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Boards Chemistry Part 1
Boards Chemistry Part 1
ontents
CBSE–XII (PART-1)
Syllabus I - II
Sr.No. Topic Page No.
1. Solutions (Chapter-2) 001–026
2. Electrochemistry (Chapter-3) 027–050
3. Chemical Kinetics (Chapter-4) 051–076
4. d-and f-Block Elements (Chapter-8) 077–096
5. Coordination Compounds (Chapter-9) 097–124
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II
Unit IX : Coordination Compounds
Coordination compounds - Introduction, ligands, coordination number, colour, magnetic
properties and shapes, IUPAC nomenclature of mononuclear coordination compounds. Bonding,
Werner's theory, VBT, and CFT; structure and stereoisomerism, the importance of coordination
compounds (in qualitative analysis, extraction of metals and biological system).
Unit X : Haloalkanes and Haloarenes.
Haloalkanes : Nomenclature, nature of C–X bond, physical and chemical properties, optical
rotation mechanism of substitution reactions.
Haloarenes : Nature of C–X bond, substitution reactions (Directive influence of halogen in
monosubstituted compounds only). Uses and environmental effects of - dichloromethane,
trichloromethane, tetrachloromethane, iodoform, freons, DDT.
Unit XI : Alcohols, Phenols and Ethers
Alcohols : Nomenclature, methods of preparation, physical and chemical properties (of primary
alcohols only), identification of primary, secondary and tertiary alcohols, mechanism of
dehydration, uses with special reference to methanol and ethanol.
Phenols : Nomenclature, methods of preparation, physical and chemical properties, acidic nature
of phenol, electrophilic substitution reactions, uses of phenols.
Ethers : Nomenclature, methods of preparation, physical and chemical properties, uses.
Unit XII : Aldehydes, Ketones and Carboxylic Acids
Aldehydes and Ketones : Nomenclature, nature of carbonyl group, methods of preparation,
physical and chemical properties, mechanism of nucleophilic addition, reactivity of alpha
hydrogen in aldehydes, uses.
Carboxylic Acids : Nomenclature, acidic nature, methods of preparation, physical and chemical
properties; uses.
Unit XIII : Amines
Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
Diazonium salts : Preparation, chemical reactions and importance in synthetic organic chemistry.
Unit XIV : Biomolecules
Carbohydrates - Classification (aldoses and ketoses), monosaccharides (glucose and fructose),
D-L configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides (starch, cellulose,
glycogen); Importance of carbohydrates.
Proteins - Elementary idea of - amino acids, peptide bond, polypeptides, proteins, structure of
proteins - primary, secondary, tertiary structure and quaternary structures (qualitative idea only),
denaturation of proteins; enzymes. Hormones - Elementary idea excluding structure.
Vitamins - Classification and functions.
Nucleic Acids : DNA and RNA.
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CBSE 1
SOLUTIONS : (CHAPTER-2)
CHAPTER AT A GLANCE
INTRODUCTION :
When two or more chemically non-reacting substances are mixed together forming homogeneous
mixture the mixture is called solution.
For binary solution : Solution = solute + solvent
• Generally the component present in lesser amount than, other component in solution, is called
solute.
• Generally, the component present in greater amount than all other components, is called the
solvent.
CONCENTRATION TERMS
(a) Molarity (M)
The number of moles of solute present in one litre solution is called its molarity(M).
Number of molesof solute n
Molarity =
volume of solution (L) VL
(b) Molality (m)
The number of moles of solute present in 1000 gram of the solvent is called molality of the
solution.
Number of moles of solute Number of moles of solute 1000
Molality of a solution = =
Amount of solvent kg Amount of solvent g
(c) Concentration in terms of percentage
(i) Percent By Mass (w/W)
Mass of solute (in g) present in 100 g of solution (g) is called mass percent of the solute.
Where 'w' gram of solute is dissolved in W gram of solvent.
Mass of solute g 100 w 100
Mass percent
Mass of solution g w W
Mass percent is independent of temperature.
(ii) Percent By Volume (v/V)
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This method is used for solutions of liquid in a liquid. The volume of liquid (solute) in mL
present in 100 mL of solution in is called volume percent.
Volume of solute 100
Volume percent =
Volume of solution
w
(iii) Percent by strength/percentage mass by volume : Mass of solute (in g) present in
V
100 mL solution is called mass by volume.
w mass of solute g
% 100
V volume of solution mL
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2 Chemistry
(d) Parts Per Million (ppm)
This method is used for expressing the concentration of very dilute solutions such as hardness
of water, air pollution etc.
Mass of solute g 106
ppm of substance (by mass) =
Massof solution (g)
Volume of solute(mL) 106
ppm (by volume) =
Volume of solution(mL)
w mass of solute g
ppm by 106
V volume of solution mL
(e) Mole Fraction
The ratio of the number of moles of one component to the total number of moles of all the
components present in the solution, is called the mole fraction of that component.
moles of solute n
Mole fraction of solute XB =
moles of solute n moles of solvent N
moles of solvent N
Mole fraction of solvent XA =
moles of solute n moles of solvent N
SOLUBILITY
Maximum amount of solute which can be dissolved in a specified amount of solvent at constant
temperature is solubility. Solubility is affected by nature of solute and solvent as well as by
temperature and pressure.
(a) Solubility of Solid in Liquid
Polar solutes are soluble in polar solvent and non-polar solutes are soluble in non-polar solvent
due to similar intermolecular forces.
When solid solutes are dissolved in solvent then following equilibrium exists.
Dissolution
Solute + Solvent Crystallization
Solution
Solubility of solids is affected by temperature and pressure according to Le-chatlier's principle.
If dissolution is exothermic then solubility decreases with increase in temperature and if
endothermic then solubility increases with increase in temperature.
Solubility of solids is not affected by pressure significantly since solids are highly incompressible.
(b) Solubility of Gases in Liquid
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Certain gases are highly soluble in water like NH3, HCl etc. and certain gases are less soluble in
water like O2, N2, He etc. Solubility of gases is affected by pressure and temperature. Increasing
pressure increases solubility and increase in temperature decreases solubility. During dissolution
of gas pressure of gas decrease and dissolution of gas is exothermic in nature.
HENRY'S LAW
The partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the gas
(X) in the solution. (This is most common definition)
P = KHX KH = Henry's Constant
Henry's Constant is not a universal constant.
It depends on nature of gas and temperature.
KH increases with increase in temperature therefore solubility of gas decreases.
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CBSE 3
VAPOUR PRESSURE
At a constant temperature, the pressure exerted by the vapours of a liquid on its surface when
they (liquid and its vapours) are in equilibrium, is known as vapour pressure.
Factor affecting vapour pressure :
(a) Nature of liquid (b) Temperature
Raoult's Law
According to Raoult's law, the partial vapour pressure of each volatile component in any solution
is directly proportional to its mole fraction.
For liquid-liquid system : PS = P0A + XB(PB0–P0A)
IDEAL SOLUTIONS (mixture of two liquids A and B)
• A solution which obeys Raoult's law exactly at all concentrations and at all temperatures is
called an ideal solution.
• For ideal solutions; A-A interactions = B-B interactions = A-B interactions.
NON-IDEAL SOLUTIONS (mixture of two liquids A and B)
• A solution which do not obeys Raoult's law exactly at all concentrations and at all
temperatures is called an non-ideal solution.
• For non-ideal solutions; A–A interactions + B–B interactions A – B interactions.
AZEOTROPIC MIXTURES :
• Some liquids on mixing, form azeotropes which are binary mixtures having the same
composition in liquid and vapour phase and boil at a constant temperature, the liquid and
vapour have the same composition, and no further separation occurs.
• Components form azeotrope can't be separated by fractional distillation but can be separated
by azeotropic distillation.
• Solutions showing Positive deviation form minimum boiling azeotrope and solutions
showing negative deviation form maximum boiling azeotrope.
lowered i.e. the vapour pressure of a solution is always lower than that of pure solvent,
because the escaping tendency of solvent molecules decreases (due to lesser solvent molecules
per unit surface area).
PA0 PS nB
Relating lowering in vapour pressure =
PA0 NA nB
PA0 PS nB nB
For a dilute solution nB << nA so P
PA0 NA NA
• Relative lowering depends upon relative number of solute particles. Therefore it is called
colligative properties.
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4 Chemistry
• It has been observed that difference in the observed and calculated molecular masses of
solute is due to association or dissociation of solute molecules in solution. It results in a
change in the number of particles in solution.
• Van't hoff factor (i) : Tells about relationship between normal colligative properties and
abnormal colligative properties.
observed colligative properties
i=
calculated colligative properties
i -1
Degree of dissociation :
n -1
n i 1
Degree of association :
1 n
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CBSE 5
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6 Chemistry
4. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively at 350 K. Find
out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the
composition in vapour phase.
Ans. Ps = PBo + X A (PAo – PBo ) PA0 = 450 mm,
o
600 = 700 + XA (450 – 700) PB = 700 mm,
100
XA = = 0.40 Ptotal = 600 mm
250
XB = 1 – XA = 1 – 0.40 = 0.60
PA = PA0 X A = 450 × 0.40 = 180 mm
M = 18 for H2O,
m = 60 for urea
6. Boiling point of water at 750 mm is 96.63ºC. How much sucrose is to be added to 500 g of water
such that it boils at 100ºC ? Kb = 0.52 K kg/mol.
K b × w ×1000
Ans. Tb = Tb = 100 – 96.63 = 3.37
M×W
0.52 × w ×1000
or 3.37 = w = ?, W = 500 g,
342 × 500
M = 342 for sucrose,
or w = 1108.2 g Kb = 0.52 K kg/mol
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CBSE 7
7. Calculate the mass of ascorbic acid (vitamin C, C6H8O6) to be dissolved in 75g acetic acid to
lower its melting point by 1.5ºC. Kf = 3.9 K kg/mol.
K f × w ×1000
Ans. Tf = Tf = 1.5º, w = ?, W = 75g,
M× W
3.9 × w ×1000
1.5 = M for ascrobic acid = 176
176 × 75
or w = 5.08 g
8. Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0g of
polymer of molar mass 185000 in 450 mL of water at 37ºC.
wRT
Ans. Since mass of solute is given, V = =?
m
1× 8.314 ×103 × 310
× 0.450 = V = 0.450 litre,
185000
or = 30.96 Pa w = 1g,
m = 185000,
R = 8.314 kPa LK–1 mol–1
9. Calculate the molarity of a solution containing 5 g of NaOH in 450 mL solution.
5 1000
Sol. Molarity 0.278M
40 450
10. Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
w 1000
Ans. Molality(m)
m w
2.5 1000
m m = 0.556 mol kg–1
60 75
11. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile,
non-electrolyte solid weighing 0.5 g when added to 39.0 g of benzene (molar mass 78 g mol-1).
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Vapour pressure of the solution, then, is 0.845 bar. What is the molar mass of the solid substance ?
P1 P w1 M2
Ans. p10 = 0.850 bar:
P1 m1 W2
1
0.850 bar 0.845 bar 0.5g 78 g mol
p = 0.845 bar :
0.850 bar m1 39 g
Therefore, m1 = 170 g mol–1. M1 = 78 g mol–1;
w2 = 0.5 g;
w1 = 39 g
m1 = ?
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8 Chemistry
12. 18 g of glucose, C6H12O6, is dissolved in 1 kg of water in a saucepan. At what temperature will
water boil at 1.013 bar ? Kb for water is 0.52 K kg mol–1.
Ans. Tb = Kb × m = 0.52 K kg mol–1 × 0.1 mol kg–1 = 0.052 K
Tb = Tbo Tb
Tb = 373.15 + 0.052
Tb = 373.202 K
13. The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile solute was dissolved in
90 g of benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of the solute.
Kb for benzene is 2.53 K kg mol–1.
Ans. ( Tb) = 354.11 K – 353.23 K = 0.88 K.
w 1000
Tb Kb
m W
2.53 K kg mol 1 1.8 g 1000 g kg 1
1
w 58 g mol
0.88 K 90 g
14. 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic pressure
of such a solution at 300 K is found to be 2.57 × 10–3 bar. Calculate the molar mass of the
protein.
Ans. The various quantities known to us are as follows : P = 2.57 × 10–3 bar,
V = 200 cm3 = 0.200 litre
T = 300 K
R = 0.083 L bar mol–1K–1
w 2 RT
Substituting these values in equation M 2 we get
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CBSE 9
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10 Chemistry
4. What is meant by positive and negative deviations from Raoult's law and how is the sign of solH
related to positive and negative deviations from Raoult's law ?
Ans. According to Raoult's law, the partial vapour pressure of each volatile component in any solution
is directly proportional to its mole fraction. The solutions which obey Raoult's law over the entire
range of concentration are known as ideal solutions. The solutions that do not obey Raoult's law
(non - ideal solutions) have vapour pressure either higher or lower than that predicted by Raoult's
law. If the vapour pressure is higher, then the solution is said to exhibit positive deviation, and if
it is lower, then the solution is said to exhibit negative deviation from Raoult's law.
Vapour pressure
of solution
Vapour pressure
Vapour pressure
p1
p2 of ideal solution
Vapour pressure of a two - component solution showing positive deviation from Raoult's law.
Vapour pressure
of ideal solution
Vapour pressure
Vapour pressure
p2 of solution
p1
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CBSE 11
6. At 300 K, 36g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar.
If the osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its
concentration ?
Ans. Here,
T = 300 K p = 1.52 bar
–1 –1
R = 0.083 bar L K mol Applying the relation,
1.52
= CRT C = = 0.061 mol
RT 0.083bar, L.K 1mol 1
300 K
Since the volume of the solution is 1L, the concentration of the solution would be 0.061 M.
7. Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic
pressure is 0.75 atm at 27°C.
n
Ans. We know that, i RT
V
w MV
i RT w df
MV iRT
= 0.75 atm V = 2.5 L
i = 2.47 T = (27 + 273) K = 300 K
Here, R = 0.082 L atm K mol–1–1
i=3
Given, w = 25 mg = 0.025 g
V=2L
T = 25°C = (25 + 273) K = 298 K
Also, we know that : R = 0.0821 L atm K–1 mol–1
M = (2 × 39) + (1 × 32) + (4 × 16) = 174 g mol–1
Applying the following relation,
n w1 0.025 1
i RT = i RT = 3 0.0821 298 = 5.27 × 10–3 atm
v Mv 174 2
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12 Chemistry
9. A 10% solution (by mass) of sucrose in water has a freezing point of 269.15 K. Calculate the
freezing point of 10% glucose in water if the freezing point of pure water is 273.15 K.
Given :
(Molar mass of sucrose = 342 g mol–1)
(Molar mass of glucose = 180 g mol–1)
(b) Define the following terms :
(i) Molality (m)
(ii) Abnormal molar mass
w2 / m 2 k f w2 1000
Ans. (a) (i) Tf = Kf × m kf
w1 /1000 m 2 w1
k f 10 1000
273.15 – 269.15
342 90
kf = 12.3 k kgmol–1.
(ii) Tf = Kfm
= 12.3 × 10 × 1000 × 180 × 90
= 7.6 K
Tf = 273.15 – 7.6 = 265.55 K
(b) (i) Number of moles of solute dissolved in per kilo gram of the solvent.
(ii) Abnormal molar mass : If the molar mass calculated by using
any of the colligative properties to be different than theoretically
10. (a) 30 g of urea (M = 60 g mol–1) is dissolved in 846 g of water. Calculate the vapour pressure
of water for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
(b) Write two differences between ideal solutions and non-ideal solutions.
Ans. (a) (PA0 PA ) / PA0 = (wB × MA)/(MB × wA)
23.8 PA
(30 18) / 60 846
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CBSE 13
11. (i) Write the colligative property which is used to find the molecular mass of macromolecules
(ii) In non-ideal solution, what type of deviation shows the formation of minimum boiling
azeotropes ?
Ans. (i) Osmotic pressure
(ii) Positive deviation from Raouts’ law/ Positive deviation
12. Calculate the boiling point of solution when 2 g of Na2SO4 (M = 142 g mol–1) was dissolved
in 50 g of water, assuming Na2SO4 undergoes complete ionization. (Kb for water = 0.52 K kg mol–1)
K b w b 1000
Ans. Tb i
M b wa
3 0.52 2 1000
Tb
142 50
= 0.439 K
Tb = Tb – Tb0
Tb = 0.439 + 373 = 373.439 K
13. (i) Why are aquatic species more comfortable in cold water than in warm water ?
(ii) What happens when we place the blood cell in saline water solution (hypertonic solution)?
Give reason.
Ans. (i) As solubility of gases decreases with increase of temperature, less oxygen is available in
summer in the lakes / as cold water contains more oxygen dissolved.
(ii) They will shrink , due to osmosis.
14. Vapour pressure of water at 20°C is 17.5 mm Hg. Calculate the vapour pressure of water at 20°C
when 15 g of glucose (Molar mass = 180 g mol–1) is dissolved in 150 g of water.
Ans. PAo = 17.5 mm of Hg WB = 15 g MB = 180 g/mol
WA = 150 g PS = ?
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PAo PS WB M A PAo PS 15 18
0.01
PAo M B WA PAo 180 150
PAo PS 17.5 PS
0.01
PAo 17.5
PS = 17.325 mm of Hg
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14 Chemistry
EXERCISE-3 RACE
Type 1 : Passage question 1 :-
Henry was the first to give a quantitative relation between pressure and solubility of a gas in a
solvent which is known as Henry’s law. The law states that at a constant temperature, the
solubility of a gas in a liquid is directly proportional to the pressure of the gas. Dalton, a
contemporary of Henry, also concluded independently that the solubility of a gas in a liquid
solution is a function of partial pressure of the gas. If we use the mole fraction of a gas in the
solution as a measure of its solubility, then it can be said that the mole fraction of gas in the
solution is proportional to the partial pressure of the gas over the solution. The most commonly
used form of Henry’s law states that “the partial pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas (x) in the solution” and is expressed as : p = KHx
(a) “The partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the
gas (x) in the solution” is :
(i) Raoult’s law (ii) Dalton’s law
(iii) Henry’s law (iv) None of these
(b) Value of Henry’s constant KH ____________.
(i) increases with increase in temperature.
(ii) decreases with increase in temperature.
(iii) remains constant.
(iv) first increases then decreases.
(c) The value of Henry’s constant KH is _____________.
(i) greater for gases with higher solubility.
(ii) greater for gases with lower solubility.
(iii) constant for all gases.
(iv) not related to the solubility of gases.
(d) KH value for Ar(g), CO2(g), HCHO (g) and CH4(g) are 40.39, 1.67, 1.83 × 10–5 and 0.413
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CBSE 15
Type 2 : Assertion and Reason :-
Question 2 to 6 :- Note :- In the following questions a statement of assertion followed by a
reason. Choose the correct answer out of the following choices –
(i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of Assertion (A).
(ii) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of Assertion (A).
(iii) Assertion (A) is correct, but Reason (R) is incorrect statement.
(iv) Assertion (A) is incorrect, but Reason (R) is correct statement.
2. Assertion : Molarity of a solution in liquid state changes with temperature.
Reason : The volume of a solution changes with change in temperature.
3. Assertion : When methyl alcohol is added to water, the boiling point of water decreases.
Reason : When a volatile solute is added to a volatile solvent elevation in the boiling point is
observed.
4. Assertion : When NaCl is added to water a depression in freezing point is observed.
Reason : The lowering of vapour pressure of a solution causes depression in the freezing point.
5. Assertion : When a solution is separated from the pure solvent by a semipermeable membrane,
the solvent molecules pass through it from pure solvent side to the solution side.
Reason : Diffusion of solvent occurs from a region of high concentration solution to a region of
low concentration solution.
6. Assertion : Low concentration of oxygen in the blood and tissues of people living at high
altitude suffer from anoxia.
Reason : due to low atmospheric pressure.
Type 3 : Multiple choice question (one correct answer) (Questions 7 to 16) :-
7. On dissolving sugar in water at room temperature solution feels cool to touch. Under which of
the following cases dissolution of sugar will be most rapid ?
(i) Sugar crystals in cold water
(ii) Sugar crystals in hot water
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16 Chemistry
10. Maximum amount of a solid solute that can be dissolved in a specified amount of a given liquid
solvent does not depend upon ____________.
(i) Temperature (ii) Nature of solute
(iii) Pressure (iv) Nature of solvent
11. Low concentration of oxygen in the blood and tissues of people living at high altitude is due to
____________.
(i) low temperature
(ii) low atmospheric pressure
(iii) high atmospheric pressure
(iv) both low temperature and high atmospheric pressure
12. Considering the formation, breaking and strength of hydrogen bond, predict which of the
following mixtures will show a positive deviation from Raoult’s law?
(i) Methanol and acetone (ii) Chloroform and acetone
(iii) Nitric acid and water (iv) Phenol and aniline
13. Colligative properties depend on ____________.
(i) the nature of the solute particles dissolved in solution.
(ii) the number of solute particles in solution.
(iii) the physical properties of the solute particles dissolved in solution.
(iv) the nature of solvent particles.
14. The unit of ebulioscopic constant is _______________.
(i) K kg mol–1 or K (molality)–1 (ii) mol kg K–1 or K–1 (molality)
(iii) kg mol–1 K–1 or K–1 (molality)–1 (iv) K mol kg–1 or K (molality)
15. An unripe mango placed in a concentrated salt solution to prepare pickle, shrivels because _____.
(i) it gains water due to osmosis. (ii) it loses water due to reverse osmosis.
(iii) it gains water due to reverse osmosis. (iv) it loses water due to osmosis.
16. If two liquids A and B form minimum boiling azeotrope at some specific composition then ____.
(i) A–B interactions are stronger than those between A–A or B–B.
(ii) Vapour pressure of solution increases because more number of molecules of liquids A and B
can escape from the solution.
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(iii) Vapour pressure of solution decreases because less number of molecules of only one of the
liquid.
(iv) A–B interactions are weaker than those between A–A or B–B.
ANSWER-KEY
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CBSE 17
(a) Hmix = 0 and Vmix = 0 (b) Hmix > 0 and Vmix > 0
(c) Hmix < 0 and Vmix < 0 (d) Hmix > 0 and Vmix < 0
Ans. (a)
3. For determination of molar mass of polymers and proteins, which colligative property is
used ? [1]
(CBSE 2022 Term-I)
(a) Relative lowering in vapour pressure (b) Elevation in boiling point
(c) Osmotic pressure (d) Depression in freezing point
Ans. (c) Osmotic pressure
Because this is the only method which takes place at room temperature and all biomolecules are
unstable above room temperature.
4. Pure water boils at 373.15 K and nitric acid boils at 359.15 K. An azeotropic mixture of H2O and
HNO3 boils at 393.55 K. Distilling the azeotropic mixture will cause : [1]
(CBSE 2022 Term -I)
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18 Chemistry
5. A 5% (by mass) solution of glucose (molar mass = 180 g mol–1) is isotonic with 1% solution (by
mass) of a substance 'X'. The molar mass of 'X' is : [1]
(CBSE 2022 Term -I)
–1 –1 –1
(a) 36 g mol (b) 18 g mol (c) 72 g mol (d) 900 g mol–1
Ans. (a)
For isotomic solution
C1 = C2
n1 n 2
v v
w1 / m 1 w 2 / m 2
v v
5 1
180 x
x = 180/5 = 36 g mol–1.
6. When 2.5g of a non-volatile solute was dissolved in 50 mL of water, it gave boiling point
elevation of 0.52 °C. The molar mass of the solute is (Kb for water = 0.52 Km–1) [1]
(CBSE 2022 Term -I)
–1 –1 –1
(a) 100g mol (b) 50g mol (c) 25g mol (d) 75g mol–1
W2 1000
Ans. (b) Tb = kbm = k b
M2 W1
2.5 1000
0.52 = 0.52 ×
50 w1
0.52 2.5 1000
w1 50 g mol 1
50 0.52
7. To increase the solubility of CO2 gas in soft drinks, the bottle is sealed under : [1]
(CBSE 2022 Term -I)
(a) Low pressure (b) High temperature (c) Constant pressure (d) High pressure
Ans. (d)
To increase the solubility of CO2 gas in soft drink the bottle are sealed under low temperature and
high pressure. Because solubility of gas in liquid increases under low temp and high pressure.
(acc. to Henry's law).
8. A solution of a pair of volatile liquids A and B shows negative deviation from Raoult's law. This
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
is because :- [1]
(CBSE 2022 Term -I)
o o
(a) p A p A x A and p B pB x B
(b) The intermolecular forces A –A, B – B < A – B
(c) Both Hmixing and Vmixing are positive
(d) All of the above
Ans.. (b)
Properties of Raoult's law of negative deviation.
(i) Hmix < 0
(ii) Vmix < 0
(iii) PT < PAo XA + PBo XB
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CBSE 19
9. Assertion (A) : Relative lowering in vapour pressure is a colligative property. [1]
(CBSE 2022 Term-I)
Reason (R) : Relative lowering in vapour pressure depends upon mole fraction of pure solvent.
(i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of Assertion (A).
(ii) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of Assertion (A).
(iii) Assertion (A) is correct, but Reason (R) is incorrect statement.
(iv) Assertion (A) is incorrect, but Reason (R) is correct statement.
Ans. (iii)
Relative lowering in vapour pressure depends on upon number of solute particles.
reason is false.
10. Which of the following analogies is correct ? [1]
(CBSE 2022 Term -I)
(a) Chloroform-acetone : Positive deviation : : Ethanol H2O : Negative deviation.
(b) pA p Ao x A : Henry 's law : : p = KH x : Raoult's law.
(c) PTotal = pA + pB : Non-ideal solution : : PTotal > pA + pB : Ideal solution
(d) = CRT : Osmotic pressure :: P > : Reverse osmosis.
Ans. (d)
= CRT : Osmotic pressure : : P > reverse osmosis.
Chloroform : acetone show negative derivation due to formation of H-Bond between chloroform
and acetone molecules.
Ethanol : H2O show positive derivation due to weak inter molecular force of attraction.
P = KHX is Henry's law & P = P A 0 XA is Raoult's law.
Ptotal = PA + PB for ideal solution = Ptotal > PA + PB for Non ideal solution.
11. Assertion (A) : Molarity of a solution in liquid state changes with temperature.
Reason (R) : The volume of solution changes with the change in temperature. [1]
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20 Chemistry
12. (a) State Henry’s law and mention its two applications. [2]
(b) 5% aqueous solution of a non-volatile solute was made and its vapour pressure at 373 K was
found to be 745 mm. Vapour pressure of pure water at this temperature was 760 mm. Calculate
the molar mass of solute. [3]
OR
(a) Give two differences between ideal and non-ideal solutions. [2]
(b) Calculate the amount of NaCl (M = 58·5 g mol–1) that must be added to 100 g of water so that
freezing point is depressed by 2 K. Kf for water is 1·86 K/m. [3]
(CBSE 2021 Compartment)
Ans. (a) The partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the
gas (X) in the solution. (This is most common definition) [1]
P = KHX KH = Henry's Constant
Applications : [1]
(1) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under
high pressure.
(2) At high altitudes the partial pressure of oxygen is less than that at the ground level. This
leads to low concentration of oxygen in the blood and tissues of people living at high
altitudes or climbers. Low blood oxygen causes climbers to become weak and unable to
think clearly, symptoms of a condition known as anoxia.
PA0 Ps n B
(b) Raoult's law, [1] WB(mass of solute) = 5g in 100 g of solution
PA0 nA
760 745 5 / mB
[1] WA = 95 g mass of solvent) ;
760 95 / m B
5 18 760
mB = 48g / mol [1] mA (molecular mass of water) = 18 g
15 95
mB (molecular mass of solute) = ?
U.P. of pure water) PAo = 760 mmHg ;
Ps (V.P. of solution after addition of solute)
= 745 mm Hg
OR
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CBSE 21
13. Identify which liquid will have a higher vapour pressure at 90°C if the boiling points of two
liquids A and B are 140°C and 180°C, respectively. [1]
(CBSE 2020)
Ans. (A)
14. For a 5% solution of urea (Molar mass = 60 g/mol), calculate the osmotic pressure at 300 K.
[R = 0.0821 LatmK-1mol-1] : (CBSE 2020)
OR
Visha took two aqueous solutions - one containing 7.5 g of urea (Molar mass = 60 g/mol) and the
other containing 42.75 g of substance Z in 100 g of water, respectively. It was observed that both
the solutions froze at the same temperature. Calculate the molar mass of Z. [2]
Ans. = CRT (Volume of solution = 100 mL) [½]
n
RT [½]
v
5 0.0821 300
[½]
60 0.1
= 20.5 atm [½]
OR
Tf(urea) = Tf(Z) [½]
w urea 1000 wz 1000
kƒ kf [½]
Murea w solvent Mz wsolvent
7.5 1000 42.75 1000
[½]
60 100 Mz 100
42.75 60
Mz = 342 g / mol [½]
7.50
15. Calculate the mass of ascorbic acid (Molar mass = 176gmol–1) to be dissolved in 75g of acetic
acid, to lower its freezing point by 1.5°C. (Kf = 3.9 K kgmol–1) [3]
(CBSE 2020)
Ans. Tf Kfm [1]
w 1000
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
Tf Kf [1]
m W
w 1000
1.5 3.9 [1]
176 75
mass of ascorbic acid (w) = 5.08 g
16. Give reasons : [2]
(a) Cooking is faster in pressure cooker than in cooking pan. (CBSE 2019)
(b) Red Blood Cells (RBC) shrink when placed in saline water but swell in distilled water.
Ans. (a) Due to increase of pressure in cooker, boiling point of water increases [1]
(b) RBC looses water in saline water and absorb water in distilled water due to osmosis. [1]
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22 Chemistry
17. A solution containing 1.9 g per 100 mL of KCl (M = 74.5 g mol–1) is isotonic with a solution
containing 3 g per 100 mL of urea (M = 60 g mol–1). Calculate the degree of dissociation of KCl
solution. Assume that both the solutions have same temperature. [3]
(CBSE 2019)
Ans. 1
(urea) = 2
[KCl]
C1RT = iC2RT [1]
n1 n2
i (V1 = V2)
V1 V2
3 1.9
i [1]
60 74.5
i = 1.96
i 1 1.96 1
= 0.96 or 96% [1]
n 1 2 1
18. Give reasons : [2]
(a) A decrease in temperature is observed on mixing ethanol and acetone. (CBSE 2019)
(b) Potasium chloride solution freezes at a lower temperature than water.
Ans. (a) Due to positive deviation. [1]
(b) Due to more van't hoff factor. [1]
19. Give reasons : [2]
(a) An increase in temperature is observed on mixing chloroform and acetone. (CBSE 2019)
(b) Aquatic animals are more comfortable in cold water than in warm water.
Ans. (a) Due to negative deviation [1]
(b) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen
decreases, It means the solubility of oxygen is less in warm, because of this reason Aquatic
animals are more comfortable in cold water than in warm water. [1]
20. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1)
in 250 g of water. (CBSE 2018)
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
–1
(Kf of water = 1.86 K kg mol )
Ans. W1 = 250 g ; w2 = 60g ; M2 = 180g/mol or 180g mol–1
Kf = 1.86 k kg mol–1
Tf = Kf m [1/2]
w 2 (g) 1000 60 1000
Tf = Kf × 1.86 [1/2]
M2 w1 (g) 180 250
= 2.48 K [1/2]
Tf = t(solvent) – t(solution) [1/2]
t(solution) = t(solvent) – Tf
= 273.15 – 2.48 = 270.67 K [1]
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CBSE 23
21. Give reasons for the following : [3]
(CBSE 2018)
(a) Measurement of osmotic pressure method is preferred for the determination of molar
masses of macromolecules such as proteins and polymers.
(b) Aquatic animals are more comfortable in cold water than in warm water.
(c) Elevation of boiling point of 1 M KCl solution is nearly double than that of 1M sugar
solution.
Ans. (a) Protein are high molecular mass material, the magnitude of colligative property depends
inversely on the molecular mass and osmotic pressure is the only colligative property have
measurable magnitude. So, the Osmotic pressure method is preferred for the determination
of molar mass of macromolecules as proteins & polymers. [1]
(b) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen
decreases, It means the solubility of oxygen is less in warm, because of this reason Aquatic
animals are more comfortable in cold water than in warm water. [1]
(c) The value of Van't Haff factor is twice in 1M KCl than 1M sugar solution due to which
elevation of Boiling point is more.
The solvent is somewhat but KCl is ionic due to which it dissociates completely.
The elevation of B.P. is Tb i K b m {In both 1 M KCl & 1M sugar solution} [1]
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24 Chemistry
EXERCISE-5 MOCK TEST
1. Define the term 'osmotic pressure. [1]
4. State the Raoult’s law in its general form in reference to solutions. [2]
5. State the Henry’s law about partial pressure of a gas in a mixture. [2]
7. What type of deviation is shown by a mixture of ethanol and acetone ? Give reason. [2]
8. Write three differences between ideal solutions and non-ideal solutions. [3]
9. A solution of glucose (molar mass = 180 g mol–1) in water is labelled as 10% (by mass). What
10. Calculate the freezing point of a solution containing 60 g of glucose (Molar mass = 180 g mol–1)
(i) Measurement of osmotic pressure method is preferred for the determination of molar masses
(ii) Aquatic animals are more comfortable in cold water than in warm water.
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
(b) 30g of urea (M = 60 g mol–1) is dissolved in 846 g of water. Calculate the vapour pressure of
water for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
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CBSE 25
(c) mix
V=0 (c) mix
V is not equal to 0
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
w 1000
9. Molality (m) =
m w
10 1000
m ; m = 0.62
180 90
10 1000 100
Molarity (M) = ; V
100 1.2
180
1.2
10 1000 1.2
M ; M = 0.67 M
180 100
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26 Chemistry
10. W1 = 250 g ; w2 = 60g ; M2 = 180g/mol or 180g mol–1
Kf = 1.86 k kg mol–1 ; Tf = Kf m
11. (a) (i) Protein are high molecular mass material, the magnitude of colligative property depends
inversely on the molecular mass and osmotic pressure is the only colligative property have
measurable magnitude. So, the Osmotic pressure method is preferred for the determination
(ii) In water, oxygen is in dissolved state & as temperature rises, the solubility of oxygen
decreases, It means the solubility of oxygen is less in warm, because of this reason Aquatic
(b) (PA0 PA ) / PA0 = (wB × MA) / (MB × wA) node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\02_Solution
23.8 PA
(30 18) / 60 846
23.8
23.8 – PA = 0.2532
PA = 23.55 mm Hg
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CBSE 27
ELECTROCHEMISTRY : (CHAPTER-3)
CHAPTER AT A GLANCE
INTRODUCTION
Electrochemistry is the branch of physical chemistry which deals with the study of
interconversion of chemical energy and electrical energy.
ELECTROCHEMICAL CELL
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28 Chemistry
CELL POTENTIAL ( E 0cell ) :
E 0cell = SRP of cathode – SRP of anode.
NERNST EQUATION :
2 2
0 RT Zn 0 0.0591 Zn
E cell E cell n 2
Ecell E cell log 2
2F Cu 2 Cu
EQUILIBRIUM CONSTANT (Kc) FROM NERNST EQUATION :
Zn 2 2.303RT
Ecell 0 & Kc E0cell log K c ...(1)
Cu 2
nF
GIBBS FREE ENERGY :
r
G = –nF Ecell r
Gº = –nF Eºcell ...(2)
Put Eºcell from equation (1) r
Gº = –2.303 RT log Kc
ELECTROLYTIC CONDUCTANCE
(a) Resistance (R) : Metallic and electrolytic conductors obey ohm's law according to which
the resistance of a conductor is the ratio of the applied potential difference (V) to the current (I)
V
flowing . R = R is expressed in ohms.
I
(b) Conductance (G) : It is the property by virtue of which it favours flow of current. The
conductance of a conductor is equal to reciprocal of resistance G = 1
R
unit of G is mho or ohm–1 or Siemens (S).
(c) Specific resistance/Resistivity ( ) :- The resistance (R) of a conductor is directly
proportional to its length ( ) and inversely proportional to its area of cross section (A).
A
= R × ; Therefore, resistance offered by 1 cm3 electrolytic solution is known as
G G*
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
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CBSE 29
DETERMINATION OF MOLAR CONDUCTANCE OF
ELECTROLYTES AT INFINITE DILUTION
Debye Huckel Onsager equation –
400
/(S cm mol )
CH3COOH
–1
m m b C [only for strong electrolyte]
(Weak electrolyte)
where = molar conductance at concentration C,
2
m
m
= molar conductance at dilution,
b = constant and its value is same for a particular type of 200
electrolyte.
m
KCl
If a graph is plotted between m vs C a straight line is obtained (Strong electrolyte)
for strong electrolyte. On extrapolation this line touches m axis.
Therefore m for strong electrolyte can be found out from 0 0.2 0.4
intercept. For weak electrolyte the slope of curve is not constant 1/2
c /(mol/L)
1/2
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30 Chemistry
(b) Second law of electrolysis :
When same amount of charge is passed through different electrolyte solutions connected in
series then weight of substances deposited or liberated at electrodes are in ratio of their
W1 E1
respective equivalent weights. i.e. .
W2 E2
COMMERCIAL VOLTAIC CELLS
Batteries can be classified as primary and secondary. Primary batteries cannot be returned to
their original state by recharging, so when the reactants are consumed, the battery is "dead" and
must be discarded. Secondary batteries are often called storage batteries or rechargeable
batteries. The reactions in these batteries can be reversed; thus, the batteries can be recharged.
(A) PRIMARY CELL : Dry cells
Anode Zn(s) Zn+2 + 2e–
Cathode MnO2 + NH4+ + e– MnO(OH) + NH3
EMF 1.5 V
(B) SECONDARY OR RECHARGEABLE BATTERY : Lead Storage Battery
The most important secondary cell is the lead storage battery. It consists of a lead as anode and
a grid of lead dioxide as cathode.
EMF 2 V. So, a lead storage battery consisting of six cells will give 12V.
At Anode : Pb(s) + SO42– (aq.) PbSO4(s) + 2e–
At Cathode : PbO2(s) + 4H+ (aq.) + SO4–2 (aq.) + 2e– PbSO4(s) + 2H2O( )
——————————————————————————
Net cell reaction : Pb(s) + PbO2(s) + 2H2SO4(aq.) 2PbSO4(s) + 2H2O( )
(C) Fuel Cells
Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen,
methane, methanol, etc. directly into electrical energy are called fuel cells.
EMF 1.23 V.
The electrode reactions are :
At anode : 2[H2(g) + 2OH– (aq) 2H2O( ) + 2e– ]
At cathode : O2(g) + 2H2O( ) + 4e– 4OH– (aq)
————————————————
Net cell reaction : 2H2(g) + O2(g) 2H2O( )
CORROSION
Corrosion is basically an electrochemical phenomenon. The rusting of iron, the tarnishing of
silver, development of a green coating on copper and bronze are some of the examples of
corrosion. Corrosion causes enormous damage to building, bridges, ships and to many other node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
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CBSE 31
0 0.059 PH
Ecell = Ecell – log 2 2
2 [H ]
Eocell = 0, PH 2 = 1atm, [H ] = 10 = 10
+ –pH –10
0.059 1
Ecell = – log = -0.59V
2 (10-10 )2
2. Calculate the emf of the cell in which following reaction takes place :
Ni(s) + 2Ag+ (0.002 M) Ni2+ (0.160 M) + 2Ag(s)
Given that Eocell = 1.05 V
Ans. Applying Nernst equation we have:
0.16
1.05 0.02955log = 1.05 – 0.02955 log 4 × 104
0.000004
= 1.05 – 0.02955 (log 10000 + log 4)
= 1.05 – 0.02955 (4 + 0.6021)
= 1.05 – 0.02955 (4.6021)
= 1.05 – 0.14 = 0.91 V
3. The cell in which the following reaction occurs :
2Fe 3 (aq.) 2I (aq.) 2Fe 2 (aq.) I 2 (s) has Eocell = 0.236 V at 298 K
Calculate the standard Gibbs energy and equilibrium constant of the cell reaction.
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
Go = –2.303 RT log Kc
r
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32 Chemistry
0
5. Suggest a way to determine the m value of water.
Ans. Applying Kohlrausch’s law of independent migration of ions, the value of water can be
determined as follows :
0 0 0
m(H 2 O) H OH
0 0 0 0 0 0
H Cl Na OH Na Cl
0 0 0 0
m (H 2 O) m (HCl ) m (NaOH ) m (NaCl)
Hence, by knowing the values of HCl, NaOH, and NaCl, the value of water can be determined.
6. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons
would flow through the wire ?
Ans. I = 0.5 A, t = 2 hours = 2 × 60 × 60 s = 7200 s
Q = It = 0.5A × 7200 s = 3600C
96500 coulomb are equivalent of 6.023 × 1023 number of electrons
—————————————————————————
Net cell reaction : Pb(s) + PbO2(s) + 2H2SO4(aq.) 2PbSO4(s) + 2H2O( )
When a battery is charged, the reverse of all these reactions takes place. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
Hence, on charging, PbSO4 (s) present at the anode and cathode is converted into Pb(s) and
PbO2(s) respectively.
8. The standard electrode potential for Daniell cell is 1.1 V. Calculate the standard Gibbs energy for
the reaction : Zn(s) Cu2 (aq) Zn 2 (aq) Cu(s)
Ans. r G nF E(Cell)
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CBSE 33
9. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 . If the resistance
of the same cell when filled with 0.02 mol L–1 KCl solution is 520 . Calculate the conductivity
and molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1 mol L–1 KCl
solution is 1.29 S/m.
Ans. The cell constant is given by the equations: Cell constant = G* = conductivity × resistance
= 1.29 S/m × 100 = 129 m–1 = 1.29 cm–1
Conductivity of 0.02 mol L–1 KCl solution = Cell constant/resistance
G* 129 m 1
0.248 S m 1
R 520
Concentration = 0.02 mol L–1
= 1000 × 0.02 mol m–3 = 20 mol m–3
248 10 3 S m 1
Molar conductivity = m = 124 10 4 S m2 mol 1
c 20 mol m 3
1
1.29 cm (Scm 1 ) 1000 (cm 3 L–1 )
Alternatively, 0.248 10 2 S cm 1
and m
520 molarity(mol L 1 )
0.248 10 2 S cm 1 1000 cm3 L 1
2 1
= 124 S cm2 mol–1
0.02 S cm mol L
10. The electrical resistance of a column of 0.05 mol L–1NaOH solution of diameter 1 cm and length
50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
Ans. A = r2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2
= 50 cm = 0.5 m
0.01148 S cm 1 1000 cm 3 L 1
1
= 229.6 S cm2 mol–1
0.05 mol L
If we want to calculate the values of different quantities in terms of m instead of cm.
RA 5.55 103 0.785 10 4 m 2 2
87.135 10 m
0.5 m
1 100 1
m 1.148 S m
87.135
1.148 S m 1
and m 229.6 10 4 S m2 mol 1
c 50 mol m 3
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34 Chemistry
11. Calculate o
m for CaCl2 and MgSO4 If Ca 2
119.0 Scm 2mol 1 , Cl
76.3Scm 2mol 1 ,
Mg2
106 Scm 2 mol 1 , SO24
160 Scm 2 mol 1 .
Ans. o
m(CaCl 2 )
0
Ca 2
2 Cl
119.0 S cm 2 mol 1
2(76.3) S cm 2 mol 1
4.95 10 5 S cm 1 1000 cm 3
Ans. m 48.15 Scm 3 mol 1
c 0.001028 mol L 1 L
48.15 S cm 2mol 1
m
o
0.1233
m 390.5 S cm 2 mol 1
2
c 0.001028 mol L 1 (0.1233)2
K 1.78 10 5 mol L 1
(1 ) 1 0.1233
13. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the
mass of copper deposited at the cathode ?
Ans. t = 600 s
charge = current × time = 1.5 A × 600 s = 900 C
According to the reactions
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CBSE 35
Ans. The galvanic cell of the given reaction is depicted as : Cr(s) Cr 3 (aq ) Cd 2 (aq ) Cd (s)
r G nFEcell
In the given equation, n = 6
F = 96487 C mol–1 Ecell 0.34V
–1 –1 –1
Then, r G = –6 × 96487 C mol × 0.34 V = – 196833.48 CV mol = –196833.48 J mol
= –196.83 kJ mol–1
Again, r G = –RT ln K
r G = –2.303 RT log K
G 196.83 103
log K = – = –r
2.303RT 2.303 8.314 298
log K = 34.496
K = antilog (34.496) = 3.13 × 1034
2. Write the Nernst equation and emf of the following cells at 298K :
(i) Fe(s) Fe 2 (0.001M) H 1M H 2 (g) (1bar) Pt(s)
Ans. (i) For the given reaction, the Nernst equation can be given as :
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
1 1
= – 1.09 0.02955 log = 1.09 0.02955 log 8
0.00000009 9 10
= –1.09 – 0.02955 × log(1.11 × 107) = –1.09 – 0.02955 (0.0453 + 7)
= –1.09 – 0.208 = –1.298 V
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36 Chemistry
3. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity.
If om for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant ?
Ans. Given, = 7.896 × 10–5 S cm–1 C = 0.00241 mol L–1
7.896 10 5 Scm 1 1000 cm3
Then, molar conductivity, m = 1
= 32.76 S cm2 mol–1
C 0.00241mol L L
Again, 0
m = 390.5 S cm2 mol–1
m 32.76 S cm 2 mol 1
Now, 0
= 0.084
m 390.5Scm 2 mol 1
2
c 2 0.00241mol L 1 0.084
Dissociation constant, K a = = 1.86 × 10–5 mol L–1
1 1 0.084
4. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode ?
Ans. Given, Current = 5A
Time = 20 × 60 = 1200 s
Charge = current × time = 5 × 1200 = 6000 C
According to the reaction, Ni 2 (aq ) 2e Ni (s)
58.7g
Nickel deposited by 2 × 96487 C = 58.71 g
58.71 6000
Therefore, nickel doposited by 6000 C = g = = 1.825 g
2 96487
Hence, 1.825 g of nickel will be deposited at the cathode.
5. Three electrolytic cells A, B, C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively
are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of
silver deposited at the cathode of cell B. How long did the current flow ? What mass of copper
and zinc were deposited ?
Ans. According to the reaction : Ag ( aq ) e Ag s
108g
i.e., 108 g of Ag is deposited by 96487 C.
96487 1.45
Therefore, 1.45 g of Ag will be deposited by = C = 1295.43 C
108 node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
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CBSE 37
6. Write the name of the cell which is generally used in inverters. Write the reactions taking place
at the anode and the cathode of this cell.
Ans. Lead storage battery
Anode : Pb(s) + SO42–(aq.) PbSO4(s) + 2e– [1/2]
n=2
0 0.059 [Cr 3 ]2
Ans. (a) Ecell E cell log [1/2]
n [Fe 2 ]3
0 0.059 [0.01]2
0.261V E cell log [1/2]
6 [0.01]3
0.059
0.261V E 0cell log100 [1/2]
6
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38 Chemistry
9. (a) The conductivity of 0.001 mol L–1 solution of CH3COOH is 3.905 × 10–5 S cm–1.
Calculate its molar conductivity and degree of dissociations (a).
Given °(H+) = 349.6 S cm2 mol–1 and °(CH3COO–)= 40.9 S cm2 mol–1.
(b) Define electrochemical cell. What happens if external potential applied becomes greater
than of electrochemical cell ?
c
Ans. (a) m
= k × 1000/C = 3.905 × 10–5 × 1000/0.001 = 39.05 S cm2/mole [1]
– +
CH3COOH CH3COO + H
0
CH3COOH = CH3COO– + 0
H+
= 40.9 + 349.6
CH3COOH = 390.5 S cm2/mol
= 39.05/390.5 = 0.1 [1]
(b) An electrochemical cell is a device in which chemical energy of the redox reaction is
converted into electrical energy. While electrolytic cell do the reverse. e– flow from Cu
to Zn and current flows from Zn to Cu. [1]
10. Calculate the time to deposit 1.5 g of silver at cathode when a current of 1.5 A was passed
through the solution of AgNO3. (Molar mass of Ag = 108 g mol–1, 1 F = 96500 C mol–1)
Ans. Wt. of Ag = 1.5g Current = i = 1.5amp
Molecular mass = 108 g/mol F = 96500 C/mol
n = number of electron transferred
M I t
W [1]
n F
M n F 1.5 1 96500
t [1]
M I 108 1.5
= 893.51 s or 14.89 min [1]
0 0
11. Calculate E cell and G for the following reaction at 25° C :
r
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
A2+ + B+ A3+ + B
Given : Kc = 1010, 1 F = 96500 C mol–1
Ans. A2+ + B+ A3+ + B (n = 1)
Kc = 1010 F = 96500C/mol T = 25º C = 298K
Go = ? Eo = ? R = 8.314J/K/mol
Go = –2.303 RT log Kc [1]
o 10
G = –2.303 × 8.314 J/K/mol × 298K × log 10 .
Go = –57058.4 J/mol or –57.0584 kJ/mol
Go = –57058.4 J/mol = –nFEo = –1 × 96500 × Eo [1]
0.59127.
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CBSE 39
EXERCISE-3 RACE
Type 1 : Passage question 1 :-
Type 1 : Passage question 1 :-
Molar conductivity of solution is the conductance of solution containing one mole of electrolyte,
kept between two electrodes having unit length between them and large cross-sectional area, so
as to contain the electrolyte. In other words, molar conductivity is the conductance of the
electrolytic solution kept between the electrodes of a conductivity cell at unit distance but having
area of cross-section large enough to accommodate sufficient volume of solution that contains
one mole of the electrolyte. It is denoted by .
m
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40 Chemistry
5. Assertion : Current stops flowing when Ecell = 0.
6. Assertion : E Ag / Ag
increases with increase in concentration of Ag+ ions.
Reason : E Ag / Ag
has a positive value.
10. The difference between the electrode potentials of two electrodes when no current is drawn
through the cell is called ___________.
11. An electrochemical cell can behave like an electrolytic cell when ____________.
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CBSE 41
12. Which of the statements about solutions of electrolytes is not correct ?
(i) Conductivity of solution depends upon size of ions.
(ii) Conductivity depends upon viscosity of solution.
(iii) Conductivity does not depend upon solvation of ions present in solution.
(iv) Conductivity of solution increases with temperature.
13. m[NH 4 OH ]
is equal to ______________.
14. E Cell 1.1V for Daniel cell. Which of the following expressions are correct description of state of
1 A G* l
(i) (ii) (iii) m
(iv)
R R A
(ii) Cu is anode
(iii) The cell reaction is Mg + Cu2+ Mg2+ + Cu
(iv) Cu is the oxidising agent
ANSWER-KEY
Q. No. 1 (a) (b) (c) (d) 2 3 4 5 6 7 8
Ans. (ii) (i) (ii) (iii) (iii) (i) (i) (i) (ii) (iii) (iv)
Q. No. 9 10 11 12 13 14 15 16
Ans. (iii) (ii) (iii) (iii) (ii) (iii) (ii) (iii)
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42 Chemistry
EXERCISE-4 PREVIOUS YEARS QUESTION
1. Define conductivity for the solution of an electrolyte. Why does the conductivity of a solution
decreases with dilution ? [2] (CBSE 2022 Term - II)
Ans. Specific conductance/ Conductivity ( ) :-
1
It is defined as the reciprocal of specific resistance, =
R=
A
1
.
R A
G G*
Specific conductance = Conductance × Cell constant
Hence specific conductivity of a solution is defined as the conductance offered by 1 cm3 of
1 1
electrolytic solution. Unit of is ohm cm
The number of ions (responsible for carrying current) decreases when the solution is diluted. As
a result, the conductivity of a solution decreases with dilution.
2. (a) Calculate rG° and log KC for the following cell : (CBSE 2022 Term - II)
+ 2+
Ni(s) + 2Ag (aq) Ni (aq) + 2Ag(s)
Given that E ocell = 1.05 V, 1F = 96,500 Cmol–1 [3]
OR
(b) Calculate the e.m.f. of the following cell at 298 K.
Fe(s) | Fe2+(0.001 M) || H+(0.01 M) | H2(g) (1 bar) | Pt(s)
Given that E°cell = +0.44 V
[log 2 = 0.3010, log 3 = 0.4771, log 10 = 1] [3]
Ans. (a) r
G° = –nF E ocell [½]
= –2 × 96500 × 1.05
r
G° = –202.65 kJ mol–1 [½]
G° = –2.303 RT log KC [½]
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Go 202.65
log K C r
[½]
2.303RT 2.303 8.314 298
log KC = 35.54 Kc = antilog (35.54) = 3.47 × 1035 [1]
OR
o 0.0591 [Fe 2 ]
(b) Ecell E cell log [1]
2 [H ]2
0.0591 0.001
0.44V log [1]
2 (0.01) 2
0.0591
0.44V log10 0.41V [1]
2
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CBSE 43
3. Predict the products of electrolysis in each of the following : [1 × 2 = 2]
(a) An aqueous solution of CuSO4 with Pt electrode
OR
How many seconds does it require to reduce 3 moles of Fe3+ to Fe2+ with 2 A current ?
(Given : 1 F = 96500 C mol–1) [2]
Ans. (a) At anode : 2H2O( ) O2(g) + 4H+(aq.) + 4e– [½]
At Cathode : Cu+2 + 2e– Cu(s) [½]
Bubbles of O2 gas are formed at Anode & Copper deposited at Cathode.
(b) At Cathode : Ag+(aq.) + e– Ag(s) ; Eocell = 0.80 V
1
H+(aq.) + e– H2 (g); Eocell = 0V [½]
2
The value of Eocell is high (Ag ions have low discharge potential than H ions) then Ag ions
+ + +
deposited at cathode.
At Anode : Pt electrodes are inert, OH– ions have low discharge potential will be discharged in
preference to NO3– ions. OH– ions will de compose to give oxygen. [½]
4OH–(aq.) H2O( ) + O2(g) + 4e–
OR
Given, Current = 2.0 Ampere
3Fe3+ + 3e– 3Fe2+
Charge required = 3 Faraday = 3 × 96500 C = 289500 C [1]
We know, Charge = Current × Time
289500 144750
or Time = = 144750 sec. = min. = 2412.5min.
2 60
2412.5
= sec. = 40.20 sec. [1]
60
4. Conductivity of 0.002 M acetic acid is 8 × 10–5 S cm–1. Calculate its molar conductivity and degree of
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
dissociation ( ) if o
m for acetic acid is 390.5 S cm2 mol–1. (CBSE 2021 Compartment) [3]
Ans. = 8 × 10–5 Scm–1
C = 0.002 M or 0.002 mol L–1.
1000 5 1000
Molar conductivity ( m) = 8 10 40 Scm2 mol–1 [1]
C 0.002
40
Degree of dissociation ( ) = m
0
0.102 [1]
m 390.5
2
C 2
0.002mol L 1 0.102 0.002mol L 1 0.0104
Dissociation constant (Ka) =
1 1 0.102 0.898
–5 –1
Ka = 2.31 × 10 mol L . [1]
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44 Chemistry
5. Predict the change in molar conductivity with decrease in concentration.
(CBSE 2021 Compartment)
Ans. Molar conductivity increases with decrease in concentration. Because the total volume (V) of the
solution containing one mole of electrolyte also increases.
6. (a) Calculate rG° for the reaction (CBSE 2020)
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) [3 + 2 = 5]
o
Given: E cell for Zn /Zn = –0.76 and
2+
OR
(a) (i) Silver wire at 30ºC because as temperature decreases, resistance decreases so
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CBSE 45
7. (a) The conductivity of 0.001 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate the
0
dissociation constant if m for acetic acid is 390.5 S cm2 mol–1. [5]
(CBSE 2019)
(b) Write Nernst equation for the reaction at 25°C :
OR
(a) Represent the cell in which the following reaction takes place : [5]
(b) How does molar conductivity vary with increase in concentration for strong electrolyte and
0
weak electrolyte ? How can you obtain limiting molar conductivity ( m ) for weak electrolyte ?
0
0.126 [1]
m 390.5Scm 2 mol 1
2
c 2
0.001 mol L-2 0.126
1.8 10 4 mol L 1
[1]
1 1 0.126
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2
0.059 Al3
(b) Ecell E cell log 3
[1]
6 Cu 2
Example- Lead storage, Ni-Cd batteries (Or any other one example)
OR
(a) Al(s) | Al3+(0.01 M) || Ni2+(0.1 M) | Ni(s)
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46 Chemistry
2
0.059 Al3
E cell E cell log 3
[1]
6 Ni 2
2
0.059 0.01
E cell 1.41V log 3
[1]
6 0.1
8. (a) Write the cell reaction and calculate the e.m.f. of the following cell at 298 K: (CBSE 2018)
Sn (s) | Sn2+ (0.004 M) || H+ (0.020 M) | H2(g) (1 bar) | Pt (s) [3+2 = 5]
(Given : E0 0.14V )
Sn 2 /Sn
(a) For the reaction, 2AgCl(s) + H2 (g) (1 atm) 2Ag (s) + 2H+ (0.1 M) + 2Cl– (0.1 M),
GO = – 43600 J at 25°C.
Calculate the e.m.f. of the cell. [log 10–n = –n]
(b) Define fuel cell & write its two advantages.
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Ans. (a) Sn(s) |Sn2+ (0.004 M) || H+(0.020 M)| H2(g), 1 bar |Pt(s)
(given E0 0.14V )
Sn 2 /Sn
__________________
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CBSE 47
0.0591 [Sn 2 ]
Ecell Ecell log [1/2]
2 [H ]2
0.0591 0.004
0.14 log 0.11045 V [1/2]
2 [0.020]2
(b) (i) E° value of O2 is higher Cl2 but O2 will be liberated from H2O only when higher
voltage is applied. NaCl Na+ + Cl–
G nF E cell [1/2]
G ( 43600)
Ecell 0.23V [1/2]
nF 2 96500
0.0591
0.23 log (0.1)2 (0.1)2 [1/2]
2
0.0591
0.23 log (0.0001) [1/2]
2
0.0591
0.23 log (10)4
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2
= 0.23 + 0.1182 = 0.3482 V
E cell 0.35 V [1]
(b) The are galvanic cell that are designed to convert the energy of combustion of fuel like
hydrogen, methane, methanol directly into electrical energy. eg. : H2 – O2 Fuel cell [1]
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48 Chemistry
EXERCISE-5 MOCK TEST
1. What is meant by ‘limiting molar conductivity’ ? [1]
2. Define the Molar conductivity ( m
). [1]
3. Express the relation between the conductivity and the molar conductivity of a solution. [1]
4. Conductivity of CH3COOH decreases on dilution. Why ? [2]
5. Define electrochemical cell. What happens if external potential applied becomes greater than
Ecell of electrochemical cell ? [2]
6. Calculate r
Gº for the reactions [2]
7. On the basis of E cell cell values, O2 gas should be liberated at anode but it is Cl2 gas which is
9. How does molar conductivity vary with increase in concentration for strong electrolyte and weak
0
electrolyte ? How can you obtain limiting molar conductivity ( m ) for weak electrolyte ? [3]
2AgCl(s) + H2 (g) (1 atm) 2Ag (s) + 2H+ (0.1 M) + 2Cl– (0.1 M),
r
GO = – 43600 J at 25°C.
Calculate the e.m.f. of the cell.
[log 10–n = –n]
(b) Calculate the potential for half–cell containing
0.10 M K2Cr2O7 (aq), 0.20 M Cr3+ (aq) and 1.0 × 10–4 M H+ (aq)
The half–cell reaction is :
Cr2 O27 (aq) 14 H (aq) 6 e 2 Cr 3 (aq) 7H 2 O(l ), and the standard electrode potential
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CBSE 49
3. The relationship between conductivity (k) and molar conductivity of a solution is given by
k 1000
m
M
where C is molarity of concentration.
4. Conductivity changes as the concentration of electrolyte changes.
The conductivity will always decrease with decrease in the concentration because the no. of ions
per unit volume carrying current decreases on dilution. Hence, the conductivity of CH3COOH
decreases on dilution.
5. An electrochemical cell is a device in which chemical energy of the redox reaction is converted
into electrical energy. While electrolytic cell do the reverse.
e¯ flow from Cu to Zn and current flows from Zn to Cu.
6. G° = – nF E cell
r
= 40.9 + 349.6
m(CH3COOH) = 390.5 S cm2/mol
= m
0
m
= 39.05/390.5 = 0.1
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50 Chemistry
0
9. m decreases with increase in concentration for both strong & weak electrolyte m can be
obtained for weak electrolyte by applying Kohlrausch law.
10. Ag (s) | Ag+ (10–3 M) || Cu2+ (10–1 M) | Cu(s)
E cell = +0.46 V
Cell reaction is 2Ag(s) + Cu2+ (aq) 2Ag (aq) Cu (s)
2
0.0591 [Ag ]2 0.0591 10 3
Ecell = E cell – log E cell 0.46 log
2 [Cu2 ] 2 10 1
0.059 5
Ecell = 0.46 – log10
2
= 0.46 + .1477
E cell 0.6077 V
11. (a) 2AgCl (s) + H2(g) (1 atm) 2Ag(s) + 2H+ (0.1 M) + 2Cl¯(0.1M)
rG nF E cell
rG ( 43600)
Ecell 0.23 V
nF 2 96500
0.0591
0.23 log (0.1)2 (0.1)2
2
o 0.0591 [H | ]2 [C ]2
E cell E cell log10
n PH2
0.0591 0.0591 4
0.23 log (0.0001) 0.23 log 10 0.23 0.1182
2 2
= 0.23 + 0.1182 = 0.3482 V
E cell 0.35 V node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\03_Electrochemistry
0.0591 (0.2)2
E Cell 1.33 log 14
6 1.0 10 4 (0.1)
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CBSE 51
eg. 1 A + B C+D
A/c to Rate law Rate [A] [B]
eg. 2 aA + bB cC + dD
a,b,c,d are stoichiometric coefficients of reactants and products.
The rate expression, rate [A]x [B]y ....(i)
x, y can have any numerical value.
x, y may or may not be equal to the stoichiometric coefficient of reactant.
Eq.(i) can be written as
Rate = k[A]x [B]y ....(ii)
d[R]
or k[A]x [B]y . ...(iii)
dt
Eq. (iii) is known as differential rate equation.
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52 Chemistry
where k = Rate constant.
eg.1 2NO(g) + O2 (g) 2NO2(g)
2
Rate = k [NO] [O2]
d[R]
= k [NO]2 [O2]
dt
Order of reaction : The sum of powers of the molar concentration of the reactants in the rate
law expression is called the order of that chemical reaction. Order of reaction can be 0,1,2,3...
and even a fraction.
eg. Rate [A]x [B]y (experimental)
x y
Rate = k[A] [B] over all order of reaction n = x + y
Molecularity : The total number of molecules, atoms, ion taking part in the chemical reaction is
known as molecularity of reaction. If one, two, three molecules take part in the reaction then the
reaction are known as unimolecular, bimolecular, trimolecular respectively.
eg. H2O2 H2O + O2 unimolecular
H2 + I2 2HI bimolecular
Pseudo first order reaction : Such reaction whose order of reaction is one but molecularity are
different then it is called as pseudo first order reaction.
H
eg. Inversion of cane sugar : C12H22O11 + H2O C6 H 12 O6 C6H 12 O6
Glucose Fructose
Rate [C12H22O11]
order of reaction = 1 Molecularity = 1 + 1 = 2
Units of rate constant k : aA + bB Product
Rate = k[A]x [B]y x+y=n order of reaction
Rate concentration 1 (mol L–1 )1 n
k= = = = mol1–n Ln–1 s–1
x y time n sec.
[A] [B] (concentration)
n = order of the reaction
Reaction Order Units of Rate const.
Zero order 0 mol L–1s –1
First order 1 s–1
Second order 2 mol –1 L s–1
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Zero order reaction : Zero order reaction means that the rate of the reaction is proportional to
zero power of the concentration of reactant. Reactant (R) Product (P)
[R]0
[R] slope = – k
x Rate
slope = k
(t) t concentration
[R]0 - [R] x
[R]= – k t + [R]0 k= = x = kt Rate = k[R]0 or Rate = k
t t
y –mx c
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CBSE 53
Example of first order reactions :
1130K
(i) 2NH3(g) N2(g) + 3H2(g)
Pt
Au
(ii) 2HI(g) H2(g) + I2(g)
h
(iii) H2 + Cl2 2HCl
Half life of a reaction(t1/2) : The half life of a reaction is the time in which the concentration
of a reactant is reduced to one half of its initial concentration. It is represented as (t1/2).
Half life for zero order reaction :
t1/2
[R]0 slope = 1/2 k
t1/2 =
2K
concentration
[R]
0
t t concentration
Rate = k[R]1
2.303 [R]0 [R]0 kt or
n[R] = -kt + n[R]0 k= log10 or log =
t [R] [R] 2.303 Rate = k[R]
2.303 a
k= log10
t (a – x)
Example of first order reactions :
(i) C2 H 4 H 2 C2 H6 (g) ; Rate = k[C2H4]
(g) (g)
226 4 222
(ii) All radioactive reactions : 88 Ra 2 He 86 Rn Rate = k[Ra]
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1
(iii) Decomposition of N2O5 : N 2O5 2NO2 O2 Rate = k[N2O5]
(g) (g) 2
(g)
Half life for first order reaction :
t1/2
0.693 0.693
t1 = k
2 k
concentration
Rate expression for first order reaction in gas phase :
Let us consider a typical first order gas phase reaction -
A B C
(g) (g) (g)
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54 Chemistry
Let Pi be the initial pressure of A and Pt the total pressure at time t.
A B + C
(g) (g) (g)
at t = 0 Pi atm 0 atm 0 atm
At time t : (Pi – x) x x
If PA, PB, PC are the partial pressure of A, B and C respectively and Pt is total pressure.
PA 2Pi Pt
2.303 P 2.303 Pi
k log10 i k log10
t PA t 2Pi Pt
value is very high for gaseous reactions (1025 to 1028 Energy Barrier
[A.....B....C]
collisions/sec-cm3). Ea
Potential
Energy
A–B+C [A ....... B ....... C] A+B–C AB+C
(Reactant)
H
A+BC (product)
reactant Activated complex Product Reaction coordinates
Relation between rate constant of first order reaction and activation energy :
K = Ae –Ea /RT K = rate constant; A = pre-exponential factor; lnA
Reaction path t
with catalyst reaction path Fraction of This area shows fraction of additional
without catalys molecules molecules which react at (t + 10)
Potential energy
Reactant
Products Kinetic energy
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CBSE 55
reduce to 3g ?
2.303 [R]0 2.303 5
Ans. We know that for a 1st order reaction, t log 3
log
k [R] 1.15 10 3
2.303
= 3
0.2219 444.38s = 444 s
1.15 10
2. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the
decomposition is a first order reaction, calculate the rate constant of the reaction.
st 0.693
Ans. We know that for a 1 order reaction, t1/2 .
k
It is given that t1/2 = 60 min
0.693 0.693 –1 –2 –1
k = = 0.01155 min = 1.155 × 10 min
t1/ 2 60
3. The rate of the chemical reaction doubles for an increase of 10K in a absolute temperature from
298K. Calculate Ea.
Ans. It is given that T1=298 K T2=(298 + 10) K = 308 K
We also know that the rate of the reaction doubles when temperature is increased by 10°.
Therefore, let us take the value of k1= k and that of k2=2k
Also, R = 8.314 J K–1 mol–1
k2 Ea T2 T1
Now, substituting these values in the equation : log
k1 2.303R T1T2
2k Ea 10
We get : log
k 2.303 8.314 298 308
Ea 10
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log 2
2.303 8.314 298 308
2.303 8.314 298 308 log 2
Ea = 52897.78 J mol–1 = 52.9 kJ mol–1
10
4. The decomposition of N2O5 in CCl4 at 318 K has been studied by monitoring the concentration
of N2O5 in the solution. Initially the concentration of N2O5 is 2.33 mol L–1 and after 184 minutes.
it is reduced to 2.08 mol L–1. The reaction takes place according to the equation
2N 2 O 5 (g) 4NO 2 (g) O2 (g)
Calculate the average rate of this reaction in terms of hours minutes and seconds. What is the
rate of production of NO2 during this period ?
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56 Chemistry
= 6.79 × 10–4 mol L–1/min = (6.79 × 10–4 mol L–1 min–1) × (60 min/1h)
= 4.07 × 10–2 mol L–1/h = 6.79 × 10–4 mol L–1 × 1 min/60s = 1.13 × 10–5 mol L–1s–1
1 [NO 2 ]
It may be remembered that, Rate =
4 t
[NO2 ] 4
6.79 10 4 mol L 1 min 1
2.72 10 3 min 1
t
5. The following data were obtained during the first order thermal decomposition of N2O5(g) at
give two moles of N2O4(g) and one mole of O2(g), the pressure of N2O4(g) increases by 2x atm
and that of O2 (g) increases by x atm.
x pt 0.5
2.303
0.0216 4.98 10 4 s 1
100s
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CBSE 57
6. Show that in a first order reaction, time required for completion of 99.9% is 10 times of half-life
(t1/2) of the reaction.
2.303 [R]0
k log
t [R]
2.303 [R]0 2.303
log log103
t [R]0 0.999[R]0 t
t = 6.909/k
For half-life of the reaction, t1/2 = 0.693/k
t 6.909 k
10
t1/ 2 k 0.693
7. The first order rate constant for the decomposition of ethyl iodide by the reaction
at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol. Calculate the rate constant of
the reaction at 700 K.
Ans. We know that
Ea 1 1
log k 2 log k1
2.303R T1 T2
Ea 1 1
log k 2 log k1
2.303R T1 T2
209000 J mol L 1 1 1
log(1.60 10 5 )
2.303 8.314 J mol L 1K 1
600K 700K
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58 Chemistry
EXERCISE-2 NCERT EXERCISE
2 –6 –2 2 –1
1. For the reaction : 2A + B A2B the rate = k [A][B] with k = 2.0 × 10 mol L s . Calculate the
–1 –1
initial rate of the reaction when [A] = 0.1mol L . [B] = 0.2 mol L . Calculate the rate of
–1
reaction after [A] is reduced to 0.06 mol L .
Ans. The initial rate of the reaction is
2 –6 –2 2 –1 –1 –1 2 –9 –1 –1
Rate = k[A][B] = (2.0 × 10 mol L s ) (0.1 mol L ) (0.2 mol L ) = 8.0 × 10 mol L s .
–1 –1
when [A] is reduced from 0.1 mol L to 0.06 mol L , the concentration of A reacted = (0.1 – 0.06)
–1 –1
mol L = 0.04 mol L
1
Therefore, concentration of B reacted = 0.04 mol L 1 0.02 mol L 1
2
–1 –1
Then, concentration of B available, [B] = (0.2 – 0.02) mol L = 0.18 mol L
–1
After [A] is reduced to 0.06 mol L , the rate of the reaction is given by.
2 –6 –2 2 –1 –1 –1 2 –9 –1 –1
Rate = k [A][B] = (2.0 × 10 mol L s ) (0.06 mol L ) (0.18 mol L ) = 3.88 × 10 mol L s .
2. The decomposition of NH3 on platinum surface is zero order reaction. What are the rate of
–4 –1 –1
production of N2 and H2 if k = 2.5 × 10 mol litre s .
3. The following results have been obtained during the kinetic studies of the reaction :
2A + B C+D
Experiment A/mol L–1 B/mol L–1 Initial rate of formation of D/mol L–1
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–2
III 0.3 0.4 2.88 × 10–1
IV 0.4 0.1 2.40 × 10–2
Determine the rate law and the rate constant for the reaction.
Ans. Let the order of the reaction with respect to A be x and with respect to B be y.
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CBSE 59
Therefore, rate of the reaction is given by,
x y
Rate = k[A] [B]
According to the question,
–3 x y
6.0 × 10 = k[0.1] [0.1] ...(i)
–2 x y
7.2 × 10 = k[0.3] [0.2] ...(ii)
–1 x y
2.88 × 10 = k[0.3] [0.4] ...(iii)
–2 x y
2.40 × 10 = k[0.4] [0.1] ...(iv)
2
2.4 10 k[0.4]x [0.1]y
Dividing equation (iv) by (i), we obtain 3
6.0 10 k[0.1]x [0.1]y
x
[0.4]x 0.4 1
4 4 4 4x x 1
[0.1]x 0.1
Dividing equation (iii) by (ii), we obtain
2.88 10 1 k[0.3]x [0.4]y
7.2 10 2 k[0.3]x [0.2]y
y
0.4
4 4 2y 22 2y y 2
0.2
Therefore, the rate law is
2
Rate = k[A] [B]
Rate
k
[A][B]2
From experiment I, we obtain
6.0 10 3 mol L 1 min 1
k 2
6.0 L2 mol 2 min 1
1 1
0.1mol L 0.1mol L
2.88 10 1 m ol L 1 min 1
from exp. III, we obtain, k 2
= 6.0 L2 mol–2 min–1.
0.3mol L 1 0.4mol L 1
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60 Chemistry
14
4. The half life for radioactive decay of C is 5730 years. An archaeological artifact contained
14
wood had only 80% of the C found in a living tree. Estimate the age of the sample.
0.693 0.693 1
Ans. Here, k years
t2 5730
2.303 a
t= log
k (a x)
14
t1/2 of C = 5730 yr ; Also, a = 100, (a - x) = 80
Hence, the time required for 99% completion of a first order reaction is twice the time required
for the completion of 90% of the reaction.
7. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Ans. For a first order reaction,
2.303 [R]0
t log
k [R]
2.303 100 2.303 10 3 1
k log log 8.918 10 min
40 min 100 30 40 min 7
Therefore, t1/2 of the decomposition reaction is
0.693 0.693
t1/ 2 min 77.7 min (approx)
k 8.918 10 3
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CBSE 61
8. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume.
SO2Cl2(g) SO2(g) + Cl2(g)
Experiment Times/s–1 Total pressure/atm
1 0 0.5
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
Ans. The thermal decomposition of SO2Cl2 at a constant volume is represented by the following
equation.
SO2Cl2(g) SO2(g) + Cl2(g)
At t = 0 Pi 0 0
At t = t Pi – x x x
After time, t, total pressure, Pt = (Pi – x) + x + x
Pt = Pi + x x = Pt – P i
Therefore, Pi – x = Pi – (Pt – Pi) = 2Pi – Pt
2.303 P 2.303 Pi
For a first order reaction, k log i log
t Pi x t 2Pi Pi
2.303 0.5
When t = 100 s, k log 2.231 10 3 s 1
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62 Chemistry
10. The decomposition of A into product has value of k as 4.5 × 103 s–1 at 10°C and energy of
activation 60 kJ mol–1. At what temperature would k be 1.5 × 104 s–1 ?
k2 Ea T2 T1
Ans. From Arrhenius equation, we obtain, log
k1 2.303R T1T2
T2 283
0.5229 3133.627
283T2
0.5229 283T2
T2 283
3133.627
0.9528 T2 = 283
0.1054 0.2877 k2
2.73
k1 k 2` k1
k2 Ea T2 T1
log
k1 2.303 R T1T2
Ea 308 298
log 2.73
2.303 8.314 298 308
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CBSE 63
12. 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.
k2 Ea T2 T1
Ans. From Arrhenius equation, we obtain, log
k1 2.303R T1T2
It is given that, k2 = 4k1
T1 = 293 K
T2 = 313 K
4k1 Ea 313 293
Therefore, log
k1 2.303 8.314 293 313
20 Ea
0.6021
2.303 8.314 293 313
0.6021 2.303 8.314 293 313
Ea = 52863.33 J mol–1 = 52.86 kJ mol–1
20
Hence, the required energy of activation is 52.86 kJ mol–1
13. What is the effect of adding a catalyst on :
(a) Activation energy (Ea), and (b) Gibbs energy ( G) of a reaction ?
Ans. (a) Decreases
(b) No change
14. A first order reaction takes 20 minutes for 25% decomposition. Calculate the time when 75% of
the reaction will be completed.
(Given : log 2 = 0.3010, log 3 = 0.4771, log 4 = 0.6021)
Ans. t 2.303 [A]0
log
k [A]
2.303 100 ...(i)
20 min log
k 75
2.303 100 ...(ii)
t log
k 25
Divide (i) equation by (ii)
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
2.303 00
log
20 k 75 log 4 / 3
t 2.303 00 log 4
log
k 25
20/t = 0.1250/0.6021
t = 96.3 min
15. For a reaction : 2NH3(g) Pt N2(g) + 3H2(g)
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k.
Ans. (i) zero order , bimolecular
(ii) mol L–1 s–1
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64 Chemistry
16. The rate constant for the first order decomposition of H2O2 is given by the following equation :
1.0 10 4 K
log k 14.2
T
Calculate Ea for this reaction and rate constant k if its half-life period be 200 minutes.
(Given : R = 8.314 JK–1 mole–1)
Ea / 2.303 RT = 1 × 104 k/ T
Ea =1.0 × 104 × 2.303 × 8.314
=191471.4 J/mol
17. For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained :
t/s 0 30 60
1
[CH 3COOCH3 ]mol L 0.60 0.30 0.15
(i) Show that it follows pseudo first order reaction as the concentration of water remains
constant.
(ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds
Ans. (i) A0 = 0.60 A = 0.30 when t = 30s
2.303 [A ]
k log 0
t [A]
2.303 0.60
k log
30 0.30 node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
2.303 2.303
k log 2 0.3010
30 30
0.693 1
k 0.231 s
30
When A0 = 0.60
A = 0.15 when t = 60s
2.303 0.60
k log
t 0.15
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CBSE 65
2.303 0.60 [1/2]
k log
60 0.15
2.303 2.303
k log 4 0.6021
60 60
1.3866 1 [1]
k 0.231s
60
As for both cases k is approximately same reaction is of pseudo first order
(ii) Average rate during the interval 30 – 60 sec = Change in concentration [1/2]
Change in time
0.15 0.30 [1/2]
60 30
0.15 [1/2]
0.005 mol L 1S 1
30
18. (a) For a reaction A + B P, the rate is given by
Rate = k [A]2 [B]
(i) How is the rate of reaction affected if the concentration of A is doubled ?
(ii) What is the overall order of reaction if B is present in large excess ?
(b) A first order reaction taken 23.1 minutes for 50% completion. Calculate the time required
for 75% completion of this reaction.
(Given : log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)
Ans. (a) (i) Rate increases by 4 times [1]
(ii) 2nd order [1]
(b) Reaction is 50% completed in 23.1 min i.e. Half-life is 23.1 min
0.693
k
t1/2
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
0.693 1 [1]
0.03 min
23.1
2.303 [A ] [1]
k log 0
t [A]
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66 Chemistry
EXERCISE-3 RACE
Type 1 : Passage question 1 :-
Rate [A]x [B]y
This form of equation is known as differential rate equation, where k is a proportionality
constant called rate constant. The equation like which relates the rate of a reaction to
concentration of reactants is called rate law or rate expression. Thus, rate law is the expression
in which reaction rate is given in terms of molar concentration of reactants with each term
raised to some power, which may or may not be same as the stoichiometric coefficient of the
reacting species in a balanced chemical.
(a) Identify the reaction order from each of the following rate constant. k = 2.3 × 10–5 L mol–1 s–1
(i) first order (ii) zero order (iii) second order (iv) pseudo first order
(b) For a reaction, A + B Product; the rate law is given by, r = k [ A]1/2 [B]2 . What is the order.
of the reaction ?
(i) 1.5 (ii) 2.5 (iii) 2.0 (iv) 0
(c) The slope in the plot of ln [R] v/s time gives
k k
(i) + k (ii) (iii) – k (iv)
2.303 2.303
(where [R] is the final concentration of reactant)
(d) The unit of rate constant is:
(i) (conc.)1–n time–1 (ii) (conc.)n time–1
(iii) (conc.)n–1 time–1 (iv) (conc.)1–n time
Type 2 : Assertion and Reason :-
Question 2 to 6 Note :- In the following questions a statement of assertion followed by a
reason. choose the correct answer out of the following choices –
(i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
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CBSE 67
4. Assertion : The rate constant of a zero order reaction has same units as the rate of reaction.
Reason : Rate constant of a zero order reaction does not depend upon the units of concentration.
5. Assertion : Half life period of a reaction of first order is independent of initial concentration.
2.303
Reason : Half life period for a first order reaction t1/ 2 log 2 .
k
6. Assertion : An increase in surface area increases the rate of reaction.
Reason : Stronger the intermolecular attractive forces, faster is the rate of reaction.
Type 3 : Multiple choice question (one correct answer) (Questions 7 to 16):-
7. Which of the following statements is not correct about order of a reaction.
(i) The order of a reaction can be a fractional number.
(ii) Order of a reaction is experimentally determined quantity.
(iii) The order of a reaction is always equal to the sum of the stoichiometric coefficients of
reactants in the balanced chemical equation for a reaction.
(iv) The order of a reaction is the sum of the powers of the molar concentration of the reactants
in the rate law expression.
8. Which of the following statement is correct ?
(i) The rate of a reaction decreases with passage of time as the concentration of reactants decreases.
(ii) The rate of a reaction is same at any time during the reaction.
(iii) The rate of a reaction is independent of temperature change.
(iv) The rate of a reaction decreases with increase in concentration of reactant(s).
9. Rate law for the reaction A + 2B C is found to be : Rate = k [A][B]
Concentration of reactant ‘B’ is doubled, keeping the concentration of ‘A’ constant, the value of
rate constant will be______.
(i) the same (ii) doubled (iii) quadrupled (iv) halved
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
10. A first order reaction is 50% completed in 1.26 × 1014 s. How much time would it take for 100%
completion ?
(i) 1.26 × 1015 s (ii) 2.52 × 1014 s
(iii) 2.52 × 1028 s (iv) infinite
11. The value of rate constant of a pseudo first order reaction ____________.
(i) depends on the concentration of reactants present in small amount.
(ii) depends on the concentration of reactants present in excess.
(iii) is independent of the concentration of reactants.
(iv) depends only on temperature
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68 Chemistry
12. Which of the following statement is applicable to a balanced chemical equation of an elementary
reaction ?
(i) Order is same as molecularity.
(ii) Order is less than the molecularity.
(iii) Order is greater than the molecularity.
(iv) Molecularity can be zero.
13. At high pressure the following reaction is zero order,
1130 K
2NH 3 (g) Platinum catalyst
N 2 (g) 3H 2 (g)
k
t1/2 t1/2 slope =
2.303
Molar
[R]0
(i) (ii) (iii) (iv) log
[R]
[R]0 [R]0 Time
Time
16. Rate law can be determined from balanced chemical equation if _______.
(i) reverse reaction is involved.
(ii) it is an elementary reaction.
(iii) it is a sequence of elementary reactions.
(iv) any of the reactants is in excess.
ANSWER–KEY
Q. No. 1 (a) (b) (c) (d) 2 3 4 5 6 7 8
Ans. (iii) (ii) (iii) (i) (ii) (iv) (i) (i) (iii) (iii) (i)
Q. No. 9 10 11 12 13 14 15 16
Ans. (ii) (iv) (ii) (i) (ii) (iv) (ii) (ii)
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CBSE 69
2.303 6
t= 3
log [½]
2 10 2
t = 549.38 sec. [½]
OR
0.693
t1/2 [1]
k
0.693
k= [1]
6930
k = 10–4 year–1 [1]
2.303 100
t= 4 1
log [1]
10 year 75
t 496 years [1]
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70 Chemistry
2. A biochemical reaction was carried out in the absence of enzyme and the rate of reaction was
found to be 10–6 min–1. If the same reaction is now carried out in the presence of enzyme, then the
Ea for the reaction will be : [1]
(A) same
Ans. (D)
3. Define rate constant and give the mathematical relation between rate constant and half–life
period for a first order reaction. [2]
(CBSE 2021 Compartment)
Ans. Rate constant :
In a chemical reaction –
n1A + n2B m1C + m2D
according to law of mass action
n1 n2
Rate k A B
but according to rate law (experimental concept)
Rate = k[A]x[B]y
if [A] = [B] = 1 mol/L
then, Rate = k
Rate of reaction at unit concentration of reactants is called as rate constant or specific reaction rate. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
Rate constant does not depend on concentration of reactant but it depends on temperature and
catalyst. [1]
Half-life Period for first order reaction : The time in which half of the initial amount of
reactant is consumed.
At t = t1/2 ; x = a/2 ; a–x = a/2
1 a n2 2.303 0.693
t1/2 = n or t1/2 = = (log2) or t1/2
k a/2 k k k
0.693
k [1]
t1/2
Half-life period for first order reaction is independent of the initial concentration of reactant.
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CBSE 71
4. A first order reaction has a rate constant 4.9 × 10–3 s–1. How long will 4 g of this reactant take to
reduce to 3 g ? [log 4 = 0·6020, log 3 = 0·4771. [3]
OR
The hydrolysis of sucrose is represented by the following chemical equation :
C12H22O11 + H2O (excess) C6H12O6 + C6H12O6
For the above equation, predict
(a) molecularity,
(b) order, and
(c) rate of reaction in terms of all the reactants and products. [1 × 3 = 3]
(CBSE 2021 Compartment)
2.303 [R]0
Sol. t log [½]
k [R]
2.303 4
3 1
log [½]
4.9 10 s 3
= 0.47 × 103 (log 4 – log 3} = 0.47 × 103 (0.6020 – 0.4771) [½]
3 3
= 0.47 × 10 × 0.125 = 0.0587 × 10 = 58.7 sec [½]
OR
d[C12 H 22 O11 ] d[H 2 O] d(C6 H12 O6 ) d(C6 H12 O6 )
(a) 2 (b) 1 (c) Rate
dt dt dt dt
5. Will the rate constant of the reaction depend upon T if the Ea (activation energy) of the reaction
is zero ? [1] (CBSE 2020)
Ans. No.
6. Assertion (A): The molecularity of the reaction H2 + Br2 2HBr [2] (CBSE 2020)
Reason (R) : Two molecules of the reactants are involved in the given elementary reaction.
Ans. (i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of the Assertion (A).
7. Analyse the given graph, drawn between concentration of reactant vs. time: [1 × 2 = 2]
(CBSE 2020)
1.6
Concentration of reactant
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
0.8
0.4
0.2
0 10 20 30
time
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72 Chemistry
8. How will the rate of the reaction of affected when (CBSE 2020)
(a) Surface area of the reactant is reduced,
(b) Catalyst is added in a reversible reaction, and
(c) Temperature of the reaction is increased ? [3]
Ans. (a) Decreases (b) Increases (c) Increases
9. Define order of reaction. Predict the order of reaction in the given graphs : [2]
[R]0 [R]0
where [R]0 is the initial concentration of reactant and t1/2 is half-life.
Ans. It is defined as the sum of powers to which the concentration terms are raised in the rate law
equation.
(a) First order (b) zero order
10. The following data were obtained for the reaction : [3]
A + 2B C (CBSE 2019)
(a) Find the order of reaction with respect to A and B. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
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CBSE 73
11. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K.
Calculate the activation energy of the reaction. (Given : log 2 = 0.3010, log 4 = 0.6021,
R = 8.314 JK–1 mol–1). (CBSE 2018)
2.303 100 2.303
Ans. T1 = 300 K ; K1 log log 2 0.0575 0.3010 0.0173 [1/2]
t1 100 50 40
2.303 2.303
T2 = 320 K ; K 2 log 2 log 2 0.1151 0.3010 0.0346 [1/2]
t2 20
K2 Ea T2 T1
log [1]
K1 2.303R T1T2
[NO 2 ]
(given 2.8 10 3 M / sec. or M sec–1)
t
Rate of the Reaction
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\PC\04_Chemical Kinetics
1 [N 2 O 5 ] 1 [NO2 ] [O 2 ]
[1/2]
2 t 4 t t
1 [N 2 O5 ] 1 [NO 2 ]
[1/2]
2 t 4 t
[N 2 O5 ] 2 [NO 2 ]
t 4 t
1 3
2.8 10 M sec–1 [1/2]
2
[N 2O 5 ] 3
1.4 10 M sec–1 or M/sec. [1/2]
t
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74 Chemistry
(R)
11. The decomposition of phosphine, (PH3) proceeds according to the following equation: [5]
4 PH3 (g) P4 (g) + 6 H2 (g)
It is found that the reaction follow the following rate equation:
Rate = k [PH3]
The half-life of PH3 is 37.9 s at 120ºC.
(i) How much time is required for 3/4th of PH3 to decompose?
(ii) What fraction of the original sample of PH3 remains behind after 1 minute?
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CBSE 75
0.693 0.693
8. t1/2 = = 0.126 × 1014 sec.
k 5.5 10 14
9. 2NH3 N2 + 3H2
1 d NH 3 d N2 1 d[H 2 ]
Rate of reaction (r) = – =
2 dt dt 3 dt
Rate (r) = k[NH3]° = k ( zero order reaction) = 2.5 × 10–4
d N2
= r = 2.5 × 10–4 mol lit–1s–1
dt
d H2
= 3r = 3 × 2.5 × 10–4 = 7.5 × 10–4 mol lit–1 sec–1
dt
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76 Chemistry
2.303 a
10. t= log t1/2 of 14C = 5730 yr
k (a x)
0.693 –1
k= yr Also a = 100, (a – x) = 80
5730
2.303 5730 100 10
t= log 19042 log
0.693 80 8
19042 × {log 10 – log 8} 19042 × {1– 0.9030}
19042 × 0.097 = 1847 years
11. (i) Here t1/2 = 37.9 s
Let initial concentration = a
3
x a
4
2.303 a
Using the formula, t log
k a x
2.303 a 0.693 t1/2 a
t log k t 2.303 log
0.693 3 t1/2 0.693 1
a a a
t1/ 2 4 4
2.303 t1/2 2.303 t1/2 2 log 2 2.303 37.9 2 0.3010
t log 4 t [ t1/2 = 37.9s]
0.693 0.693 0.693
52.544
75.82 sec.
0.693
(ii) Here, t = 1 min = 60s and t1/2 = 37.9s
2.303 [R]0 0.693
Using the formula, t log and k
k [R] t1/ 2
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CBSE 77
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
La Hf Ta W Re Os Ir Pt Au Hg
Zn Cd Hg
Melting point (data based)
Half filled d5
weak metallic bond
Fully filled d10
weak metallic bond
Cu Ag Au
(iii) Metallic character : They are solid, hard, ductile, malleable, good conductor of heat and
electricity and exhibit metallic lusture, high tensile strength. Hg is liquid
Elect. cond. Ag Cu Au Al
p block
d block
In transition metals, left to right net nuclear charge increases due to poor shielding effect. Due to
this, the atomic and ionic radii for transition elements for a given series show a decreasing trend
for first five elements and then becomes almost constant for next five elements of the series.
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78 Chemistry
(v) Enthalpies of Atomisation
Transition elements exhibit higher enthalpies of atomization because of large number of unpaired
electrons in their atoms. They have stronger interatomic interaction and hence, stronger bond.
(vi) Ionisation Enthalpies
• In a series from left to right, ionization enthalpy increases due to increase in nuclear
charge.
• The irregular trend in the first ionization enthalpy of the 3d metals, though of little
chemical significance, can be accounted for by considering that the removal of one electron
alters the relative energies of 4s and 3d orbitals.
(vii) Oxidation States
Transition metals shows variable oxidation state due to two incomplete outermost shells. Only
stable oxidation states of the first row transition metals are Sc(+3), Ti(+4), V(+5), Cr(+3, +6),
Mn(+2, +7), Fe(+2, +3), Co(+2, +3), Ni(+2), Cu(+2), Zn(+2)
• Some more stable oxidation states of d-block elements
Cu +2 Mn +2 Pt +4 Ag +1
Cr +3 Sc +3 Au +3 Ni +2
• Common oxidation states
Ti(+4), V(+5) Cr(+3,+6) Mn(+2,+4,+7)
Fe(+2, +3), Co(+2,+3) Ni (+2) Pt (+2+4)
• In p-block lower oxidation states of heavier elements are more stable while in d-block
heavier element, higher oxidation state are more stable.
eg. In VIB gp Mo(+6) & W(+6) are more stable than Cr(+6)
(viii) Trends in the Standard Electrode Potentials node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\08_D & F block
• Transformation of the solid metal atoms to M2+ ions in solution and their standard electrode
potentials.
• If sum of the first and second ionization enthalpies is greater than hydration enthalpy
standard potential will be positive and reactivity will be lower and vice-versa.
(ix) Trends in Stability of Higher Oxidation States
The higher oxidation numbers are achieved in TiX4, VF5 and CrF6. The + 7 state for Mn is not
represented in simple halides but MnO3F is known and beyond Mn no metal has a
trihalide except FeX3 and CoF3 and increasing order of oxidizing power in the series
VO2+ < Cr2O72– < MnO4.
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CBSE 79
(x) Magnetic Properties
• When a magnetic field is applied to substances, mainly two types of magnetic behavior are
observed : diamagnetism and paramagnetism. Paramagnetism due to presence of unpaired
electrons, each such electron having a magnetic moment associated with its spin angular
momentum.
• The magnetic moment is determined by the number of unpaired electrons.
Magnetic moment = n(n 2)
Coloured – Fe3+ yellow , Fe2+ green, Cu2+ blue, Co3+ blue & vacant d-orbitals etc
(xii) Formation of Complex Compounds
• Transition metals have small size high nuclear charge which facilitates the acceptance of
lone pair of electron from ligands.
(xiii) Catalytic Properties
• Transition metals have two outermost shells incomplete and ability to adopt multiple
oxidation states and to form complexes, therefore used as a catalyst.
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• Transition metals also provide larger surface area for the reactant to be adsorbed.
(xiv) Formation of Interstitial Compounds
• Small size of non-metals (H, C, N) fit into the voids of crystalline solid of transition metals
and form interstitial compounds.
(xv) Alloy Formation
• Alloy is the homogeneous mixture of two or more metals. Transition metals have
approximate same size therefore, in molten form they can fit to each other crystalline
structure and form homogeneous mixture and form the alloy.
E.g., Brass (copper-zinc) and bronze (copper-tin) etc.
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Atomic radius
3d series Sc > Ti > V> Cr >Mn Fe CO Ni Cu < Zn
Smallest radius – Ni
e.g.% Ti < Zr Hf
Largest radius – La
Zn, Cdm Hg of group 12 have full d10 configuration in their ground state as well as in their
common oxidation states thus, they are not regarded as transition metals.
Cu+ is unstable in aqueous solution and undergoes disproportionation.
+
2Cu Cu 2 Cu; Cu 2 is more stabe than Cu due to much more (-) ve H (hydration) of
Cu2+ (aq) than Cu+. This is more than requires to compensate high lE2 of Cu.
Transition elements exhibit colour due to d-d transition, structure defects and charge transfer.
Electrons of lower energy level of d-orbital absorb energy from visible region for excitation to
higher level.
The Inner Transition Elements (f-Block)
The f-block consists of the two series, lanthanoids and actinoids. Lanthanoids are known as rare
earth metals and actinoids are known as radioactive elements (Th to Lr).
Lanthanoids
General characteristics
General configuration [Xe] 4f1–14, 5d0–1, 6s2.
Atomic and ionic size from left to right, decreases due to increase in nuclear charge. This is
known as lanthanoid contraction.
Oxidation states Ce4+; (Some elements) is favoured by its noble gas conguration, but it is
a strong oxidant reverting to the common + 3 state.
Lanthanoid are very reactive metals like alkaline earth metals.
+O2
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M2O 3
+N2
MN
+S
M
Lanthanide metal +C MC2
(M) +X MX3
+H2O M(OH)3+H2
Misch metals, contain lanthanoids about 90-95% (Ce 40-5%, Lanthanum and neodymium
44%) iron 4.5%, calcium, carbon and silicon about 10.5% are used in cigarette and gas
lighters, toys, tank and tracer bullets.
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7. Explain why Cu+ ion is not stable in aqueous solutions ?
Ans. In an aqueous medium, Cu2+ is more stable than Cu+. This is because although energy is required
to remove one electron from Cu+ to Cu2+, high hydration energy of Cu2+ compensates for it.
Therefore, Cu+ ion in an aqueous solution is unstable. It disproportionates to give Cu2+ and Cu.
8. Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Ans. In actinoids, 5f orbitals are filled. These 5f orbitals have a poorer shielding effect than 4f orbitals
(in lanthanoids). Thus, the effective nuclear charge experienced by electrons in valence shells in
case of actinoids is much more that that experienced by lanthanoids. Hence, the size contraction
in actinoids is greater as compared to that in lanthanoids.
9. On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is
not ?
Ans. On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state (3d1),
it is regarded as a transition element. On the other hand, zinc atom has completely filled
d orbitals (3d10) in its ground state as well as in its oxidised state, hence it is not regarded as a
transition element.
10. Why do the transition elements exhibit higher enthalpies of atomisation ?
Ans. Because of large number of unpaired electrons in their atoms they have stronger interatomic
interaction and hence stronger bonding between atoms resulting in higher enthalpies of
atomisation.
11. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration ?
Ans. Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t2g level.
On the other hand, the change from Mn2+ to Mn3+ results in the half-filled (d5) configuration
which has extra stability.
12. How would you account for the increasing oxidising power in the series
VO2 Cr2 O27 MnO 4 ?
Ans. This is due to the increasing stability of the lower species to which they are reduced.
13. For the first row transition metals the Eo values are :
Eo V Cr Mn Fe Co Ni Cu
(M2+/M) –1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34
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The non-transition elements either do not have a d- orbital or have a fully filled d-orbital.
Therefore, the electronic configuration of non-transition elements is ns1-2 or ns2 np1-6.
5. Explain giving reasons :
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
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Ans. (i) Transition metals show paramagnetic behaviour. Paramagnetism arises due to the presence
of unpaired electrons with each electron having a magnetic moment associated with its spin
angular momentum and orbital angular momentum.
(ii) Transition elements have high effective nuclear charge and a large number of valence
electrons. Therefore, they form very strong metallic bonds. As a result, the enthalpy of
atomization of transition metals is high.
(iii) Due to d-d transition.
(iv) The catalytic activity of the transition elements can be explained by two basic facts.
(a) Owing to their ability to show variable oxidation states and form complexes,
transition metals form unstable intermediate compounds. Thus, they provide a new
path with lower activation energy, Ea, for the reaction.
(b) Transition metals also provide a suitable surface for the reactions to occur.
6. What are interstitial compounds ? Why are such compounds well known for transition metals ?
Ans. Transition metals are large in size and contain lots of interstitial sites. Transition elements can
trap atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites
of their crystal lattices. The resulting compounds are called interstitial compounds.
7. Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate ?
Ans. Potassium dichromate is prepared from chromite ore (FeCr2O4) in the following steps.
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8. Compare the chemistry of actinoids with that of the lanthanoids with special reference to :
(i) electronic configuration (ii) atomic and ionic sizes
(iii) oxidation state (iv) chemical reactivity.
Ans. (i) Electronic configuration : The general electronic configuration for lanthanoids is [Xe]54 4f1-14
5d0-1 6s2 and that for actinoids is [Rn]86 5f1-14 6d0-1 7s2.
(ii) Atomic and Ionic sizes : Similar to lanthanoids, actinoids also exhibit actinoid contraction
(overall decrease in atomic and ionic radii). The contraction is greater due to the poor shielding
effect of 5f orbitals.
(iii) Oxidation states : The principal oxidation state of lanthanoids is (+3). However, sometimes
we also encounter oxidation states of +2 and +4. This is because of extra stability of fully-filled
and half-filled orbitals. Actinoids exhibit a greater range of oxidation states. This is because the
5f, 6d, and 7s levels are of comparable energies.
(iv) Chemical reactivity : In the lanthanide series, the earlier members of the series are more
reactive. They have reactivity that is comparable to Ca. With an increase in the atomic number,
the lanthanides start behaving similar to Al. Actinoids, on the other hand, are highly reactive
metals, especially when they are finely divided.
9. How would you account for the following :
(i) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is strongly oxidising.
(ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is
easily oxidised.
(iii) The d1 configuration is very unstable in ions.
2+ 4
Ans. (i) Cr is strongly reducing in nature. It has a d configuration. While acting as a reducting
agent, it gets oxidized to Cr3+ (electronic configuration, d3). This d3 configuration can be
written as t 32g configuration, which is a more stable configuration. In the case of Mn3+ (d4),
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it acts as an oxidizing agent and gets reduced to Mn2+ (d5). This has an exactly half- filled
d-orbital and is highly stable.
(ii) Co(II) is stable is aqueous solutions. However, in the presence of strong field complexing
reagents, it is oxidized to Co(III). Although the 3rd ionization energy for Co is high, but the
higher amount of crystal field stabilization energy (CFSE) released in the presence of
strong field ligands overcomes this ionization energy.
(iii) The ions in d1 configuration tend to lose one more electron to get into stable d0
configuration. Also, the hydration or lattice energy is more than sufficient to remove the
only electron present in the d-orbital of these ions. Therefore, they act as reducing agents.
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86 Chemistry
10. What is meant by 'disproportionation' ? Give two examples of disproportionation reaction in
aqueous solution.
Ans. It is found that sometimes a relatively less stable oxidation state undergoes an oxidation - reduction
reaction in which it is simultaneously oxidised and reduced. This is called disproportionation.
For example,
11. Give examples and suggest reasons for the following features of the transition metal chemistry :
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
Ans. (i) In the case of a lower oxide of a transition metal, the metal atom has a low oxidation state.
This means that some of the valence electrons of the metal atom are not involved in
bonding. As a result, it can donate electrons and behave as a base.
On the other hand, in the case of a higher oxide of a transition metal, the metal atom has a
high oxidation state. This means that the valence electrons are involved in bonding and so,
they are unavailable. There is also a high effective nuclear charge.
For example, MnIIO is basic and Mn 2VII O 7 is acidic. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\08_D & F block
(ii) Oxygen and fluorine act as strong oxidising agents because of their high electronegatives
and small sizes. Hence, they bring out the highest oxidation states from the transition
metals. In other words, a transition metal exhibits higher oxidation states in oxides and
fluorides. For example, in OsF6 and V2O5, the oxidation states of Os and V are +6 and +5
respectively.
(iii) Oxygen is a strong oxidising agent due to its high electronegativity and small size. So,
oxo-anions of a metal have the highest oxidation state. For example, in MnO4–, the
oxidation state of Mn is +7.
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12. What are alloys ? Name an important alloy which contains some of the lanthanoid metals.
Mention its uses.
Ans. An alloy is a solid of two or more elements in a metallic matrix. It can either be a partial solid
solution or a complete solid solution. Alloys are usually found to possess different physical
properties than those of the component elements.
An important alloy of lathanoids is Mischmetal. It contains lanthanoids (94-95%), iron (5%), and
traces of S, C, Si, Ca and Al.
Uses :
(1) Mischmetal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.
13. (a) Account for the following :
(i) Transition metals show variable oxidation states.
(ii) Zn, Cd and Hg are soft metals.
(b) Write one similarity and one difference between the chemistry of lanthanoid and actinoid
elements.
Ans. (a) (i) Vailability of partially filled d-orbitals/comparable energies of ns and (n-1) d orbitals
(ii) Completely filled d-orbitals/absence of unpaired d electrons cause weak metallic bonding
(b) Similarity-both are stable in +3 oxidation state/both show contraction/irregular electronic
configuration (or any other suitable similarity) Difference-actinoids are radioactive and
lanthanoids are not/actionoids show wide range of oxidation states but lanthanoids don't
(or any other orrect difference).
14. (a) Following are the transition metal ions of 3d series :
Ti4+, V2+, Mn3+, Cr3+
(Atomic numbers : Ti = 22, V =23, Mn = 25, Cr = 24)
Answer the following :
(i) Which ion is most stable in an aqueous solution and why ?
(ii) Which ion is a strong oxidising agent and why ?
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15. (a) Account for the following
(i) Mn shows the highest oxidation state of +7 with oxygen but with fluorine it shows the
highest oxidation state of +4.
(ii) Zirconium and Hafnium exhibit similar properties.
(iii) Transition metals act as catalysts.
(b) Complete the following equations:
(i) 2MnO2 + 4KOH + O2
(ii) Cr2O72 + 14H+ + 6I–
Ans. (a) (i) Ability of oxygen to form multiple bond .
(ii) Due to lanthanoid contraction.
(iii) Due to variable oxidation state/unpaired electrons
(b) (i) 2MnO2 + 4KOH + O2 2K2MnO4+ 2H2O
(ii) Cr2O72 – + 14 H+ +6I– 2Cr3++ 7H2O + 3I2
16. The elements of 3d transition series are given as:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:
(i) Write the element which is not regarded as a transition element. Give reason.
(ii) Which element has the highest m.p ?
(iii) Write the element which can show an oxidation state of +1.
(iv) Which element is a strong oxidizing agent in +3 oxidation state and why ?
Ans. (i) Zn, because of not having partially filled d-orbital in its ground state or ionic state.
(ii) Cr
(iii) Cu
(iv) Mn, because Mn+2 has extra stability due to half filled d-orbital
17. (i) Transition metals form coloured compounds. Why?
(ii) Complete the following equation :
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2MnO–4 + 16 H + 5C2O 4
+ 2–
Ans. (i) Due to d – d transition / due to presence of unpaired electrons in d – orbitals which absorb
light in visible region
(ii) 2MnO4– + 16H+ + 5C2O42 – 2Mn2+ + 8H2O + 10CO2
18. How is the variability in oxidation states of d-block different from that of the p-block elements ?
Ans. In transition elements, oxidation states differ from each other by unity whereas in case of
p- block elements, the oxidation states differ by units of two / In transition elements, the higher
oxidation states are more stable for heavier elements in a group. In p – block elements, the lower
oxidation states are more stable for heavier members due to inert pair effect. (Any one difference)
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EXERCISE-3 RACE
Type 1 : Passage question 1 :
The d-block of the periodic table contains the elements of the groups 3 – 12 and are known as
transition elements. In general, the electronic configuration of these elements is (n – 1) d1–10 ns1–2.
The d-orbitals of the penultimate energy level in their atoms receive electrons giving rise to the
three rows of the transition metals i.e., 3d, 4d and 5d series. However, Zn, Cd and Hg are not
regarded as transition elements. Transition elements exhibit certain characteristic properties like
variable oxidation states, complex formation, formation of coloured ions and alloys, catalytic
activity, etc. Transition metals are hard (except Zn, Cd and Hg) and have a high melting point.
(b) Which transition metal of 3d series does not show variable oxidation states ?
(d) Cu2+ ion coloured while Zn2+ ion is colourless in aqueous solution due to :-
(i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of Assertion (A).
(ii) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of Assertion (A).
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2. Assertion : Cu2+ iodide is not known.
Reason : Cu2+ oxidises I– to iodine.
3. Assertion : Transition metals have low melting points.
Reason : The involvement of greater number of (n – 1)d and ns electrons in the interatomic
metallic bonding.
4. Assertion : Separation of Zr and Hf is difficult.
Reason : Because Zr and Hf lie in the same group of the periodic table.
5. Assertion : Cu cannot liberate hydrogen from acids.
Reason : Because it has positive electrode potential.
6. Assertion : The highest oxidation state of osmium is +8.
Reason : Osmium is a 5d-block element
Type 3 : Multiple choice question (one correct answer) (Questions 7 to 16) :-
7. Electronic configuration of a transition element X in +3 oxidation state is [Ar]3d5. What is its
atomic number ?
(i) 25 (ii) 26 (iii) 27 (iv) 24
8. Which of the following oxidation state is common for all lanthanoids ?
(i) +2 (ii) +3 (iii) +4 (iv) +5
9. Transition elements show magnetic moment due to spin and orbital motion of electrons. Which
of the following metallic ions have almost same spin only magnetic moment ?
(i) Co3+ (ii) Cr2+ (iii) Mn2+ (iv) Cr3+
10. Which of the following statements is not correct ?
(i) Copper liberates hydrogen from acids.
(ii) In its higher oxidation states, manganese forms stable compounds with oxygen and fluorine. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\08_D & F block
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12. The electronic configuration of Cu(II) is 3d9 whereas that of Cu(I) is 3d10. Which of the following
is correct ?
13. The magnetic nature of elements depends on the presence of unpaired electrons. Identify the
configuration of transition element, which shows highest magnetic moment.
(i) V2O5, Cr2O3 (ii) Mn2O7, CrO3 (iii) CrO, V2O5 (iv) V2O5, V2O4
15. Transition elements form binary compounds with halogens. Which of the following elements will
form MF3 type compounds?
ANSWER KEY
Q. No. 1(a) (b) (c) (d) 2 3 4 5 6 7 8
Ans. (i) (ii) (i) (ii) (i) (iv) (ii) (i) (ii) (ii) (ii)
Q. No. 9 10 11 12 13 14 15 16
Ans. (iv) (i) (iii) (i) (ii) (i) (ii) (i)
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EXERCISE-4 PREVIOUS YEARS QUESTION
1. Account for the following : (CBSE_Term-II_2022)
(i) Cr2+ is a strong reducing agent.
(ii) Ti3+ is coloured whereas Sc3+ is colourless in aqueous solution.
(iii) Due to completely filled d-orbitals in their ground state as well as in oxidized state.
2. What is Lanthanoid contraction ? What is the cause of Lanthanoid contraction ? Write two
consequences of Lanthanoid contraction. [3]
(CBSE_Term-II_2022)
Ans. A regular decrease (contraction) in the atomic and ionic radii of lanthanoides with increasing
atomic number is known as lanthanoid contraction.
Alloy containing lanthanoid metals is mischmetal.
(i) There is similarity in the properties of second and third transition series.
(ii) Separation of lanthanoids is possible due to lanthanide contraction.
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(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide
hydroxides. (Basic strength decreases from La (OH)3 to Lu (OH)3.)
3. Calculate the number of unpaired electrons in the following gaseous ions:
(Compartment _CBSE 2021)
3+ 3+
Mn and Cr (Atomic number of Cr = 24, Mn = 25)
Which one of them is most stable in aqueous solution and why ?
Ans. The number of unpaired electrons in Mn3+ = 4
The number of unpaired electrons in Cr3+ = 3
Cr3+ is most stable in aqueous solution due to t 32g half field stability.
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4. Explain all the steps along with the chemical equation which are used in the preparation of
K2Cr2O7 from chromite ore. (Compartment _CBSE 2021)
Ans. Potassium dichromate is prepared from chromite ore (FeCr2O4) in the following steps.
Step (1) : Preparation of sodium chromate
4FeCr2O4 + 16NaOH + 7O2 8Na2CrO4 + 2Fe2O3 + 8H2O
Step (2) : Conversion of sodium chromate into sodium dichromate
2Na2CrO4 + conc. H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Step (3) : Conversion of sodium dichromate to potassium dichromate
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
Potassium dichromate being less soluble than sodium dichromate is obtained in the form of
orange coloured crystals and can be removed by filtration.
5. Out of the following transition elements, the maximum number of oxidation states are shown by
(CBSE 2020)
(A) Sc (Z = 21) (B) Cr (Z = 24) (C) Mn (Z = 26) (D) Fe (Z = 26)
Ans. (C)
6. (a) Account for the following : (CBSE 2020)
(i) Copper (I) compounds are white whereas Copper (II) compounds are coloured. [1×3=3]
(ii) Chromates change their colour when kept in an acidic solution.
(iii) Zn, Cd, Hg are considered as d-block elements but not as transition elements.
(b) Calculate the spin-only moment of Co2+ (Z = 27) by writing the electronic configuration of
Co and Co2+
OR
(a) Give three points of difference between lanthanoids and actinoids. [3]
[1 × 2 = 2]
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(b) Give reason and select one atom/ion which will exhibit asked property :
(i) Sc+3 or Cr3+ (Exhibit diamagnetic behaviour)
(ii) Cr or Cu (High melting and boiling point)
Ans. (a) (i) Cu+1 (3d10) compounds are white because of absence of unpaired electrons while Cu+2 (3d9)
compounds are coloured due to unpaired e-/shows d-d transition.
(ii) chromate (CrO42–) changes to dichromate (Cr2O72-) ion in acidic medium.
(iii) due to completely filled d-orbitals in their ground state as well as in oxisized state.
(b) Co = [Ar]4s23d7, Co+2 = [Ar]3d7
= n(n 2) = 3(3 2) 15 3.92 B.M.
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94 Chemistry
OR
(a) Lanthanoids Actinoids
(1) most of them are not radioactive All are radioactive
(2) don't show a wide range of oxidation state Show a wide range of oxidation states
(3) Most of their ions are colourless ,
Most of their ions are coloured
(b) (i) Sc+3, because of absence of unpaired electron
(ii) Cr, because of presence of strong intermetallic bonding than Cu.
7. When FeCr2O4 is fused with Na2CO3 in the presence of air it gives a yellow solution of compound
(A). Compound (A) on acidification gives compound (B). Compound (B) on reaction with KCl
forms an orange coloured compound (C). An acidified solution of compound (C) oxidises
Na2SO3 to (D). Identify (A), (B), (C) and (D). [2]
(CBSE 2019)
Ans. A = Na2CrO4 ; B = Na2Cr2O7 ; C = K2Cr2O7 ; D = Na2SO4
8. Give reasons for the following : [3]
(a) Transition metals form complex compounds. (CBSE 2019)
2+ 2+
(b) E° values for (Zn / Zn) and (Mn / Mn) are more negative than expected.
(c) Actinoids show wide range of oxidation states.
Ans. (a) Due to small size, high ionic charge and availability of d-orbital
(b) Due to stable 3d10 configuration in Zn2+ and 3d5 configuration in Mn2+.
(c) Due to comparable energies of 5f, 6d and 7s orbitals/level
9. Give reasons for the following : [3]
(a) Transition metals have high enthalpies of atomization. (CBSE 2019)
(b) Manganese has lower melting point even though it has a higher number of unpaired
electrons for bonding.
(c) Ce4+ is a strong oxidising agent.
Ans. (a) Because of strong interatomic interactions/strong metallic bonding between atoms.
(b) Due to stable 3d5 configuration, interatomic interaction is poor between unpaired electrons.
(c) Because Ce is more stable in +3 oxidation state.
10. Give reasons : (CBSE 2018)
0
(a) E value for Mn /Mn couple is much more positive than that for Fe /Fe .
3+ 2+ 3+ 2+
(b) Iron has higher enthalpy of atomization than that of copper. node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\08_D & F block
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0 3+ 2+ 3+ 2+
(a) E value for Mn /Mn couple is much more positive than that for Fe /Fe .
(b) Iron has higher enthalpy of atomization than that of copper.
(c) Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured.
11. (a) Account for the following : [5]
(i) Transition metals show variable oxidation states.
(ii) Zn, Cd and Hg are soft metals.
(iii) Eo value for the Mn3+/Mn2+ couple is highly positive (+1.57 V) as compared to Cr3+/Cr2
(b) Write one similarity and one difference between the chemistry of lanthanoid and actinoid
elements.
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MOCK TEST SOLUTIONS
1. Mn3+ easily changes to Mn2+ and Mn2+ is more stable due to half-filled d5 configuration and
hence Mn3+ is oxidising.
2. Ce+4
3. Due to high nuclear charge presence of vacant d-orbital and variable oxidation state it have great
tendency to from complex.
4. This is because F can form only one bond and structure of MnF4 is which is tetrahedral but
F
F Mn F
F
In Mn2O7 as 0 is present which can form 2 bonds or 1 and 1 bond so 0 can be present in
between two Mn atoms giving it a structure.
O O
Mn Mn
O O O
O
O
Mn2+ have higher stability than M3+ due to half filled d5 configuration.
(b) Iron has higher enthalpy of atomization than that of copper because Iron has higher number
of unpaired e¯ than Cu due to which extent of covalent bonding is more.
(c) Sc3+ is colourless is due to the absence of unpaired e¯ as it attains 3d° configuration while Ti+3
has 3d1-configuration
11. (a) (i) Availability of partially filled d-orbitals/comparable energies of ns and (n-1) d orbitals
(ii) Completely filled d-orbitals/absence of unpaired d electrons cause weak metallic bonding
(iii) Because Mn2+ has d5 as a stable configuration whereas Cr3+ is more stable due to stable t32g
(b) Similarity-both are stable in +3 oxidation state/both show contraction/irregular electronic
configuration (or any other suitable similarity) Difference-actinoids are radioactive and
lanthanoids are not/actionoids show wide range of oxidation states but lanthanoids don't (or any
other correct difference).
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Ambidentate ligand : Unidentate ligands with more than one co-ordinating atoms. e.g.
–CN—, and –NC—, –SCN — and –NCS—, NO2 — and ONO—, –OCN— and NCO—.
These ligands are responsible for linkage isomerism.
Polydentate ligand : Those ligands which possess two or more than two donar atoms which can
link to metal ions are called polydentate ligands. e.g. EDTA4–. (ethylene diamine tetra acetate)
ion hexadentate ligand.
Chelating ligand: These are the polydentate ligands which bind to the central metal to form a
puckered ring structure. Chelation leads to extra stability, for example, EDTA (ethylene diamine
tetra acetate).
On the basis of crystal field splitting energy (CFSE) ligands are of 2 types –
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98 Chemistry
(1) Strong ligands : They possess high CFSE values e.g. –CO, CN, NH3, H2O etc.
(2) Weak ligands : They possess less CFSE values e.g. –F–, Cl–, Br–, I– etc.
LIGANDS
Neutral Monodentate
Classical Non-classical
Anionic Bidentate
Cationic Polydentate
Flexidentate e— acid
Ambidentate donating ligand ligand
Bonding in Coordination Compounds
Werners Theory
(i) In complex compounds, metal atom exhibit two types of valencies. primary valency and
secondary valency.
Primary valency Secondary Valency
It is oxidation no. of metal. It is coordination number
It is variable It is non variable.
Satisfied by anions (present in Satisfied by ligands
coordination or ionisable sphere). (present in coordination sphere)
Ionisable Nonionisable
Ionic nondirectional Directional decide geometry
of complex ion.
Represented by dotted line in Represented by solid lines in
Werner structure. Werner structure.
Valence Bond Theory
According to this theory, the metal atom or ion under the influence of ligands form inner orbital
and outer orbital complex. These hybridized orbitals are allowed to overlap with ligand orbitals
that can donate electron pairs for bonding.
Coorination No. Type of hybrid orbital
2 sp
2
3 sp
square planar -dsp2
4
tetrahedral -sp3
dsp3 node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
5
sp3d
3 2
sp d - outer orbital complex (high spin)
6 2 3
d sp - inner orbital complex (low spin)
Coordination No. 4: Example
2— 3
[NiCl4] sp -----Tetrahedral
2— 2
[Ni(CN)4] dsp ----- Square planar
[Ni(CO)4] sp3 -----Tetrahedral
2+ 3
[Zn(NH3)4] sp -----Tetrahedral
2+ 2
[Cu(NH3)4] dsp -----Square planar
Coordination No. 6 : Example
[Fe(CN) 6]4— d2sp3
[Fe(CN) 6]3— d2sp3
[Co(NH 3) 6]3+ d2sp3
[Ni(H 2O) 6]2+ sp3d2
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CBSE 99
Crystal Field Theory
The five d-orbitals are split into lower and higher energy level due to approach of ligands is
known as crystal field theory. The five d-orbitals in a gaseous metal atom/ion have same energy.
Crystal field splitting in octahedral coordination entities.
• Energy separation is denoted by o (the subscript o is for octahedral).
• The energy of the two eg orbitals (higher energy orbitals) will increase by (3/5) o and that
• If o < p, the fourth electron enters one of the eg, orbitals giving the configuration t 32g e1g .
Ligands for which o < p are known as weak field ligands and form high spin complexes.
• If o > p, it becomes more energetically favourable for the fourth electron to occupy a t2g
orbital with configuration t 42g eg . Ligands which produce this effect are known as strong
field ligands and form low spin complexes, where p represents the energy required for
electron pairing in a single orbital.
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100 Chemistry
Structural Isomerism
In structural isomerism, isomers have different bonding pattern. Different types of structural
isomerism is as follows :
(i) Linkage isomerism, arises in a coordination compound containing ambidentate ligand.
e.g., [Co(NH3)5(NO2)]Cl2
[Co(NH3)5(ONO)]Cl2
(ii) Coordination isomerism, arises from the interchange of ligands between cationic and
anionic entities of different metal ions present in a complex.
e.g., [Co(NH3)6][Cr(CN)6] ; [Cr(NH3)6][Co(CN)6]
(iii) Ionisation isomerism, when the ionisable anion exchange with anion ligand.
e.g., [CO(NH3)5SO4]Br and [Co(NH3)5Br]SO4
(iv) Solvate isomerism, is also known as .hydrate isomerism. In this case water is involved as a
solvent.
e.g., [Cr(H2O)6]Cl3, [Cr(H2O)5Cl2.H2O, [Cr(H2O)4Cl2]Cl.2H2O
Crystal field splitting in tetrahedral coordination entities.
• In tetrahedral coordination entities, t = (4/9) o. Consequently the orbital splitting energies
are not sufficiently large for forcing pairing and, therefore, low spin configurations are
rarely observed.
• Due to less crystal field stabilization energy, it is not possible to pair electrons and so all
the tetrahedral complexes are high spin.
4
• The value of t
(CFSE for tetrahedral complexes) for tetrahedral complexes is t 0
9
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CBSE 101
Exercise-1 INTEXT QUESTIONS
1. Write the formulas for the following coordination compounds :
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate (II)
(iii) Tris (ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromideochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Ans. (i) Co(H 2O) 2 (NH 3 ) 4 Cl3 (ii) K 2 Ni(CN) 4
(i) Co NH3 6
Cl3 (ii) Co NH3 5 Cl Cl2
(iii) K3 Fe CN 6
(iv) K3 Fe C2O4 3
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102 Chemistry
4. Explain on the basis of valence bond theory that [Ni(CN)4]2– ion with square planar structure is
diamagnetic and the [NiCl4]2– ion with tetrahedral geometry is paramagnetic.
d8 configuration :
3d 4s 4p 4d
There are 4 CN– ions. Thus, it can either have a tetrahedral geometry or square planar geometry.
Since CN– ion is a strong field ligand, it causes the pairing of unpaired 3d electrons.
3d 4s 4p 4d
2
dsp
It now undergoes dsp2 hybridization. Since all electrons are paired, it is diamagnetic.
In case of [NiCl4]2–, Cl– ion is a weak field ligand. Therefore, it does not lead to the pairing of
unpaired 3d electrons. Therefore, it undergoes sp3 hybridization.
3d 4s 4p 4d
3
sp
5. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why ?
Ans. Though both [NiCl4]2– and [Ni(CO)4] are tetrahedral, their magnetic characters are different. This
is due to a difference in the nature of ligands. Cl– is a weak field ligand and it does not cause the
Ni+2
3d 4s 4p 4d
In Ni(CO)4, Ni is in the zero oxidation state i.e., it has a configuration of 3d8 4s2.
3d 4s 4p 4d
But CO is a strong field ligand. Therefore, it causes the pairing of unpaired 3d electrons. Also, it
causes the 4s electrons to shift to the 3d orbital, thereby giving rise to sp3 hybridization. Since no
unpaired electrons are present in this case, [Ni(CO)4] is diamagnetic.
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CBSE 103
6. '[Fe(H2O)6]3+ is strongly paramagnetic whereas [Fe(CN)6]3– is weakly paramagnetic. Explain.
3 3
Ans. In both Fe(H2O)6 and Fe(CN)6 , Fe exists in the +3 oxidation state i.e., in d5 configuration.
5
d
Since CN– is a strong field ligand, it causes the pairing of unpaired electrons. Therefore, there is
only one unpaired electron left in the d-orbital.
On the other hand, H2O is a weak field ligand. Therefore, it cannot cause the pairing of electrons.
This means that the number of unpaired electrons is 5.
Therefore, n(n 2) = 5(5 2) = 35 = 6 BM
3 3
Thus, it is evident that Fe(H2O)6 is strongly paramagnetic, while Fe(CN)6 is weakly
paramagnetic.
7. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2– ion.
2
Ans. Pt(CN)6
In this complex, Pt is in the +2 state. It forms a square planar structure. This means that it
undergoes dsp2 hybridization. Now, the electronic configuration of Pd(+2) is 5d8.
8
3d
CN– being a strong field ligand causes the pairing of unpaired electrons. Hence, there are no
2
unpaired electrons in Pt(CN) 4 .
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
8. The hexaquo manganese(II) ion contains five unpaired electrons, while the hexacyanoion
contains only one unpaired electron. Explain using Crystal Field Theory.
Ans.
[Mn(H2O)6]2+ [Mn(CN)6]4–
Mn is in the +2 oxidation state. Mn is in the +2 oxidation state.
The electronic configuration is d5. The electronic configuration is d5.
The crystal field is octahedral. Water is a weak The crystal field is octahedral. Cyanide is a
field ligand. Therefore, the arrangement of the strong field ligand. Therefore, the arrangement
2 4
electrons in Mn(H 2O)6 is t2g3eg2. of the electrons in Mn(CN)6 is t2g5eg0.
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104 Chemistry
9. On the basis of the following observations made with aqueous solutions, assign secondary
valences to metals in the following compounds :
Ans. (i) Secondary 4; (ii) Secondary 6; (iii) Secondary 6; (iv) Secondary 6; (v) Secondary 4
10. Write the formulas for the following coordination compounds :
(a) Tetraammineaquachloridocobalt(III) chloride
(b) Potassium tetrahydroxidozincate (II)
(c) Potassium trioxalatoaluminate (III)
(d) Dichloridobis(ethane-1,2-diamine)cobalt(III)
(e) Tetracarbonylnickel(0)
Ans. (a) [Co(NH3)4(H2O)Cl]Cl2 (b) K2[Zn(OH)4]
(c) K3[Al(C2O4)3] (d) [CoCl2(en)2]+ (e) [Ni(CO)4]
11. Write the IUPAC names of the following coordination compounds:
(a) [Pt(NH3)2Cl(NO2)] (b) K3[Cr(C2O4)3]
(c) [CoCl2(en)2]Cl (d) [Co(NH3)5(CO3)]Cl
(e) Hg[Co(SCN)4]
Ans. (a) Diamminechloridonitrito-N-platinum(II)
(b) Potassium trioxalatochromate(III)
(c) Dichloridobis(ethane-1, 2-diamine)cobalt(III) chloride
(d) Pentaamminecarbonatocobalt(III) chloride
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
(e) Mercury tetrathiocyanatocobaltate(III)
12. Why is geometrical isomerism not possible in tetrahedral complexes having two different types
of unidentate ligands coordinated with the central metal ion ?
Ans. Tetrahedral complexes do not show geometrical isomerism because the relative positions of the
unidentate ligands attached to the central metal atom are the same with respect to each other.
13. Draw structures of geometrical isomers of [Fe(NH3)2(CN)4]– Solution Out of the two, (a)
cis - [CrCl2(ox)2]3- is chiral (optically active).
NH3 NH
NC NH NC CN
Ans. Fe Fe
NC CN NC C
CN NH3
cis
trans
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CBSE 105
14. Out of the following two coordination entities which is chiral (optically active )?
(a) cis-[CrCl2(ox)2]3–
(b) trans-[CrCl2(ox)2]3–
15. The spin only magnetic moment of [MnBr4]2– is 5.9 BM. Predict the geometry of the complex ion ?
Ans. Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either tetrahedral
(sp3 hybridisation) or square planar (dsp2 hybridisation). But the fact that the magnetic moment of
the complex ion is 5.9 BM, it should be tetrahedral in shape rather than square planar because of
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106 Chemistry
M L M
(a) (b)
L
L L
Square planar L Tetrahedral
(v) Homoleptic complexes :
These are those complexes in which the metal ion is bound to only one kind of a donor
group.
3 2
For e.g. Co(NH3 )6 , PtCl 4 etc.
(vi) Heteroleptic complexes :
Heteroleptic complexes are those complexes where the central metal ion is bound to more
than one type of a donor group.
2
For e.g. Co(NH3 )4 Cl2 , Co(NH3 )5 Cl
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CBSE 107
2. What is meant by unidentate, didntate and ambidentate ligands ? Give two examples for each.
Ans. (a) Unidenatate ligands : Ligands with only one donor sites are called unidentate ligands. For
e.g., N H3,Cl — etc.
(b) Didentate ligands : Ligands that have two donor sites are called bidentate ligands. For e.g.,
(i) Ethane-1, 2-diamine (ii) Oxalate ion
H2N—CH2 COO—
2–
(C2O ) or
H2N—CH2 4
COO
—
Cis-isomer Trans-isomer
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108 Chemistry
en Co Co en
en en
3+ 3+
[Co(en)3] Mirror [Co(en)3]
(dextro) (Laevo)
(c) Linkage isomerism :
This type of isomerism is found in complexes that contain ambidentate ligands.
For example : [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)Cl2
Yellow form Red form
(d) Coordination isomerism :
This type of isomerism arises when the ligands are interchanged between cationic and anionic
entities of different metal ions present in the complex. For example
[Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(e) Ionization isomerism :
This type of isomerism arises when a counter ion replaces a ligand within the coordination
sphere. For example
[Co(NH3)5 SO4] Br and [Co(NH3)5Br] SO4
(f) Solvate isomerism :
Solvate isomers differ by whether or not the solvent molecule is directly bonded to the metal ion
or merely present as a free solvent molecule in the crystal lattice.
[Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2. H2O, [Cr(H2O)4Cl2]Cl. 2H2O
Violet Blue-green Dark green
4. How many geometrical isomers are possible in the following coordination entities ?
(i) [Cr(C2O4)3]3+ (ii) [Co(NH3)3Cl3]
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
Ans. (i) For [Cr(C2O4)3]3–, no geometrical isomer is possible as it is a bidentate ligand.
O O
O Cr O
O O
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CBSE 109
5. Draw the structure of optical isomers of :
(i) [Cr(C2O4)3]3– (ii) [PtCl2(en)2]2+ (iii) [Cr(NH3)2Cl2(en)]+
Ans. (i) [Cr(C2O4)3]3–
en en
en Co Co en
en en
3– 3–
[Cr(OX)3] Mirror [Cr(OX)3]
(dextro) (Laevo)
(ii) [PtCl2(en)2]2+
Cl Cl
Cl
en Pt en
Pt
en en
Mirror
(iii) [Cr(NH3)2Cl2(en)]+
en en
H3N NH3
Cr Cr
H3 N Cl Cl NH3
Cl Cl
Mirror
en Co en Co en
en
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
Cl Cl
Mirror
+
Trans [CoCl2(en)2] isomer-optically inactive
(Superimposable mirror images)
Cl Cl
Cl Cl
en Co Co en
en en
Mirror
+
Cis [CoCl2(en)2] isomer-optically active
(non-superimposable mirror images)
In total, three isomers are possible.
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110 Chemistry
(ii) [Co(NH3)Cl(en)2]2+
Cl Cl
NH3
en en en
Co Co
NH3 en
Trans Cis
Cl Cl
NH3 H3N
en Co Co en
en en
Cis Mirror
Trans - isomers are optically inactive.
Cis - isomers are optically active.
(iii) [Co(NH3)2Cl2(en)]+
Cl Cl
Cl Cl
en Co Co en
NH3 NH3
NH3 NH3
Mirror
7. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit
optical isomers ?
Ans. [Pt(NH3)(Br)(Cl)(py)]
H3N Cl H3N Br H 3N Cl
Pt Pt Pt
Py Br Py Cl Br Py
From the above isomers, none will exhibit optical isomers. Tetrahedral complexes rarely show node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
3d 4s 4p
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CBSE 111
As CN— ion is a strong field ligand, it causes the pairing of the unpaired 3d electrons.
3d 4s 4p
Since there are six ligands around the central metal ion, the most feasible hybridization is d2sp3.
d2sp3 hybridized orbitals of Fe2+ are :
3d 4s 4p
d sp
2 3
6 electron pairs from CN ions occupy the six hybrid d2sp3 orbitals.
–
Then,
3d 4s 4p
6 pairs of electrons from 6CN ions —
Hence, the geometry of the complex is octahedral and the complex is diamagnetic (as there are
no unpaired electrons).
(ii) [FeF6]3–
In this complex, the oxidation state of Fe is +3.
Orbitals of Fe+3 ion :
3d 4s 4p 4d
There are 6 F– ions. Thus, it will undergo d2sp3 or sp3d2 hybridization. As F– is a weak field ligand,
it does not cause the pairing of the electrons in the 3d orbitals. Hence, the most feasible
hybridization is sp3d2.
sp3d2 hybridized orbitals of Fe3+ it are :
3d 4s 4p 4d
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
sp3d2
3d 4s 4p 4d
sp3d2
6 electron pairs from F—ions
3d 4s 4p 4d
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112 Chemistry
Oxalate ion is a weak field ligand. Therefore, it cannot cause the pairing of the 3d orbital
electrons. As there are 6 ligands, hybridization has to be d2sp3.
d2sp3 hybridized orbitals of Co3+.
3d 4s 4p
d sp2 3
The 6 electron pairs from the 3 oxalate ions (oxalate anion is a bidentate ligand) occupy these
d2sp3 orbitals.
3d 4s 4p
6 pairs
electron pairs from
of electrons 3 oxalate
from 6CN—ions
ions
Hence, the geometry of the complex is found to be octahedral.
(iv) [CoF6]3–
Cobalt exists in the +3 oxidation state.
Orbitals of Co3+ ion :
3d 4s 4p 4d
Again, fluoride ion is a weak field ligand. It cannot cause the pairing of the 3d electrons. As a
result, the Co3+ ion will undergo sp3d2 hybridization.
sp3d2 hybridized orbitals of Co3+ ion are :
3d 4s 4p 4d
sp d
3 2
3d 4s 4p 4d
y +3/5
Barycentre
Ans. –2/5
x
Average energy t2g
of the d orbitals dxy dyz dxz
in a spherical field
Splitting of the d
Metal orbitals in a
d orbitals octahedral crystal field
2 2 2
dx –y –dz , dxydyzdxz
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CBSE 113
10. What is spectrochemical series ? Explain the difference between a weak field and a strong field
ligand.
Ans. A spectrochemical series is the arrangement of common ligands in the increasing order of their
crystal - field splitting energy (CFSE) values. The ligands present on the R.H.S of the series are
strong field ligands while that on the L.H.S are weak field ligands. Also, strong field ligands
cause higher splitting in the d orbitals that weak field ligands.
I–< Br– <S2– <SCN– <Cl– <N3– <OH– <C2O42– <~H2O < NCS– <edta4– < NH3 < en– <CN– < CO
11. What is crystal field splitting energy ? How does the magnitude of o
decide the actual
configuration of d-orbitals in a coordination entity ?
Ans. The degenerate d-orbitals (in a spherical field environment) split into two levels i.e., eg and t2g in
the presence of ligands. The splitting of the degenerate levels due to the presence of ligands is
called the crystal – field splitting while the energy difference between the two levels (eg and t2g) is
called the crystal - field splitting energy. It is denoted by 0.
After the orbitals have split, the filling of the electrons takes place. After 1 electron (each) has
been filled in the three t2g orbitals, the filling of the fourth electron takes place in two ways. It can
enter the eg orbitals (giving rise to t2g3 eg1 like electron configuration) or the pairing of the
electrons can take place in the t2g orbitals (giving rise to t2g4 eg0 like electronic configuration). If
the 0 value of a ligand is less than the pairing energy (P), then the electrons enter the eg orbital.
On the other hand, if the 0 value of a ligand is more than the pairing energy (P), then the
electrons enter the t2g orbital.
12. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why ?
Ans. In [Cr(NH3)6]3+, Cr is in the +3 oxidation state i.e., d3 configuration. Since there are three unparied
electrons in 3d– orbitals.
Cr3+
3d 4s 4p 4d
2
d sp 3
Therefore, it undergoes d2sp3 hybridization and the electrons in the 3d orbitals remain unpaired.
Hence, it is paramagnetic in nature.
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
3d 4s 4p
CN– is a strong field ligand. It cause the pairing of the 3d orbital electrons. Then, Ni2+ undergoes
dsp2 hybridization.
3d 4s 4p
dsp2
As there are no unpaired electrons, it is diamagnetic.
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114 Chemistry
M C O
(ii) cis-[Cr(en)2Cl2]Cl
The central metal ion is Cr3+.
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
The coordination number is 6.
The oxidation state can be given as : x + 2(0) + 2(–1) = +1 x – 2 = +1 x = +3
The d orbitals occupation for Cr3+ is t32g .
(iii) (NH4)2[CoF4]
The central metal ion is Co2+.
The coordination number is 4.
The oxidation state can be given as : x – 4 = –2 x = +2
The d orbitals occupation for Co2+ is eg4 t2g3.
(iv) [Mn(H2O)6]SO4
The central metal ion is Mn2+.
The coordination number is 6.
The oxidation state can be given as : x + 0 = +2 x = +2
The d orbitals occupation for Mn2+ is t2g eg .
3 2
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CBSE 115
16. Write down the IUPAC name for each of the following complexes and indicate the oxidation
state, electronic configuration and coordination number. Also give stereochemistry and magnetic
moment of the complex :
(i) K[Cr(H2O)2(C2O4)2]. 3H2O (ii) [Co(NH3)5Cl]Cl2 (iii) CrCl3(py)3 (iv) Cs[FeCl4]
(v) K4[Mn(CN)6]
Ans. (i) K[Cr (H2O)2 (C2O4)2]. 3H2O
IUPAC Name: Potassium diaquadioxalatochromate (III) trihydrate.
Oxidation state of chromium = +3
Electronic configuration : 3d3: t2g3
Coordination number = 6
Shape : octahedral
Stereochemistry :
OH2 OH2
OH2 OH2
O O O O
O O O OH2
Cr Cr
Cr Cr O O
O O
O O O O
O OH2 OH2
OH2
Trans Cis Trans optically inactive
OH2 OH2
O OH2 H2O O
Cr Cr
O O O O
O O
= 33 2 = 5 ~4BM
(ii) [Co(NH3)5Cl]Cl2
IUPAC name : Pentaamminechloridocobalt (III) chloride
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
Oxidation state of Co = +3
Coordination number = 6
Shape : octahedral.
Electronic configuration : d6: t2g6.
Stereo chemistry :
OH2 OH2
O OH2 H2O O
Cr Cr
O O O O
O O
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116 Chemistry
(iii) CrCl3(py)3
IUPAC name : Trichloridotripyridinechromium (III)
Oxidation state of chromium = +3
Electronic configuration for: d3 t 32g
Coordination number = 6
Shape : octahedral.
Stereochemistry :
Cl Cl
Py Cl Py Cl
Cr Cr
Py Cl Py Py
Py Cl
Facial isomer Meriodional isomer
(v) K4[Mn(CN)6]
IUPAC Name : Potassium hexacyanomanganate (II)
Oxidation state of manganese = +2
Electronic configuration :d5: t2g5
Coordination number = 6
Shape : octahedral
Streochemistry : optically inactive
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CBSE 117
17. Discuss briefly giving an example in each case the role of coordination compounds in :
(i) biological system
(ii) medicinal chemistry
(iii) analytical chemistry
(iv) extraction/metallurgy of metals
Ans. (i) Role of coordination compounds in biological system
We know that photosynthesis is made possible by the presence of the chlorophyll pigment.
This pigment is a coordination compound of magnesium.
(ii) Role of coordination compounds in medicinal chemistry
Certain coordination compounds of platinum (for example, cis-platin) are used for
inhibiting the growth of tumours.
(iii) Role of coordination compounds in analytical chemistry
During salt analysis, a number of basic radicals are detected with the help of the colour
changes they exhibit with different reagents.
(iv) Role of coordination compounds in extraction or metallurgy of metals
From [Au(CN)2]+ solution, gold is extracted by the addition of zinc metal.
18. Using IUPAC names write the formulae for the following :
(a) Tris (ethane-1,2-diamine)chromium(III)chloride
(b) Potassium tetrahydroxozincate(II)
Ans. (a) [Cr(en)3]Cl3 (b) K2[Zn(OH)4]
19. (a) What type of isomerism is shown by the complex [Co(NH3)5(SCN)]2+ ?
(b) Why is [NiCl4]2– paramagnetic while [Ni(CN)4]2– is diamagnetic ?
(Atomic number of Ni = 28)
(c) Why are low spin tetrahedral complexes rarely observed
node06\B0BB-BC\Kota\Board Material\Chemistry\Booklet\CBSE\Booklet Final_2022-23\Part-1\IOC\09_Coordination Compounds
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118 Chemistry
21. (a) For the complex [Fe(CN)6]4–, write the hybridization, magnetic character and spin type of the
en
22. (i) Write down the IUPAC name of the following complex :
[Pt(NH3)(H2O)Cl2]
(ii) On the basis of crystal field theory, write the electronic configuration for d4 ion if 0
< P.
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CBSE 119
Exercise-3 RACE
Type 1 : Passage question 1 :-
In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will
be repulsion between the electrons in metal d orbitals and the electrons (or negative charges) of
the ligands. Such a repulsion is more when the metal d orbital is directed towards the ligand than
when it is away from the ligand. Thus, the dx2-y2 and dz2 orbitals.
Which point towards the axes along the direction of the ligand will experience more repulsion
and will be raised in energy; and the dxy, dyz and dxz orbitals which are directed between the
axes will be lowered in energy relative to the average energy in the spherical crystal field. Thus,
the degeneracy of the d orbitals has been removed due to ligand electron-metal electron
repulsions in the octahedral complex to yield three orbitals of lower energy, t2g set and two
orbitals of higher energy, eg set. ?
(a) The relation between t and O is :-
(i) t = O (ii) O = t (iii) O = t (iv) t = O
(b) For SFL what is relation between pairing energy and crystal field splitting for octahedral :-
(i) O > P (ii) O < P (iii) O = P (iv) None of these
(c) eg orbital experience more repulsion that t2g orbitals due to ?
(i) d orbital are on axis (ii) d orbital are on equatorial
(iii) d orbital between axis (iv) None of these
4
(d) Write the electronic configuration of d on the basis of SFL when O < P :-
(i) t2g4eg0 (ii) t2g3eg1 (iii) t2g2eg2 (iv) t2g0eg4
Type 2 : Assertion and Reason :-
Question 2 to 6 Note :- In the following questions a statement of assertion followed by a reason.
Choose the correct answer out of the following choices –
(i) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct
explanation of Assertion (A).
(ii) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct
explanation of Assertion (A).
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ANSWER–KEY
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Exercise-4 Previous Years question
1. (a) Using valence bond theory, predict the hybridization and magnetic character of following :
[CoF6]3– [Atomic number of Co = 27] (CBSE-Term-II_ 2022)
+
(b) Write IUPAC name of the following complex : [CoBr2(en)2]
(c) How many ions are produced from the complex [Co(NH3)6]Cl2 in solution ? [1× 3=3]
3– 3 2
Ans. (a) [CoF6] Hybridization = sp d
Magnet character = Paramagnetic
(b) dibromidobis – ethane-1,2-diamine.cobalt(I)
(c) [Co(NH3)6]Cl2 [Co(NH3)6]3+ + 2Cl–
(aq. sol.) 3 ions produced
2. Draw the geometrical isomers of [CoCl2(en)2]+. (Compartment _CBSE 2021)
Cl Cl
Cl
en en Co
Ans. Co en
en Cl
Cis Trans Mirror
3. Assertion (A) : Linkage isomerism arises in coordination compounds becauses of ambidentate ligand.
Reason (R) : Ambidentate ligand like NO2 has two different donor atoms i.e., N and O.
(CBSE 2020)
Ans. (i) Both Assertion (A) and Reason (R) are correct statement and Reason (R) is the correct
explanation of the Assertion(A)
4. Give the formulae of the following compounds : (CBSE 2020)
(i) Potassium tetra hydroxydozincate [II] (ii) Hexaammine platinium [IV] Chloride
Ans. (i) K2[Zn(OH)4] (ii) [Pt(NH3)6]Cl4
5. Write IUPAC name of the complex [Co(en)2(NO2)Cl]+. What type of structural isomerism is
shown by this complex ? [2]
OR
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Using IUPAC norms, write the formulae for the following complexes : [2]
(a) Hexaaquachromium (III) chloride (b) Sodium trioxalatoferrate (III) (CBSE 2019)
Ans. Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III)ion
Linkage isomerism
OR
(i) [Cr(H2O)6]Cl3 (ii) Na3[Fe(OX)3]
6. (a) Although both [NiCl4]2– and [Ni(CO)4] have sp3 hybridisation yet [NiCl4]2– is paramagnetic
and [Ni(CO)4] is diamagnetic. Give reason. (Atomic no. of Ni = 28) [2]
(b) Write the electronic configuration of d5 on the basis of crystal field theory when
(i) 0 < P and (ii) 0 > P (CBSE 2019)
2
Ans. (a) In [NiCl4] , Cl is a weak field ligand due to which there are two unpaired electrons in 3d
orbital whereas in [Ni(CN)4]2, CN is a strong field ligand due to which pairing leads to no
unpaired electron in 3d-orbital/Or structural representation.
(b) (i) t2g3eg2 (ii) t2g5eg0
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Exercise-5 MOCK TEST
1. Define Homoleptic complex. [1]
2. Write the hybridization and shape of [Fe(CN)6]3–. (Atomic number of Fe = 26) [1]
3. What do you mean by chealate ligand. [1]
4. Why is [NiCl4]2– paramagnetic while [Ni(CN)4]2– is diamagnetic ? (Atomic number of
Ni = 28) [2]
5. Why are low spin tetrahedral complexes rarely observed [2]
6. Write the coordination number and oxidation state of Platinum in the complex [Pt(en)2Cl2]. [2]
7. Write the hybridisation and number of unpaired electrons in the complex [CoF6]3–.
(i) 0
>P
(ii) 0
<P
(b) (i) Write the IUPAC name of the complex [Cr(NH3)4 Cl2]Cl.
(ii) Write IUPAC name of the complex [Co(en)2(NO2)Cl]+.
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