ni Nitrile to Amine

DEHYDRATING AGENTS
1. H2SO4 Alcohol to alkene
2. H3PO4 Alcohol to alkene
3. P2O5 Carboxylic acid to Acid anhydride

HALOGENATING REAGENTS
1. PCl5 Alcohol to Chloroalkane
Carboxylic acid to Acid chloride
2. PCl3 Alcohol to Chloroalkane
Carboxylic acid to Acid chloride
 3. SOCl2 Alcohol to Chloroalkane
Carboxylic acid to Acid chloride
4. SO2Cl2 Allylic chlorination
5. PBr3 Alcohol to Bromoalkane
6. Red P/I2 Alcohol to Iodoalkane
7. NBS Allylic bromination
8. AgF or Hg2F2 or CoF2 or SbF3 Chloroalkane and Bromoalkane to Fluoroalkane

OTHERS
1. NaOH + CaO Salt of carboxylic acid to alkane with one carbon less
2. HNO2 Aomatic amines to Diazonium Salts
3. HBF4 Diazonium salt to Fluorobenzene
4. KI Diazonium salt to Iodobenzene
5. CuCl/HCl and Cu/HCl Diazonium salt to chlorobenzene
6. CuBr/HBr and Cu/HBr Diazonium salt to Bromobenzene
7. Benzenesulphonylchloride Distinction between Primary, Secondary and Tertiary
(Hinsberg Reagent) Amines
8. Grignard Reagent(RMgX) With CO2/H3O+ gives Carboxylic acid
With Nitrile /H3O+ gives Ketones
Formaldehyde/H3O+ gives Primary alcohol
Aldehyde other than formaldehyde/H3O+ gives
secondary alcohol
Ketones/H3O+ gives Tertiary alcohol
9. Mg Alkyl halide to Grignard Reagent

BOARD QUESTIONS ON REAGENTS

S.NO. QUESTION YEAR

1. How will you prepare 2009,2010
(i) benzoic acid from ethylbenzene
(ii) propene from propanone

Ans I) C6H5C2H5 KMnO4/KOH, H+ C6H5COOH

ii) CH3COCH3 LiAlH4 CH3CH(OH)CH3 conc H2SO4 CH3CH=CH2
2. Complete C6H5COCl H2,Pd-BaSO4 ------------------------- 2009, 13
Ans C6H5CHO
3. How would you obtain the following: 2009,11
i) Benzoquinone from phenol
ii) Propan-2-ol from propene
Ans I)

ii)

4. Complete the following reaction equations: 2009, 2010, 11

i)RCONH2 LiAlH4,H2O
ii) C6H5N2Cl + H3PO2 + H2O

Ans I) RCH2NH2 ii) C6H6

5. Complete the following chemical equation: 2010
C6H5N2Cl + CH3CH2OH
Ans C6H6
6. How are the following conversions carried out: 2010,11
i) Butan-1-ol to butanoic acid
ii) Methylbenzene to benzoic acid
iii) Ethylbenzene to benzoic acid
Ans I) CH3CH2CH2CH2OH KMnO4, H+ CH3CH2CH2COOH
ii) C6H5CH3 KMnO4/KOH, H+ C6H5COOH
iii) C6H5C2H5 KMnO4/KOH, H+ C6H5COOH
7. Name the reagents used in the following reactions: 2015
i) CH3COOH ------------------->→CH3COCl
ii) C6H5COCH3 ----------------->→ C6H5CH2CH3
iii) CH3COOH -------------------->→ ClCH2COOH
iv) CH3COCH3 ------------------->→ CH3CH(OH)CH3
v) C6H5CH2CH3 ------------->→ C6H5COO-K+
vi) C6H5COCl -------------->→ C6H5CHO
vii) CH3COONa -------------->→ CH4
viii) CH2=CHCH2OH ----------->→ CH2=CHCHO
Ans I) SOCl2 v) KMnO4/KOH
ii) Zn-Hg/HCl vi) H2, Pd-BaSO4
iii) Cl2/Red P vii) NaOH-CaO, Δ
iv) LiAlH4 viii) PCC
8. Write a simple chemical equation to complete each of the following 2012
transformations:
i) Butan-1-al to butanoic acid
ii) 4-Methylacetophenone to benzene-1,4-
dicarboxylic acid
Ans i) CH3CH2CH2CHO KMnO4 ,H+ CH3CH2CH2COOH
ii)

9. How will you convert the following? 2013

i) Propan-2-ol to propanone
ii) Phenol to 2,4,6- tribromophenol
Ans i) CH3CH(OH)CH3 PCC CH3COCH3
Br2(aq)
ii) C6H5OH

10. How will you convert the following? 2013

i) Propanone to propane
ii) Benzoyl chloride to benzaldehyde
iii) Propanone to Propan-2-ol
iv) Toluene to benzoic acid
Ans I) CH3COCH3 Zn-Hg/HCl CH3CH2CH3
ii)

iii) CH3COCH3 LiAlH4 CH3CH(OH)CH3

iv) C6H5CH3 KMnO4-KOH,H+ C6H5COOH

11. Write the products of the following reactions: 2013

i) CH3COCH3 Zn-Hg, conc HCl
ii) CH3COCl + H2 Pd-BaSO4

iii) C6H5COO-Na+ NaOH, CaO,∆

Ans I) CH3CH2CH3
ii) CH3CHO
iii) C6H6
12. How will you convert Nitrobenzene to Aniline? 2014
Ans

13. Complete: CH3CN LiAlH4 2014

Ans CH3CH2NH2
14. Write the products of following: 2014
CH3CHO LiAlH4

Ans CH3CH2OH
15. How will you convert acetone to propene 2014
Ans CH3COCH3 LiAlH4 CH3CH(OH)CH3 conc H2SO4 CH3CH=CH2
16. Name the reagents used in the following reactions: 2008,2014
i) Butanal to Butanol
ii) Oxidation of primary alcohol to aldehyde
iii) Butan-2-one to Butan-2-ol
iv) Oxidation of primary alcohol to carboxylic acid
v) Phenol to benzene
vi) Dehydration of propan-2-ol to propene
vii) Dehydrogenation of ethanol to ethanal
Ans I) LiAlH4 v) Zn dust
ii) PCC vi) conc H2SO4
iii) LiAlH4 vii) Cu at 573 K
iv) acidified KMnO4
17. How do you convert Prop-1-ene to Propan-1-ol 2015
Ans CH3CH=CH2 B2H6, H2O2-OH- CH3CH2CH2OH
18. What happens when ethanol is treated with Cu at 573 K? 2015
Ans Ethanal is formed
19. Predict the products of the following reactions: 2015
i) CH3COCH3 NH2NH2,KOH/Glycol,∆

ii) C6H5CH3 KMnO4/KOH, H+

Ans I) CH3CH2CH3
ii) C6H5COOH
20. Write the product of the following reaction: 2016
DIBAL-H, H2O
CH3CH=CHCH2CN

Ans CH3CH=CHCH2CHO

21 Write the product of the following reaction: 2017

PCC
CH3CH=CHCH2OH

Ans CH3CH=CHCH2CHO
 NAMED REACTIONS
Aldol condensation. The aldol and ketol readily lose water to give α,β-unsaturated carbonyl compounds which
are aldol condensation products and the reaction is called Aldol condensation

Balz-Schiemann When arenediazonium chloride is treated with fluoroboric acid, arene diazonium
Reaction fluoroborate is precipitated which on heating decomposes to yield aryl fluoride.

Cannizzaro reaction: Aldehydes which do not have an α-hydrogen atom, undergo self oxidation and reduction
(disproportionation) reaction on treatment with concentrated alkali. In this reaction, one
molecule of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid
salt.

Carbylamine reaction Aliphatic and aromatic primary amines on heating with chloroform and ethanolic
potassium hydroxide form isocyanides or carbylamines which are foul smelling substances.
This reaction is known as carbylamines reaction or isocyanide test.

Note: Secondary and tertiary amines do not show this reaction and is used as a test for
primary amines
Clemmensen Reduction The carbonyl group of aldehydes and ketones is reduced to CH2 group on treatment with
zincamalgam and concentrated hydrochloric acid. This is known as Clemmensen reduction.

Coupling Reactions: Benzene diazonium chloride reacts with phenol in which the phenol molecule at its para
position is coupled with the diazonium salt to form p-hydroxyazobenzene. This type of
reaction is known as coupling reaction.
Cross aldol When aldol condensation is carried out between two different aldehydes and / or ketones,
condensation: it is called cross aldol condensation. If both of them contain α-hydrogen atoms, it gives a
mixture of four products.

Dow’s process In this process, chlorobenzene is heated with aqueous sodium hydroxide under
pressure. Sodium phenoxide so produced on acidification gives phenol.

Diazotisation The nitrosation of primary aromatic amines with nitrous acid (generated in situ from sodium
nitrite and a strong acid, such as hydrochloric acid, sulfuric acid, or HBF 4) leads to
diazonium salts,

Etard reaction Chromyl chloride oxidizes methyl group to a chromium complex, which on hydrolysis gives
corresponding benzaldehyde. This reaction is called Etard reaction

Fehling’s test Fehling reagent comprises of two solutions, Fehling solution A and Fehling solution B.
Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium
potassium tartarate (Rochelle salt). These two solutions are mixed in equal amounts
before test. On heating an aldehyde with Fehling’s reagent, a reddish brown precipitate is
obtained. Aldehydes are oxidised to corresponding carboxylate anion. Aromatic aldehydes
do not respond to this test.

Finkelstein Reaction Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI in
dry acetone. This reaction is known as Finkelstein reaction.

Note: This reaction in forward direction can be favoured by precipitating NaX formed in
dry acetone (according to Le Chatelier’s principle).
Fittig Reaction Aryl halides also give analogous compounds when treated with sodium in dry ether, in
which two aryl groups are joined together. It is called Fittig reaction.

Friedel-Crafts acylation The reaction of benzene with an acyl halide or acid anhydride in the presence of Lewis
reaction acids (AlCl3) yields acyl benzene
Friedel-Crafts alkylation When benzene is treated with an alkyl halide in the presence of anhydrous aluminium
Reaction chloride, alkylbenene is formed.

Gabriel phthalimide Gabriel synthesis is used for the preparation of pure primary amines. Phthalimide on
synthesis treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide which
on heating with alkyl halide followed by alkaline hydrolysis produces the corresponding
primary amine.

Gatterman – Koch When benzene or its derivative is treated with carbon monoxide and hydrogen chloride in
reaction the presence of anhydrous aluminium chloride or cuprous chloride, it gives benzaldehyde
or substituted benzaldehyde. This reaction is known as Gatterman-Koch reaction.

Gatterman Reaction Chlorine or bromine can be introduced in the benzene ring by treating the benzene
diazonium salt solution with corresponding halogen acid in the presence of copper
powder. This is referred as Gatterman reaction.
Hell-Volhard-Zelinsky Carboxylic acids having an α-hydrogen are halogenated at the α-position on treatment
(HVZ )reaction with chlorine or bromine in the presence of small amount of red phosphorus to give α-
halocarboxylic acids. The reaction is known as Hell-Volhard-Zelinsky reaction

Hinsberg’s Test Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s reagent, reacts
with primary and secondary amines to form sulphonamides. (a) The reaction of
benzenesulphonyl chloride with primary amine yields N-ethylbenzenesulphonyl amide.
The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence
of strong electron withdrawing sulphonyl group. Hence, it is soluble in alkali.

(b) In the reaction with secondary amine, N,N-diethyl- benzenesulphonamide is formed.

Since N, Ndiethylbenzene sulphonamide does not contain any hydrogen atom attached to
nitrogen atom, it is not acidic and hence insoluble in alkali.

(c) Tertiary amines do not react with benzenesulphonyl chloride.

Note: This test is used for the distinction of primary, secondary and tertiary amines and
also for the separation of a mixture of amines. However, these days benzenesulphonyl
chloride is replaced by p-toluenesulphonyl chloride.
Hoffmann bromamide An amide with bromine in an aqueous or ethanolic solution of sodium hydroxide gives
degradation reaction primary amines. In this degradation reaction, migration of an alkyl or aryl group takes
place from carbonyl carbon of the amide to the nitrogen atom. The amine so formed
contains one carbon less than that present in the amide

Iodoform test Shows positive test for:

Acetaldehyde (Ethanal) and methyl ketones

Reactions:
the methyl group of the ketone is removed from the molecule and
produces iodoform (CHI3)
Kolbe’s Reaction Phenol with sodium hydroxide gives sodium phenoxide ion which with carbon dioxide in
acidic medium results hydroxybenzoic acid (salicylic acid). This is known as Kolbe’s
reaction.

Reimer-Tiemann On treating phenol with chloroform in the presence of sodium hydroxide, a –CHO group is
Reaction introduced at ortho position of benzene ring resulting salicylaldehyde. This reaction is
known as Reimer - Tiemann reaction.

Rosenmund Reduction Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on barium sulphate.
This reaction is called Rosenmund reduction.

Sandmeyer Reaction The Cl , Br and CN nucleophiles can easily be introduced in the benzene ring of benzene
diazonium salt in the presence of Cu(I) ion. This reaction is called Sandmeyer reaction.

Stephen reaction Nitriles are reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction is called
Stephen reaction.

Swarts Reaction Heating an alkyl chloride/bromide in the presence of a metallic fluoride such as AgF,
Hg2F2, CoF2 or SbF3 gives alkyl fluorides. The reaction is termed as Swarts reaction.

Tollens’ test On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution (Tollens’
reagent), a bright silver mirror is produced due to the formation of silver metal. The
aldehydes are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline
medium.
Wolff Kishner Reduction The carbonyl group of aldehydes and ketones is reduced to CH2 group on treatment with
hydrazine followed by heating with sodium or potassium hydroxide in high boiling solvent
such as ethylene glycol. This is known Wolff Kishner reduction.

Williamsons reaction The Williamson ether synthesis is a reaction that converts alcohols (R-OH) into
ethers (R-O-R). The first step in this reaction is forming the conjugate base of the
alcohol (called an alcoxide) by reacting the alcohol with sodium metal. This reaction
forms hydrogen gas (H2) as a biproduct, so if you perform this reaction take caution
to keep all flame sources away during sodium addition.

Wurtz Reaction Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the halide. This reaction is known as Wurtz reaction.

Wurtz-Fittig Reaction A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium
in dry ether and is called Wurtz-Fittig reaction.