केंद्रीय विद्यालय संगठन लखनऊ संभाग

KENDRIYA VIDYALAYA SANGATHAN LUCKNOW REGION

बोर्ड कक्षाओं के वलए पू रक अध्ययन सामग्री

SUPPLEMENTARY STUDY MATERIAL FOR
BOARD CLASSES

कक्षा/CLASS XII
विषय/SUBJECT रसायन विज्ञान/CHEMISTRY

CHIEF MENTOR
Smt. Sona Seth, Deputy Commissioner, KVS Regional Office Lucknow

MENTOR
Sh. Anup Kumar Awasthi, Assistant Commissioner, KVS Regional Office Lucknow
Smt. Archana Jaiswal, Assistant Commissioner, KVS Regional Office Lucknow
Sh. Vijay Kumar, Assistant Commissioner, KVS Regional Office Lucknow

COORDINATOR
Sh. A. H. Ansari, Principal, PM SHRI KV Mati Akbarpur

CONTENT DEVELOPMENT TEAM

Sh. Pankaj Asthana, PGT (Chemistry), KV Chakeri No. 3 Kanpur
Sh. Ajay Pratap Singh, PGT (Chemistry), PM SHRI KV Balrampur
Sh. Shishir Kumar Pandey, PGT (Chemistry), PM SHRI KV Mati Akbarpur
Sh. Amit Saxena, PGT (Chemistry), PM SHRI KV Mati Akbarpur
Sh. Anoop Dwivedi, PGT (Chemistry), PM SHRI KV Aliganj Lucknow
Smt. Kalpna Maheshwari, PGT (Chemistry), KV IFFCO Bareilly
Smt. Nisha Singh, PGT (Chemistry), PM SHRI KV Raebareli
Sh. Piyush Mishra, PGT (Chemistry) PM SHRI KV No. 1 Armapur Kanpur

1
 INDEX

S.No CHAPTER’s WEIG SELECTED TOPICS WEIGHTA Page

. NAME HTAG GE OF Nos.
E SELECTE
D TOPICS
1. Solutions 7 Definition of Important terms like molarity, 4 2-6
molality etc. Laws like raoults law and henry law
and application formula for numerical, ideal and
non-ideal solution colligative property, Vant’s
hoff factor.
2. Electrochemistry 9 Nernst equation, relation between Gibb’s energy 5 7-11
and emf of cell, kohlrausch’s law, faraday’s laws,
cell and batteries, corrosion.
3. Chemical Kinetics 7 Rate of reaction, rate constant , rate law, order 4 12-18
and molecularity of reactions , half life period ,
formulae based numericals on integrated rate
law and Arrnenius equation.
4. d- and f –block 7 Transition metals, oxidation state, enthalpy of 7 19-25
elements atomization, metallic character, ionization
enthalpy, color of cations & its salts, catalytic
property, magnetic property, interstitial
property, Eo value, lanthanoid and actinoid
contraction and its consequences, alloy
formation, significance of of d and f block
elements, preparation and property of K2Cr2O7&
KMnO4 .
5. Coordination 7 Basic terms, Nomenclature, Isomerism in 6 26-32
Compounds coordination compounds, Werner theory of
coordination compounds, Valence bond theory,
Crystal field theory.
6. Haloalkanes and 6 Important name reactions, nucleophillic 4 33-38
Haloarenes substitution reactions, reason based questions,
definition of chiral carbon, enantiomer and
diastereomers.
7. Alcohol, Phenols 6 Physical properties of alcohol, Acidic strength of 3 39-43
and Ethers phenols and derivatives, name reactions,
reasoning, questions, and distinction test.
8. Aldehydes, Ketones 8 Name reactions, Reasoning questions, 4 44-48
and Carboxylic Distinction test.
Acids
9. Amines 6 Important name reaction, Physical properties, 5 49-52
Basic nature, Reasoning questions and
distinction test.
10. Biomolecules 7 Definition of Important terms, Important 5 53-58
reactions and Previous year questions.
11. Chemical - - - 59-60
Distinction Test
12. Tips to avoid - - - 61-62
common mistakes.

TOTAL 70 47

2
 UNIT 1 - SOLUTION
WEIGHTAGE – 7 MARKSSELECTED - 4 MARKS
GIST OF THE CHAPTER
ConcentrationofSolutions:-

w/w%Composition: Mass ofsolutepresentper100g.ofsolution

Molarity[M]: No. of moles of solute present per liter of solution in called ‘molarity of
solution’. . It is temperature dependent. M=No.of Moles of solute /Volume of
solution in litre
Molality[m]: No. of moles of solute present per kg. of solvent is called molality. It is
temperatureindependent. m=No.of Moles of solute /Massof Solvent in kg

Normality[N]: No. of gram equivalent of solute present per liter of solution is called
normality ofsolution.
N =No.of Gram equivalentofsolute/Volumeofsolution inlitre

PartsPer Million[ppm]: Itisusedforverydilutesolutions,Partsofsoluteinpermillionpartsofsolutionarecalle

dppm.Ppm =Partofsolutex106/ Partof solution

MoleFraction: Ratioofmoleofone
componenttototalno.ofmolesofallthecomponentsofsolutioniscalled
molefraction(x) ofthatcomponent.
Henry’s law:-“The partial pressure of the gas in vapour phase p isproportional to the mole fraction of
thegasxin the solution.” P=KH x
Applications of Henery Law- (1)In Packing of soda/ Soft drinks
(2) In Deep see diving( He = 11.7 % , N2 = 56.2 %andO2=32.1%)
(3) Functions of lungs
(4)At high altitudes pressure is low there for breathing problems lead toANOXIA(unabletothinkand
weak)
Vapour Pressure: The pressure exerted by vapours over the liquid surface at equilibrium is
called vapourpressureof theliquid.
Raoult’sLaw:“TheV.P.ofanyvolatilecomponentinthesolutionisdirectlyproportional toitsmolefraction”.
Raoult’sLawforSolutionsContainingNon-Volatile Raoult’sLawforSolutionContainingVolatile
Solute Solute

IdealandNon-IdealSolutions:

3
 IdealSolution NonIdealSolution

FollowsRaoult’slawatalltemperatureand Does notfollowRaoult’slaw atall

Concentrations.P=PA+PB Temperatureand pressure.P≠PA+PB
interrmolecular forces in resulting solution are same Intermolecular forces in resulting
asinpurecomponents. solutionaredifferentfromtheintermolecularforc
A – B=A– A=B– B e
of purecomponents.A–B ≠ A–A, B– B
Nochangeinvolumewhilemixing components. Changeinvolumewhilemixing components.
Δ Vmix= 0 Δ Vmix≠ 0
Noheat changetakeplacewhilemixing the Heat changestakeplacewhilemixingthe
components. ΔH mix= 0 components. ΔHmix≠0
Eg:n – hexane + n–heptanes&benzene+ toluene Eg:Acetone+Water&Acetone+CHCl3

NonIdealSolution

Showing Positive Deviation from Raoult’sLaw Showing Negative Deviation from Raoult’s Law
Vapour pressure of resulting solution is greater than Vapour pressure of resulting solution is less than
sum of partial pressure of components. sum of the partial pressure of pure components.
P>PA+PB P < PA+ PB
Resulting intermolecular force is weaker than pure Result inginter molecular forceisstrongerthan
components. Purecomponents.
ΔV mix=+ve Δ Vmix=–ve
Volumeofsolution>Sumofvolumeof Volumeofsolution<Sumofvolumeof
Purecomponents Purecomponents
Δ H mix=+ve Endothermicmixingprocess ΔH mix=–ve Exothermicprocess
Acetone + Acetone+ CHCl3,HNO3+H2O
WaterAlcohol+WaterCarboxylicAcid+W
ater

Azeotropes:(ConstantBoilingMixture):-Solutionin which components are present in a fixed proportion,

boils at a constant temperature irrespective of boiling point of pure components
=>Minimum Boiling Azeotropes Boils at a temperature lower than b.ps. of pure components.
[95%Alcohol( Aq. Solution) ]
=>Maximum Boiling Azeotropes: Boils at a temperature higher than b.p.s. of pure components. [68%
HNO3(aq. Solution)]
ColligativeProperties:-
The properties of dilute solutions which depend only on number particles of solute present in the solution and
not on their identity are called colligative properties.

4
1-RelativeLoweringofVapourPressure The relative lowering of vapour pressure of a solution
containing a non-volatile solute is equal to the mole fraction
of the solute present in the solution.

2-Osmosis and Osmotic Pressure Osmosis:-The phenomenon of the passage of pure solven from
Diffusion:-Movement of solute particles a region of lower concentration (of the solution) to a region f its
from higher conc. to lower conc.
higher concentration through a semi-permeable membrane.
Reverse Osmosis: If pressure greater than osmotic pressure is
Osmotic Pressure: Excess pressure which applied then, flow of solvent molecules is reversed, i.e. from a
must be applied to a solution in order to
higher concentration solution to lower concentrated solution.
prevent flow of solvent into the solution This phenomenon is called “Reverse Osmosis”. It is used in
through the semi-permeable membrane. water purification and desalination of water.
V=nRT =Osmotic pressure R
=Gas constant
3- Elevation of Boiling Point ΔTb m[molality]
:Difference between boiling of
solution containing non volatile ΔTb=Kbm
solute and B.P. of pure solvent is Kb=Molal Elevation Constant
called elevation of B.P.

ΔTb=Tb–Tob

4-Depression of Freezing Point ΔTfm[molality]

Difference in freezing point of pure ΔTf=Kfm

solvent and freezing point
ofsolution is called ‘Depression Kf= molal depression constant
inFreezingPoint’.

ΔTf =T0f–Tf

Van'tHoffFactor:

5
 Association Dimerisation Trimerisation Tetramerisation Pentamerisation

i= ½ 1/3 ¼ 1/5

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

i= 2 3 4 5

PYQ/FREQUENTLY ASKED QUESTIONS-

Q. 1 – Define the following terms-
Molarity, Molality, Mole fraction, Henry’s law, Raults Law for a solution of volatile and non- volatile liquid, Ideal
solution and Non Ideal solution, Colligative property, Elevation in Boiling point and Depression in freezing point,
Osmosis and Reverse Osmosis, Osmotic Pressure, Isotonic solution, Hypertonic and Hypotonic solution, Edema and,
Anoxia, Abnormal molar mass, Van’t Hoff factor, Azeotrope mixture, Molal elevation constant and molal depression
constant.
Ans. For answer see the gist.
Ques. What is Osmotic Pressure?
Ans:- The minimum pressure that must be applied to a solution to halt the flow of solvent molecules through a
semipermeable membrane (osmosis).
Ques. Define the following terms: (i) Ideal solution (ii) Azeotrope
Ideal Solution :Ideal solutions obey Raoult’s law over the entire range of concentration. Examples: n-hexane and n-
heptane.
Azeotrope - A mixture of two or more liquids that displays the same level of concentration in the liquid and vapour
phase is known as Azeotrope.
Ques: Differentiate between molarity and molality of a solution.
Ans: Molarity: Molarity (M) can be defined as the number of moles of solute dissolved in one litre of solution.
Molality: Molality (m) can be defined as the number of moles of the solute per thousand grams of solvent.
Ques. What is the Van’t Hoff Factor?
Ans. Denoted by the symbol ‘i’. The ratio of the concentration of particles formed when a substance is dissolved to
the concentration of the substance by mass.
Ques. Define Association & Dissociation.
Ans. Association is the joining of two or more particles to form one entity.e.g. association of two particles is the
dimerization of carboxylic acids when dissolved in benzene.
Dissociation refers to the splitting of a molecule into multiple ionic entities. For example, sodium chloride (NaCl)
dissociates into Na+ and Cl– ions when dissolved in water.
Ques. What is the unit for Henry’s law constant?
Ans. Henry’s law constant is expressed in mol L–1 bar–1.
Ques.Whatare the Limitations of Henry’s Law?
Ans.See the gist of topic.
Que. Why are aquatic species more comfortable in cold water in comparison to warm water?
Ans: Due to more oxygen present in cold water.
Que. (a) Explain the following phenomena with the help of Henry’s law.
(i) Painful condition known as bends.
(ii) Feeling of weakness and discomfort in breathing at high altitude.
(b) Why does soda water bottle kept at room temperature fizzes on opening?
Ans:(i) solubility of gas in a blood due to high pressure.(ii) low level of oxygen present in atmosphere.
(b) Due to difference in pressure.
Que. Why is the vapour pressure of an aqueous solution of glucose lower than that of water?

6
Ans: The more the surface area available, the more the evaporation of the liquid. Now glucose is a non-volatile
solute. It occupies a certain surface area of water. This means evaporation of water from the surface gets reduced
and its vapour presence also gets lowered.
Que. How does sprinkling of salt help in clearing the snow-covered roads in hilly areas? Explain the phenomenon
involved in the process.
Ans: Depression in freezing point.
Que. What is a “semi-permeable membrane”?
Ans: The membranes which allow only the movement of the solvent molecules through them is called semi-
permeable membrane.
Que. Give an example of a material used for making semipermeable membrane for carrying out reverse osmosis.
Ans: Polymer cellulose acetate is used for making semipermeable membrane for carrying out reverse osmosis.
Que. Define Azeotrope mixture.
Ans :see the answer in gist.
Que.. When kept in water, raisins swell in size. Name and explain the phenomenon involved. Give three applications
of the phenomenon.
Ans: Due to osmosis
Applications of osmosis: see the gist of topic.
Que. Calculate the freezing point of solution when 1.9 g of MgCl 2(M = 95 g mol-1) was dissolved in50g
ofwater,assumingMgCl2undergoescomplete ionization.(Kfforwater=1.86K kgmol-1)
Ans. Formula used: ΔTf=Kfm.
Que. .Calculate the mass of ascorbic acid (vitamin C, C 6H8O6) to be dissolved in 75 g of acetic acid to lower its freezing
point by 1.5°C. (Kffor CH3COOH = 3.9 K kg mol-1)
Ans.. Formula used: ΔTf = Kf m.
Que.What would be the elevation in boiling point of a 0.1 m NaCl solution? (Assume that NaCldissociates completely)
(Kb=0.512 O C kg mol−1)
Ans.. Formula used: ΔTb = Kb m.
Que.The osmotic pressure of a solution containing 5g of a solute per litre is 0.025 atm at
27°C. Find the molecular weight of the substance.
Ans. πV = nRT , n= w2/m2
Que. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4in 2 L of water at 25°C
assuming it to be completely dissociated.(At. mass of K=39u, S=32u, O=16u).
Ans.πV =i nRT , i= 3
Que.For a 5% solution of urea (Molar mass = 60 g/ mol), calculate the osmotic pressure at 300 K.
[R = 0.0821 L atm K–1 mol–1]
Ans. πV = nRT
Que. Calculate the freezing point of an aqueous solution containing 10.50 g of MgBr2 in 200g of water (Molar mass of
MgBr2 = 184 g mol-1, = for water = 1.86 K kg mol-1).
Ans.. Formula used: ΔTf = Kf m
Que. Calculate the molarity of 9.8 % (w/w) solution of H2SO4 if the density of the solution is 1.02 g/ml. (Molar mass
of H2SO4 = 98 g/mol).
Que. Calculate the amount of NaCl to be dissolved in 2L of solution so that it’s osmoticpressure becomes 3.0 bar at
27oC , assume that NaCl completely ionises in solution.( R=0.083LbarK-1mol -1, molar mass of NaCl is 58.5 g/mol)
Ans. Formula used: πV = nRT
Que.When 2.56 g of sulphur was dissolved in 100 g of CS2, the freezing pointlowered by 0.383 K. Calculate the
formula of sulphur (Sx). (Kffor CS2 = 3.83 K kg mol-1, Atomic mass of Sulphur = 32 g mol-1).
Ans.. Formula used: ΔTf =iKf m
Que. Calculate the boiling point of solution when 4 g of MgSO4 (M =120 g/mol-1) was dissolved in 100 g of water,
assuming MgSO4 undergoes complete ionization. (Kb for water = 0.52 K kg mol-1).
Ans. Formula used: ΔTb =i Kb m

7
 Unit 2: Electrochemistry
S.No. GIST OF THE CHAPTER
1. Conductance:Reciprocaloftheresistance G=RUnit is −1

2 SpecificResistance/Resistivity: ρ=RA/l Unitisohmcm-1

3 SpecificConductanceorConductivity:
k= 1/ρ=l/ RA
Conductivityofanyconductoristhereciprocalofspecificresistanceandisdenotedby (GreekworkKappa)
unitScm-1
4 MolarConductivity:Itisdefinedastheconductingpowerofalltheionsproducedbyonegrammole
ofanelectrolyteinasolution. It isdenoted bymunitScm2mol-1.
1000
 m=
Molarity
5 VariationofmolarconductivitywithconcentrationForstrongelectrolytesλ
decreasesslightlywithincreaseinconcentrationduetoincreaseinnumberof
ionsperunitvolume.e.gKCl
Forweakelectrolytesitincreasessharplywithdecreaseinconcentrationasio
nizationofweakelectrolytesincreaseson dilutione.gCH3COOH

6 Kohlrausch’sLaw:Accordingtothislaw,molarconductivityofanelectrolyte,atinfinitedilutioncanbeexpre
ssedasthesumofcontributions fromitsindividualions
e.g.CaCl2=(Ca2+)+2(Cl−)
ApplicationofKohlrausch’sLaw
1. Forcalculation oflimiting molarconductivityλ o=λc/ λm
2. Forcalculationof degree ofdissociation = ^m / ^m0
7 Faraday– Faraday – Second Law : The amount of different
Firstlawofelectrolysis:Theamountofsubstancede substanceslibrated by the same quantity of electricity
positedduringelectrolysisisdirectlyproportionalt passing through
oquantityofelectricitypassed. theelectrolyticsolutionisproportionaltotheirchemicalequivale
nt

ElectrochemicalCell ElectrolyticCell

8
1.Itis a 1.Itisdevicetoconvert
devicetoconvertchemicalenergytoelectricalenergy. electricalenergyintochemicalenergy.
2. Itisbaseduponredoxreactionwhichisspontaneous. 2.Theredoxreactionis non-spontaneousandtakes
placeonlywhenelectrical energy is supplied.
SN Nameofc Electrolyte ChemicalReaction Remark
O. ell
1 Mercury Paste Anode:-zinc-mercuryamalgam Provide constant
Cell ofKOH Zn(Hg)+2OH−→ZnO(s)+H2 O+2e− voltage anddoes not
&Zn(OH Cathode:-HgOandcarbon corroded due
)2 HgO+H2 O+2e−→Hg(1)+2OH− toabsence of ion in
overallreaction.
Overallreaction:-Zn(Hg)+HgO→ZnO+H2
Voltage1.35V
2 DryCell: ZnCl2and Anode:-Zincrod Corroded due to the
NH4Cl Zn(s)→Zn2++2e- presence of ion in
Cathode:-Carbon rod surrounded overall reaction.
by MnO2 ZnCl2 is used to make a
2MnO2+2NH4++2e-→Mn2O3+2NH3
complex
OverallReaction:- [Zn(NH3)2Cl2] it saves
Zn(s)+ 2MnO2+2NH4+→ Zn2+ + the bursting of cell,
Mn2O3+2NH3
Voltage1.5V
3 Lead 38% H2SO4 Anode:-Pbgrid Can be Recharged
Storage PbSO4(s)+2e−→Pb(s)+SO2− (aq) byreversing the
4
Battery Cathode:-PbgridfilledwithPbO2 electrodesReactant
PbO2(S)+SO42-+ 4H+(aq)+2e-→PbSO4(s)+2H2O(l) become productsand
OverallCellReaction:- products become
Pb(s)+PbO2(s)+2H2SO4→2PbSO4(s)+2H2O(1) reactants
4 Fuel Cell KOH Anode:- Ecofriendly,
Solution 2H2+4OH →4H2 O+4e
- -
Efficiency60-70%
Cathode:-
O2 + 2H2O + 4 e-→
O2(g)+2H 2 O(l)+4e−→4OH− (aq)
OverallReaction:-2H2(g)+O2(g)→2H2O(l)
5 Corrosio H2CO3 Anode(oxidation):-Fe(s)+Fe2+(aq)+2e− Formula of rust
n Cathode(Reduction):- Fe2O3.xH2O
O2(g)+4H+ (ag)+4e−→2H2 O(l)
AtmosphericOxidation:-
2Fe2+(aq)+2H2O(l)+1/2O2→Fe O (s)+4H+(aq)
2 3

PreventionofCorrosion By covering the surface with paint or by some chemicals

(e.g. bisphenol)./ Cover the surface by othermetals (Sn,
Zn, etc.) that are inert or react to save the object. An
electrochemical method (sacrificialelectrodelike Mg,
Zn,etc.)whichcorrodesitselfbut saves theobject.

9
 PYQ/ FREQUENTLY ASKED QUESTIONS WITH MODEL ANSWERS

1 Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.

Ans For hydrogen electrode,H+ + e– —>1/2 H2,

2 Calculate the emf of the cell in which the following reaction takes place:
Ni(s)+2Ag+ (0.002 M) -> Ni2+ (0.160 M)+2Ag(s) Given that E(-)(cell) = 1.05 V .
Ans

3 Write the Nernst equation and emf of the following cells at 298 K:

Product of electrolysis:
NaCl(molten) Cathode:Na+(l)+e–→Na(s) Anode:Cl–→½Cl2+e–
NaCl Cathode:H2O(l)+e–→½H2(g)+OH– Anode:Cl–→½Cl2+e–
(aq)
H2SO4(dil) Cathode:H++e-→½ H2 Anode:2H2O(l)→O2(g)+4H+(aq)+4e–
AgNO3(aq)- Cathode:Ag+(aq)+e-→Ag(s) Anode:Ag(s)→Ag+(aq)+e-
Agelectrodes
AgNO3(aq)- Cathode:Ag+(aq)+e-→Ag(s) Anode:2H2O(l)→O2(g)+4H+(aq)+4e–
Ptelectrodes
CuCl(aq)- Cathode:Cu+(aq)+e-→Cu(s) Anode:2H2O(l)→O2(g)+4H+(aq)+4e–
Ptelectrodes

10
Ans.

4. Calculate the standard cell potentials of the galvanic cells in which the following reactions take place.

Also calculate ∆G° and equilibrium constant for the reaction.

Ans

5 The molar conductivity of 0.025 mol L-1 methanoic acid is 46.1 S cm2 mol-1. Calculate its degree of
dissociation and dissociation constant Given λ °(H+)=349.6 S cm2 mol-1 andλ°(HCOO-) = 54.6
S cm2 mol-1
Ans

6 Why does the conductivity of a solution decrease with dilution?

Ans The conductivity of a solution is linked with the number of ions present per unit volume. With
dilution, these decrease and the corresponding conductivity or specific conductance of the solution
decreases.
7 Consider the reaction: Cr2O72--+ 14H+ + 6e- -> 2Cr3+ + 7H2O What is the quantity of electricity in
coulombs needed to reduce 1 mol of Cr2O72- ?

11
Ans

8 Write the chemistry of recharging the lead storage battery, highlighting all the materials that are
involved during recharging.
Ans During Recharging reactions are as follows:
Anode Reaction:PbSO4 + 2 e- ͍→ Pb + SO4- -
Cathode reaction:PbSO4 + 2H2O → PbO2 + SO4- - + 4H+ + 2 e-
Overall reaction:2PbSO4 + 2H2O → Pb + 2SO4- - + PbO2 + 4H+
During Discharging reactions will be reversed:

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

Ans The water present on the surface of iron dissolves acidic oxides of air like CO 2 , SO2 , etc. to form
acids which dissociate to give H+ ions :

Thus, an electrochemical cell is set up on the surface.

Ferrous ions are further oxidised by atmospheric oxygen to ferric ions which combine with water to
form hydrated ferric oxide, Fe2O3. xH2O, which is rust.
10 Given the standard electrode potentials, K+/K=-2. 93 V, Ag+/Ag = 0.80 V, Hg2+/Hg =0.79V,
Mg2+/Mg=-2.37V, Cr3+/Cr=0.74V.Arrange these metals in their increasing order of reducing power.
Ans Higher the oxidation potential more easily it is oxidized and hence greater is the reducing power.
Thus, increasing order of reducing power will be Ag<Hg<Cr<Mg<K.
11 How much charge is required for the following reductions:
(i) 1 mol of Al3+ to Al? , (ii) 1 mol of Cu2+ to Cu ?, (iii) 1 mol of Mn04- to Mn2+?
Ans (i) The electrode reaction is Al3+ + 3e ——> Al
∴ Quantity of charge required for reduction of 1 mol of Al3+=3F=3 x 96500C=289500C.
(ii) The electrode reaction is Cu2+ + 2e– ——–> Cu
∴ Quantity of charge required for reduction of 1 mol of Cu 2+=2F=2 x 96500=193000 C.
(iii) The electrode reaction is Mn04- ———-> Mn2+.
i.e., Mn7+ + 5e–——-> Mn2+.
∴ Quantity of charge required = 5F
=5 x 96500 C=4825000.
12 How much electricity in terms of Faraday is required to produce :
(i) 20·0 g of Ca from molten CaCl2(ii) 40·0 g of Al from molten Al2O3 ?

12
Ans

UNIT3: CHEMICAL KINETICS

GIST OF THE CHAPTER
RATE OF Thechangeinconcentrationofeither
REACTION reactantorproductperunittime.Example:N2+3H2→2NH3

Unit of rate MolL-1time-1ormolL-1S-1

Rate Law The expression of rate of reaction in term of concentration of reactant
aA+bB→Product Rate=K[A]x[B]y
Rate Constant Specific Rate of reaction :-Rate of reaction when concentration are taken asunity.
Rate=k[A]x[B]y, [A]=1[B]=1 Rate=k
Unit of rate
constatnt

n= Orderofreaction
Order of reaction The sum of powerof concentration of reactant in rate law
expressionaA+bB→ Product Rate=k[A]x[B]yOrderofreaction= x+y
ItmaybeZero,PositiveorNegativeorfraction.It is experimental quantity.
Mechanism of Elementary reaction:-Chemical reaction complete in single step and
Reaction haveexponant in rate law expression equal to their stochiometric
cofficient.Zeroorderreactioncannotbe anelementry reaction.
ComplexReaction:-Forthecomplexreaction,Theoverallreactioniscontrolledbythe
sloweststep.
In the rate law expression,rate of reaction depends on concentration of
reactantofsloweststepwhichmustbe free from intermediate.
(i)Thermal decomposition of (ii)Reactionof
2N2O5→−→4 NO2+O2 NO2andF2
2NO2 + F2→2NO2 F
𝒔𝒍𝒐𝒘 𝒔𝒍𝒐𝒘
Step(i)N2 O5→−→NO 2+NO3 Step(i)NO2 +F2→−→NO2 F+F
f𝒂𝒔𝒕
Step(ii)N2 O5 +NO3→−→3NO2 +O2 𝒇𝒂𝒔𝒕
Step(ii)NO2 +F→−→NO2F
Difference Order of Reaction Molecularity
between Order of ➢ 1.The sum of the ➢ 1.The no. atoms , ions or molecule
Reaction and exponents(powers) by which thatmust collide with one
Molecularity theconcentrationtermsareraisedin anothersimultaneouslysothatchemi
ratelaw. cal reactiontakeplace
➢ 2.DeterminedExperimentlybyra ➢ 2.Theoriticalconcept,determin
telaw edbyslowest step
➢ 3.MaybeZeroandnegetive ➢ 3.NeverbeZeroandnegetive
➢ 4.MaybeFraction ➢ 4.NeverbeFraction
13
Pseudo firstAchemicalreactionwhichseemstobe higherorderbutactuallytheyare offirstorder
➢ For these reaction,Order of reaction is one but molecularity is more than
order reaction
oneExample:-Hydrolysisofesterinacedicmedium,
+
CH3COOC2H5+H2O→CH3COOH+C2H5OH
Rate=K[CH3COOC2H5][H2O]
Whenwateris inexcessthen Rate = K’[CH3COOC2 H5]
Inversionofcanesugar inacidicmedium
C12H22O11+H2O→C6H12O6+C6H12O6
Rate=K[C12H22O11][H2O] Whenwaterisin excessthen
= K’[C12H22O11]
METHOD OF InitialRateMethod:
DETERMINING The data’s are given in term of different rates at different concentrations, thus
ORDER OF we calculate
REACTION thrateexpressionandthenfindtheorderofreaction.Example:ReactionA+B→Produc
t

Example:ConsiderthefollowingdataforthereactionA+B=ProductsandDeterminetheordero
fthereactionwithrespecttoAandw.r.t.Bandtheoverallorderofthereaction.

Factor Affacting 1.Natureofreactant:-

rate of reaction Chemical Nature of Reactant:-Reaction having less value of activation
energywilltakes place faster
2.ConcentrationofReactant:-RateofreactionαConc.ofReactant
3. Temperature:-On increasing temperature, rate of reaction
increasesweatherthereaction isexothermicorendothermicbecause
KEofmoleculeincrease on increases temperature which led to increasing
activatedmolecule.
Relation between rate constant and temperature
0
(a) Generally it isfound that for every 10 C rise in temperature rate
ofreactionbecome 2to3times
TemperatureCofficient:-Itisdefinedasratioofrateofareaction
0
attwodifferenttemperature whichwillbedifferby 10 C

14
 ➢ 5.Presence of catalyst:-In the presence of catalyst, Ea(Activation
energy)decreasesthereforerateofreactionincreases
➢ 6.Exposure of radiation:-Rate of some reaction increases on exposure of
radiation.Thesereactionarecalledphotochemicalreaction .
THRESHOLD The minimum extra amt. ofenergywhichthereactantsmoleculesmust
ENERGY havesothatreactantmoleculereacts andovercome the
energybarriersandconvertsintoproducts.
ACTIVATION The minimum extraamt. ofenergyabsorbedby the reactantmoleculeso
ENERGY thattheirenergybecomesequaltothresholdenergy.
Applications (i) Rateofreaction∞1/ActivationEnergy
ofActivationEn (ii) Tofindthenatureofreaction(Exothermic/Endothermicreaction)
ergy:- (A) ActivationEnergyofProducts-
ActivationEnergyofReactants=+iveExothermic
(B) ActivationEnergyofProducts –ActivationEnergyofReactants =-
iveEndothermic.

Collision Theory • Collision frequency (Z):-The number of collisions taking place per second per
of Reaction Rate unit volume of the reaction mixture is known as collision frequency (Z).

• Rate = ZAB e-Ea/RT Where Z = collision frequency and -Ea/RT = Fraction

of molecule having equal or more then activation energy.

• For a collision to be effective, the following two barriers are

to be cleared. 1. Energy Barrier 2.OrientationBarrier

• To account for the orientation factor for the collision to be effective, Probability
or Orientation or Steric factor (P) has been introduced
Rate=PZABe-Ea/RT

PYQ/ FREQUENTLY ASKED QUESTIONS

Rate of Reactions , Rate Law & Rate Constant and Order of reaction and Molecularity.
1
Ans. It may be defined as the change in concentration of a reactant or product in unit time.
For a general reaction, conversion of R → P, the average rate of reaction may be expressed as

Rate of Reaction depends upon- Temperature, Concentration of reactants, presence of catalyst.

2 What is instantaneous rate of reaction ?
Ans. It is the rate of reaction at a particular moment of time and measured as a very small concentration
change over a very small interval of time.
Mathematically, Instantaneous rate = (Average rate) Δt → 0

3 Define following –a) rate law of reaction b) Rate constant

Ans. a) Rate Law- It is an experimentally determined expression which relates the rate of reaction
with concentration of reactants.
For a hypothetical reaction, A + B → Products, the rate law may be given as
Rate of reaction = k[A]m [B]n
where k is a constant called specific rate of reaction or rate constant
b)Rate Constant- the rate constant may be defined as the rate of reaction when the concentration
of each reactant in the reaction is unity.
It depends upon nature of reaction and temperature of reaction.
15
4 What do you mean by order of areaction ?
Ans. Order Of A Reaction: It is the sum of the powers of all concentration terms in the rate law
expression. It can be zero, one, two etc or fractional.
5 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]–1
Ans.

6 A reaction is first order in A and second order in B.

(i) How is the rate affected on increasing the concentration of B three times?
(ii) How is the rate affected when concentration of both A and B are doubled?
Ans. the rate law for reaction is , Rate = k[A] [B]2 , hence

7 Define following- a) Elementary Reaction b) Complex reaction c) Molecularity

Ans. a)Elementary Reactions: Reactions which get completed in one step.
b)Complex Reactions: Reactions which take place in two or more steps
c) Molecularity- The number of reacting species which collide simultaneously to bring about a
chemical reaction.
8 Write two differences between ‘order of reaction’ and ‘molecularity of reaction
Ans. 1. Order is determined experimentally but molecularity is a theoretical concept
2. Order can be zero or a fraction but molecularity can not be zero or a fraction .
3. Order is applicable to elementary as well as complex reactions but Molecularity is applicable only
for elementary reactions , for complex reactions it has no meaning.
9. (a)For which type of reactions, order and molecularity have the same value?
(b)How does order of a reaction differ from molecularity for a complex reaction?
Ans. a) If the reaction is an elementary reaction, order is same as molecularity.
b) Order is applicable to elementary as well as complex reactions whereas molecularity is applicable
only for elementary reactions. For a complex reaction molecularity has no meaning and order is
given by the slowest step. Molecularity of the slowest step is same as the order of the overall
reaction.

10. Write unit of ‘k’ for (a) Zero order reaction (b) First order reaction.
Ans. Unit of rate constant ‘k’ = (conc.)1-n Time-1
For Zero order , k = mole L-1 s-1
For First order , k = s-1 (or time-1)

11 What do you mean by Pseudo first order reaction ?

Ans. A reaction which is not truely of first order but under certain conditions becomes a reaction of first
order is called pseudo first order reaction, e.g., acid hydrolysis of ethyl acetate is a bimolecular
reaction but it follows first order rate law when water is taken in large excess.

Rate ∝ [CH3COOC2H5] as H2O is in excess

Integrated Rate Law and Half Life of a reaction

16
where [R]0 is initial concentration and [R] is the final concentration at time ‘t’.
12 Define Half life period of reaction (t1/2)
An The half life (t 1/2) of a reaction is the time in which the concentration of reactant is reduced to one
s. half of its initial concentration [R] 0.
For a first order reaction, t1/2 =0.693/k , i.e., independent of [R]0.
For a zero order reaction, t 1/2 = [R]0//2k, i.e., t 1/2∝ [R]0.
13 A first order reaction is found to have a rate constant k = 5.5 x 10 –14 s–1. Find the half life
of the reaction.
An
s.

14 The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the
initial concentration of the reactant to 1/10 th of its initial value?
An
s.

Arrhenius Equation, Energy of Activation, Effect of Temperature and Catalyst on rate –

Threshold Energy- The minimum energy required for the reactant molecules to cause chemical
reaction
Activation energy: The energy required by the reactant molecules to change to products.
Activation Energy= Threshold Energy – Average Energy of reacting species

Temperature coefficient: It is defined as the ratio of rate constants of the reaction at two
temperatures
differing by 10°. A change in temp. by 10 oC generally doubles or triples the rate of reaction.
Arrhenius Equation-
Ea is energy of activation, k1 and k2 are rate constant at
temp. T1 and T2 , R=Universal gas constant= 8.314 JK-
1
mol-1
Note- a change in temperature changes the rate constant
and rate of reaction in same ratio.
That is , k2/k1 = r2/r1

15 What is the effect of temperature on rate of reaction ?

An Rate of reaction increases with increase in temperature due to increase in average energy of
s. reactants and decrease in activation energy.
16 How a catalyst change the rate of reaction ?
An A catalyst decreases the activation energy by providing an alternate path of lower threshold energy,
s. thus rate of reaction get increased..
17 The rate of a reaction quadruples when the temperature changes from 293 K to 313 K.
Calculate the energy of activation of the reaction assuming that it does not change with
temperature.

17
Ans.

18. The rate constant of a first order reaction increases from 2 x 10 –2 to 4 x 10–2 when the
temperature changes from 300 K to 310 K. Calculate the energy of activation (Ea).

An
s.

18
Important Graphs-

Variation of concentration with time for a Plot of t1/2 versus initial concentration [R]0 for a
zero order reaction zero order reaction

Plot of log [R] versus t Plot of log [R]0/[R] versus time (t)

Effect of catalyst on activation energy

log k vs 1/T

19
 (Unit -4) d and f Block Elements
GIST OF THE CHAPTER

• Those elements whose last electron enters in d sub shell (electronic configuration ns 1-2(n-1)d1-10) are
called d block elements.
• Those elements whose last electron enters in 3d sub shell (Z= 21 to 30) called 3d series elements.
• Those elements whose last electron enters in 4d sub shell (Z= 39 to 48) called 4d series elements.
• Those elements whose last electron enters in 5d sub shell (Z= 57, 72 to 80) called 5d series elements.
• Those elements of d block which have partially filled d orbitals in its atomic or ionic state are called
transition metals.
• Zn, Cd and Hg are not considered as transition metal because they have completely filled d orbitals.
• Transition metals are hard and high enthalpy of atomization due to partially filled d orbitals and d𝜋-d𝜋
bonding.
• Transition metal shows variable oxidation state/ large number of oxidation state due to presence of
unpaired electron or partially filled d orbitals.
• Transition metals form colored ion and colored compounds due to partially filled d orbital and d-d
transition.
• Transition metals are used as catalysts due to partially filled d orbital, variable oxidation state and large
surface area.
• Transition metals and its compounds are paramagnetic in nature due to partially filled d orbital.
• Transition metals form complex ion and complex compounds due to partially filled d orbital and vacant
d orbitals.
• Transition metals are used to make alloy due to comparable metallic radii.
• Transition metals form interstitial compounds due to availability of interstitial spacein metal lattice.
• The manganate (MnO42-) and permanganate (MnO4-) ions are tetrahedral, and the pi bonding takes
place by overlap of p orbitals of oxygen with d orbitals of manganese.
• The green colored manganate ion is paramagnetic due to presence of one unpaired electron but
permanganate ion is diamagnetic due to absence of unpaired electron.
• The color of KMnO4 is due to charge transfer from O- to Mn+ (ligand to metal).
• Lanthanoid contraction- regular decrease in atomic or ionic radii of Lanthanoid with increase in
atomic number is called Lanthanoid contraction.

Couse- It is due to poor shielding effect (imperfect shielding of one 4f orbital by another 4f orbital due to
which ENC regularly increases with increase in atomic number).
Consequences-
1. Resemblance in the properties of second and third transition series from Zr & Hf atomic size of 2nd and 3rd
transition series become same.
2. Similarity in the properties of Lanthanoids:- the decrease in atomic radii from Lanthanoid to Lanthanoid is
very less henceit is very difficult to separate these elements in pure state.
1 d-blockelementsarecalledtransitionelements as theyhaveincomplete d-orbitals in neutralor most
stable oxidationstate.
2 Zn,Hg,Cd,arenotincluded as Astheyhavefilledd-
transitionelements andwhy? orbitalsinneutralandmoststable+2oxidationstate.
1
3 Sc3+hasd0configurationbutitistransition Becauseofpartiallyfilledd configurationofSc
metal

20
4 Firstseriestransitionelementsshowsirregulartre Duetoshieldingeffectofinner3delectronswhichovercome
ndof atomicradii ENC.

5 Atomic radiiofZrtoHf arealmostsame. DuetoLanthenoidContraction.

6 Firstseriestransitionelementsshows irregular Itisbecauseofmutualexchangeofenergybetweendandforb

rtrendof IE italsafter removalof one electron.

7 Transitionmetalshavestrongmetallicbond,hav Duetopresenceofunpairedelectrons.
e high enthalpy of atomization and
meltingpoint.
8 Zn,Cd,HgarenotveryhardandhavelowM.P.and Duetopresenceofallpairedelectronstheyhaveleastenthal
B.P. py of atomization, very weak metallic bond & are
notveryhardwith lowM.P.andB.P.
9 d- Duetopresenceofunpairedelectronsorpartiallyfilledd-
blockelementsshowsalargeno.ofoxidationstate orbitals.

10 Whichfirstseriestransitionmetalshowshighestn Mnshowshighestnumberofoxidationstateduepresenceof
umberofoxidationstates andwhy? highestnumber of unpairedelectrons.
11 Whichfirstseriestransitionmetaldonotshowvari Sc,duetoachievingnoblegasconfigurationin+3O.S
ableoxidationstatesandwhy?
12 Cr3+is morestableas comparedtoCr2+ Duetostablehalffilledt 2g3configuration.
2+
13 Cu2+ismorestableinsolutionthanCu+ Duetohighhydration enthalpyof Cu ionin solution.
14 Whichfirstseriestransitionmetalshows+1oxidat Cushows+1oxidationstateingaseousformduetostable
ionstatesandwhy? fulfilled 3d10 configuration.
15 Higheroxidationstatesoftransitionmetalsfoundi Becausehigheroxidationstatesstabilizedbyhighlyelectron
ntheiroxides andfluorides egativeelementssuch as OandF
16 higher oxidation states are more common in due to formation of dπ-pπ bond between metal and
oxides rather than fluorides of transition oxygen.
metals.
17 +2 O.S becomes more stable in first series as number of unpaired electrons decreases.
transition elements moving from left to right
18 Write oxoanions of first series transition MnO4-, Cr2O72-, VO3-, CrO42-
metals in which group number and O.N. of
transition metal are same-
19 Moving from left to right E0 for M2+/M trends due to irregular variation of IE1 + IE2.
becomes less negative but it shows irregular
trend
20 For copper E0 Cu2//Cu is +ve (+0.34 V) it is due to low hydration enthalpy of Cu2+ which
cannotcompensate ∆subH0 + IE1 + IE2.
21 For Mn , E0 Mn3+/Mn2+ is +ve because by converting into Mn2+ it achieves half filled
configuration.
22 For Cr , E Cr /Cr is −ve
0 3+ 2+
because Cr3+ is more stable due to half filled t 2g
configuration.
23 Most of the compounds of transition metal are It is due to d-d transition
coloured in solid state as well as in their
solution form.

21
24 (Sc3+, Ti4+) does not exhibit any colour Ions with vacant d-orbitals (d0) as d-d transition is not
possible in this type of ions.
2+ +
25 (Zn , Cu ) does not exhibit any colour full filled d-orbitals (d10) as d-d transition is not
possible in this type of ions.
26 Transitionmetalsorionsareparamagneticinnatur Duetopresenceofunpairedelectrons (d1-9)
e
27 Transition metal form large number Highchargebymassratio,availabilityofvacantd-orbital&
ofcoordinationcomplexes variableoxidationstate

28 WhatareInterstitialcompounds? CompoundsinwhichsmallelementslikeH,B,C,Ntrappedi
nthe interstitialspace ofmetal lattice.

29 TransitionmetalsformInterstitialcompounds. Duetoavailabilityofinterstitialspaceinmetallattice.

30 Whyinterstitialcompoundsarefoundtobemoreu ThesecompoundshavehighM.Pascomparedtopuremetal
sefulthanpuremetal? s. These are very hard. Retain metallic
conductivityandareChemicallyinert.
31 Transitionmetalsandtheircompoundsarewidely Duetolargesurfacearea,variableoxidationstate&Availabi
used ascatalyst lityof vacantd-orbitals

32 transitionmetals formalloy. Duetocomparablemetallicradii

33 Whyoxides of Higher oxidation states of Higheroxidationstatesaremorepolarizinginnature.

Transitionmetalsareacidicinnaturewhereaslow HenceareacidicinnaturewhereaslowerO.S.arelesspolarizi
erO.S. arebasicinnature? nghence are basicinnature.
34 Actinoidsshowsgreaternumberofoxidation Duetocomparableenergyof5f,6d,and7s orbitals.
States thanlanthanoids
35 It is difficult to study chemistry of actinoids. Due to radio active nature and small half life

36 Ce(IV) is a good oxidizing agent in aq. soln because in aq. solution its E0Ce4+/ Ce3+ is +1.74 V

37 Actinoid contraction is greater from element because of poor shielding by 5f orbitals due to
to element as compared to lanthanoids . its superficial position.

22
PYQ/ FAQ(Frequently Asked Questions)
Que 1:- d-block elements are called transition elements?
Answer :- Because they have incomplete d-orbitals in neutral or most stable oxidation state.
Que2 :- Zn, Hg, Cd, are not included as transition elements and why?
Answer :- Because they have filled d-orbitals in neutral and most stable +2 oxidation state
Que3 :-Sc3+ has d0 configuration but it is transition metal?
Answer:- Because of partially filled d1 configuration of Sc.
Que4 :-Mn has maximum Paramagnetism? Explain.
Answer:- Due to 3d5configuration having 5 unpaired electron.
Que5:- First series transition elements shows irregular trend of atomic radii?
Answer:- Due to shielding effect of inner 3d electrons which overcome ENC.
Que6:- Atomic radii of Zr to Hf are almost same?
Answer:- Due to Lanthanoid Contraction
Que7:- First series transition elements shows irregular trend of I.E?
Answer:-Because of mutual exchange of energy between 3d and 4s orbitals after removal of one
electron.
Que8 : Eo value for Fe2+/Fe3+ is more feasible than Mn+2 /Mn+3 ,why?
Answer: Because Fe2+ (3d6) easily converted into more stable Fe3+(3d5) so more feasible, while
Mn+2 (3d5) more stable state not easily converted into Mn+3 (3d4) less stable.
Que9 : Sc3+ form colour less and diamagnetic compound?
Answer: Because Sc3+ has d0 configuration.
Que10:- Transition metal behaves as good catalyst?
Answer:-Due to partially filled d orbitals and large surface area.
Que11:-Transition metals have strong metallic bond, have high enthalpy of atomization and melting point.
Answer:- Due to presence of unpaired electrons and d𝜋-d𝜋 bonding .
Que12:-Zn, Cd, Hg are not very hard and have low M.P. and B.P?

23
 Answer:- Due to absence of unpaired electrons they are unable to form d𝜋-d𝜋 bonding so they have
least enthalpy of atomization, very weak metallic bond & are not very hard with low M.P. and B.P.
Que13:-d-block elements shows a large no. of oxidation state?
Answer:- Due to presence of unpaired electrons or partially filled d orbitals.
Que14:- Which first series transition metal shows highest number of oxidation states and why?
OR
Mn has maximum paramagnetism why?
Answer:-Mn shows highest number of oxidation state and maximum paramagnetism due presence of
highest number of unpaired electrons.
Que15 :- 3rd I.E of Mn is exceptionally high. Why?
Answer: Because Mn2+ ion has more stable 3d5configuration.
Que17:-Which first series transition metal do not show variable oxidation states and why?
Answer:- Sc, due to achieving noble gas configuration in +3 O.S.
Que18:-Cr3+ is more stable as compared to Cr2+?
Answer:-Due to stable half filled t2g3 configuration in Cr3+.
Que19:-Cu2+ is more stable in solution than Cu+?
OR
+
Que20:- Cu ion is not stable in aqueous solution ?
OR
+
Que21 :- Cu undergoes disproportionation reaction in aqueous state?
Answer:-Due to high hydration enthalpy of Cu2+ ion in solution
Que22:- Which first series transition metal shows +1 oxidation states and why?
Answer:- Cu shows +1 oxidation state in gaseous form due to stable full filled 3d 10 configuration.
Que23 :- Higher oxidation states of transition metals found in their oxides and fluorides ?
Answer :- Because higher oxidation states stabilized by highly electronegative elements such as O and
F
Que24 :- Higher oxidation states are more common in oxides rather than fluorides of transition metals.
Answer:-Due to formation of double bond and dπ-pπ band between metal and oxygen.
Que25:- +2 O.S becomes more stable in first series transition elements moving from left to right?
Answer:-Because number of unpaired electrons decreases.
Que25 :- Write Oxo anions of first series transition metals in which group number and O.N. of transition metal
are same
Answer:- MnO4–, Cr2O7²–, VO3–, CrO4²–
Que26:- Moving from left to right E° for M2+/M becomes less negative but it shows irregular trend?
Answer:- Trends due to irregular variation of IE 1 + IE2 + ΔsubH° and Hydration Enthalpy.
Que26 :- For copper E° Cu2+/Cu is +ve (+0.34 V)?
Answer:- If is due to low hydration enthalpy of Cu 2+ which cannot Compensate ΔsubH° +IE1+ IE2
Que27 :- For Mn, E°Mn3+/Mn2+ is +ve?
Answer:-Because by converting into Mn2+ it achieves half filled configuration
Que28:-For Cr, E°Cr3+/Cr2+ is – ve?
Answer:-because Cr3+ is more stable due to half-filled t2g3 configuration
Que29:-Most of the compounds of transition metal are colored in solid state as well as in their solution form?
Answer :-It is due to d-d transition.
Que30 (Sc3+, Ti4+) does not exhibit any colour?
Answer:- Ions with vacant d-orbitals(d0) as d-d transition is not possible in this type of ions
Que31:- (Zn2+, Cu+) does not exhibit any colour?
Answer:-full filled d-orbitals (d10) as d-d transition is not possible in this type of ions.
Que32:- Transition metals or ions are paramagnetic in nature?
Answer:- Due to presence of unpaired electrons (d1-9).

24
Que33:- Transition metal form large number of coordination complexes?
Answer:- High charge by mass ratio, availability of vacant d orbital & Variable oxidation state
Que34:-What are interstitial compounds?
Answer:- Compounds in which small elements like H, B, C, N trapped in the interstitial space of metal
lattice.
Que35:- Transition metals form Interstitial compounds?
Answer:- Due to availability of interstitial space in metal lattice.
Que36:- Why interstitial compounds are found to be more useful than pure metal?
Answer :-These compounds have high M.P as compared to pure metals. These are very hard. Retain
metallic conductivity and are chemically inert.
Que37 :-Transition metals and their compounds are widely used as catalyst?
Answer:-Due to large surface area, variable oxidation state & Availability of vacant d-orbitals
Que38:-Transition metals form alloy?
Answer:-Due to comparable metallic radii.
Que39:-Why oxides of higher oxidation states of transition metals are acidic in nature whereas lower O.S. are
basic in nature?
Answer:-Higher oxidation states are more polarizing in nature. Hence are acidic in nature whereas
lower O.S. are less polarizing hence are basic in nature
Que40:- Actinoids shows greater number of oxidation states then lanthanoids why?
Or
Unlike Lanthanoids the elements of actinoids show large range of variable Oxidation state?
Answer:- Due to comparable energy of 5f, 6d, and 7s orbitals.
Que41:- It is difficult to study chemistry of actinoids.
Answer:- Due to radioactive nature and small half-life period .
Que42:- Ce(IV) is a good oxidizing agent in aq. Solution?
Answer:- Because in aqueous, solution its E°Ce4+/Ce3+ is +1.74 V.
Que43:- Actinoid contraction is greater form Element to element as compared to lanthanoids?
Answer:- Because of poor shielding by 5f orbitals due to its superficial position.
Que44:- Define Lanthanoid contraction and give any two consequences of Lanthanoid contraction ?
Answer:- The steady decrease in the atomic size of lanthanides on increasing the atomic number from
left to right.
Cause of lanthanoid contraction- Due to the poor shielding of 4d orbital
Consequences:-
(i) Small change in the atomic radii because of Lanthanide contraction leads to difficulty in the
separation of lanthanides.
(ii) Due to Lanthanide contraction , these elements occurs together in natural minerals and are difficult to
separate

Que45 :- Mn+2 is more stable than Fe+2 towards +3 Oxidation State?

Answer :-Mn in (+2) state has a stable d5 configuration.
Que46:-Mn exhibit the highest oxidation state + 7 among the 3d series of Transition Element?
Answer:-Mn is due to the presence of 5 unpaired electrons in its 3d subshell
Que47 :- Although F is more electronegative than O the highest fluoride of Mn is MnF4 whereas the highest
oxide is Mn2O7?
Answer:- Oxygen has tendency to stabilize higher oxidation states. because oxygen can form multiple bonds
with Mn.
Que48 :- Cu and Ag both are transition element although both have complete d orbital?
Answer:-Because they have incompletely filled d-orbitals in at least one of their oxidation states
Que49:-Which element of 3d transition series show only + 3 Oxidation State?
Answer:- Scandium(Sc).
25
 Que50:- Which element of 3d series has least enthalpy of atomization?
OR
from Sc to Zn in 3d series the least value of ΔatmH°?
Answer:- The enthalpy of atomization of zinc is the lowest (126kJmol−1) due to absence of unpaired
electron .
Que51:- Chemical properties of 4d and 2nd transition series similar with 5d and 3rd transition series?
Answer: Due to lanthanoid contraction and comparable similar atomic radii.
Que52:-Complete the following ionic reactions.
(a)Cr2O72-+ H+ +I- ————>
(b)MnO4-(aq) + Fe2+(aq)+ H+(aq)———>
Answer: (a)Cr2O72-+ H+ +I- ————>Cr3+ +I2 +H2O
(b)MnO4-(aq) +5 Fe2+(aq)+ 8H+(aq)———> Mn2+ + 5Fe3+ + 4H2O
Que53:- Chromium is hard metal while mercury is a liquid metal?
Answer:-Chromium is a hard metal due to strong metallic bonding due to unpaired electrons while Hg has
no unpaired electron.
Que54:-Describe the preparation of potassium dichromate from chromite ore. What is the Effect of change
of pH on dichromate ion?
Answer:- 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2 .
The yellow solution of sodium chromate is filtered off and acidified with H 2SO4 to give orange sodium
dichromate
2Na2CrO4 + 2H+ → Na2Cr2O7 + H2O + 2Na+.
Sodium dichromate is then treated with KCl to give potassium dichromate
As orange crystals. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
The chromate and dichromate ions are interconvertible in aqueous solution depending upon pH of the
solution.In Acidic medium(pH<7) dichromate ionCr2O7-2exist in orangecolour whereas in basic medium
(pH>7) chromate ion (CrO4-2) exists and show yellow colour.
2CrO4-2 + 2H+ → Cr2O7-2 + H2O
Cr2O7-2+ 2OH–→ 2CrO4-2+ H2O
Que55:- Complete the following reactions
(i)MnO4-(aq) + S2O32-(aq) + H2O (l) →
(ii) MnO4-+ SO32– + 6H+→
(iii)MnO4-(aq) + I- + H2O (l) →
Answer: (i) 8MnO4-(aq) + 3S2O32-(aq) + H2O(l) → 8MnO2 + 6SO42- + 2OH-
(ii)MnO4-+ SO32– + 6H+→ 2Mn2+ + 5SO42– + 3H2O
(iii)2MnO4-(aq) + I- + H2O (l) → 2MnO2 + IO3- + 2OH-
Ques56: - With the same d-orbital configuration (d4) Cr2+ is a reducing agent while Mn3+ is an oxidizing agent?
Answer:-Cr2+ has the configuration 3d4 which easily changes to d3due to stable half-filled t2g orbitals.
Therefore Cr2+ is reducing agent. While Mn2+ has stable half filled d5 configuration. Hence Mn3+ Easily
changes to Mn2+ and acts as oxidizing agent.
Que57:-What is the effect of change of pH on dichromate ion?
Answer:- The chromates and dichromates are interconvertible in aqueous solution depending upon pH of the
solution.
2CrO4-2+ 2H+ → Cr2O7-2 + H2O
Cr2O7-2+ 2OH-→ 2CrO4-2+ H2O
Que58:-Write the ionic equation for reaction of KI with acidified K2Cr2O7.
Answer:-Cr2O7-2+ 14H+ + 6I- → 2Cr3+ + 3I2 + 7H2O
Que59:-La(OH)3 is more basic than Lu(OH)3. Why?

26
Answer:- Due to lanthanoid contraction the size of lanthanoid ion decreases regularly with the increase in
atomic number . Thus covalent character between lanthanoid ion and OH -increases from La3+ to Lu3+. Thus
the basic character of hydroxides decreases from La(OH)3 to Lu(OH)3
Que60:- Generally there is an increase in density of elements from titanium (Z = 22) to copper (Z = 29) in the
first series of transition elements. Explain why?
Answer:- From titanium to copper the atomic size of elements decreases and mass increases as a result of
which density increases.
Que61:-E° value for the Mn3+/ Mn2+ couple is much more positive than that for Cr 3+/Cr2+
Answer:-The large positive E° value for Mn3+/Mn2+ shows that Mn2+ is much more stable than Mn+3due to
stable half-filled configuration (3d5). Therefore the 3rd ionization energy of Mn will be very high and Mn3+
is unstable and can be easily reduced to Mn2+. E° value for Cr3+/ Cr2+ is positive but small i.e. Cr3+ can also
be reduced to Cr2+ but less easily. Thus Cr3+ is more stable than Mn3+.
Que62;- Sc+3 form colorless and diamagnetic compound?
Answer:-Due to its d0 configuration when it loses 3 electrons
Que63 : Why [Ti(H2O)6]3+ is coloured but [Sc(H₂0)6]3+ is colorless?
Answer: Because, in [Ti(H2O)6]3+has unpaired electron for d-d transition( responsible for colorless of a
complex compound) so it is coloured .while [Sc(H₂0)6]3+cannot undergo d-d transition as do not have
unpaired electrons so it is colorless.
Que64: Find out magnetic moment of Mn2+?
Answer: Magnetic moment is given by
 = √𝑛(𝑛 + 2) BM
Where n= no of unpaired electrons.
Since n=5.
Therefore  = 5.9 BM
UNIT – 5 COORDINATION COMPOUNDS
GIST OF THE CHAPTER

SimpleSalt DoubleSalt ComplexSalt

Containonetypeofcationando Contain two types of cations. Containcomplexion.

ne typeof anion. eg. K4Fe(CN)6 = 4K+
e.g.NaCl. e.g. Mohr’s salt (NH4)2SO4.
+[Fe(CN)6]4-
FeSO4.6H2O,
Potash Alum- Al2(SO4)3. K2SO4.24H2O

BasicTerms

1. CoordinationSphere- Centralmetalatomandligands bonded to CMA called coordination sphere ⭢represented in

asquare bracket.
2. CentralMetalAtom –Acceptelectronsfortheformation of coordinate bond is called central metalatom.
3. Ligand- Providepair ofelectronforformationofcoordinate bond to central metal atom is called ligand.(Lewis Base)
4.Coordination Number- Numberofcoordinate bondsformedbyligandswithcentralmetalatominthe complex is called
coordination number of complex.
5 .HomolepticandHeterolepticComplexes -
Acomplexwithsametypeofligandssurroundingcentral metal atom is called homoleptic complex.
e.g.-[Cu(NH3)4]2+,[Pt(NH3)4]2+
A complex with different types of ligands surroundingcentral metal atom is called heteroleptic complex.
e.g.[Pt(NH3)2Cl2]
6. Coordination Polyhedron- Spatial arrangement
ofligandsaroundcentralmetalatomorioniscalledcoordinationpolyhedron.
NomenclatureofCoordinationCompounds:
27
1) Cationiswrittenfirstfollowedbyanion.
2) Whilewritingnameofcoordinationsphereligands are named first followed by central metalatom.
3) To indicate number of ligands prefix di, tri, tetra,penta,hexa,heptaetcareused.Ifligandsitselfinvolve such
prefixes in its name then prefix bis,tris andsoonareusedtoindicatenumberof ligands.
4) Whilewritingnameofcentralmetalatom:-
a. Ifcoordinationsphereiscationnameofmetalatoms written as such: Fe – Iron, Au – Gold, Cu –Copper,Cr –
Chromium, Ag–Silver.
b. If, coordination sphere is anion suffix ‘ate’ is usedto write name of central metal atom. Such as: Fe –
Ferrate,Hg–Mercurate,Cu–Cuprate,Ag–Argentate ,Au–Aurate ,Pd–Palladate,Cr-Chromate
5) Afterwritingnameofcentralmetalatom its oxidationnumberisindicatedinparentheses’()’.

IsomerisminCoordinationCompounds
(a) Structuralisomerism
(i) Linkageisomerism-Arisesinacoordinationcompound containing ambidentate ligand.
M–SCN, M–NCS&(–NO2), (–ONO)
(ii) Coordinationisomerism-Arisesfromtheinterchange of ligands between cationic and anionicentities of
different metal ions present in a complex. [Co(NH3)6][Cr(CN)6]&[Cr(NH3)6][Co(CN)6]
(iii) Ionisation isomerism- Arises when the counterion in a complex salt is itself a potential ligand and can
displace a ligand which can then become the counterion. [Co(NH3)5(SO4)]Br&[Co(NH3)5Br]SO4.
(iv) Solvateisomerism-Arisesduetoexchangeof H2O as ligand and counter anion in the complex.
[Cr(H2O)6]Cl3&[Cr(H2O)5Cl]Cl2.H2O
(b) Stereoisomerism
(i) Geometricalisomerism-Arisesinheterolepticcomplexesduetodifferentpossiblegeometricarrangements
of the ligands.
Ifsameligands areonsameside –cis isomer.
If same ligands are on opposite side – trans isomer.
*Tetrahedralcomplexesdonotexhibitgeometricalisomerismduetosomerelativepositionofligandsaroundcentral
metal atom.
*SquareplanarcomplexeswithformulaMA2B2-two geometrical isomers, MABCD- Three isomers
*Octahedral complexes- MA4B2, M(AA)2B2– cis & transMA3B3-fac&merisomers
(ii) Optical isomerism-Opticalisomersare mirrorimages that cannot be superimposed on one
another.Theseare calledas enantiomers.
Bondingincoordinationcompounds-
Werner’sTheory-
(i)Primary valences are ionizable and are satisfied by negative ions .
(ii)Secondaryvalencesare non
ionizableandreferscoordinationnumberofcomplex.
(iii)Theions/groupsboundbythesecondarylinkagestothemetalhavecharacteristicspatialarrangements
Correspondingtodifferentcoordinationnumbers.

Valence bond theory –

Complex Oxidationst Hybridi Geometry Magneti Number Outer orbital
ate -zation cnature o /Innerorbital
ofC funpairedele
MA ctrons
[Co(NH3)6]3+ +3 d2sp3 Octahedral Diamagnetic 0 Innerorbital
[CoF6]3- +3 sp3d2 Octahedral Paramagnetic 4 Outerorbital
[Co(C2O4)3]3- +3 d2sp3 Octahedral Diamagnetic 0 Innerorbital
[Mn(CN)6]4- +2 d2sp3 Octahedral Paramagnetic 1 Innerorbital

28
 [Fe(CN)6]3- +3 d2sp3 Octahedral Paramagnetic 1 Innerorbital

[Fe(H2O)6]2+ +2 sp3d2 Octahedral Paramagnetic 4 Outerorbital

[Ni(NH3)6]2+ +2 sp3d2 Octahedral Paramagnetic 2 Outerorbital

[NiCl4]2- +2 sp3 Tetrahedral Paramagnetic 2 ------------------

[Ni(CO)4] 0 sp3 Tetrahedral Diamagnetic 0 ----------------

[Ni(CN)4]2– +2 dsp2 Squareplanar Diamagnetic 0 -----------------

CrystalField Theory-
Splittingofd-orbitalsinoctahedral field: Splittingofd-orbitalsintetrahedralfield:

Metal Carbonyls:Homoleptic complex of transitionmetal with carbonyl ligand are called metal
carbonyls.E.g.[Ni(CO)4],[Fe(CO)5],[Cr(CO)6],[CO2(CO)8],[CO3(CO)12],[Mn2(CO)10]

Themetal-carbon bond in metal carbonyls possess both σ and π character. The M–C σ bond is formed
bythe donation of lone pair of electrons on the carbonylcarbon into a vacant orbital of the metal. The M–C
πbond is formed by the donation of a pair of electrons from a filled dorbital of metal into the vacant anti
bonding π* orbital of carbon monoxide. The metal to ligand bonding creates a synergic effect which
strengthens the bond between CO and the metal.

Application of Coordination Complexes:

a) Chlorophyll–complex of Mg, Haemoglobin – complex of Fe, Vit. B-12 – complex ofCo

b) Metallurgy: Extraction of Au, Ag, by cyanide process.Refining of Ni by Mond’s process Refining of Zr

by Van Arkel process.
c) Quantitative Analysis : Estimation of hardness of water Ca2+ and Mg2+ are estimated by complex matric
titrationusing EDTA.

PYQ / FAQ:-

Q-1 Explainthefollowingtermsgivingasuitableexampleineachcase:
(a)Ambidentateligand(b)Denticityofa ligand
29
Ans- (a) Ambidentate ligand - A monodentate ligand which can coordinate to central metal atom through two
different atomsiscalledambidentateligand.ForexampleNO2– ioncancoordinate either throughnitrogenorthrough
oxygen to the central metal atom/ion.
(b) Denticity- The number of coordinating groups present in a ligand is called the denticityof ligand. For
example,bidentateligandethane-1,2-diaminehastwodonornitrogenatomswhichcanlinktocentralmetal atom.
Q-2 Define the following terms :
(a) Homoleptic complex (b) Chelating ligand
Ans -Homoleptic complex – Complex in which metal is bound to only one type of donor groups are called
homoleptic complex .
Chelating ligand -When polydentate ligand attaches to central metal atom or ion through two or more donor
atoms in such a way that it forms a five or six membered ring with the central metal atom then the ligand is
called chelating ligand and the ring thus formed is called chelate.

Q-3 Write the IUPAC name of following complexes –

(a) K4[Fe(CN)6] (b) [Ni(CO)4] (c)[Ag(NH3)2]Cl (d)[Pt(NH3)2Cl(NO2)] (e)K3[Cr(C2O4)3]
2+
(f)[CoCl2(en)2]Cl(g)[Cu(NH3)4] (h)NH4[Cr(NCS)4(NH3)2] (i) [Cr(en)3]Cl3
(j) [Co(NH3)5(ONO)]2+(k)K2[NiCl4]
Ans – (a) Potassium hexacyanidoferrate (II)
(b) Tetracarbonyl nickel (0)
(c) Diammine silver(I)chloride
(d) Diamminechloridonitrito-N-platinum(II)
(e) Potassium trioxalatochromate (III)
(f) Dichloridobis (ethane -1,2-diamine)cobalt(III) chloride
(g) Tetraammine copper (II)ion
(h) Ammonium diamminetetraisothiocyanato chromate(III)
(i) tris(ethane-1,2-diamine)chromium(III)chloride
(j) Pentaamminenitrito-O-cobalt(III)ion
(k)Potassiun tetrachloridonickelate(II)

Q-4 UsingIUPACnormswritetheformulaeforthefollowing coordination compounds:

(a) Hexaamminecobalt(III) chloride
(b) Potassium tetrachloridonickelate(II)
(c) Potassium tetrahydroxidozincate (II)
(d) Potassium trioxalatochromate (III)
(e) Hexaammineplatinum(IV) chloride
(f) Tetraammineaquachloridocobalt (III) chloride
(g) Pentaamminecarbonatocobalt (III) chloride
(h)Potassium tetracyanidonickelate (II)
(i) dichloridobis (ethane -1,2-diamine)platinum(IV)nitrate
(j)Iron(III) hexacyanidoferrate(II)
Ans-(a)[Co(NH3)6]Cl3(b)K2[NiCl4](c) K2[Zn(OH)4](d)K3[Cr(ox)3]
(e) [Pt(NH3)6]Cl4(f) [Co( NH3)4H2OCl] Cl2(g) [Co(NH3)5CO3]Cl
(h) K2[Ni(CN)4](i) [PtCl2(en)2](NO3)2(j) Fe4[Fe(CN)6]3
Q-5 Give the formula of each of the following coordination entities:
(a) Co3+ ion bound to one Cl- , one NH3 moleculeandtwoethylenediaminemolecules.
(b) Ni2+ionisboundtotwowatermoleculesandtwooxalate ions.
Ans-(a)[Co(NH3)Cl(en)2]2+
(b) [Ni(H2O)2(ox)2]2-

Q-6 Draw structures of geometrical isomers of [Pt(NH3)2Cl2] and state the isomer which is used in treatment
of the cancer.
Ans- i) cis form ii) trans form

30
 Cis form is called cis platin used in treatment of cancer.

Q-7 What type of isomerism is exhibited by the complex [Co(en) 3]3+ ? Draw the structures of isomers.
Ans-

Q-8 What type of isomerism [Co (NH3)5(SO4) ]Cl is expected to exhibit and why ?
Ans- Ionization isomerism and due to exchange in position by sulphate and chloride ions.

Q-9What type of structural isomerism is exhibited by the following compounds?

(a) [Cr(NH3)5Br]SO4 (b) [Cr(NH3)6][Co(CN)6]
Ans- a) Ionisation isomerism b) Coordination isomerism

Q-10 A metal complex having composition Cr(NH3)4Cl2Br has been isolated in two forms A and B. The form
A reacts with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammonia whereas B gives a
pale yellow precipitate soluble in concentrated ammonia. Write the formulae of isomers A and B.
Ans- Formula of isomer A : [Cr(NH3)4ClBr]Cl, Formula of isomer B : [Cr(NH3)4Cl2]Br
Q-11 Draw all the isomers (geometrical and optical) of – [ CoCl2(en)2]+.
Which geometrical isomer is optically inactive and why ?
Ans- Geometrical isomers- Optical isomers -

Q-12 If PtCl2.2NH3 does not react with AgNO3 , what will be its formula ?
Ans - [Pt(NH3)2Cl2 ]
Q-13When a coordination compound CrCl3.5H2O is mixed with AgNO3, two moles of AgCl are
precipitated per mole of the compound. What is the structural formula of the coordination compound?
Ans- [Cr(H2O)5Cl]Cl2
Q-14 When a co-ordination compound CrCl3.6H2O is mixed with AgNO3, 2 moles of AgCl are precipitated
per mole of the compound. Write (a) Structural formula of the complex. (b) IUPAC name of the complex.
Ans – (a) [Cr(H2O)5Cl]Cl2.H2O
(b) pentaaquachloridochromium(III) chloride monohydrate
Q-15AcoordinationcompoundCrCl3.4H2Oprecipitatessilverchloridewhentreatedwithsilvernitrate.The molar
conductance of its solution corresponds to a total of two ions. Write the structural formula of the compound
and name it.
Ans- Silver chloride precipitates when treated with silver nitrate because there is chloride ion outside the
complex. There is only one chloride ion outside the complex since only two ions are generated. As a result,
thecompound’sstructuralformulaandnomenclatureare:
[Co(H2O)4Cl2]Cl–Tetraaquadichloridocobalt(III) chloride
31
Q-16Forthecomplex[Fe(H2O)6]3+,writethehybridization ,magneticcharacterandspinofthecomplex.(At
number Fe = 26)
Ans-

Thecomplexionhasouterorbitaloctahedralgeometry(highspin)and is paramagnetic due to the presence of five

unpaired electrons.
Q-17 [Ni(CO)4] possessestetrahedralgeometrywhile[Ni(CN)4]2-issquareplanar. Why?
Ans -[Ni(CO)4]Niisin0oxidationstateanditselectronicconfigurationis3d84s2.COisstrongligand. Hybridization
is sp3 and it is tetrahedral.

Q-18 Comparethefollowingcomplexeswithrespecttotheirshape,magneticbehaviourandthehybridorbitals
involved (a) [CoF4] 2- (b) [Cr(H2O)2(C2O4)2]– (c) [Ni(CO)4]
(Atomic number : Co = 27, Cr = 24, Ni = 28)
Ans -

Q-19 Writethestate ofhybridization,the shapeandthemagneticbehaviour ofthefollowing complexentities

:(a)[Cr(NH3)4Cl2]Cl(b)[Co(en)3]Cl3(c)K2[Ni(CN)4]

32
Q-20 Forthecomplex[Fe(en)2Cl2],Cl(en=ethylenediamine),identify
(a)theoxidationnumberofiron (b) the hybrid orbitals and the shape of the complex,
(c) the magnetic behaviour of the complex,
Ans-(a)[Fe(en)2Cl2]Cl
x+0 ×2 +(–1) ×2+(–1) ×1 =0
x=3 Oxidation numberof iron =3
2
(b) d sp3hybridisationandoctahedralshape.
(c) Paramagneticdueto presenceof oneunpaired electron.
Q-21WritetheIUPACname,deducethegeometryandmagneticbehaviourofthecomplexK4[Mn(CN)6].
[Atomic no. of Mn = 25]
Ans -

Q-22 Explainwhy[Fe(H2O)6]3+hasamagneticmomentvalueof5.92 BMwhereas[Fe(CN)6]3 – hasavalueof only

1.74 BM.
Ans - [Fe(CN)6]3–involvesd2sp3hybridisationwithoneunpairedelectron and[Fe(H2O) 6]3+involvessp3d 2
hybridisation with five unpaired electrons. This difference is due to the presence of strong ligand CN– and
weak ligand H2O in these complexes.
Q- 23 Givereasons-(a) WhyCuSO45H2O is blueincolour whileCuSO4is colourless.
Ans -InCuSO45H2O,wateractsasligandand causescrystalfieldsplitting.Henced-dtransition ispossible and
shows colour.
(b) Lowspintetrahedralcomplexesnotformed
Ans – Inatetrahedralcomplex,thed-orbitalissplittoosmallascomparedtooctahedralcomplexForthesame
metalandsameligandΔt=4/9Δo.Hence,theorbitalenergiesarenotenoughtoforcepairing.Asaresult,low spin
configurations are rarely observed in tetrahedral complexes.
Q-24 [Ni(CN)4] 2-iscolourlesswhere as[Ni(H2O)6]2+isgreen. Why?
Ans -In[Ni(CN)4]2-,Niisin+2oxidationstatewithelectronicconfiguration3d8.Inthepresenceofstrong CN-
ligandthetwounpairedelectronin3dorbitalpairup.Asthereisnounpairedelectron,itis colourless In
[Ni(H2O)6]2+Niis+2oxidationstateandelectronicconfiguration3d8. Thetwounpaired electronsdonot pair up in
the presence of weak ligand H2O. The d-d transition absorbs red light and complementary green light is
emitted.
Q-25 On the basis of CFT, write the electronic configuration for d 5 if -
(a) ∆o < P (b) ∆o > P
3 2
Ans - (a) t2g eg (b) t2g 5 eg0
Q-26 Give the electronic configuration of the following complexes based on Crystal Field Splitting
theory.
[CoF6]3– , [Fe(CN)6]4– and [Cu(NH3)6]2+
Ans- [CoF6]3– :Co3+(d6)

33
Q-27 (a) The Complex [Ti(H2O)6]3+is a coloured compound. Justify.
(b) Explain [Co(NH3)6]3+is an inner orbital complex whereas [CoF6]3-is an outer orbital complex.
Ans- a) Ti3+contains one unpaired electron hence d-d transition.
(b) NH3 is a strong ligand hence cause pairing in 3d orbitals and d 2sp3 hybridisation takes place whereas F is
a weak ligand can not cause pairing hence undergo sp3d2 hybridisation.
Q-28 (a) In a coordination entity, the electronic configuration of central metal ion is t 2g3eg1. Is the
coordination compound high spin or low spin. Identify the nature of ligand.
(b) Draw diagram for spilliting of five d-orbitals in octahedral crystal field.
Ans- (a) High Spin and weak field ligand.
(b) Correct diagram and labelled properly.
Q-29Explain the following: (a) Low spin octahedral complexes of nickel are not known.
(b) CO is a stronger ligand than NH3 for many metals.
Ans - (a) Ni in its atomic or in its ionic state cannot afford two vacant 3d orbitals hence d 2sp3 hybridisation
is not possible.
(b) Because in case of CO back bonding takes place in which the central metal uses its filled d orbital with
empty anti bonding 𝜋* molecular orbital of CO
Q-30 Arrangethefollowingcomplexesintheincreasingorderofconductivityoftheirsolution:[Co(NH 3)3Cl3],
[Co(NH3)4Cl2]Cl , [Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2
Ans -Co(NH3)3Cl3]<[Co(NH3)4Cl2]Cl<[Cr(NH3)5Cl]Cl2<[Co(NH3)6]Cl3Here,thenumberofions increases and
conductivity increases.

Unit-6 : Haloalknes and Haloarenes

Gist of The Chapter

Important Name Reactions-

1.Finkelstein Reaction: Chloroalkanes or bromoalkanes are converted into corresponding iodoalkanes

by treating with sodium iodide dissolved in acetone.

2.Swarts reaction – Conversion of Chloroalkanes or bromoalkanes in to fuoroalkane using metal fluorides.

3.Wurtz Reaction- Alkyl halides react with metallic sodium in the presence of dry ether to form alkanes.
This reaction is used for the preparation of higher alkanes. For example

34
4.Fittig’s Reaction: In this reaction two molecules of haloarene combine with metallic sodium in the
presence of dry ether to give diphenyl or biphenyl.

5. Sandmeyer’s Reaction: Benzene diazonium chloride is converted to chlorobenzene, bromobenzene,

cyanobenzene on treatment with CuCl/HCl, CuBr/HBr and CuCN/KCN, respectively

6. Friedel–Crafts Alkylation: Benzene and other aromatic compounds react with alkyl halides in the
presence of anhydrous AlCl3 to form alkyl benzene.

7.Dehydrodehalogenation( 1,2-Elimination)- When haloalkane with b-hydrogen atom is heated with

ethanolic potassium hydroxide, there is elimination of hydrogen atom from b-carbon atom and a halogen
atom from a-carbon atom. As a result, an alkene is formed.

8. Nucleophilic Substitution Reactions (SN Reactions- SN1 & SN2)-

Displacement of halogen by a nucleophile (Nu:-) – OH-, CN- , OR- etc.

R-X + NaOH (aq) → R-OH + NaX ; R-X + NaOR (aq) → R-OR + NaX
35
R-X + NaCN(aq) → R-CN + NaX; R-X + AgCN (aq) → R-NC + NaX

Substitution nucleophilic bimolecular (SN2)

• It is bimolecular and second order reaction, Rate of reaction = k [R-X][ Nucleophile]
• Take place in single step, involve a pentavalent transition state.
• It proceeds with inversion of configuration .
• Reactivity of Haloalkanes having different halogens R-F < R-Cl < R-Br < R-I
( because bond energy of C-X bond is drcreasing)
• Order of reactivity for different haloalkanes : CH3-X > R-CH2-X (1O ) > R2CH-X (2o)> R3C-X
(3o)
With increase in number of carbon chain around C-X , steric hindrance increases, hence, reactivity
decreases.
Substitution nucleophilic unimolecular (SN1)
• It is unimolecular and first order reaction, Rate of reaction = k [R-X]
• Take place in 2 steps and involve formation of intermediate carbocation .
• It proceeds with retention of configuration .
• Reactivity of Haloalkanes having different halogens R-F < R-Cl < R-Br < R-I
( because bond energy of C-X bond is drcreasing)
• Order of reactivity for different haloalkanes :CH3-X < R-CH2-X (1O ) < R2CH-X (2o)< R3C-X (3o).
• With increase in number of carbon chain around C-X , stability of intermediate carbocation increases,
hence, reactivity decreases

SN1 mechanism
• It isTwostepreactions.
• StepI:Inthefirststepslowdissociationofalkylhalidetakesplacebyreversiblereactionforminga
carbocation.

• StepII:Thecarbocationatoncecombineswiththenucleophiletoformfinalproduct
(racemicmixture)

• SN2mechanism
It isOnestepreaction

sp3 Pentavalent transition state( sp 2) Inversion of configuration (sp3)

Q.1 Write the structure of the major organic product in each of the following reactions
organic product in each of the following reactions:

𝒅𝒓𝒚 𝒂𝒄𝒆𝒕𝒐𝒏𝒆
(i) CH3CH2Br + NaI > ……………………………………………….?
𝒉𝒆𝒂𝒕

36
 𝒉𝒆𝒂𝒕
(ii) CH3Br + AgF > ……………………………………………………………….?
𝑵𝒂
(iii) (CH3 )2CH-Cl > ……………………………………………………. ?
𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓

𝑪𝒖/𝑯𝑪𝒍
(iv) C6H5N2Cl > ………………………………………………………………?

Ans. 𝑑𝑟𝑦 𝑎𝑐𝑒𝑡𝑜𝑛𝑒

(i) CH3CH2Br + NaI > CH3CH2-I + NaBr
ℎ𝑒𝑎𝑡
ℎ𝑒𝑎𝑡
(ii) CH3Br + AgF > CH3-F + AgBr
𝑁𝑎
(iii) 2 (CH3 )2CH-Cl > (CH3 )2CH-CH-(CH3)2
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
𝐶𝑢/𝐻𝐶𝑙
(iv) C6H5N2Cl > C6H5- Cl
Q.2 Which compound in each of the following pair will react faster in S N2 reaction with OH−
and why ?
(i) CH3Br or CH3I
(ii) (CH3)3CCl or CH3Cl
(iii)

(iv)

Ans i) CH3-I will give faster SN2 reaction because bond energy of C-I bond is less than C-Br bond
ii) CH3Cl will undergo faster SN2 reaction because it is a primary alkyl halide and has less
steric hindrance about C-Cl bond .

iii) Will undergo faster SN2 reaction because it is a primary alkyl halide
and has less steric hindrance about C-Cl bond

iv) will give faster SN2 reaction because bond energy of C-I bond is less than C-
Cl bond
Q.3 Which compound in each of the following pair will react faster in S N1 reaction with OH−
and why ?
a) (CH3)3CCl or CH3CH2CH (Cl)CH3 (b)
Cl
H3C Cl
H3C
CH3

Ans. a) (CH3)3CCl Will undergo faster SN1 reaction because it is a tertiary alkyl halide and produce
more stable carbocation intermediate.

b) will undergo faster SN1 reaction because it is a 2o alkyl halide and

produce more stable carbocation intermediate.
Q.4 Which compound in the following couples will react faster in SN2 displacement and why?
(a) 1-Bromopentane or 2-bromopentane
(b) 1-Bromo-2-methylbutane or 2-bromo-2-methylbutane
Ans. a) 1-Bromopentane, as it is a primary alkyl halide and has less steric hindrance.
b) 1-Bromo-2-methyl butane, as it is a primary alkyl halide and has less steric hindrance
Q.5 Haloarenes are less reactive towards SN reaction than haloalkanes .Explain why ?
Ans The C-X bond in Haloarenes acquire partial double bond character due to resonance hence it is
difficult to displace halogen in Haloarenes as compared to haloalkanes.
Q.6 Vinyl chloride (CH2=CH-Cl ) is hydrolysed more slowly than ethyl chloride (CH3CH2-
Cl).Explain

37
Ans. The C-X bond in vinyl chloride acquire partial double bond character due to resonance hence
it is difficult to displace Cl in vinyl chloride as compared to ethyl chloride which has single C-
Cl single bond.
Q.7 Alkyl halides, though polar, are immiscible with water.Explain
Ans. Alkyl halides are insoluble in water due to inability of alkyl halides to form intermolecular
hydrogen bonds with water molecules.
Q.8 Grignard’s reagents should be prepared under anhydrous conditions, why?
Ans. This is because Grignard reagent forms alkanes by reacting with moisture.
RMgX +H2O → RH +Mg(OH)X
Q.9 The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.Explain
Ans. Since chlorobenzene has lower magnitude of negative charge on Cl atom and shorter C—Cl
bond than cyclohexyl chloride due to resonance therefore chlorobenzene has lower dipole
moment than cyclohexyl chloride.
Q.10 Chloroform is stored in closed dark brown bottles.Why ?
Ans Because chloroform is slowly oxidised by air in the presence of light to an extremely
poisonous
gas phosgene. COCl2
Q.11 Alkyl halides on treatment with aq KOH forms alcohols but with alc KOH alkenes are
produced, Why?
Ans. An Aq KOH provides OH- where as alc KOH provides RO-(alkoxide) which is a stronger base
than OH-, so it abstracts H+ from 𝛽−𝐶𝑜𝑓𝑎𝑙𝑘𝑦𝑙 ℎ𝑎𝑙𝑖𝑑𝑒.
Q.12 Haloalkanes dissolve easily in organic solvents.
Ans. Both have non polar hydrocarbon chain which have strong Vander Waal forces.
Q.13 Thionyl chloride method is preferred for preparing alkyl chlorides from alcohols
Ans. R-OH + SOCl2→ R-Cl + SO2 +HCl
The byproducts of the reaction, i.e., SO2 and HCl being gases escape into the atmosphere
leaving
behind alkyl chlorides in almost pure state
Q.14 Out of SN1 and SN2, which reaction occurs with
(a) Inversion of configuration (b) Racemisation
Ans. (a) SN2 reaction occurs with inversion of configuration.
(b) SN1 reaction occurs with racemization.
Q.15 Although chlorine is an electron withdrawing group, yet it is ortho, para directing in
electrophilic aromatic substitution reactions. Why?
Ans. 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.
Q.16 The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
Ans The sp2 hybridised carbon of C–Cl bond in chlorobenzene is more electronegative due to
greater % of s-character and has less tendency to release electrons to Cl than an sp 3 hybrid
carbon of cyclohexyl chloride. As a result, the magnitude of negative charge is less on Cl atom
of chlorobenzene than in cyclohexyl chloride.
Q.17 Nucleophilic substitution of iodoethane is easier than chloroethane.
Ans Because the Bond energy of C-I bond is less than C-Cl bond
Q.18 Write in short about – (a) Asymmtric carbon (b) Chirality (c) Enantiomers (d)
Racemic mixture
Ans. a) Asymmetric carbon: The carbon atom which is attached with four different groups of
atoms is called asymmetric carbon. The molecule having asymmetric carbon atom is called
asymmetric.
38
 b) Chirality : An object which is non-superimposable on its mirror image is said to be chiral.
The property of being chiral is known as chirality.
c) Enantiomers: The stereoisomers which are non-superimposable mirror images are called
enantiomers. Enantiomers rotate the plane of polarised light to the same extent but in opposite
direction.
d) Racemic mixture: An equimolar mixture of a pair of enantiomers is called racemic
mixture.A
racemic mixture is optically inactive due to external compensation.
GiveReasonsforthefollowing:
PYQ/FAQ
QUESTION-REASONING ANSWER- REASON
1 Benzylchlorideishighlyreactive Due tothe stabilityofbenzyl
towardstheSN1reaction. carbocation/resonance/Diagram
2 2-bromobutaneisopticallyactivebut1- Because2-Bromobutanehasa chiralcentre
bromobutaneisopticallyinactive
3 Electrophilicsubstitutionreactionsinhaloar Dueto– Ieffectofhalogen.
enesoccurslowly.
5 A solution of KOH hydrolyses CH3CH2ClCHCH3moreeasilyhydrolysedasitformss
CH3CH(Cl)CH2CH3andCH3CH2CH2CH econdarycarbocationwhichis more
2Cl.Whichoneoftheseismore easily stable than primary carbocation
hydrolysed and why?
6 State one use each of DDT and iodoform DDT: It is used as insecticide to control flies,
mosquitoes, etc.
Iodoform: Iodoform is used as an antiseptic.
7 Of the two bromo derivatives, C6H5CH(C6H5)Br
C6H5CH(CH3)Br and C6H5CH(C6H5)Br, the intermediate obtained from C6H5CH(C6H5)Br
which one is more reactive in SN1 is morestable than obtained from C6H5CH(CH3) Br
substitution reaction and why? because it is stabilised by two phenyl groups due to
resonance.
8 Rearrange the compounds of each of the (i) 1-Bromopentane > 2-Bromopentane > 2-
following sets in order of reactivity Bromo- 2methyl butane.
towards SN2 displacement:
(i) 2-Bromo-2-methylbutane, 1- (ii) 1-Bromo-2-methyl butane > 3-Bromo-2-methyl
Bromopentane, 2-Bromopentane butane
(ii) 1-Bromo-3-methylbutane, 2- > 2-Bromo-2-methyl butane
Bromo- 2methylbutane,
3-Bromo-2-methylbutane (iii) 1-Bromobutane > 1-Bromo-2-methylbutane > 1-
(iii) 1-Bromobutane, 1-Bromo-2, 2- Bromo-2,2-dimethyl butane
dimethylpropane,1-Bromo-2-methylbutane

39
 UNIT 7 : ALCOHOLS, PHENOLS AND ETHERS
GIST OF THE CHAPTER
1

3 Classification of alcohols:
• Primary Alcohol CH3 CH2OH, , Secondary Alcohol (CH3)2CHOH, Tertiary Alcohol
(CH3)3COH
• Vinyl Alcohol : CH2=CH-OH, Allyl Alcohol: CH2 =CH-CH2-OH
• Benzyl Alcohol: C6H5-CH2OH
4 IUPAC Name Pattern: Preffix + rootword+ primary suffix + ol
5 Acidity of Alcohols & Phenols and their derivatives:
*Alcohols are weaker acid than water due to +I effect caused by Alkyl group decreases polarity of O-
H bond.
*Order of acidity of Alcohols is CH3 CH2OH >(CH3)2CHOH > (CH3)3COH
*Relative Order of acidity of alcoholsis RCOOH > H2CO3>C6H5OH > H2O > ROH.
*Phenol is more acidic than Alcohols due stabilized phenoxide ion through resonance.
*Presence of electron withdrawing groups in Phenol increases its acidic strength where as presence
of electron realeasing groups in Phenol decreases its acidic strength.
* Electron withdrawing groups are: -NO2, -CN, -X etc.
*Electron releasing groups are: -R, -NH2, -OR etc.
*Increasing order of acidic strength is
o-cresol < p-cresol < m- cresol < Phenol < 0-Nitro Phenol < 2,4,6-Trinitrophenol( Picric acid)
*Acidic strength is directly proportional to Ka value and inversely proportional to pKa value.

6 MechanismfortheHydrationofalkenestoalcohol
Mechanism-Themechanismofthereaction involvesthefollowingthreesteps:
Step1:Protonationofalkenetoformcarbo
cationbyelectrophilicattackof H3O+.

40
 Step2:Nucleophilicattackofwateroncarbo
cation

Step3:Deprotonationtoformanalcohol

MechanismfortheacidicDehydrationofalcoholstogivealkenes:
Step1:Formationofprotonatedalcohol.

Step2:Formationofcarbocation:
Itisthesloweststepandhence,theratedetermi
ningstepofthereaction.
Step3:Formationofethenebyeliminationofap
roton

PYQ/FAQ
1 Write the equations involved in the following reactions:
(i) Reimer-Tiemann reaction
(ii) Kolbe’s reaction
(iii) Williamson ether synthesis
Ans Reimer Tiemann reaction

Kolbe’s reaction

(iii) Williumson’s synthesis

2 Explain why propanol has higher boiling point than that of the hydrocarbon, butane?
Ans The molecules of butane are held together by weak van der Waal’s forces of attraction while those of
propanol are held together by stronger intermolecular hydrogen bonding.
3 Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses.
Explain this fact.
Ans Alcohols can form hydrogen bonds with water and by breaking the hydrogen bonds already existing
between water molecules. Therefore, they are soluble in water.
4 While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer
which will be steam volatile. Give reason.
Ans 0-N itrophenol is steam volatile due to chelation (intramolecular H – bonding) and hence can be
separated by steam distillation .
5 Explain why is orthonitrophenol more acidic than orthomethoxyphenol?
Ans Nitro (NO2) group is an electron withdrawing group while methoxy (OCH3) group is electron releasing
in nature.

41
 6 Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans Ethanol undergoes intermolecular H-bonding due to the presence of a hydrogen atom attached to the
electronegative oxygen atom.
7 Write equations of the following reactions:
(i) Friedel-Crafts reaction -alkylation of anisole
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium
(iv) Friedel-Craft’s acetylation of anisole.
Ans

8 Name the reagents used in the following reactions:

(i) Oxidation of a primary alcohol to carboxylic acid.(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Brominationofphenolto2,4,6-tribromophenol(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-oI to propene.(vi) Butan-2-one to butan-2-oL .
Ans (i) Acidified potassium dichromate or neutral/ acidic/ alkaline potassium permanganate.
(ii) Pyridinium chlorochromate (PCC), (C5H5NH)+ ClCrO3– in CH2Cl2
or Pyridinium dichromate (PDC),[(C5H5NH)2]2+Cr2O72-in CH2Cl2
(iii) Aqueous bromine, i.e., Br2/H2O.
(iv) Acidified or alkaline potassium permanganate.
(v) 85% H2S04 at 440 K.
(vi) Ni/H2 or NaBH4 or LiAlH4.
9 Distinguish between
(i) Propan-1-ol and propan-2-ol (ii) Methanol and ethanol
(iii)Phenol and benzoic acid ( iv)Ethanol and propanol
(i)Ans propan-2-ol gives iodoform test. Yellow ppt of iodoform
(ii) Ethanol gives iodoform test. Yellow ppt of iodoform
(iii) Phenol gives violet colour with neutral Ferric chloride solution.
(iv) Ethanol gives iodoform test. Yellow ppt of iodoform
10 Give reason:
a.Phenol is more acidic than alcohol.
b.Boiling point of ethanol is higher in comparision to methoxy methane.

42
 c.(CH3)3C-O-CH3 on reduction with HI gives CH3 OH and (CH3)3C-I as the main products and not
.(CH3)3C-OH and CH3I
Ans a.Because phenoxide ion is more stable than ethoxide ion, due to resonance.
b.Due to intermolecular hydrogen bonding in ethanol it is more compact and has higher boiling popint.
c.This reaction follows SN1 reaction and CH3)3C+ , thus formed, is more stable which reacts with
Iodide ion to form (CH3)3C-I.
11 The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol (142 pm).
Explain.
Ans This is due to
(i)partial double bond character of C-O bond because of resonance in phenol and
(ii)sp2 hybridised state of carbon of phenol to which oxygen is attached.
12 Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain
Ans o-nitrophenol, due to intramolecular hydrogen bonding, is more volatile in nature. In para-nitrophenol,
there is intermolecular hydrogen bonding.
13 In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with carbon dioxide. Why?
Ans Phenoxide ion is more activating than phenol towards electrophilic substitution reaction. Hence, it
undergoes electrophilic substitution with carbon dioxide, a weak electrophile.
14

Ans

GiveReasons forthefollowing:
QUESTION-REASONING ANSWER- REASON
1 p-nitrophenol is more acidic Due to–I /–Reffectof –NO2group&+I /+Reffectof–
than p-methylphenol CH3group or 4-nitrophenoxide ion is more stable than 4-
methylphenoxideion
2 Bond length of C – O bond in phenol DuetoResonanceeffectof –OHgroupinphenol
is shorterthanthatinmethanol
3 Arrange in increasing order of
boiling pointC2H5OH,
CH3CH2NH2,H3NHCH3
4 (CH3)3C – Br on reaction with (CH3)3C–Brbeinga3ohalideprefers toundergo β–
sodiummethoxide (NaOCH3) gives eliminationonreactingwithstrongbaselikeNaOCH3.
alkene as the mainproductandnot
anether
5 p-nitrophenol is more acidic Due to intramolecular H-bonding in o-nitrophenol it
than o-nitrophen l isweakacidic
6 Bond angle C – O – C in ethers is Themutualrepulsionbetweenbulkyalkylgroup
slightly s is stronger than the l.p-l.pelectronic
higherthanthetetrahedralangle(109o28’) repulsions
.
7 o-nitrophenol is more acidic Because–NO2isanelectronwithdrawinggroup
than o-methoxyphenol
8 Butan-1-ol has a higher boiling DuetoH-Bonding
point thandiethylether
9 Boiling point of ethanol is higher Becauseof hydrogenbondinginethanol
incomparisontomethoxymethane.
10 (CH3)3C O CH3on reaction with HI Because it follows S N1 path way which results in
givesCH3OH and (CH3)3C I as the theformationof stable (CH3)3C+.
main products
andnot(CH3)3COHandCH3I

43
 11 The C – O – H bond angle in alcohols Duetolonepair-lonepairrepulsiononoxygen
is slightlyless thanthetetrahedral
angle(109o28’).
12 o-and p-nitrophenols are more Dueto–Ieffector–Reffectof–NO2group
acidic thanphenol
13 IdentifychiralinCH3CH(OH)CH2CH3a
ndCH3CH(OH)CH3

14 Alcoholsaremoresolubleinwaterthantheh due to their ability to form hydrogen bonds with

ydrocarbons of comparable watermolecules
molecularmasses
15 Ofthetwoalcohols;
(a) CH2=CH—CH2OHand
(b) CH2=CH—CH2—CH2OH,
(it will give more stable resonace stablised carbocation)
which one willreact more easily
with conc. HCl in thepresenceof
ZnCl2?
16 O-nitrophenolissteamvolatilewhereasp- p-nitro phenol has intermolecular H-bond while o-
nitrophenolisnot nitrophenolhasintramolecularH-bond.
17 InPhenol,the– Because the OH group attachedto the benzene ringactivates
OHgroupactivatesthebenzene ring it towards electrophilic substitution. Also, itdirects the
towards elecrophilic substitutionand incoming groupto ortho and para positions
directs the substituents to Ortho and intheringasthesepositionsbecomeelectronrich dueto
parapositions inbenzene ring the resonance effect caused by –OH group.(also draw
theresonatingstructuresofphenol)
18 Inalcoholstheboilingpointdecre becauseofdecreaseinvanderWaalsforceswithdecreaseinsu
aseswithincreaseinbranching. rface area
19 Although phenoxide ion has more Carbonyl group of carboxylate ion is stronger
number ofresonating structures than electronwithdrawinggroupthanphenylgroupofphenoxideion
carboxylate
ion,carboxylicacidisastrongeracidthanph
enol.

44
 Unit 8 : ALDEHYDE, KETONES AND CARBOXYLIC ACIDS
GIST OF THE CHAPTER
1

45
 ALDEHYDES,KETONES&CARBOXYLICACIDS
GivemechanismforNucleophilicadditionreactionincarbonylcompounds

PYQ/FAQ (GiveReasons forthefollowing):

QUESTION-REASONING ANSWER-
REASON
1 Arrange the following compounds
inincreasingorderoftheirpropertyasindicated
-CH3COCH3,C6H5COC6H5,CH3CHO
(reactivity towards nucleophilic
additionreaction)
2

5 (ii)ClCH2COOH,FCH2COOH,CH3COOH(ac CH3COOH<Cl-CH2-COOH<F-CH2-COOH
idic
character)
6 Arrange the following compounds in
anincreasing order of their acid
strengths:(CH3) 2 CHCOOH, CH3CH2CH(Br)
COOH,CH3CH(Br)CH2COOH
7 Aldehydes are more reactive than duetosterichindranceofalkylgroup
ketonestowardsnucleophilic addition due to +I effect of alkyl group +ve charge of
carbonylcarbondecreases.
8 The boiling points of aldehydes and due to intermolecular hydrogen bonding in
ketonesarelowerthanofthecorrespondingacids carboxylicacids
46
9 The aldehydes and ketones Duetogreaterelectronegativityofoxygenthancarbon ,
undergonucleophilicadditionreactions the C atom of the bond acquires a partial
positivecharge in aldehydes and ketones and hence
readilyundergonucleophilicadditionreactions
10 MonochloroethanoicacidhasahigherpKa Because of two -I group in dichloroethanoic acid, it
valuethandichloroethanoicacid. is astrongeracidthanmonochloroethanoic acid
11 Ethanoic acid is a weaker acid than because methyl group due to its positive inductive
benzoicacid effectdestabilize the acetate anion by intensifying the
negativecharge.
12 Why are lower members of aldehydes Lower member of aldehydes are able to
easilymisciblewithwater? formintermolecular hydrogen bonds with water
molecules.Hence,theyareeasilymisciblewithwater
13 Arrange the following compounds in (i)Acidstrength:4-Methoxybenzoic acid<Benzoicacid
anincreasingorderoftheirindicatedproperty: <4-Nitrobenzoicacid
(i) Benzoic acid, 4-Nitrobenzoic acid, 3,4- <3,4-Dinitrobenzoicacid.
Dinitrobenzoicacid,4-Methoxybenzoicacid
(acidstrength)
14 (ii) CH3CH2CH(Br)COOH, CH3CH(Br) (ii) Acid strength: (CH3)2CHCOOH <
CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH < CH3CH(Br)CH2COOH
CH3CH2CH2COOH (acid strength) < CH3CH2CH(Br)COOH

15 What is Tollen’s reagent? Write one A solution of AgNO3 dissolved in NH4OH is known as
usefulness Tollen’s reagent. This is
of this reagent used to detect the presence of –CHO group in an
organic compound. For example:
RCHO + 2Ag (NH3)2 OH → RCOONH4 + 2Ag¯ +
H2O + 3NH3.
16 Arrange the following compounds in Butanone < Propanone < Propanal < Ethanal
increasing order of their reactivity in
nucleophilic addition reactions: ethanal,
propanal, propanone, butanone
17 Cyclohexanone forms cyanohydrin in good Due to presence of three methyl groups, the
yield but 2, 4, 6-trimethylcyclohexanone does nucleophilic attack by CN– ion does not occur
not. due to steric hindrance in 2, 4, 6-trimethyl
cylcohexanone. As there is no such steric hindrance in
cyclohexanone so nucleophilic attack by the CN– ion
occurs readily and hence cyclo hexanone cyanohydrin
is obtained in good yield
18 Acetaldehyde, Acetone, Methyl tert- Methyltert-butylketone<Acetone<Acetaldehyde
butylketone(reactivitytowards HCN)
19 Benzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxy benzoic acid < Benzoic acid <
4-Methoxybenzoicacid(acidstrength) 3,4-Dinitrobenzoic acid
20 CH3CH2CH(Br)COOH,CH3CH(Br)CH2COO (CH3)2CHCOOH < CH3CH(Br)CH2COOH
H,(CH3)2CHCOOH(acidstrength) <CH3CH2CH(Br)COOH
21 Ethanal is more reactive than acetone DuetosterichinderenceofalkylgroupOR
towardsnucleophilic additionreaction due to +I effect of alkyl group +ve charge of
carbonylcarbondecreases.
22 (CH3)3C—CHO does not undergo 𝖺−hydrogen is not present in(CH3)3C—
aldolcondensation CHO
23 There are two – NH2 group in Since the NH2 group attached to carbonyl group
semicarbazidehoweveronlyoneisinvolved isstabilizedbyresonanceandhasdoublebondcharacter
in theformationofsemicarbazones.

47
24 It is necessary to control the pH during In weakly acidic medium protonation of carbonyl
thereaction of aldehydes and ketones carbonis required, in case of strongly acidic
withammoniaderivatives. medium,protonation of ammonia derivative will be
also takesplaceandwillnot beabletoactasanucleophile
25 Would you expect benzaldehyde to be The carbon atom of the carbonyl group of
morereactive or less reactive in nucleophilic benzaldehydeis less electrophilic than carbon atom of
additionreactionsthanpropanal. thecarbonylgroup present in propanal. The polarity of
the carbonylgroup is reduced in benzaldehyde due to
resonance asshownbelowandhenceitisless
reactivethanpropanal
26 FormaldehydedoesnottakepartinAldolco Duetoabsenceof𝖺-hydrogenatom
ndensation.
27 Carboxylic acids are higher boiling liquids due to more extensive association of carboxylic
thanalcohols acidmolecules through intermolecular
hydrogen bonding

1 Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone(ii) Acetophenone and Benzophenone(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone.(vii) Ethanal and Propanal
Ans (i)By Iodoform test: Propanone gives positive test(yellow ppt)
(ii) By Iodoform test: Acetophenone gives positive test(yellow ppt)
(iii) By FeCl3Test: Phenol gives positive test(Violet colour)
(iv)By NaHCO3Test: Benzoic acid gives positive test(effervesnceof CO2)
(v) By NaHSO3 Test: Pentan-2-one gives solid adduct( only methyl ketones and cyclic ketones give
solid adduct).. (vi) By Iodoform test: Acetophenone gives positive test(yellow ppt)
(vii) By Iodoform test: Ethanal gives positive test(yellow ppt)
2 Give reason:

Ans (i)Due to steric hindrance in 2,2,6-Trimethylcyclohexanone,it does not form cyanohydrin.

(ii)NH2 , attached with C=O, undergoes resonance so becomes less nucleophilic and doesnot involve
in semicarbazone formation.
(iii)In order to shift equilibrium in forward direction, water or ester should be removed as soon as
possible.
3 Why Pka of F-CH2COOH is lower than that of Cl–CH2COOH?
Ans Stronger –I effect of fluorine makes F-CH2COOH to be stronger acid than Cl–CH2COOH and has
less Pka.
4 Carboxylic acids do not give characteristic reactions of carbonyl group. Why?
Ans The carboxylic carbon is less electrophilic due to resonance than the carbonyl carbon.
5 Aldehydes and Ketones have lower boiling points than corresponding alcohols. Why?
Ans Aldehydes and ketones have weak intermolecular interactions dipole – dipole interactions whereas
alcohols have intermolecular hydrogen bonding.
6 Arrange ClCH2COOH , FCH2COOH , BrCH2COOH in decreasing order of acidic strength.
Ans ClCH2COOH > BrCH2COOH > FCH2COOH
7 Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions:(i)Ethanal, Propanal, Propanone, Butanone.
(ii)Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone
Ans (i)Butanone<Propanone<Propanal<Ethanal
48
 (ii) Acetophenone<p-Tolualdehyde<Benzaldehyde <p-nitro benzaldehyde
8 Arrange the following compounds in increasing order of their boiling points:
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans CH3CH2CH3 < CH3OCH3 < CH3CHO <CH3CH2OH
9 Arrange the following in increasing order of the property indicated :
(i) Acetaldehyde, Acetone, Di tert. butyl ketone, Methyl tert. butyl ketone (reactivity towards HCN).
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (acid
strength) (iii) Benzoic acid, 4-Nitrobenzoic acid, 3, 5-Dinitrobenzoic acid, 4-Methoxybenzoic acid
(acid strength)
Ans (i)Di tert. butyl ketone< Methyl tert. butyl ketone< Acetone< Acetaldehyde
(ii)(CH3)2CHCOOH<CH3CH2CH2COOH< CH3CH(Br)CH2COOH < CH3CH2CH(Br) COOH
(iii)4-Methoxybenzoicacid<Benzoicacid<4-Nitrobenzoicacid<3, 5-Dinitrobenzoic acid

49
 Unit 9.AMINES
GIST OF THE CHAPTER
Hoffmann bromamide degradation RCONH2+4NaOH+Br2→RNH2+ 2
reaction:primary amides are treated with NaBr+Na2CO3+2H2O
bromine in thepresence ofanalkali,a
primaryaminecontainingonecarbonless CH3 CO NH2 Br2 4KOH CH3NH2 K2CO3
thantheamideisformed.
2KBr 2H2
O
Gabriel phthalimide synthesis: Phthalimide on treatment with KOH which on heating with alkyl
halidefollowed byalkalinehydrolysis produces thecorrespondingprimaryamine.

Carbylamine reaction(Isocyanide
heat
test):Aliphaticand aromatic primary amines R-NH2+CHCl3 3KOH R NC 3KCl 3H2O
on heating withchloroform and ethanolic
potassium
hydroxideformisocyanidesorcarbylaminesw
hicharefoul
smellingsubstances.
Diazotizationreaction-

Sandmeyers reaction:The Cl–, Br– and

CN–nucleophiles can easily be introduced in
thebenzene ring inthe presence of Cu(I)
ion[cuprouschlorideorcuprousbromide
orcuprouscyanide]

Gatterman reaction:Chlorine or bromine

canalso be introduced in the benzene ring
bytreatingthediazoniumsaltsolutionwith
corresponding halogen acid in the presence
ofcopperpowder
Coupling reaction: Benzene diazonium chloride reacts with phenol in which the phenol molecule at
its paraposition is coupled with the diazonium salt to form p-hydroxyazobenzene.. Similarly the
reaction ofdiazonium saltwithanilineyields p-aminoazobenzene

50
 PYQ/FAQ (GiveReasons forthefollowing):

QUESTION-REASONING ANSWER- REASON

Arrange the following in increasing C6H5-NH2<C6H5-NH-CH3<CH3-CH2-NH2

1 order ofbasic strength
C6H5NH2,CH3CH2NH2,C6H5NHCH3

2 In increasing order of solubility in

waterCH3NH2,(CH3)3N,CH3NHC
H3
3 p-methylaniline is more basic ―CH3 group shows +I – effect (electron
than p-nitroaniline releasinggroup) whereas –NO2group shows –I-
Effect(electronwithdrawinggroup)
4 Acetylationof–NH2groupis Toreduceactivatingeffectof –NH2group.
doneinanilinebeforepreparingits
orthoandpara
compounds.
5 Arrangeinorderofbasicstrength.

6 pKb for aniline is more than In aniline due to resonance the lone pair of
that formethylamine electronsonthenitrogenatomaredelocalizedoverthebenze
ne ring. As a result, the electron density on
thenitrogendecreases.Ontheotherhand,inmethylamine +I
effect of CH3increases the electron densityon the
nitrogen atom. Therefore aniline is a weakerbase than
methyl amine and hence its pKb value ishigherthanthatof
methylamine
7 Methylamine solution in water reacts
withferric chloride solution to give a
precipitateof ferric
Hydroxide

8 Aniline does not undergo Friedel- Aniline being a Lewis base, reacts with lewis
Craftsreaction acidAlCl3toform asalt.Dueto this Natomof
aniline acquires positive charge and hence acts as
astrongdeactivationgroupforfurther
reaction.
9 Whydoaminesbehaveasnucleophiles? Due to the presence of a lone pair of electrons
onnitrogenatom
10 pKbof methylamine is less than Lone pair of nitrogen in aniline invole in resonance,LP
that ofaniline. is not available for donation. On the other hand,
inmethyl amine +I effect of CH3 increases
theelectrondensity on the nitrogen atom.

51
 Thereforeaniline is a weaker base than methyl amine
andhenceitspKbvalueishigherthanthat ofmethyl
Amine

11 Ethylamine is freely soluble in because ethylamine forms hydrogen bonds

waterwhereasanilineisonlyslightlysolub withwater,
le and due to hydrophobic benzene ring, aniline
henceanilineisslightlysoluble

12 Why is an alkylamine more basic Due to electron donating nature of

thanammonia? alkylgroup

13 Arrange the following compounds in NH3<(CH3)3N<CH3—NH2<(CH3)2NH.

anincreasing order of basic strengths
in theiraqueoussolutions:
NH3,CH3NH2,(CH3)2NH,(CH3)3N
14 Arrange the following compounds in NH3<C2H5NH2<(C2H5)3N<(C2H5)2NH
anincreasing order of their basic
strength inaqueoussolutions:
NH3,C2H5NH2,(C2H5)2NH,(C2H5)3N
15 Inanincreasingorderofbasic strength: Inanincreasingorder ofpKbvalues:
C6H5NH2,C6H5N(CH3)2,(C2H5)2NHa C2H5NH2,C6H5NHCH3,(C2H5)2NHandC6H5NH2
nd CH3NH2
16 In a decreasing order of basic p-Toluidine>Aniline>tr-nitroaniline
strength:Aniline,p-nitroanilineandp-
toluidine
17 In an increasing order of pKb (C2H5)2NH2<C2H5NH2<C6H5NHCH3<C6H5NH2
values:C2H5NH2,C6H5NHCH3,(C2H5)
2NHandC6H5NH2
18 Theorderofbasicityofaminesinthegaseous Because the more the number ofElectron
phase follows the donatinggroups(EDG)i.ealkylgroupsmoreisthebasicity
order:Tertiaryamine>Secondaryamine>
Primaryamine>NH3.
19 Aromatic primary amines cannot because inpreparation by Gabriel phthalimidesynthesis,
Ar-X is needed and aryl halides do notundergo
bepreparedbyGabrielphthalimidesynthesi
nuleophilic substitution esily due
s. topresenceofpartialdoublecharacter
20 Although amino group is o– and p– because Nitration is usually carried out with a mixture of
directingin aromatic electrophilic conc HNO3 and conc H2SO4. In presence ofthese acids
aniline getsprotonated to form theanilinium ion
substitutionreactions, anilineon nitration
whichismetadirecting
gives asubstantialamountofm-
nitroaniline.
21 Acetylationof— Because withacetylation of aniline result in
NH2groupofanilinereduceitsactivatingeff decreaseofelectrondensityonNitrogen
ect
22 NH2groupofanilineacetylatedisbeforecarr Because the acetyl groupreduces the reactivity of ofthe
yingout nitration. ring thus its oxidation does not occur easily
withHNO3andmonosubstitutioncarriedout.

52
 23 Why are diazonium salts of aromatic due to dispersal of the positive charge on thebenzene
aminesmorestablethanthoseofaliphaticam ring.
ines?
DISTINGUISH TEST

1. IsocyanidetestPrimaryAliphatic&A Chloroform(CHCl3) Unpleasent odur (foulsmelling)

romatic +AlcoholicKOH of isocyanides orcarbylamines.
amines.

2. Heinsbergtest(Todistinguishbetwee BenzenesulphonylchlorideC Product of 1o

n(10),(20),&(30)Amines. 6H5SO2Cl Aminessolubleinalkali.
Product of 2o Amines
areinsoluble inalkali
3oaminesdonot react.
3. Azodyetest(Aniline) (NaNO2+HCl ReactionwithNaNO2+HCl at
)[Nitrousacid]followedbyrea 273-278 K gives BDCwhich
ctionwith forms a brilliantorange Azo dye
napthol with β-naptholin
sodiumhydroxide

CH3OH NOREACTION
1) C6H5OHANDC6H5NH2:-(AZODYETEST)
+ - -
2C6H5N2 Cl +C6H5OH+OH C6H5N=NC6H4OH(ORANGE DYE)+H2O
+ - +
C6H5N2 Cl +C6H5NH2+H C6H5N=NC6H4NH2(YELLOWDYE)+Cl-+H2O
2

2) C6H5NH2ANDC6H5NHCH3(CARBYLAMINETEST)
C6H5-NH2 +CHCl3+3KOH R-NC (FOULSMELL)+3KCl+3H2O

C6H5NHCH3+CHCl3+3KOH NOREACTION

3) C2H5NH2AND(C2H5)2NH(HINSBERGTEST)

C6H5SO2Cl+NH2C2H5 C6H5SO2NH-C2H5(SOLUBLEINALKALI)+HCl
C6H5SO2Cl+NH(C2H5)2 C6H5SO2N-(C2H5)2(INSOLUBLEIN ALKALI)+HCl

53
 Unit 10:- BIOMOLECULES
GIST OF THE CHAPTER
Carbohydratesareclassifiedonthebasisoftheirbehavioronhydrolysis:
Monosaccharide: A carbohydrate that cannot be hydrolyzed further to
givesimplerunitofpolyhydroxyaldehydeorketoneiscalleda
monosaccharide.examplesareglucose,fructose,ribose,etc.
Oligosaccharides: Carbohydrates that yield two to ten monosaccharide units, onhydrolysis, are
called oligosaccharides. They are further classified asdisaccharides,
trisaccharides, tetra saccharides, etc., depending uponthe number of
monosaccharides, they provide on hydrolysis. Forexample, sucrose on
hydrolysis gives one molecule each of glucoseandfructose.
Polysaccharides: Carbohydrates which yield a large number of
monosaccharideunitsonhydrolysisarecalledpolysaccharides.Somecommonex
amplesare starch, cellulose,glycogen,gums,etc.
Polysaccharides are not sweet in taste, hence they are also callednon-sugars.
Reducingsugars: All those carbohydrates which reduce Fehling’s solution and Tollens’reagent
are referred to as reducing sugars. Examples:
Allmonosaccharides,MaltoseandLactose.
Non-reducingsugars: In disaccharides, if the reducing groups of monosaccharides i.e.,aldehydes or
ketone groups are bonded, these are non-
reducingsugarse.g.Allpolysaccharides sucrose
Anomers: α& β- Glucose ,whichdifferinthe orientationof− OHgroupatC1.
Proteins: proteins are polymer of α- amino acids ,joined by peptide bonds .Theyalso
knownaspolyamides.
TypesofProteins: Fibrous proteins:- The polypeptide chains runparallelandareheldbyH-
bondordisulphidelinkage ,InsolubleinwaterEg:
Keratin,Myocin
Globular proteins:- Polypeptides coil around to give a
sphericalshape,SolubleinwaterEg: Insulin,Albumins
Structure and shape of Primarystructure:Itisaspecificsequenceofaminoacids
Proteins: Secondary structure: It represent shape ie. α - halix and β-pleatedsheet.
α - halix :polypeptide chain twisted in to a right handedscrewbyformingH-
bondsb/wNHgroupand>C=Ogrup.
β- pleated sheet : peptide chains laid side by side and heldtogetherbyH-
bonds
Tertiary structure: It represent further folding of the secondarystructure. It
gives rise to two major molecular shapes viz. fibrousandglobular.
Quaternary structure of proteins: composed of two or morepolypeptide
chains referred to as sub-units. The spatial arrangementofthese subunitswith
respecttoeachother.
Denaturationofproteins Disturbing the 20 and 30 structures of proteins by heating or
changingpH.eg:coagulationofeggwhiteonboiling .
Nucleicacids Polymerofnucleotideslinkedbyphosphodiesterlinkage-3’5’linkage
Nucleotide EachnucleotidecontainsN-base,SugarandPhosphate.
Nucleoside ContainsN-base&Sugar.
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Double helical structure Two strand of DNA coiled around each other and held togetherbyH-
of DNA bondsb/wpairsofbases.Suchas−C≡G−,and−A=T−
Purines: A&G AndPyrimidines:C, U&T
DNA N-Bases:A,G,C&T,Doublehelix,Contains2-deoxyribose
sugar,Transferhereditycharacters.
RNA N-Bases:A,GC&U,Singlehelix,ContainsRibosesugar,Helps
inproteinssynthesis.
Preparation of Glucose

Structure of Glucose

Reactions of Glucose

Reactions that prove Aldehydegrouppresentbutglucose does notreactwith NaHSO3&NH3.

cyclic structure of GlucosedoesnotgivetheSchiff’sTest&2,4-DNPtestforaldehyde.
Glucose Glucosepenta-
acetatedoesnotreacthydroxylamine,whichshowsthataldehydegroupisabsentingluco
se.
Glucoseexistintwostereo-isomericforms( & ).
Allobservationsindicatethatfreealdehydicgroupisnotpresentinglucose.

55
Cyclic Structure of
Glucose

Structure of
Nucleotide

Vitamins: They are organic compounds required in the diet in small amounts to perform specific biological
functions .
They are classified asfollows:
(a)Fat Soluble Vitamins: Vitamin A,D,E and K. They are stored in liver and adiposetissues.
(b)Water Soluble Vitamins: B group vitamins and vitamin C. They need to supplied regularlyin diet as
they are excreted in urine and cannot be stored(except vitamin B12) in our body.

S.No. Name of Vitamins Sources Deficiency diseases

1. Vitamin A Fish liver oil ,carrots Xerophthalmia , Night
blindness
2. Vitamin B1 Yeast , milk ,green vegetables Beri beri
3. Vitamin B2 Milk , egg white Cheilosis
4. Vitamin B6 Yeast , milk ,egg yolk Convulsions
5. Vitamin B12 Meat ,fish, egg and curd Pernicious anaemia
6. Vitamin C Citrus fruits ,amla Scurvy
7. Vitamin D Exposure to sunlight , egg Rickets (in children),
yolk Osteomalacia (in adults)
8. Vitamin E Vegetable oils Muscular weakness
9. Vitamin K Green leafy vegetables Increased blood clotting
time
Previous year questions/Frequently asked questions:-
Q. Whatisthedifferencebetweennucleotideandnucleoside?
Ans. Nucleosidecontainsriboseordeoxyribosesugarandheterocyclicbase.Nucleotide contains phosphoric
acid residue along with heterocyclic base and pentose sugar.
Q. Name a water-soluble vitamin which is a powerful antioxidant? Give one of itssources.
Ans.VitC,citrus fruitslike orange,lemonetc.
Q. Write2differencesbetweenRNAandDNA.
RNA – a) It has ribose sugar with adenine, uracil, cytosine, guanine as heterocyclicbases.
It is single helix.
DNA – a) It has deoxyribose sugar along with adenine, thiamine, cytosine, guanine asheterocyclic bases.
b) It is double helix.
Whatarethetwotypesofsecondarystructureofproteins?Howwillyou differentiate between them?
Ans. Alpha–helixandBetapleatedhelixstructure.
Those polypeptide chains stabilized by intramolecular hydrogen bonds are alpha helix structure.
56
Betapleatedstructureofproteinsarestablilisedbyintermolecularhydrogen bonding.
Q. Whatarepolysaccharides?Givetwoexamples.
Ans.Those carbohydrates which on hydrolysis give large number of monosaccharides. Eg:- Starch,
Cellulose.
Q. Differentiatebetween
a). AmyloseandAmylopectinb). PeptidelinkageandGlycosidiclinkage
c). Fibrousproteins andGlobular proteins.
Ans. a) Amylose is a branched chain polymer of alpha glucose, water soluble. Amylopectin is a branched
chain polymer of alpha glucose, water insoluble.
b). The bond CONH between two or more amino acids in polypeptides and proteins is called peptide
linkage. The oxide linkage between two or more monosaccharide units in oligosaccharides and
polysaccharides is called glycosidic linkage.
c). Fibrousproteins-Threadlikestructures,insolubleinwater.Eg–Keratin,Myosin Globular proteins – Chains of
polypeptides coil around spherical shape, soluble in water. Eg – Insulin, Albumin.
Q.Definethefollowingwithasuitableexample.
a). Oligosaccharides b). Denaturationofproteinsc).Vitamins
Ans.a)Gives twoto tenunitsof monosaccharideson hydrolysis.
Eg – Lactose, Raffinose
b). OnheatingorchangeinpHhydrogenbondsaredisturbed,globulesunfoldandhelix get uncoiled and leads to
loss of biological activity. Eg – Coagulation of egg white, milk converted to curd.
Q-Classifythefollowingintomonosaccharidesand
disaccharides.Ribose,2deoxyribose,maltose,galactose,fructoseandlactose.
Ans- Monosaccharides - Ribose,2-deoxyribose,galactose,fructose
Disaccharides -Maltose and lactose
Q- Namethesugarpresentinmilk.Howmanymonosaccharideunitsarepresentinit?Whataresuch
oligosaccharides called?
Ans- Thesugarpresentinmilkislactose.Lactosecontainstwomonosaccharides,glucoseandgalactose.
Oligosaccharides containing two monosaccharide units are called disaccharides.
Q- WhathappenswhenD-glucoseistreatedwiththefollowingreagents?
(i) HI (ii) Bromine water (iii) HNO3
Ans- (i)whenglucoseistreatedwithHI,itforms n-hexane.
(ii) when glucoseistreatedwithBrominewater,gluconicacidisformed.
(iii) whenglucoseistreatedwithnitricacid,Saccharicacidis formed.
Q- Definethefollowingterms : (i) Glycosidiclinkage(ii)Invertsugar (iii)Anomers (iv) Peptide linkage (v)
Phosphodiester linkage
Ans- (i)Glycosidiclinkage:Thetwomonosaccharideunitsarejoinedtogetherthroughanoxide linkage formed by
loss of a molecule of water called glycosidic linkage
(ii)Invertsugar:Anequimolarmixtureofglucoseandfructoseobtainedbyhydrolysisofsucrosein presence of an
acid such as dil. HCl or the enzyme invertase or sucrase is called invert sugar.
(iii)The isomers (carbohydrates) having a change in configuration at C-1.
(iv)It is an amide linkage formed between – COOH group of one α-amino acid and NH2 group of the other
α-amino acid by loss of a molecule of water. – CO – NH – bond is called Peptide linkage.
(v)Linkage through which two nucleotides are joined together.
Q- Which of the two components of starch is water soluble?
Ans - Amylose is water soluble component of starch.

57
Q- Write a reaction which shows that all the carbon atoms in glucose are linked in a straight chain.
Ans - On prolonged heating with HI, it forms n-hexane, shows that all the six carbon atoms are linked in a
straight chain .

Q- What are essential and non-essential amino acids in human food? Give one example of each type .
Ans - Essential amino acids - Amino acids which the body cannot synthesize are called essential amino
acids.
Therefore they must be supplied in diet. e.g. Valine, leucine etc.
Non-essential amino acids -Amino acids which the body can synthesize are called non-essential amino
acids. Therefore, they may or may not be present in diet. e.g. Glycine, alanine etc.
Q- Differentiate between fibrous proteins and globular proteins.
Ans-
Globular Proteins Fibrous Proteins
Globular proteins have almost spheroidal shape Polypeptide chains of fibrous proteins consist of
due to folding of the polypeptide chain. thread like molecules which tend to lie side by side
to form fibres.
Globular proteins are soluble in water. Fibrous proteins are insoluble in water.
e.g. All enzymes and hormones like insulin Keratin in skin, hair, nails .
Q- What is meant by the denaturation of a protein?
Ans- Loss of biological activity when protein is subjected to change in temperature , pH etc .
Q- Where does the water present in the egg go after boiling the egg?
Ans-When an egg is boiled in water, the globular proteins present in it change to a rubber like insoluble
mass which absorbs all the water present in the egg by making hydrogen bond with it.
Q- What is difference between a nucleoside and nucleotide ?
Ans- Nucleoside → Nitrogenous base + Sugar whereas
Nucleotide → Nitrogenous base + Sugar + Phosphate group
Q- Write the structural and functional differences between DNA and RNA
Ans - Structural difference :
DNA RNA
The sugar present in DNA is β-D- The sugar present in RNA is β-D –
2-deoxyribose. ribose
DNA contains cytosine and RNA contains cytosine and uracil
thymine as pyrimidine bases. as pyrimidine bases.
DNA has double standard α-helix RNA has single stranded α-helix
structure. structure.
The base which are common to both DNA and RNA are : Adenine(A), Guanine (G) ,Cytosine (C)
Functional difference : DNA transfer genetic information from one generation to other.
RNA helps in protein synthesis .
Q-What are nucleic acids ? Why two strands in DNA are not identical but are complementary ?
Ans – Nucleic acids are the polymers of Nucleotides.
Because the H-bonds are formed between specific pairs of bases (A &T and G&C) .
Q- Name a water soluble vitamin which is a powerful antioxidant. Give its one natural source.
Ans- Water soluble vitamin : Vitamin C , Natural source : Amla

58
 CHEMICALDISTINCTIONTEST
S.N Test Reagent Inference
.

1. Lucas test :To ZnCl2/HCl (30) Alcohols givesTurbidity

distinguishbetweenPrimar (immediately), 20Turbidity
y(10),Secondary(20),&Ter after sometime(5-10 min) 10
tiary does not giveTurbidity at
(30)Alcohols)
roomtemperture
2. Iodoform test I2/NaOH YellowPptofCHI3.isformed
(AlcoholscontainingC
H3-CH(OH)-linkage)
3. Neutralferricchloridetest(P NeutralFeCl3 Phenols give
henol) Violetcolouration
4. Tollens test Ammoniacal.AgNO3 Brightsilvermirror[Ag]isprod
[AliphaticAldehydes(e.g.E uced dueto
thanal,Propanaletc)&Arom theformationofsilvermetal.
atic Aldehydes
(Benzaldehydeetc.)]
5. Fehling’stest[O Fehling solution Reddish brown
nlyAliphaticAld A(aqueouscopper sulphate precipitateof[Cu2O]isobtained.
ehydes] & Fehlingsolution B
alkalinesodiumpotassiumtar
**Aromatic tarate(Rochellesalt)
aldehyde do
notgivethistest
6. Iodoformtest I2/NaOH YellowPptofCHI3.isformed
(Aldehydes&Keto
nes
containing–COCH3
linkage)
7. Sodium NaHCO3 Effervescence due to evolution of
bicarbonate test Sodium Hydrogencarbonate CO2gas.
(Aliphatic &
AromaticCarbox
ylic acids)
8. Isocyanide test Chloroform(CHCl3) Unpleasent odur (foul smelling)
Primary + Alcoholic KOH of isocyanides or carbylamines .
Aliphatic &
Aromatic
amines.
9. Heinsberg test(To Benzenesulphonyl chloride Product of 1o Amines soluble in
distinguish C6H5SO2Cl alkali.
between (10), Product of 2o Amines are
(20), & (30) insoluble in alkali
Amines. 3o amines do not react.
10. Azo dye (NaNO2 + HCl Reaction with NaNO2 + HCl at
test(Aniline) )[Nitrous acid] followed by 273-278 K gives BDC which
reaction with forms a brilliant orange Azo dye
Napthol with β- napthol in
sodium hydroxide
59
11. Test for Amm . AgNO3 & Fehling Bright silver mirror [Ag] is
Methanoic acid solution A&B produced due to the formation of
(Formic acid) silver metal Reddish brown
Tollens test & precipitate of [Cu2O] is obtained.
Fehling’s
Test

Question for Practice

CHEMICAL TEST TO DISTINGUISH BETWEEN
1 Ethanol & Methanol
2 Ethanol & Ethyl Ethanoate
3 Benzoic Acid & Methyl Benzoate
4 Propanoic Acid & Propanoyl Chloride
5 Propanol & Ethanol
6 Ethanoic Acid & Methonoic Acid
7 Acetophenone & Benzophenone
8 Acetone & Pentane 3-one
9 Benzoic Acid & Phenol
10 Isopropanol & n-Propanol
11 Ethanal & Benzaldehyde
12 Ethan Amine & Aniline
13 Propanamine & N-Methyl propanamine
14 Aniline & N-Methyl Aniline
15 N-Methyl propanamine & N, N'-Dimethyl propanamine
16 Butan-2 -ol, Butan-1-ol
17 1o,2o,3o Alcohol
18 1o,2o,3o Amine
19 Benzyl Alcohol & Isopropyl Alcohol
20 Phenol & Aniline
21 Ethanol & Benzaldehyde
22 Butan -2-ol & 2-Methyl propan-2-ol
23 Ethanol & Phenol
24 Pentan -2-one & Pentan -3-one
25 Acetophenone & Bendaldehyde
26 Acetophenone & Benzophenone
27 Propanone & Propanal
28 Ethanol & Ethanamine
29 Benzylamine & Aniline

60
 TIPS TO AVOID COMMON MISTAKES

In the Chemistry theory exam for Class 12 under the CBSE board, students often make several common
errors. These errors impact their performance that results in reduction of marks. If the students are aware
of them, they can improve upon it. Some of these common mistakes include:

1. Overlooking step wise answers that result in reducing marks both in numerical and theoretical
questions
• In numerical- first write correct formula, in second step, place the value with appropriate units,
Don't do calculation in second step- do calculation in 3rd steps and in final step, write the answers
with unit.
• Similarly for theoretical question give definitions, differences etc., write the answer in proper steps
along with examples.

2. Lacking good presentation

• Make answer sheet examiner friendly , Leave proper margin in left hand side, give extra space for
rough work, start the new question after leaving 3 to 4 lines so that if any point is required to be
added during revision, it can be included.
• Ensure neat and clean presentation, avoid overwriting and cutting. If anything is wrong cut it neatly
rather than making it messy.
• Misplaced Decimal Points or Units: In numerical answers, students may forget to write units or
incorrectly place decimal points, leading to a wrong final answer.
• Rushed Diagrams: Some questions require the drawing of structures, mechanisms, or graphs. If
these are rushed, they can be inaccurate and unclear, leading to lost marks.

• 3. Lack of Proper Conceptual Understanding

• Superficial Understanding: Students sometimes memorize definitions, formulas, or reactions
without fully understanding the underlying concepts, which leads to incorrect application in
questions.
• Failing to link topics: Students often fail to connect concepts from different chapters (e.g., Organic
Chemistry with Physical Chemistry), which may result in incomplete or incorrect answers.

4. Incorrect Application of Formulas

● Overlooking Significant Figures: In numerical problems, students sometimes round off numbers too
early or do not consider significant figures, which affects the accuracy of the answer.

5. Inadequate Writing Skills

● Lack of Proper Explanation: In descriptive answers, students often fail to explain steps or reasoning,
making it difficult to earn full marks even if the final answer is correct.

6. Inability to Manage Time Effectively

● Students sometimes waste too much time on challenging questions and neglect easier ones, leaving
them with insufficient time to complete the paper, due to time pressure, students may skip
important steps in the problem-solving process, particularly in numerical questions.

61
7. Incorrect Use of Chemical Equations
● Students often make mistakes in balancing chemical equations or fail to include the correct states
of reactants and products.
● Sometimes students don't write all the reactants and products involved in a reaction, leading to
incomplete answers.

8. Overlooking Instructions
● Not Following Question Format: Not adhering to the instructions for a particular question, such as
answering in point form, writing chemical equations in a certain way, or presenting the answer in a
specific order.
● Not Paying Attention to the Marks Distribution: Ignoring the marks assigned to each question can
lead to students providing too little detail for higher-mark questions or wasting time on low-mark
questions.

9. Overlooking Common Mistakes in Organic Chemistry

● Failure to Mention Conditions for Reactions: In organic chemistry, students sometimes omit the
reaction conditions (e.g., temperature, solvent, catalyst) while writing organic reactions.
● Incorrect Naming or Structural Formula: Incorrect nomenclature, drawing errors, or failure to
mention the correct isomer can lead to mistakes in organic chemistry answers.

10. Inconsistent Knowledge of Physical Chemistry

● Confusion Between Related Concepts: Students sometimes confuse related concepts like molarity
and molality, or pH and pOH, which can lead to incorrect answers in calculation-based questions.
● Inability to Interpret Graphs and Data: In Physical Chemistry, questions often involve interpretation
of graphs or experimental data. Students who lack practice in this area might misinterpret the
information or omit key observations.

11. Failure to Revise or Review

● Overlooking Basic Concepts: During revision, some students focus on complex topics and forget to
review basic concepts, which could be crucial for answering straightforward questions.

Tips to Avoid These Mistakes:

● Understand Concepts Thoroughly: Focus on grasping the fundamental concepts and their
applications.
● Practice Regularly: Solve previous years' question papers and sample papers to get a feel for the
types of questions and improve time management.
● Revise Important Reactions and Formulas: Make sure you have a strong grasp of essential chemical
equations and mechanisms.
● Write neatly and clearly: Ensure your handwriting is legible and your answers are well-structured.
● Follow the Instructions Carefully: Pay attention to the format and instructions provided in each
question.

If these mistakes are taken care, it can significantly improve students’ performance in Chemistry exam.

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