Chemistry (043) / XII / TERM-2 /2021-22

KENDRIYA VIDYALAYA SANGATHAN AHMEDABAD REGION

STUDENT SUPPORT MATERIAL TERM-2
CLASS- XII

SUBJECT- CHEMISTRY(043) SESSION- 2021-22

1
Chemistry (043) / XII / TERM-2 /2021-22

INSPIRATION

Dr Jaydeep Das
Deputy Commissioner
Kendriya Vidyalaya Sangathan Ahmedabad Region

SMT. SHRUTI BHARGAVA SMT. VINITA SHARMA

ASST. COMMISSIONER, ASST. COMMISSIONER,
KVS R O AHMEDABAD KVS R O AHMEDABAD
MENTOR

Shri Manish Jain

Principal
Kendriya Vidyalaya, ONGC , Ankleshwar
CONTENT DEVELOPMENT TEAM
1. Mrs. Sabiha Shekh, PGT-Chemistry, KV No. 1 Surat
2. Dr. M. R. Choudhary, PGT-Chemistry, KV SAC, Vastrapur
3. Sh. P.K.Patidar, PGT-Chemistry, KV ONGC, Chandkheda

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INDEX

S NO CONTENT PAGE NO

1 SYLLABUS THEORY TERM-1 & MARKING SCHEME -

2 SYLLABUS PRACTICAL TERM-1 & MARKING SCHEME -

3 ELECTROCHEMISTRY 11-21

4 CHEMICAL KINETICS 22-31

5 SURFACE CHEMISTRY 32-43

6 d-AND f-BLOCK ELEMENTS 44-51

7 COORDINATION COMPOUNDS 52-61

8 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 62-72

9 AMINES 73-79

10 PRACTICE PAPERS 79-88

3
SYLLABUS FOR SESSION 2021-22

CLASS XII - Term-II

S.No UNIT No. of

Periods MARKS
1 Electrochemistry 7

2 Chemical Kinetics 5
13
3 Surface Chemistry 5

4 d-and f-Block Elements 7

9
5 Coordination Compounds 8

6 Aldehydes, Ketones and Carboxylic 10

Acids 13
7 Amines 7

TOTAL 49 35

Electrochemistry: Redox reactions, EMF of a cell, standard electrode potential,

Nernst equation and its application to chemical cells, Relation between Gibbs
energy change and EMF of a cell, conductance in electrolytic solutions, specific
and molar conductivity, variations of conductivity with concentration,
Kohlrausch's Law, electrolysis.
Chemical Kinetics: Rate of a reaction (Average and instantaneous), factors
affecting rate of reaction: concentration, temperature, catalyst; order and
molecularity of a reaction, rate law and specific rate constant, integrated rate
equations and half-life (only for zero and first order reactions).
Surface Chemistry: Adsorption - physisorption and chemisorption, factors
affecting adsorption of gases on solids, colloidal state: distinction between true
solutions, colloids and suspension; lyophilic, lyophobic, multi-molecular and
macromolecular colloids; properties of colloids; Tyndall effect, Brownian
movement, electrophoresis, coagulation.
d and f-Block Elements: General introduction, electronic configuration,
occurrence and characteristics of transition metals, general trends in properties
of the first row transition metals – metallic character, ionization enthalpy,
oxidation states, ionic radii, colour, catalytic property, magnetic properties,
interstitial compounds, alloy formation.
Lanthanoids - Electronic configuration, oxidation states and lanthanoid
contraction and its consequences.

4
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.
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.
Amines: Amines: Nomenclature, classification, structure, methods of
preparation, physical and chemical properties, uses, identification of primary,
secondary and tertiary amines.
PRACTICALS

TERM-II Evaluation Scheme

S. No Practical Marks
1. Volumetric Analysis 4
2. Salt Analysis 4
3 Content Based Experiment 2
4 Project Work and Viva(Internal and External 5
Both)
TOTAL 15

1) Volumetric analysis (4 marks)

Determination of concentration/ molarity of KMnO4 solution by titrating it
against a standard solution of:

i. Oxalic acid,

ii. Ferrous Ammonium Sulphate

(Students will be required to prepare standard solutions by weighing
themselves).
2) Salt analysis (Qualitative analysis) (4 marks)
Determination of one cation and one anion in a given salt.
Cations- Pb2+, Cu2+, As3+, Al3+, Fe3+, Mn2+, Ni2+, Zn2+, Co2+, Ca2+, Sr2+,

Ba2+, Mg2+, NH4+ Anions – (CO3)2- , S2- , NO2 - , SO3 2- , SO42- , NO3,

Cl- , Br- , I- , PO4 3- , C2O4 2- ,CH3COO- (Note: Insoluble salts excluded)

5
3) Content based experiment
A. Preparation of Inorganic Compounds
Preparation of double salt of Ferrous Ammonium Sulphate or
Potash Alum. Preparation of Potassium Ferric Oxalate.
B. Tests for the functional groups present in organic compounds:
Unsaturation, alcoholic, phenolic, aldehydic, ketonic, carboxylic and
amino (Primary) groups.

General Instructions for Investigatory Project

In Chemistry the students of class XI and XII are supposed to conduct a

scientific investigations involving laboratory testing and collecting information
from other sources. This project is assessed as a part of practical examination at
the end of year.

At the outset, teachers must map appropriate competencies or learning

outcomes with real world problems (projects) that are age appropriate for their
students. Students in consultation with their teacher finally determine the
project question for them depending upon their interest and proclivity. A project
should ideally arise out of the need felt by the student. Students explore their
areas of interest and narrow down their ideas to a testable hypothesis or
problem question.

For example: Abdul waits for summers as his favorites fruit watermelon is
available in plenty. This year he noticed that every time he bought a watermelon
its colour was dark red and was exceptionally sweet from inside. This never
happened in earlier years. Some watermelons would be sweet some would not.
Abdul were surprised by this observation and worried if the fruit was
adulterated. He thought of conducting a test to find out if fruits and vegetables
available in his locality were adulterated. He reviewed articles and papers on
adulteration and found out simple tests to check adulteration at home. Abdul
conducted the test and shared his results with his friend and teacher. He
developed a small manual to help other check adulteration in fruits.

There are many issues in our immediate surroundings which need to be

addressed. Keen observation will help identify the problem.

Before developing a problem question, students must do research on topics and

find out what other people have already done in the selected area to avoid
repetition. During this phase, students should be encouraged to record the
reference of every bit of information they got from different sources. After
developing problem question, students should write down precise testable
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hypothesis and design an experiment or procedure to test their hypothesis by
collecting and analysing the data followed by writing conclusion and limitation
of the study. Students must also develop a timeline and checklist about
accessibility to resources required, safety of experiment/procedure,
harmlessness of experiments to environment, organisms and other people.
Teacher must ensure that it is doable within a specified period of time and
available resources and is appropriately challenging to a particular student
(neither be very complex or longer nor be very easy and short). It should not
culminate into finding information from a book or website.

A project could have the following outline:

1. Statement of Problem- A clear statement of the problem.
2. Objectives-General and specific objectives of topic.

3. Introduction-The introduction should describe the relevance of problem

or why the problem is the most appropriate for your inquiry. It should
also describe previously known facts about your problem question with
proper bibliography. Introduction towards end briefly includes hypothesis
your hypothesis and the method to test it.
4. Problem question- (specific, concrete questions to which concrete
answers can be given) and/ or hypotheses
5. Methods/Procedures-Methodology (will your research be based on
survey, an experimental investigation, historical study, ethnographic
study or content analysis).Methods describe the experiments proposed or
the observations planned to make and the detailed process of analysis of
data/observations. Methods proposed should be feasible and be able to
adequately answer problem question.
6. Materials/Resources required
7. Observations/Data gathered
Using the procedures mentioned in introduction, experiments should be
conducted and data should be recorded. Interesting things that happened
during the conduct of experiments should also be recorded.
8. Analysis of data and discussion of result
Data should be interpreted in terms of proposed hypothesis. Data should
be tabulated and interpreted with the help of graphs. The interpretation
should be done in an honest manner even if it does not support proposed
hypothesis.
9. Conclusion Reporting and writing up the report
Discussion of new learning from the study may be covered under
7
conclusion. This may have possible suggestions for future studies.
10. Limitation of the study
The limitations of the study are those features of design or procedure that
might have affected the interpretation of the results of study. The
limitations are alternatively interpreted as flaws or shortcomings due to
flawed methodology, observations, small number of experiments or non-
peer reviewed nature of study etc.
11. Bibliography

Rubric for Assessment of Project

PARAMETE Exemplary (4) Accomplishe Developing Beginner (1)

R d (3) (2)
Content covers Content Content Content does not
Factual the research well from all eras does not cover all eras and
information but has few cover all is historically
inaccuracies eras and Inaccurate
has few
inaccuracies
Multiple sources (6 Many sources Few sources Relied on only
or more) used (4-5) used used (2-3) one source
Sources (library, books, (Books,websit
interview with es, blogs )
people, different
websites, blogs etc.)
Collected data from Collected Collected Collected data
a large random data from a data from a from a small
sample (50 people fairly large small sample (10 or less
or more from random random people) OR
different age group, sample (30 - sample (20 collected data for
gender, social 50 people people from one sample and 1-
Data status) from different 2 readings
collection OR collected data different age age group,
for different samples group, gender,
and at least 5 gender, social
reading for each set social status) status) OR
of experiment OR collected collected
data for data for one
different sample and
samples and 3-5
3 reading for readings
each
set of
experiment

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In correlation with In correlation Not in Not in correlation
Interpretati data and aim of the with data and correlation with data and aim,
ons and project. Clear aim of the with data No conclusions
conclusion conclusions based project. but in
on Conclusions correlation
findings not with the
based on aim
findings Random
conclusions
Daily entries with Most of the Daily Random entries
details of entries done entries
Journal discussions and with details of without
brainstorming discussions details
sessions with the with
teacher. the teacher
Exceptionally Attractive, Information Presentation is
attractive, organized is organized confusing. There is
organized sequentially sequentiall no sequence.
sequentially and and y and
Project
logically, creatively logically, logically but
report
presented with data presented not in an
and clear some data attractive
conclusions and manner.
conclusions Random
Data
without
conclusions
Sites all sources Most of Few sources Uses other
Academic and gives due the cited people’s ideas
Honesty credits sources without giving
cited Credit

9
CHAPTER -1
ELECTROCHEMISTRY

 Electrochemical cells (Galvanic cells) produce electricity as a result of chemical

reaction, while in electrolytic cells electricity is used to produce a non-
spontaneous chemical change at the electrodes.
 In Galvanic Cells, oxidation occurs at –ve electrode called anode whereas
reduction occurs at +ve electrode called cathode.
 ELECTRODE POTENTIAL OF A CELL E0cell = E⁰ cathode - E⁰anode
(in terms of reduction potential)
 FREE ENERGY CHANGE FOR THE REACTION ∆G⁰ = -nF E⁰cell
𝟎.𝟎𝟓𝟗
 𝐄𝟎 𝐜𝐞𝐥𝐥 = 𝐧
log Kc (At 298 K) Kc is EQUILIBRIUM CONSTANT
𝟐.𝟑𝟎𝟑 𝐑𝐓
 ∆G0 = -nF 𝐧𝐅
log Kc or
 ∆G0 = -2.303 RT log Kc
 For an electrochemical cell if G0< 0 then cell will work
 E0cell is > 0 for spontaneous process.
 As per E0 values, a metal having more negative reduction potential is stronger
reducing agent than hydrogen while a metal having more positive reduction
potential is weaker reducing agent than hydrogen.
 NERNST EQUATION


 Mass of substance deposits at electrode m = Z I(amp) t(s) (FARADAYS
I LAW OF ELECTROLYSIS)
 Charge on one mole of electrons is equal to 96487 ≈ 96500 C/mol =1F.

 KOHLRAUSCH LAW
 SHE (Standard Hydrogen Electrode) is represented by
Pt/H2 (g, 1 bar)/ H+ (1M) and it is used as a reference half-cell.
2H+ (1M) + 2e– →H2 (g, 1 bar), E0 H+/H2 = 0 V
 Conductance (G) is inverse of resistance (R). Unit : Ohm–1 or S. G=1/R
 Conductivity (specific conductance) denoted by κ, is reciprocal of resistivity
and is expressed in S cm–1 . ƿ =1/κ
 Conductivity( κ) = Conductance (G) x cell constant(l/A)
(Cell constant unit is cm–1 or m–1 ).
 Molar conductance (λm ) is conductance of solution containing 1 mol of solute
in a given volume. Unit Scm2mol-1
 MOLAR CONDUCTANCE (λm) = κ x 1000/C
 Degree of dissociation (α) = λm / λm O
 K = C α2/1- α
 Conductivity decreases but molar conductivity increases with decrease in
concentration.
 In electrochemical process, the voltage required for a reaction is sometimes much
greater than that indicated by the electrode potentials. The additional voltage
required to cause electrolysis is called overvoltage.

10
QUESTIONS -ANSWERS
QUESTIONS – 2MARKS
1 Suggest a way to determine ᴧᵒm of water.
Ans: ᴧᵒm (H2O) = ʎᵒ(H+) + ʎᵒ(OH-)
= ʎᵒ(H+) + ʎᵒ(OH-) +ʎᵒ(Na+) - ʎᵒ(Na+) +ʎᵒ(Cl-) - ʎᵒ(Cl-)
= [ʎᵒ(H+) + ʎᵒ(Cl-) ]+ [ ʎᵒ(OH-) +ʎᵒ(Na+)] – [ʎᵒ(Na+) + - ʎᵒ(Cl-)]
ᴧᵒm (H2O) = ᴧᵒm (HCl) + ᴧᵒm (NaOH) -- ᴧᵒm (NaCl)
Thus the molar conductance of water can be determined.
2 Al2O3 is reduced by electrolysis at low potentials and high currents. If 4.0X 104 A
of current is passed through molten Al2O3 for 6 hrs , how much Al is produced?
Ans: Aluminium is in +3 oxidation state
so the production of 1 mol of Al requires 3 mol of electrons.
i.e 3 F = 3X96500 C
Total charge passed = 4.0 X104 A X 6 X 60 X 60 = 8.64 X 108 C
Mass of Al produced = 8.64 X 108 X27 / 3X96500
= 8.06 X104 g
3 On the basis of following data given identify the strongest oxidising agent
Fe2+ or Fe3+ or [Fe(CN)6]4- or [Fe(CN)6]3-
[Fe(CN)6] → [Fe(CN)6] +e- E = -0.35 V
4- 3- 0

Fe2+ → Fe3+ +e- E0= -0.77V

Ans: The species which have higher reduction potential can act as oxidising
agent. Among these only Fe3+ (0.77V) and [Fe(CN)6]3- (0.35 V) have positive
reduction potential.
Fe3+ is stronger oxidising agent as Reduction potential of Fe3+ is higher
than[Fe(CN)6]3-
4 ᴧᵒm for NaCl, HCl and CH3COONa are 126.0, 426, 1000 Scm2/mol respectively. If
the conductance of 0.001 M CH3COOH is 5X10-5 S/cm, calculate the degree of
dissociation of CH3COOH.
Ans:
ᴧᵒm CH3COOH = ᴧᵒm CH3COONa + ᴧᵒm HCl - ᴧᵒm NaCl
ᴧᵒm CH3COOH = 100+426-126 = 400 Scm2/mol
ᴧcm = 1000к/M = 1000x5X10-5/0.001 = 50 Scm2/mol
α = ᴧcm /ᴧᵒm = 50/400 =0.125 or
α =0.125 x100 = 12.5%
5 The molar conductance of an M/32 solution of weak monobasic acid is 8 mho cm
2
and that at infinite solution is 400 mho cm 2 . Find the dissociation constant of
the acid?
Ans: α = λm / λm O = 8 mho cm 2 /400 mho cm 2 = 0.02
Ka = c α2/1- α =(1/32)x(0.02)2/ 1-0.02
Ka = 1.25 x10-5
6 A galvanic cell has two hydrogen electrodes one is immersed in a solution with
[H+] = 1M and other is immersed in 0.85 M KOH. Determine Ecell.
Ans: The galvanic cell is Pt/H2 (g, 1 bar)/ H+ (xM)// H+ (1M)/ H2 (g),Pt
Where x= Kw/[OH-]
= 1X10-14/0.85
= 1.18 X10-14
Ecell = -0.0592log x
= 0.0592 x1.18 X10-14
= 0.82 v
7 Assess whether the following reaction is spontaneous or not?
2KMnO4 + 3H2SO4 + 5 H2C2O4 → 2MnSO4 + K2SO4 + 10CO2 + 8H2O
Ans: Separate the reactions in to oxidation and reduction half reactions.
+3 +4
11
Oxidation : H2C2O4→ 2CO2 + 2H+ +2e- E0ox = 0.49 V
+7 +2
Reduction: MnO4 - + 8H+ + 5e→ Mn2+ + 4 H2O E0red =1.47 V cell
E⁰ = E⁰ox + E⁰red
E⁰ = 0.49 +1.47 = 1.98v
E0 for the overall reaction is greater than zero so spontaneous.
8 What happens if external potential applied is greater than Eᵒcell of the
electrochemical cell?
Ans: If the external potential applied is greater than Eᵒcell , the reverse reaction
will take place and the cell starts acting like as an electrolytic cell. In this case
electrical energy is used to carry out non-spontaneous reaction.
9 If a current of 0.5 amperes flow through a metallic wire for 2 hours, then how
many electrons would flow through the wire?
Ans: Q (coulomb)= I (ampere) x t (second)
Q = 0.5 x 2 x 60 x 60 = 3600 c
A flow of 96500 C is equivalent to the flow of 1 mole of electrons
i.e 6.022x1023 electrons
Therefore 3600 C is equivalent to = 6.022x1023x3600 /96500
= 2.246x1022 electrons.
10 The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1
cm and length 50 cm is 5.55 × 103 ohm. Calculate its resistivity and conductivity.
A = πr2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2 , l = 50 cm
Ans: R = ƿ l/ A or Resistivity ƿ = R x A/l
= 5.55 × 103 x 0.785 / 50 = 87.135 ohm cm
Conductivity = 1/ƿ = 1/ 87.135 = 0.01148 S cm
QUESTIONS- 3 MARKS
11 Given two reactions
i) Cu2+ + 2 e- → Cu E⁰ Cu2+/Cu = 0.34 V
ii) Cu2+ + e- → Cu+ E⁰ Cu2+/Cu+ =0.153 V
Calculate E⁰ Cu+/Cu for the reaction Cu+ + e- → Cu
Ans: The given reaction can be obtained by subtracting (ii) from (i)
According to Thermodynamics ∆G⁰ is a state function, so
∆G0 Cu+/Cu = ∆G0 Cu2+/Cu - ∆G0 Cu2+/Cu +
-nF E0 Cu+/Cu = -(nF E0 Cu2+/Cu )- (-nF E0 Cu2+/Cu+)
= - (2F x 0. 34 V) + (1F x 0.153 V)
= -0.68F + 0.153 F
= - F (0.68 – 0.153) V
= -F x 0.527 V
So E0 Cu+/Cu = 0.527 V
12 What is the reduction potential at pH =14 for the Cu2+/Cu couple ?
Given E⁰ Cu2+/Cu = 0.34 V , Ksp of [Cu(OH)2] = 1 X1019
Ans: Ksp = [Cu2+] [OH-]2 = 1 X1019
So [Cu2+] = 1 X1019/ [OH-]2 = 1 X1019
0.059
From Nernst equation 𝐸cell = E 0 cell − log 1/Cu2+
2
E cell = 0.34-0.0295 log 1/1 X1019
E cell = 0.34-0.0295 x 19 = -0.22V
13 i) Calculate Eᵒcell for the following reaction at 298 K:
2Al(s) + 3 Cu2+(0.01M) → 2Al3+ (0.01M) + 3Cu (s) Given Ecell = 1.98V
ii) Can we store copper sulphate solution in aluminium container?

Ans:

12
i) [Al(s→Al3+(aq) + 3e-] x 2
[Cu2+(aq) + 2e- → Cu(s)] x3
___________________________________________
2Al(s) + 3 Cu2+(aq) → 2Al3+ (aq) + 3Cu (s) n= 6
__________________________________________
Substituting in Nernst equation
0.0591 [Al3+]2
Ecell = Eᵒ cell - 𝑛 log [𝐶𝑢2+]3
0.0591 [0.01]2
1.98 V = Eᵒ cell - 6
log [0.01]3
Eᵒ cell = 1.98 + 0.0197
= 1.9997 V
ii) No, we cannot store copper sulphate solution in aluminium container. Because
as per above reaction Al will displace Cu2+ from its solution.
14 One half cell in a voltaic cell is constructed from a silver nitrate solution of
unknown concentration. The other electrode consists of a zinc electrode in a 0.10
M solution of zinc nitrate. A voltage of 1.48 V is measured for this cell. Use this
information to calculate the concentration of silver ions in the solution.
Given than Eᵒ Zn2+/Zn = - 0.763V and Eᵒ Ag+/Ag = +0.80V
Ans:Electro chemical cell formed is Zn(s)/Zn2+ (0.010M) // Ag+ (x M) / Ag(s)
Eᵒcell = Eᵒ cathode - Eᵒ anode
= 0.80-(-0.763) V = 1.563 V
Nernst equation for the reaction
0.0591 [Zn2+]
E cell = Eᵒ cell - log [𝐴𝑔+]2
𝑛

0.0591 [0.10]
1.48 V= 1.563 v - 2
log [𝐴𝑔+]2
[0.10]
log [𝐴𝑔+]2
= 0.083/0.02955 = 2.8087
[0.10]
[𝐴𝑔+]2
= A.log(2.8087) = 643.7
[Ag+] =1.247 x10-2 M
15 Calculate the cell potential of galvanic cells in which the following reactions take
place. Also calculate equilibrium constant and ∆G0 of the reaction.
2Cr (s) + 3Cd2+ (aq) → 2Cr 3+(aq) + 3 Cd(s)
Given E0 Cd2+/Cd = -0.40V, E0 Cr3+/Cr =-0.74 V
Ans: E0cell = E0 Cd2+/Cd - E0 Cr3+/Cr = -0.40 –(-0.74) V = 0.34 V
∆G⁰ = -nF E0Cell = - 6 x 96500 x 0.34 = -196.86kJ/mol
= 196.86 x 10 3 J/mol
∆G0 = -2.303 RT log K
log K = ∆G0/ 2.303 RT
= 196.86 x 10 3 / 2.303 x 8.314 x 298 = 34.5014
K = A.log (34.5014)
= 3.16 x1034
16 In the Edison storage cell Fe(s)/KOH(aq) // Ni2O3(s) /Ni , the half cell reaction
are as follows.
Ni2O3(s) + H2O(l) + 2e- → 2NiO(s) + 2OH- E0 = = +0.40V
FeO (s) + H2O(l) + 2e- → Fe(s) + 2OH- E0 = = -0.87V
i) What is the cell reaction?
ii) What is the emf of the cell? How it depends upon the concentration of KOH?
iii) What is the maximum amount of electrical energy obtained from the cell?
Ans: i) The cell reaction is Fe(s) + Ni2O3(s) → FeO (s)+ 2NiO(s)
ii) E0cell = E0NI2O3/NiO – E0 FeO/Fe = 0.40 –(-0.87) V = 1.27 V
iii) The consumption of 1mol of Ni2O3 will deliver 2F charge across the electrodes
under a potential difference of 1.27 V.
13
Maximum amount of electrical energy available from the cell can be calculated
from the relation ∆G0 = -w or w = - ∆G0 = nF E0cell
= 2 x 96500 x 1.27
= 245110 J =245.11 kJ
Maximum amount of electrical energy available from the cell is 245.11 kJ
17 The emf of hydrogen-oxygen fuel cell is 1.23 V at 25ᵒC. What is the equilibrium
constant for the reaction 2H2 (g)+ O2(g) ↔ 2H2O(l)
Ans: Half cell reaction in hydrogen-oxygen fuel cell are as follows
Oxidation: H2 (g) + 2H2O → 2 H3O+ +2e-
Reduction: O2 (g) + 4H2O +4e- → 4OH-
Over all cell reaction is 2H2 (g)+ O2(g) ↔ 2H2O(l) which involves 4 F.
0.0591
At 25ᵒC E⁰cell = logK or log K = n E⁰cell / 0.0591
𝑛
log K = 4 x 1.23 / 0.0591 = 83.1081
K = antilog (83.1081) = 1.26 x 1083
18 Two students use the same stock of solution of ZnSO4 and a solution of CuSO4.
The emf of one cell is 0.03V higher than the other cell. The concentration of CuSO4
in the cell with higher emf is 0.5 M. Find the concentration of CuSO4 in the other
cell.
Ans: Let the concentration of the stock of ZnSO4 solution be C and concentration
of CuSO4 solution be C1 and C2 ( where C2>C1)
The emf of the two cells be E1 and E2
0.0591 [Zn2+] 0.0591 [C]
E1 = Eᵒcell - 𝑛 log [𝐶𝑢2+] so E1 = Eᵒcell - 2 log [𝐶1]
0.0591 [Zn2+] 0.0591 [C]
E2 = Eᵒcell - log [𝐶𝑢2+] so E2 = Eᵒcell - log [𝐶2]
𝑛 2
0.0591 [C2]
E2- E1 = 2
log [𝐶1] But E2- E1 =0.03 V as given.
[C2] [C2]
0.03 = 0.0296 log [𝐶1] so 1= log [𝐶1] or
[C2] [C2]
log [𝐶1]
= 𝐴. log(1) = 10 [𝐶1]
=10
C1 = C2/10 =0.05 M
19 Calculate the emf of the following cell when 99.99% of Cu2+ ion is consumed.
Zn(s)/Zn2+ (1M) // Cu2+ (1M) / Cu(s) Eᵒcell = 1.10 V
Ans: When 99.99% Cu2+ ion is consumed, its concentration decreases by
0.9999M and Zn2+ ion concentration increases by 0.9999 M.
Final concentration of Cu2+ ion = 0.0001M and Zn2+ ion =1.9999M
0.0591 [Zn2+] 0.0591 1.9999
Ecell = Eᵒcell - 𝑛 log [𝐶𝑢2+] = 1.10 - 2 log 0.0001
0.0591
Ecell = 1.10 - 2
log (.9999x104) Ecell = 0.97 V
20 The emf of the cell corresponding to the reaction
Zn(s) + 2H+(aq) → Zn2+ (aq, 0.1M) + H2(g ,1 atm) Given Ecell = 0.28V
Write the half cell reaction and calculate the pH of the solution.
Given EO Zn2+/Zn = -0.76V, E0 H+/H2 = 0 V
Ans: Anode reaction Zn(s) → Zn2+ (aq) + 2e-
Cathode reaction 2H+(aq) +2e-→ H2(g)
Nernst equation for the above reaction
0.0591 pH2 [Zn2+]
Ecell = Eᵒcell - 𝑛 log [𝐻+]2
0.0591 1 atm [0.1[]
Ecell = 0.76 V - 2
log [𝐻+]2
0.0591 0.0591
Ecell = 0.76 V -{ 2
log (1 x0.1) - 2 log [H+]2 }
0.0591 0.0591
0.28 = 0.76 V -{ log (1 x0.1) -2 X log [H+] }
2 2
0.28 = 0.76 –(-0.03) -0.0591pH
0.28 = 0.79 -0.0591 pH
pH = (0.79-0.28) /0.0591 = 8.6
14
QUESTIONS- 5 MARKS
21 (a) What is limiting molar conductivity? Why there is steep rise in the molar
conductivity of weak electrolyte on dilution?
(b) Calculate the emf of the following cell at 298 K :
Mg (s) | Mg2+ (0.1 M) || Cu2+ (1.0 × 10-3M) | Cu (s)
[Given = E0 Cell = 2.71 V].
Ans: (a) The molar conductivity of a solution at infinite dilution is called limiting
molar conductivity and is represented by the symbol Λ∘m
There is steep rise in the molar conductivity of weak electrolyte on dilution
because as the concentration of the weak electrolyte is reduced, more of it ionizes
and thus rapid increase in the number of ions in the solution.

22 Consider the figure given and answer the following questions :

(i) What is the direction of flow of electrons?
(ii) Which is anode and which is cathode?
(iii) What will happen if the salt bridge is removed?

(iv) How will concentration of Zn2+ and Ag+ ions be affected when the cell
functions?
(v) How will concentration of these ions be affected when the cell becomes
dead?
Ans: (i) Electrons flow from anode (Zinc plate) to cathode (Silver plate).
(ii) Zinc plate where oxidation occurs acts as anode and silver plate where
reduction occurs acts as cathode.
(iii) If the salt bridge is removed then electrons from zinc electrode will flow to
the silver electrode where they will neutralize some of Ag+ ions and
the SO42− ions will be left and the solution will acquire a negative charge.
Secondly the Zn2+ ions from zinc plate will enter into ZnSO4 solution producing
positive charge. Thus due to accumulation of charges in two solutions, further
flow of electrons will stop and hence the current stops flowing and the cell will
stop functioning.
(iv) As silver from silver sulphate solution is deposited on the silver electrode and
sulphate ions migrate to the other side, the concentration of Ag 2SO4 solution
decreases and of ZnSO4 solution increases as the cell operates.
(v) When the cell becomes dead, the concentration of these ions become equal
due to attainment of equilibrium and zero EMF.

15
23 (a) Calculate E0cell for the following reaction at 298 K:
2Al(s) + 3Cu2+ (0.01M) → 2Al2+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V
(b) Using the E0 values of A and B, predict which is better for coating the surface
of iron [E0(Fe2+/Fe) = -0.44 V] to prevent corrosion and why?
Given: E0(A2+/A) = -2.37 V; E0(B2+/B) = -0.14 V (All India 2016)
Ans: (a) For the reaction 2Al(s) + 3Cu2+ (0.01M) → 2Al3+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V E0cell = ? Nernst equation for the reaction is

(a) Element A will be better for coating the surface of iron than element
because its E° value is more negative.
24 One half-cell in a voltaic cell is constructed from a silver wire dipped in silver
nitrate solution of unknown concentration. Its other half-cell consists of a zinc
electrode dipping in 1.0 M solution of Zn(NO3)2. A voltage of 1.48 V is measured
for this cell. Use this information to calculate the concentration of silver nitrate
solution used.
(E Zn2+/Zn=−0.76V,E Ag+/Ag = + 0.80 V)
0 0

Ans:In this silver electrode act as cathode and zinc electrode act as anode.
Half cell reactions take place at silver and zinc electrode are as follows

25 a) A current was passed for 5 hours through two electrolytic cells connected in
series. The first cell contains AuCl3 and second cell CuSO4 solution. If 9.85 g of
gold was deposited in the first cell, what amount of copper gets deposited in the
second cell? Also calculate magnitude of current in ampere.
Given: Atomic mass of Au = 197 g/mol and Cu = 63.5 g/mol)

b) Two half-reactions of an electrochemical cell are given below :

MnO–4 (aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = 1.51 V
Sn2+ (aq) → Sn4+ (aq) + 2e–, E° = + 0.15 V.
Construct the redox reaction equation from the two half-reactions and calculate
the cell potential from the standard potentials and predict if the reaction is
reactant or product favoured.

16
Ans: a) According to Faraday’s II law of electrolysis

b) Redox Equation: 2MnO– 4(aq) + 16H+ + 5Sn2+ → 2Mn2+ + 5Sn4+ + 8H2O

E°cell = E°cathode – E°anode or E°cell= + 1.36 E°cell > 0 so Product Favoured
PASSAGE-BASED INTEGRATED QUESTIONS
Passage-1
Metallic conductance involves movement of electrons where as electrolytic
conductance involves movement of ions. Specific conductance increases with
increase in concentration where as m (molar conductivity) decreases with
increase in concentration. Electrochemical cell converts chemical energy of
redox reaction into electricity.
Electrochemical series is arrangement of elements in increasing order of their
reduction potential. Electrolytic cell converts electrical energy into chemical
energy which is used in electrolysis. Amount of products formed are decided
with the help of Faraday’s laws of Electrolysis. Kohlrausch law helps to determine
limiting molar conductivity of weak electrolyte, their degree of ionisation () and
their dissociation constants. Corrosion is electrochemical phenomenon. Metal
undergoing corrosion acts as anode, loses electrons to form ions which combine
with substances present in atmosphere to form surface compounds.
(a) Out of 0.5 M, 0.01 M, 0.1 M and 1.0 M which solution of KCl will have
highest value of specific conductance? Why?
Ans. 1.0 M KCl solution because it will have more number of ions per unit volume
of solution.
(b) Write the product of electrolysis of aq. NaCl on
Ans. At cathode. 2H+ + 2e–  H2 (g)
At anode 2Cl- + e-  Cl2 (g)
(c) When does electrochemical cell behaves like electrolytic cell?
Ans. When Eexternal > E°cell
(d) For a electro chemical cell Mg(s) + 2Ag+(aq)  2Ag(s) + Mg2+. Give the
cell representation and write Nernst equation.
Ans. Mg(s) | Mg2+(aq) | | Ag+(aq) | Ag(s)

(e) Which will have higher conductance, silver wire at 30° or at 60°C?
Ans. Silver wire at 30°C. Metallic conductance decreases with increase in
temperature.
17
Passage-2
Observe the graph shown in figure between m (molar conductivity) Vs C
(Molar concentration) and answer the questions based on graph.

(a)The curve ‘Y’ is for KCl or CH3COOH? Ans. It is for CH3COOH.

(b) What is intercept on m axis for ‘X’ equal to?
Ans. It is equal ° (limiting molar conductivity).
(c) Give mathematical equation representing straight line.

(d) What is slope equal to? Ans. Slope = –A

(e) What happens to molar conductivity on dilution in case of weak electrolyte
and why?
Ans. m for weak electrolyte increases sharply on dilution because both number
of ions as well as mobility of ions increases.
Passage-3
Observe the following table in which conductivity and molar conductivity of NaCl
at 298 K at different concentration for different electrolytes is given. Answer the
questions based in the table that follows:
Conductivities and molar conductivities of NaCl at 298 K at different
concentrations.

18
(a) What happens to conductivity on dilution and why?
Ans. Conductivity decreases with decrease in concentration (dilution)
because number of ions per unit volume decreases.
(b) Why is °m (limiting molar conductivity) for HCl more than NaCl?
Ans. because mobility of H+ is more than Na+ became H+ are lighter than Na+
(c) Calculate degree of dissociation (α) of NaCl of 0.001 M concentration
using the table.

(d) Calculate Λ° m of CH3COOH using the table.

(e) Calculate Ka of 0.01 M CH3COOH solution if Λ°m for CH3COOH is 390.07S

cm mol–1 and Λm = 39.07S cm–1.
2

Passage-4
The working of a galvanic cell is quite simple. It involves a chemical reaction that
makes the electric energy available as the end result. During a redox reaction,
a galvanic cell utilizes the energy transfer between electrons to convert chemical
energy into electric energy.
Galvanic cell utilizes the ability to separate the flow of electrons in the process
of oxidization and reduction, causing a half reaction and connecting each with a
wire so that a path can be formed for the flow of electrons through such wire.
This flow of electrons is essentially called a current. Such current can be made
to flow through a wire to complete a circuit and obtain its output in any device
such as a television or a watch.

19
(a) What is the electrochemical cell?
Ans:- change chemical energy in to electric energy
(b) When the salt bridge is removed from a cell, its voltage
Ans: will decrease to zero
(c) What is the direction of current flow in this galvanic cell
Ans: Ag electrode to Cu electrode
(d) How many coulombs of electricity flow in this galvanic cell?
Ans: 193000 C
(e) Write the formulation for the galvanic cell in which the reaction.

Cu (s) +2Ag+(aq) Cu (aq) + 2Ag (s) take place. Identify the cathode and
2+

anode reactions in it
2+
Ans: (i) Cu (s)  Cu (aq) + 2e - ( At anode)

(ii) 2 Ag+ (aq) + 2e -  2Ag(s) ( At cathode)

20
CHAPTER-4 CHEMICAL KINETICS
SN Question-5 MARKS

1 Observe the following graphs and answer the questions based on these graphs.

(a) What is order of reaction shown in graph I?

(b) What is slope in graph II?
(c) How does t1/2 varies with initial concentration in zero order reaction.
(d) If t1/2 of first order reaction is 40 minute, what will be t99.9% for first order
reaction?
(e) What is t1/2 of zero order reaction in terms of‘k’?
2 Observe the table given showing volume of CO2 obtained by reaction of CaCO3 and
dilute HCl after every minute. Answer the questions that follow:Table showing volume
of CO2 at one minute interval by reaction of CaCO3 with dilute HCl.
(a) What happens to rate of reaction
with time?
(b) Why does CaCO3 powder react faster
than marble chips?
(c) What happens to rate of reaction if
concentrated HCl is used?
(d) In manufacture of NH3, N2(g) +
3H2(g) 2NH3 + heat what is effect of
pressure on rate of reaction?
(e) Why does rate of reaction becomes
almost double for energy 10° rise in
temperature?
Question-2 MARKS
3 For a reaction R → P, half-life (t1/2) is observed to be independent of the initial
concentration of reactants. What is the order of reaction?
4 (a)For a reaction, A + B Product, the rate law is given by, Rate = k [A]1 [B]2 . What
is the order of reaction?
(b) Write the unit of rate constat ‘k’ for the first order reaction.
5 Define half-life of a reaction. Write the expression of half-life for (i) zero order reaction
and (ii) first order reaction
6 Define the following terms: (i) Pseudo first order reaction (ii) Half life period of
reaction (t1/2)
7 (а) For a reaction A + B P, the rate law is given by r = k [A1/2 ] [A]2 What is the

21
order of this reaction?
(b) A first order reaction is found to have a rate constant k = 5.5 X 10-14 s-1. Find the
half life of the reaction.
8 The rate constant for a first order reaction is 60 s 1. How much time will it take to
reduce the initial concentration of the reactant to 1/10 th of its initial value?
9 i) If half life period of first order reaction is x and 3/4 th life period of same reaction
is ’y’, how are V and ’y’ related to each other?
(ii) In some cases it is found that a large number of colliding molecules have energy
more than threshold energy but yet the reaction is slow. Why?
10 The rate of a reaction becomes four times when the temperature changes from 293 K
to 313 K. Calculate the energy of activation (Ea) of the reaction assuming that it does
not change with temperature. [R = 8.314 J K-1 mol-1, log 4 = 0.6021]
11 A reaction is of second order with respect to a reactant. How is its rate affected if the
concentration of the reactant is (i) doubled (ii) reduced to half
12 Distinguish between ‘rate expression’ and rate constant’ of a reaction.
13

14 Rate of reaction, A + B Product is given below as a function of different initial

concentration of A and B

(a)Determine the order of the reaction with respect of A and B.

(b)What is the half-life of A in the reaction
15 One of the hazards of nuclear explosion is the generation of Sr90 and its subsequent
incorporation in bones. This nuclide has a half life of 28.1 year. Suppose one
microgram was absorbed by a new born-child, How much Sr90 will remain in his bones
after 20 year
16 At 3800C,the half-life period for the first order decomposition of H2O2 is 360 min.The
energy of activation of the reaction is 200 KJmol-1.Claculate the time required for 75%
decomosition at 4500C
Question-3 MARKS
17 Rate constant is equal to the rate of reaction when molar cone, of reactants is unity.
Its unit depends upon order of reaction. A reactant has a half-life of 10 minutes.
(i) Calculate the rate constant for the first order reaction.
(ii) What fraction of the reactant will be left after an hour of the reaction has occurred?
18 A first order reaction takes 10 minutes for 25% decomposition. Calculate t1/2 for the
reaction. (Given: log 2 = 0.3010, log 3 = 0.4771, log 4 = 0.6021).

22
19 The following data were obtained during the first order thermal decomposition
of S02Cl2 at a constant volume: Calculate the rate constant. (Given: log 4 = 0.6021,
log 2 = 0.3010)

20 A first order gas phase reaction: A2B2(g) → 2A(g) + 2B(g) at the temperature 400°C
has the rate constant k = 2.0 × 10-4 sec-1. What percentage of A2B2 is decomposed on
heating for 900 seconds? (Antilog 0.0781 = 1.197)
21 A first order reaction is 20% complete in 10 min. Calculate
(i) the specific rate constant of the reaction, and
(ii) Time taken for the reaction to go to 75% completion.
22 Radioactive de cay is a first or der process. Radioactive carbon in wood sample de
cays with a half-life of 5770 year. What is the rate constant (in year-1) for the de cay?
What fraction would remain after 11540 year?
23 In Arrhenius equation for a certain reaction, the value of A and Ea(activation energy)
are 4 X1013 s-1 and 98.6 kJ mol–1respectively. If the reaction is of first or der, at what
temperature will its half-life period be 10 min?
24 The rate constant for an isomerisation re action, A  B is 4.5X10-3 min. If the initial
concentration of A is 1M. Calculate the rate of the reaction after 1 h.
25 A first order reaction is 20% complete in 10 min.Calculate
(i)the specific rate constant of the reaction
(ii)the time taken for the reaction to go to 75% completion,
Question-5 MARKS
26 (a)What do you mean by pseudo first order reaction? Explain with example
(b)For a reaction: H2 + Cl2 (hv)⟶ 2HCl Rate = k
(i) Write the order and molecularity of this reaction. (ii) Write the unit of k.
27 The rate of first or der reaction is 0.04 mol L-1 s–1 at 10 min and 0.03 mol L–1 s–1 at 20
min after initiation. Find the half-life of the reaction.
28 For the hydrolysis of methyl acetate in aqueous solution, the following result were
obtained.

(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.
(Given: log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)
29 (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 takes 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)
23
SN ANSWERS
1 (a) Zero order reaction. (b) k /2.303where ‘k’ is rate constant. (c) t1/2 is
directly proportional to initial concentration.
(d) t99.9% = 10 t1/2 = 10 × 40 = 400 minutes
(e) t1/2 = [R]0 /2k for zero order reaction.
2 (a) The rate of reaction first decreases with time then
becomes constant.
(b) CaCO3 powder has more surface area than marble chips therefore, more
rate of reaction.
(c) The rate of reaction will increase because rate of reaction increases with the
increase in concentration.
(d) The rate of reaction increases with increase in pressure.
(e) It is because number of molecules undergoing effective collisions become
almost double, hence rate of reaction almost doubled.
3 It is because the concentration of reactants goes on decreasing with time
4 The sum of powers to which concentration terms are raised in rate law or rate
equation.
5 The extra energy which must be supplied to the reactants so that they can
undergo effective collision to form products.
6 It is equal to the rate of reaction when molar concentration of reactant are taken
as unity
7 (i)s-1is the unit of first order rate constant. (ii) L mol-1 s-1is the unit of second
order rate constant.
8 The change in the concentration of any one of the reactants or products per unit
time is called rate of a reaction
9

10 S-1 is the unit for rate constant of first order reaction.

11 Mol L-1 S-1
12 The t1/2 of a first order reaction is independent of initial concentration of
reactants.
13

24
14

15

16

17

18

25
19

20

21

22

23

26
24

25

26 (a)Those reactions which are not truly of the first order but under certain
conditions become first order reactions are called pseudo first order reaction.eg
Hydrolysis of Ester
(i)This reaction is zero order reaction and molecularity is two. (ii) Unit of k =
mol L-1 s-1
27

28

27
29

PASSAGE-BASED
Passage-1
Observe the following graphs and answer the questions based on these graphs.

(a) What is order of reaction shown in graph I?

Ans :- Zero order reaction.
(b) What is slope in graph II?
Ans: k /2.303where ‘k’ is rate constant.
(c) How does t1/2 varies with initial concentration in zero order reaction.
Ans: t1/2 is directly proportional to initial concentration.
(d) If t1/2 of first order reaction is 40 minute, what will be t99.9% for first
order reaction?
Ans: t99.9% = 10 t1/2 = 10 × 40 = 400 minutes
(e) What is t1/2 of zero order reaction in terms of‘k’?
Ans: t1/2 = [R]0 /2k for zero order reaction.

Passage-2
Observe the table given showing volume of CO2 obtained by reaction of CaCO3
and dilute HCl after every minute. Answer the questions that follow:Table
showing volume of CO2 at one minute interval by reaction of CaCO3 with dilute
HCl.

28
(a) What happens to rate of reaction with time?
Ans:- The rate of reaction first decreases with time then becomes
constant.
(b) Why does CaCO3 powder react faster than marble chips?
Ans: CaCO3 powder has more surface area than marble chips therefore, more
rate of reaction.
(c) What happens to rate of reaction if concentrated HCl is used?
Ans: The rate of reaction will increase because rate of reaction increases with
the increase in concentration.
(d) In manufacture of NH3, N2(g) + 3H2(g) 2NH3 + heat what is effect
of pressure on rate of reaction?
Ans: The rate of reaction increases with increase in pressure.
(e) Why does rate of reaction becomes almost double for energy 10° rise
in temperature?
Ans: It is because number of molecules undergoing effective collisions
become almost double, hence rate of reaction almost doubled.
Passage-3
The rate of a chemical reaction is expressed either in terms of decrease in the
concentration of reactant per unit time or increase in the concentration of a
product per unit time . rate of reaction depends upon the nature of reactants,
concentration of reactants , temperature, presence of catalyst, surface area
of reactancts and presence of light. Rate of reaction is directly related to the
concentration of reactant. Rate law states that the rate of reaction depends
upon the concentration of terms on which the rate of reaction actually
depends, as observed experimentally. The sum of powers of the concentration
of the reactants in the rate law expression is called order of reaction while the
number of reacting species taking part in an elementary reaction which must
collide simultaneously in order to bring about a chemical reaction is called
molecularity of the reaction.
(a) If the rate of a reaction is expressed by, rate = K [A]² [B], the order
of reaction will be
Ans: 3
(b) The unit of rate constant for the reaction which has
rate =K[H2] [NO]2
Ans: mol-2 L² s-1
29
(c) For a reaction x + y → z, rate α |X|. What is (i) moleculariiy and (ii) order
of reaction?
Ans: (i) 2, (ii) 1
(d) The number of molecules of the reactants taking part in a single step
of the reaction is indicative of-
Ans:- molecularity of a reaction

Passage-4

The half-life of a reaction is the time required for the concentration of reactant
to decrease by half, i.e., [A]t = [A]/2
For first order reaction, t1/2 = 0.693/k
this means t1/2 is independent of initial concentration. Figure shows that typical
variation of concentration of reactant exhibiting first order kinetics. It may be
noted that though the major portion of the first order kinetics may be over in a
finite time, but the reaction will never cease as the concentration of reactant will
be zero only at infinite time.

The following questions are multiple choice question. Choose the most
appropriate answer:
(a) A first order reaction has a rate constant k=3.01 x 10-3 /s. How long
it will take to decompose half of the reactant?
Ans : 230.3 s
(b) The rate constant for a first order reaction is 7.0 x 10 -4 s-1. If initial
concentration of reactant is 0.080 M, what is the half-life of reaction?
Ans :- 990 s
(c) The rate of a first order reaction is 0.04 mol L-1 s-1 at 10 minutes and 0.03
mol L-1 s-1 at 20 minutes after initiation. The half life of the reaction is
Ans: 24.086 min
(d) The plot of t1/2 vs initial concentration [A]0 for a first order reaction
is given by

30
UNIT-5 SURFACE CHEMISTRY
The branch of the Chemistry which deals with the study of surface
phenomena is called surface Chemistry.
Phenomenon which occurs at surfaces- Rusting of iron, Crystallization,
dissolution, Adsorption on solids or on liquids etc.
1. Adsorption: - The accumulation of molecules species at the surface rather
in the bulk of a solid or liquid is termed adsorption.
2. Desorption:-Removal of adsorbate from the surface of adsorbent is known
as Desorption.
3. Sorption:-When adsorption and absorption both takes place
simultaneously.
4.Type of adsorption: - On the basis of interaction between adsorption and
absorption, adsorbate are of two types:
(i) Physical adsorption/physisorption: - van der Waals’ forces / not
specific /reversible /easily liquefiable gases adsorbed readily./ Enthalpy of
adsorption is low/ Low temperature is favourable / Multimolecular layers.
(ii) Chemical adsorption/chemisortion:- chemical bond /highly specific /
irreversible/Enthalpy of adsorption high / High temperature is favourable /
/unimolecular layer.
5. Adsorption is always exothermic :-
 During adsorption,There is always a decrease in residual forces
of the surface, this decrease in surface energy which appears as
heat hence Adsorption is an exothermic process.
 Adsorption is accompanied by decrease in enthalpy, hence ΔH of
adsorption is always negative (ΔH is –ve).
 There is decrease in entropy, ΔS is -ve. For a process to be
spontaneous, ΔG must be negative, so ΔH should have
sufficiently high-ve value.
6. Adsorption and Absorption :- In adsorption, the substance is
concentrated only at the surface while in absorption, the substance is
uniformly distributed throughout the bulk of the solid.
7. Adsorption isotherm:-The variation in the amount of gas adsorbed
by the adsorbent with pressure at constant temperature can be
expressed by means of a curve termed as adsorption isotherm.

8. Application of adsorption:-.
(a) Removal of colouring matter from solution using animal charcoal.
(b)Chromatographic analysis is based on adsorption.

9. Freundlich adsorption isotherm:-It is a graph which shows relationship

between the quality of gas adsorbed by unit mass of solid adsorbent and
pressure at a particular temperature.
31
X / m = k.P1/n (n > 1) log
x/m = log k + 1/n log P
where, x= amount of gas adsorbed on
mass ‘m’ of adsorbent.

10 .Factors affecting adsorption:-

(i) Surface area: - Adsorption increases with increases of surface area of
adsorbent.
(ii) Nature of adsorbate:- Easily liquefiable gases are readily adsorbed.
(iii) Temperature:-Low temperature is favorable for physical adsorption and
High temperature for chemisortion.
(iv) Pressure: - Pressure increases, adsorption increases.
11. Colloid-a colloid is a heterogeneous system in which one substance is
dispersed (dispersed phase)in another substance called dispersion medium and
size of dispersed phase is from 1nm- 1000 nm.
[Here dispersed phase as solute and dispersion medium as solvent ]
12. TYPES OF COLLOIDS
(I) On the basis of nature of interaction between dispersed phase and
dispersion medium. (a)Lyophilic colloid :- Liquid(solvent)-loving/ can be
reconstituted/ reversible/easily prepared/stable/ eg- gum, starch etc
(b) Lyophobic colloid- Liquid-hating/ not be reconstituted/ irreversible/
prepared by special methods/ precipitated on addition of
electrolytes/heating/shaking/ not stable./ eg –metal sols , sulphide sols.
(II) On the basis of types of particles of the dispersed phase
(a) Multimolecular Large number of atoms or molecules of a substance
aggregate eg- gold sol , sulphur sol.
(b) Macromolecular colloids -macromolecules are suitable solvent from
solution in which size of the particles are in range of colloidal range.eg starch sol
(c) Associated colloids (micelles)-some substances in law concentration
behaves as normal strong electrolyte but at higher concentration exhibit colloidal
behavior due to formation of aggregates. The aggregated particles are called
micelles and also known as associated colloids.
13.Kraft temperature- Temp. above which formation of micelles takes places.
14. Critical micelle concentration (cmc) - concentration above which
micelle formation takes place is known as cmc.
15. Cleansing action of soaps :- Soap molecules form micelle around the oil
droplet in such a way that hydrophobic part of the stearate ions is in the oil
droplet and hydrophilic part projects out of the grease droplet like the bristles .
Since the polar groups can interact with water, the oil droplet surrounded by
stearate ions is now pulled in water and removed from the dirty surface.
32
16. PREPERATION OF COLLOIDS
(a) Bredig’s arc method- For preparation of metallic sol. It involves
dispersion as well as condensation.
(c) Peptization- Process of converting a precipitate into colloidal sol. By
shaking it with dispersion medium in the presence of a of electrolyte (peptizing
agent).
17.PURIFICATION OF COLLIODAL SOLUTION :-
(a) Dialysis-it is a process of removing a dissolved substance from a colloidal
solution by membrane.
(b) Electro dialysis-when dialysis is carried out with an electric field applied
around the membrane.
(c) Ultra filtration- Use of special filters which are permeable to all ionic
substances except colloidal particles.
18. PROPERTIES OF COLLOIDAL SOLUTION:-
(1) Brownian movement-zig-zag motion of colloidal particles
(2) Tyndall effect-scattering of light by colloidal particles by which path of
beam becomes clearly visible. This effect is known as tyndall effect.
Conditions for Tyndall effect
 Diameter of particles is not much smaller than wavelength of the
light used;
 Refractive indices of the phase and medium differ greatly in magnitude
19. Charge on colloidal particles – Colloidal particles which carry on electric
charge and nature of charge is same on all particles.
+ve charged sols :- Hydrated metallic oxides,/methylene blue sol.
/Haemoglobin (blood)
- ve charged sols :- Metals,/ sulphides/ eosin, congo red / starch, gum,
gelatin, clay,charcoal.
Origin of charge on colloidal particles :- Preferential adsorption of ions .
The sol particles acquire positive or negative charge by preferential adsorption
of +ve or –ve ions. When two or more ions are present in the dispersion
medium, preferential adsorption of the ion common to the colloidal particle
usually takes place. AgI/I–
20. Zeta potential :- Potential difference between the fixed layer and
the diffused layer 1.Electrophoresis - Movement of Colloidal particles
towards opposite electrode in presence of external electric field.
2. Coagulation – The process of setting of colloidal particles is called
coagulation of the sol.

21.Hardy Schulze Law – Coagulating value of a coagulating ion is directly

proportional to the charge on the ion.
For coagulation of a negative sol, : Al3+>Ba2+>Na+
For coagulation of a negative sol : [Fe(CN)6]4– > PO4 3– > SO4 2– > Cl–
Coagulation value :- The minimum amount of an electrolyte in millimoles
required to coagulate 1 litre colloidal solution is called coagulating value or
Flocculation value.
33
Formation of Delta :- River water is a colloidal solution of clay. Sea water
contains a number of electrolytes. When river water meets the sea water, the
electrolytes present in sea water coagulate the colloidal solution of clay
resulting in its deposition.
Electrical precipitation of smoke(Cottrellppter) :- The smoke, before it
comes out from the chimney, is led through a chamber containing plates having
a charge opposite to that carried by smoke particles. The particles on coming
in contact with these plates lose their charge and get precipitated.
Leather tanning: Tanning is the process of treating the skins of animals to
obtain the leather. Skin of animals is also a colloidal system in which the
colloidal particles are positively charged. the charged particles of skin are
coagulated using negatively charged material like tannin and compounds of Al
and Cr.

SHORT ANSWER TYPE – 1 (2 MARKS EACH)

Q. 1. Define the terms : (a) Helmholtz electrical double layer (b) Zeta potential
Q. 2. Mention the two necessary conditions for the observation of Tyndall effect.
Q. 3.(a) Why does a gas mixed with another gas not form a colloidal system ?
(b)Why are adsorbate particles attracted and retained on the surface of
adsorbent ?
Q. 4. Explain the terms sorption and desorption.
Q 5. (a)“Adsorbents in finely divided form are more effective.” Why ?
(b) Why gas masks are used by miners in coal mines while working ?
Q6.(a) Name two compounds used as adsorbent for controlling humidity.
(b) Generally high temperature is favourable for chemisorption.’ Why ?
Q7. (a)What is the composition of colloidion solution ?
(b) Why do colloidal particles show Brownian movement ?
Q8. (a)“Chemisorption is highly specific.” Illustrate with an example.
(b) State the sign of entropy change involved when the molecules of a substance
get adsorbed on a solid surface.
Q9. Define the term peptization and mention its cause.
Q.10.(a).What do ‘x’ and ‘m’ represent in the expression for Fruendlich
adsorption isotherm x/m=kp1/n
(b)What is the main drawback of the freundlich adsorption isotherm?

SHORT ANSWER TYPE –II (3 MARKS EACH)

Q.1. What do you understand by activation of adsorbent? How is it achieved?
Q.2. (a)Why is adsorption always exothermic?
(b) What is saturation pressure in Freundlich’s isotherm ?
34
Q.3 What are lyophilic and lyophobic sols? Give one example of each type.
Q.4.(a) Why are hydrophobic sols easily coagulated?
(b) When river water meets the sea water.
Q. 5.(a) Explain the terms : (i) CMC, (ii) Kraft temperature (Tk).
(b) State the purpose of impregnating the filter paper with colloidion solution.
Q. 6. Distinguish between multimolecular, macromolecular and associated
colloids with the help of one example of each.
Q. 7. Write short notes on the following :
(a) Tyndall Effect (b) Brownian Movement (c) Hardy Schulze Rule
Q.8. .Explain what is observe when-
i) An electrolyte, NaCl is added to hydrate ferric oxide sol.
ii) Electric current is passed through a colloidal sol.
iii) When a beam of light is passed through a colloidal sol.
Q.9. (a) Name the fixed layer and the diffused layer
(1) when AgNO3 is added to KI
(2) When KI is added to AgNO3
(b) What happens when dialysis is prolonged ?
Q.10. "Action of soap is due to emulsification and micelle formation”. Comment.

LONG ANSWER TYPE QUESTIONS (5 marks each)

1. What is the difference between physisorption and chemisorption?

2. Explain the following with diagrams:
(a) Dialysis (b) Electro-dialysis (c) Electrophoresis.
3. (a) Why is ferric chloride preferred over potassium chloride in case of a cut
Leading to bleeding?
(b) Cottrell’s smoke precipitator is fitted at the mouth of the chimney used in
factories.
(C) What is the main cause of charge on a colloidal solution?
(d) How does an increase in temperature affect both physical as well as chemical
adsorption ? (e). Why the sun looks red at the time of setting? Explain on the
basis of colloidal properties.

SHORT ANSWER TYPE-I (2 MARKS EACH)

1. Ans :- (a) The combination of the two layers of opposite charges around the
colloidal particles.
E.g., AgI/I : K+
(b) The potential difference between the fixed layer and diffused layer of
opposite charges is called zeta potential.
2. Ans :- (a) The size of dispersed phase particles is not much smaller the
wavelength of light used.
(b) The refractive indices of the dispersed phase and the dispersion medium
35
differ greatly in magnitude.
3. Ans :- (a) Gaseous mixture is homogeneous.
(b) The unbalanced forces of the adsorbent are responsible for attracting
adsorbate particles at adsorbent surface.
4. Ans :- Sorption is used to describe the process when adsorption and
absorption take place simultaneously.
Desorption : Removal of adsorbate from the surface of adsorbent.
5. Ans (a) Due to their more surface area in finely divided form.
(b) To absorb poisonous gases
6. Ans.(a) Silica gel, Alumina gel (b) To provide energy of activation.
7. Ans:-: (a) 4% solution of nitrocellulose in a mixture of alcohol and ether.
(b) Due to unbalanced bombardment of the dispersed phase particles by the
molecules of the dispersion medium.
8. Ans : (a) As it involves chemical bonding between adsorbent and adsorbate
(b) Entropy decreases (-ve)
9. Ans : - It is the process of converting a ppts into a colloidal sol by shaking it
with small amount of electrolyte with dispersion medium.
Cause:- Ppts adsorbs one of the ions of the electrolyte on its surface.
10. Ans:- (a) ‘m’ is the mass of the adsorbent and ‘x’ is the number of moles of
the adsorbate when the dynamic equilibrium has been achieved between the
free gas and the adsorbed gas
(b) The main drawback of the Freundlich’s adsorption isotherm is that it does
not confirm the experimental results at high pressure i.e. it fails at high pressure
of the gas.
SHORT ANSWER TYPE –II (3 MARKS EACH)
1. Ans -By activating an adsorbent, we tend to increase the adsorbing power of
the adsorbent. Some ways to activate an adsorbent are:
(i) By increasing the surface area of the adsorbent. This can be done by breaking
it into smaller pieces or powdering it.
(ii) Some specific treatments can also lead to the activation of the adsorbent.
For example, wood charcoal is activated by heating it between 650 K and 1330
K in vacuum or air. It expels all the gases absorbed or adsorbed and thus,
creates a space for adsorption of gases.
2. Ans :-(a) Adsorption is always exothermic. This statement can be explained
in two ways.
(i) Adsorption leads to a decrease in the residual forces on the surface of the
adsorbent.
This causes a decrease in the surface energy of the adsorbent. Therefore,
adsorption is always exothermic.
(ii) ∆H of adsorption is always negative. When a gas is adsorbed on a solid
surface, its movement is restricted leading to decrease in the entropy of the gas
i.e., ∆S is negative. Now for a process to be spontaneous, ∆G should be negative.
∆G = ∆H − T∆S
Since AS is negative, AH has to be negative to make AG negative. Hence,
adsorption is always exothermic.
(b) High pressure
36
3. Ans

Lyophobic sols Lyophilic sols

solvent hating colloids solvent loving colloids
In these colloids the particles of dispersed In these colloids, the particles of
phase have no affinity for the dispersion dispersed phase have great affinity for
medium the dispersion medium
They are not stable They are stable.
They cannot be prepared by mixing They can be prepared by mixing
substances directly. They are prepared only substances directly
by special methods
They need stabilizing agents for their They do not need stabilizing agents for
preservation. their preservation.
They are irreversible sols. They are reversible sols.
colloidal solutions of gold,silver, Fe(OH)3, Eg:- gums, gelatin, starch, albumin in
As2S3, etc. or metallic sols. water.

4. Ans :-the stability of hydrophilic sols depends on two things- the presence
of a charge and the solvation of colloidal particles. On the other hand, the
stability of hydrophobic sols is only because of the presence of a charge.
Therefore, the latter are much less stable than the former. If the charge of
hydrophobic sols is removed (by addition of electrolytes), then the particles
present in them come closer and form aggregates, leading to precipitation.

(b) Delta formation takes place due to coagulation of river water.

5. Ans :- (a) (i) CMC : Concentration above which micelle formation took place.
(ii) Kraft Temperature : It is the temperature above the micelle formation took
place.

(b)To reduce pore size of filter paper, so that colloidal particles cannot pass
through.
6. Ans: (i) Multimolecular colloids formed by aggregation of small atoms or
molecules. Example, gold sol, sulphur sol.
(ii) Macromolecular colloids formed by dispersing macromolecules having
colloidal size in proper dispersion medium. Example, protein, starch colloid.
(iii) Associated colloids are formed by aggregation of particles at higher
concentration to colloidal range. Example, micelles.
7. Ans. (a) Tyndall Effect : Scattering of light by colloidal particles by which
part of beam becomes clearly visible. This effect is known as tyndall effect.
(b) Brownian Movement : Zig-zag motion of colloidal particles.
(c) Hardy Schulze Rule : Coagulating value of a coagulating ion is directly
proportional to the charge on the ion.
e.g: Na+1<Ca 2+<Al 3+for negatively changed sol.
Cl-<CO32-<PO43-<[Fe (CN)6]4- for positive sol.
8. Ans–(i)The positively charged colloidal particles of Fe(OH)3 get coagulated by
the negatively charged Cl-ions provided by NaCl.
37
(ii) On passing direct current, colloidal particles move towards the positively
charged electrode where they lose their charge and get coagulated.
(iii) Scattering of light by the colloidal particles takes place and the path of light
becomes visible (Tyndall effect).
9. (a) In the first case, AgI is formed and it adsorbs I-. AgI/I- fixed layer and K+ is
diffused layer When KI is added to AgNO3 , AgI/Ag+ is the fixed layer NO3- is the
diffused layer.
(b)When dialysis is prolonged the traces of electrolyte which stabilizes the
colloids are removed completely. This makes the colloid unstable and therefore
coagulation takes place.
10. Ans:-action of soap is due to emulsification and micelle formation. Soaps
are sodium salt of higher fatty acids like sodium stearate, C17H35COO-Na+

The anionic head of stearate ion (-COO-) is hydrophobic in nature and has great
affinity for water, while the hydrocarbon part (C17H35COO–) is hydrophilic in
nature and great affinity for oil,grease etc.When soap is used in water, the
anions (C17H35COO–) form micelle and due emulsification encapsulate oil or
grease inside. These micelle are removed by rinsing with water; while free dirt
(from oil or grease) either settle down or are washed away by water. Thus the
main function of a soap is to entrap oil or grease with the micelles through
emulsification, thereby freeing dirt from grease and oil.

LONG ANSWER TYPE QUESTIONS (5 marks)

1. Ans:
Property Physisorption Chemisorption
Type of forces/ 1. It arises because of van der 1. It is caused by chemical bond
bond Waals’ forces. formation.
38
Specificity 2. It is not specific in nature 2. It is highly specific in nature.
Reversibility 3. It is reversible in nature 3. It is irreversible.
Nature of gas 4. It depends on the nature of 4. It also depends on the nature of
gas. More easily liquefiable gas. Gases which can react with
gases are adsorbed readily. the adsorbent show
chemisorption.
Enthalpy of 5. Enthalpy of adsorption is low 5. Enthalpy of adsorption is high
Adsorption (20-40 kJ mol-1)in this case. (80-240 kJ mol-1) in this case

Temperature 6. Low temperature is 6. High temperature is favourable

favourable for adsorption. It for adsorption. It increases with
decreases with increase of the increase of temperature.
temperature.
Activation 7. No appreciable activation 7. High activation energy is
Energy energy is needed. sometimes needed.

Surface Area. 8. It depends on the surface 8. It also depends on the surface

area. It increases with an area. It too increases with an
increase of surface area increase of surface area.

2. Ans: i) Dialysis: It is a process of purification of sols containing electrolyte

by keeping the sol in a bag made of parchment or cellophane and suspending
the bag in pure water. S mall molecules or ions can pass through the membrane,
but the sol is retained.
(ii) Electro-dialysis: The process of dialysis is quite slow. It can be made faster
by applying an electric field if the dissolved substance in the impure colloidal
solution is only an electrolyte. The process is then named electrodialysis. The
colloidal solution is placed in a bag of suitable membrane while pure water is
taken outside. Electrodes are fitted in the compartment as shown in
The ions present in the colloidal solution migrate out to the oppositely charged
electrodes.
(b) Electrophoresis: The existence of charge on colloidal particles is
confirmed by electrophoresis experiment. When electric potential is applied
across two platinum electrodes dipping in a colloidal solution, the colloidal
particles move towards one or the other
electrode. The movement of colloidal particles towards positive or negative
electrode in electric field is called electrophoresis. Positively charged particles
move towards the cathode while negatively charged particles move towards the
anode.
3. Ans: (a) Blood is a colloidal solution of an albuminoid substance. The styptic
action of alum and ferric chloride solution is due to coagulation of blood forming
a clot which stops further bleeding.
(b) Smoke is a colloidal solution of solid particles such as carbon, arsenic
39
compounds, dust, etc., in air. This smoke is led through a chamber containing
plates having a charge opposite to that carried by smoke particles. The particles
on coming in contact with these plates lose their charge and get precipitated.
The particles thus settle down on the floor of the chamber.
(C ) The charge on the colloidal particles is due to adsorption of common ions
of the electrolyte on the surface of the colloidal particles, e.g: Fe3+ from FeCl3
on the , surface of Fe(OH)3 particles. .
(d) With increase of temperature, physical adsorption decreases while
chemisorption first increases and then decreases.
(e) At the time of setting, the sun is at the horizon. The light emitted by the
sun has to travel a longer distance through the atmosphere. As a result, blue
part of the light is scattered away by the dust particles in the atmosphere. Hence,
the red part is visible.

S.No CASE BASED QUESTIONS

1. The degree of interaction by which the adsorbate molecules are
accumulated onto the adsorbents defines the nature and type of
adsorption. Furthermore, the mechanism can either be classified as
physisorption (physical adsorption) or chemisorption (chemical
adsorption). Physisorption is the adsorption in which the
molecular interactions between the adsorbate molecules and the
adsorbent are primarily governed by van der Waals forces whereas
chemisorption is the adsorption that takes place if there are
chemical bonds between adsorbate molecules and the adsorbent.
Physisorption is non-specific in nature and is
generally regarded as a weak, reversible process governed by
competitive adsorption and desorption which takes place at
different rates at the heterogeneous surface. Adsorption selectivity
refers to the preferential adsorption ability of adsorbents for some
substances because of their particular composition and the
structure of the adsorbents. For example, activated carbon is
composed of covalently linked carbon atoms, and can preferentially
adsorb high-molecular-weight organic molecules due to its large
aperture.
Whereas due to specificity, the nature
of chemisorption can greatly differ, depending on the chemical
identity and the surface structural properties. The bond between
the adsorbate and adsorbent in chemisorption is either ionic or
covalent. An important example of chemisorption is
in heterogeneous catalysis which involves molecules reacting with
each other via the formation of chemisorbed intermediates. After
the chemisorbed species combine (by forming bonds with each
other) the product desorbs from the surface.
40
(A) At the same temperature and pressure, arrange in increasing order
of adsorption the following gases on the same mass of charcoal:
H2, SO2, CH4 and NH3.
(B) Which of the two adsorptions give rise to monolayer adsorption?
Why?
(C) Write one similarity between physisorption and chemisorption.
(D) Why is adsorption always exothermic?
OR
Adsorption of a gas on surface of solid is generally accompanied by
a decrease in entropy, still it is a spontaneous process. Explain.
2. Coagulation is the destabilization of Colloids by neutralizing the
electric charge of the dispersed phase particles, which results in
aggregation of the colloidal particles.
Aggregation is a formation of groups of particles bonded to each
other by van der Waals or other intermolecular forces. Aggregation
usually refers to solid particles. In a stable colloid system the
dispersed particles are electrically charged. Two charged particles
repel each other preventing collision and aggregation. When the
charges are neutralized the particles may collide and bond to each
other.
A coagulation process may be subdivided in two stages:
electric neutralization of the dispersed phase and aggregation of
the destabilized particles. The following methods are used for the
destabilization of the colloidal particles by neutralization:
 Addition of an electrolyte to the colloid. The colloidal particles are
neutralized by the oppositely charged electrolyte ions. The
destabilization of a lyophobic colloid occurs at the electrolyte
concentrations exceeding the value of the critical coagulation
concentration. The critical coagulation concentration is strongly
dependent on the valence of the electrolyte ions. The higher the
valence the lower the critical concentration of the electrolyte.
 Addition of another colloid, particles of which are charged
oppositely to the particles of the first colloid. The oppositely
charged particles of the colloids attract each other and neutralize
the electric charge.
 Using electrodes connected to a DC power supply. The electric
circuit provides the charges for neutralizing the colloidal particles.
The term coagulation is often interchangeably used with the term
flocculation. However the coagulation and flocculation processes
are similar but not the same. Flocculation is the aggregation of a
colloid by polymer molecules (flocculent) bridging between the
colloidal particles and forming large fragile network structures
41
(flocs), which may be easily removed by sedimentation/flotation
and filtering.
(A) “Using electrodes connected to a DC power supply. The electric
circuit provides the charges for neutralizing the colloidal particles.”
What is the name of technique following this principle?
(B) Which of the following is most effective in coagulating positively
charged methylene blue sol? - Na3PO4 or K4[Fe(CN)6] or Na2SO4
(C) Define “Coagulating value’.
(D) Can boiling lead to coagulation of a sol? Explain.
OR
When a small amount of lyophilic colloid is added to lyophobic
colloid it may coagulate the latter. However, the addition of large
amount of lyophilic colloid increases the stability of the lyophobic
colloid. Explain
3. The Freundlich adsorption isotherm, an adsorption isotherm, is
an empirical relationship between the quantity of a gas adsorbed
into a solid surface and the gas pressure. The same relationship is
also applicable for the concentration of a solute adsorbed onto the
surface of a solid and the concentration of the solute in the liquid
phase.

The Freundlich adsorption isotherm is mathematically expressed as

𝑥 1
= 𝐾𝑃𝑛
𝑚
K and n are constants for a given adsorbate and adsorbent at a
given temperature. At high pressure 1/n = 0, hence extent of
adsorption becomes independent of pressure.
Homogeneous surfaces have a constant ΔH of
adsorption. On the other hand, heterogeneous adsorption has a
variable ΔH of adsorption depending on the percent of sites
occupied.
Experimentally it was determined that extent of gas adsorption
varies directly with pressure, and then it directly varies with
pressure raised to the power 1/n until saturation pressure Ps is
42
reached. Beyond that point, the rate of adsorption saturates even
after applying higher pressure. Thus, the Freundlich adsorption
isotherm fails at higher pressure.
(A) What is the value of ‘1/n’ for Freundlich adsorption equation?
(B) What will happen to the curve, if the temperature of the adsorption
system increases by 20 K?
(C) Draw plot of x/m Vs T representing adsorption isobar for
chemisorption.
(D) In which pressure range, Freundlich adsorption isotherm fails?
Why?
OR
The plot of log x/m against log P is a straight line inclined at an
angle of
45°. When the pressure is 0.5 atm and K is 10, what will be the amount
of solute adsorbed per gram of adsorbent?

ANSWER KEY

S. No. ANSWER
1A H2<CH4<NH3<SO2
1B Chemisorption. In chemisorption the adsorbate is held on the
surface of adsorbent by chemical bonds. Once all the bonds on
the surface of adsorbent are used for chemical bonding, no
further adsorption is possible. Hence chemisorption is
monolayered
1C Both physisorption and chemisorption increase with increase in
pressure.
Both increase with increase in surface area. (Any one)
1D Adsorption is accompanied by decrease of randomness. For the
process to be spontaneous, ΔG must be negative. Hence,
according to equation ΔG = ΔH – TΔS, ΔG can be negative only
if ΔH is negative.
OR
We know ΔG = ΔH – TΔS for adsorption. ΔH and ΔS are negative
and ΔH > TΔS. Thus from this equation ΔG is negative.
Therefore, for adsorption ΔH, ΔG and ΔS all are negative.
2A Electrophoresis
2B K4[Fe(CN)6]
2C The minimum concentration of an electrolyte in millimoles per
litre
required to cause precipitation of a sol in two hours is called
coagulating value.
2D Yes, boiling can cause coagulation. When a sol is boiled, the
adsorbed layer is disturbed due to increased collisions with the
43
molecules of dispersion medium. This reduces the charge on the
particles and ultimately leads to settling down in the form of a
precipitate.
OR
When a small amount of lyophilic colloid is added
to lyophobic colloids it may coagulate the latter due to
neutralisation of the charge on the lyophobic colloidal particles.
However, the addition of large amount of hydrophilic
colloid increases the stability of the hydrophobic colloidal system.
This is due to adsorption of lyophilic sol on the surface of
lyophobic sol. The layer of the protective colloid prevents direct
collision between the lyophobic colloidal particles and thus
prevents coagulation.
3A Any value between 0 and 1.
3B The slope of the curve will decrease so it will move downwards.
3C

3D Freundlich adsorption isotherm fails at higher pressure range.

Because at a particular high pressure, saturation pressure Ps is
reached. Beyond that point, the adsorption saturates even after
applying higher pressure.
OR
According to Freundlich adsorption equation,
x/m = kP1/n or log(x/m) = log k+1/n log P
Plot of log x/m vs. log P is a straight line with slope=1/n and
intercept = log k.
Thus, 1/n = tan θ = tan 45∘= 1 or n = 1
At p = 0.5 atm and k = 10, x/m =10(0.5) = 5
When m = 1g, x (i.e., amount adsorbed per gram ) = 5 g

44
The d-and f-Block Elements
 Elements in which the last electron enters any one of the five
d-orbitals of their respective penultimate shell are known as
transition elements or d-block elements.
 Their general electronic configuration is (n –1)d1–10ns0–2.
Melting and boiling High due to strong metallic bonding
points
Enthalpies of High due to strong interatomic interactions
atomization
Ionisation enthalpies Generally increases from left to right in a
series
Oxidation states Variable due to participation of ns and (n – 1)d
electrons
Atomic radii Decrease from left to right but become constant
when pairing of electrons takes place
Complex formation Form complexes due to high nuclear charge
and small size
and availability of empty d-orbitals to accept
lone pair of electrons donated by ligands.
Coloured compounds Form coloured compounds due to d-d
transitions
Magnetic properties Transition metal ions and their compounds
are paramagnetic due to presence of unpaired
electrons in the (n – 1)d-orbitals and it is
calculated by using the formula,
magnetic moment μ = √n(n+2)BM where,
n is the no. of unpaired electrons.
Catalytic behaviour Due to variable oxidation states and ability to
form complexes
Interstitial compounds Due to empty spaces in their lattices, small
atoms can be easily accommodated
Alloy formation Due to similar atomic sizes

Inner Transition Elements( f-Block Elements)

Lanthanoids : Last electron enters one of the 4f-orbitals. Cerium

(At. no. 58) to Lutetium(At.no.71).
Actinoids :
Last electron enters one of the 5f-orbitals. Thorium
(At. no. 90) to Lawrencium(At. no.103).
Lanthanoid contraction
In lanthanoid series, with increasing
atomic number, there is progressive
decrease in atomic/ionic radii (M3+ ions)
from La3+ to Lu3+.

45
Question No 1 to 10 are 2 Mark questions:
1. Why Eo values for Mn, Ni and Zn are more negative than expected?
2. Why first ionisation enthalpy of Cr is lower than that of Zn ?
3.Transition elements show high melting points. Why?
4. Out of Cu2Cl2 and CuCl2, which is more stable and why?
5. Although fluorine is more electronegative than oxygen, but the ability of
oxygen to stabilise higher oxidation states exceeds that of fluorine. Why?
6. Although Cr3+ and Co2+ ions have same number of unpaired electrons but
the magnetic moment of Cr3+ is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?
7.Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and U. Why?
8 .Although Zr belongs to 4d and Hf belongs to 5d transition series but it is
quite difficult to separate them. Why?
9 .A solution of KMnO4 on reduction yields either a colourless solution or a
brown precipitate or a green solution depending on pH of the solution. What
different stages of the reduction do these represent and how are they carried
out?
10.The halides of transition elements become more covalent with increasing
oxidation state of the metal. Why?

THREE MARK QUESTIONS:

11. Explain briefly how +2 state becomes more and more stable in the first
half
of the first row transition elements with increasing atomic number?
12. What may be the stable oxidation state of the transition element with
the following d electron configurations in the ground state of their atoms :
3d5 and 3d8 ?
13. What is lanthanoid contraction? What are the consequences of lanthanoid
contraction?
14. Explain giving reasons:
(i) The enthalpies of atomisation of the transition metals are high.
(ii) The transition metals generally form coloured compounds.
(iii) Transition metals and their many compounds act as good catalyst.
15. Predict which of the following will be coloured in aqueous solution? Ti3+,
V3+, Cu+ , Sc3+, Mn2+, Fe3+ . Give reasons for each.
16. 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.
46
17. Use Hund’s rule to derive the electronic configuration of Ce 3+ ion, and
calculate its magnetic moment on the basis of ‘spin-only’ formula
18. What can be inferred from the magnetic moment values of the following
complex species ?
Compound Magnetic Moment (BM)
(i) K4[Mn(CN)6) 2.2
(ii) [Fe(H2O)6] 2+ 5.3
19. What are inner transition elements? Decide which of the following atomic
numbers are the atomic numbers of the inner transition elements : 29, 59,
74, 95, 102, 104.
20. Calculate the number of unpaired electrons in the following gaseous ions:
Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous
solution?
FIVE MARK QUESTIONS:
21. Compare the chemistry of the actinoids with that of lanthanoids with
reference to: (i) electronic configuration (ii) oxidation states
22.On the basis of Lanthanoid contraction, explain the following :
(i) Nature of bonding in La2O3 and Lu2O3.
(ii) Trends in the stability of oxo salts of lanthanoids from La to Lu.
(iii) Stability of the complexes of lanthanoids.
(iv) Radii of 4d and 5d block elements.
(v) Trends in acidic character of lanthanoid oxides.
23.(a) Answer the following questions :
(i) Which element of the first transition series has highest second ionisation
enthalpy?
(ii) Which element of the first transition series has highest third ionisation
enthalpy?
(iii) Which element of the first transition series has lowest enthalpy of
atomisation?
(b)Identify the metal and justify your answer.
(i) Carbonyl M (CO)5 (ii) MO3F
24. Mention the type of compounds formed when small atoms like H, C and N
get trapped inside the crystal lattice of transition metals. Also give physical and
chemical characteristics of these compounds.
25. (a) Transition metals can act as catalysts because these can change their
oxidation state. How does Fe(III) catalyse the reaction between iodide and
persulphate ions?
(b)Mention any three processes where transition metals act as catalysts.

47
ANSWERS
1. Negative Eo values for Mn2+ and Zn2+ are related to stabilities of half filled
and fully filled configuration respectively. But for Ni2+ , Eo value is related to
the highest negative enthalpy of hydration.
2. Ionisation enthalpy of Cr is lower due to stability of d5 and the value for Zn
is higher because its electron comes out from 4s orbital.
3. The high melting points of transition metals are attributed to the
involvement of greater number of electrons in the interatomic metallic bonding
from (n-1) d-orbitals in addition to ns electrons
4. CuCl2 is more stable than Cu2Cl2. The stability of Cu2+ (aq.) rather
than Cu+(aq.) is due to the much more negative ΔhydH of Cu2+ (aq.) than
Cu+(aq.).
5. It is due to the ability of oxygen to form multiple bonds to metals.
6. Due to symmetrical electronic configuration there is no orbital contribution
in Cr3+ ion. However appreciable orbital contribution takes place in Co2+ ion.
7. It is because in the beginning, when 5f orbitals begin to be occupied,
they will penetrate less into the inner core of electrons. The 5f electrons will
therefore, be more effectively shielded from the nuclear charge than 4f
electrons of the corresponding lanthanoids.
8. Due to lanthanoid contraction, they have almost same size (Zr, 160 pm)
and (Hf, 159 pm).
9.

10. As the oxidation state increases, size of the ion of transition element
decreases. As per Fajan’s rule, as the size of metal ion decreases, covalent
character of the bond formed increases.
11. It can be easily observed that except Sc, all others metals display +2
oxidation state. Also, on moving from Sc to Mn, the atomic number increases
from 21 to 25. This means the number of electrons in the 3d-orbital also
increases from 1 to 5. +2 oxidation state is attained by the loss of the two 4s
electrons by these metals. Since the number of d electrons in (+2) state also
increases from Ti(+2) to Mn(+ 2), the stability of +2 state increases (as d-
orbital is becoming more and more half-filled). Mn (+2) has d5 electrons (that
is half-filled d shell, which is highly stable).

48
12.
13. The 4f electrons have poor shielding effect. Therefore, the effective
nuclear charge experienced by the outer electrons increases. Consequently,
the attraction of the nucleus for the outermost electrons increases. This
results in a steady decrease in the size of lanthanoids with the increase in the
atomic number.
Consequences of lanthanoid contraction
(i)There is similarity in the properties of second and third transition series.
(ii)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.)
14. (i) 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.
(ii). This is because of the absorption of radiation from visible light region to
promote an electron from one of the d−orbitals to another. In the presence
of ligands, the d-orbitals split up into two sets of orbitals having different
energies.
(iii) The catalytic activity of the transition elements can be explained by two
basic facts.
(a) Owing to their ability to show variable oxidation states
(b)Transition metals also provide a suitable surface for the reactions to occur
15. on the basis of electronic configuration that only Sc3+ has an empty d-
orbital. All other ions, except Sc3+, will be coloured in aqueous solution
because of d−d transitions.
16. (i)Cr2+ is strongly reducing in nature. It has a d4 configuration. While
acting as a reducing agent, it gets oxidized to Cr 3+ (electronic configuration,
d3). This d3 configuration can be written as configuration, which is a more
stable configuration. In the case of Mn3+ (d4), 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 in 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.
17. n = number of unpaired electrons In Ce, n = 2 2.828 BM

49
18. (i) K4[Mn(CN)6]
For in transition metals, the magnetic moment is calculated from the spin-
only formula. Therefore,

We can see from the above calculation that the given value is closest to .
Also, in this complex, Mn is in the +2 oxidation state. This means that Mn has
5 electrons in the d-orbital.
Hence, we can say that CN− is a strong field ligand that causes the pairing of
electrons.
(ii) [Fe(H2O)6]2+

We can see from the above calculation that the given value is closest to
. Also, in this complex, Fe is in the +2 oxidation state. This means that Fe
has 6 electrons in the d-orbital.
Hence, we can say that H2O is a weak field ligand and does not cause the
pairing of electrons.
19. Inner transition metals are those elements in which the last electron
enters the f-orbital. The elements in which the 4f and the 5f orbitals are
progressively filled are called f-block elements. Among the given atomic
numbers, the atomic numbers of the inner transition elements are 59, 95,
and 102.
20. Cr3+ is the most stable in aqueous solutions owing to a t2g3 configuration.
21.Electronic configuration:
The general electronic configuration for lanthanoids is [Xe]54 4f0-14 actinoids
is [Rn]86 5f1-14 6d0-1 7s2. Unlike 4f orbitals, 5f orbitals are participate in
bonding to a greater extent. 5d0-1 6s2 and that for not deeply buried and
Oxidation states:
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. Again, (+3) is the principal oxidation state
for actinoids. Actinoids such as lanthanoids have more compounds in +3 state
than in +4 state.
22. (i) As the size decreases covalent character increases. Therefore La2O3
is more ionic and Lu2O3 is more covalent.
(ii)As the size decreases from La to Lu, stability of oxosalts also decreases.
(iii)Stability of complexes increases as the size of lanthanoids decreases.
(iv)Radii of 4d and 5d block elements will be almost same.
(v)Acidic character of oxides increases from La to Lu.
23. (a) (i) Cu, because the electronic configuration of Cu is 3d104s1. So second
electron needs to be removed from completely filled d-orbital.
(ii) Zn (iii) Zn [ No unpaired electron for metallic bonding]
50
(b) (i) Fe(CO)5 [ EAN rule]
(ii) MnO3F [ Mn shows +7 oxidation state; d-electrons are not involved in
bonding.]
24. Interstitial compounds. Characteristic properties :
(i) High melting points, higher than those of pure metals.
(ii) Very hard.
(iii) Retain metallic conductivity.
(iv) Chemically inert.
25.

1. Read the passage given below and answer the following questions:
The f-block elements are those in which the differentiating electron
enters the (n -2)f orbital. There are two series of f-block elements
corresponding to filling of 4f and 5f-orbitals. The series of 4f-
orbitals is called lanthanides. Lanthanides show different oxidation
states depending upon stability of f0 ,f7 and f14 configurations,
though the most common oxidation states is +3. There is a regular
decrease in size of lanthanides ions with increase in atomic number
which is known as lanthanide contraction.
(a) The atomic numbers of three lanthanide elements X, Y and Z are 65, 68
and 70 respectively, t What is their Ln3+ electronic configuration is
Ans. 4f 9,4f11,4f13
(b) Name a member of the lanthanoid series which is well known to exhibit
+4 oxidation state.
Ans. Cerium
(c) What is the reason of lanthanoid contraction?
Ans. The Lanthanide Contraction is caused by a poor shielding effect
of the 4f electrons..
(d) Why Zr & Hf exist together?
Ans. Due to lanthanoid contraction, their sizes are similar.
51
2.Read the passage given below and answer the following questions:

The transition elements have incompletely filled d-subshells in their ground

state or in any of their oxidation states. The transition elements occupy position
in between s- and p-blocks in groups 3-12 of the Periodic table. Starting from
fourth period, transition elements consists of four complete series : Sc to Zn,
Y to Cd and La, Hf to Hg and Ac, Rf to Cn. In general, the electronic
configuration of outer orbitals of these elements is (n - 1) d1-10 ns1-2. The
electronic configurations of outer orbitals of Zn, Cd, Hg and Cn are represented
by the general formula (n - 1)d10 n2. All the transition elements have typical
metallic properties such as high tensile strength, ductility, malleability. Except
mercury, which is liquid at room temperature, other transition elements have
typical metallic structures. The transition metals and their compounds also
exhibit catalytic property and paramagnetic behaviour. Transition metal also
forms alloys. An alloy is a blend of metals prepared by mixing the components.
Alloys may be homogeneous solid solutions in which the atoms of one metal
are distributed randomly among the atoms of the other.
(a) Why are Zn, Cd and Hg non-transition elements?
Ans. It is because neither they nor their ions have incompletely filled d-
orbital’s.
(b) Which transition metal of 3d series does not show variable oxidation
state?
Ans. Scandium (Sc) and Zinc (Zn).
(c) Why do transition metals and their compounds show catalytic activity?
Ans. It is because they show variable oxidation state, can form intermediate
complexes and have large surface area for adsorption of gases.
(d) Why are melting points of transition metals high?
Ans. It is due to strong inter atomic forces of attraction due to presence of
unpaired electron.
OR
(d) Why is Cu2+ ion coloured while Zn2+ ion is colorless?
Ans. It is because Cu2+ has one unpaired electron and undergoes d-d
transition by absorbing.light from visible region and radiate blue colour,
whereas Zn2+ is colourless due to absence of unpaired.
3. .Read the passage given below and answer the following questions:
Observe the graph of transition metal and their melting points and answer the
questions based on weak metallic bond which is due to absence of the graph
and related concepts.

52
(a) Why does W (tungsten) have highest melting point?
Ans. It is due to presence of unpaired electrons and there is more frequent
metal-metal bonding in 5dseries than 3d and 4d series.
(b) Which element in 3d series has lowest enthalpy of atomization and why?
Ans. Zinc has lowest enthalpy of atomization due to weak metallic bond
which is due to absence of unpaired electrons.
(c) Why is mercury liquid?
Ans. It is due to larger size, absence of unpaired electron and weak inter
atomic attraction and weaker metallic bond.
(d) Why are transition metals less electro positive?
Ans. It is due to smaller atomic size and higher ionization enthalpies.
OR
(d) How does density vary from left to right in 3dseries and why?
Ans. Density goes on increasing from Sc to Cu because atomic mass
increases more than atomic volume.
4. .Read the passage given below and answer the following questions:
Observe the table given below belonging to 3d series, their first, second, third
ionization enthalpyand E° M2+ /M and E° M3+ /M2+ and answer the questions
that follow based on table and related concepts.

53
(a) Why does zinc have highest first ionization enthalpy?
Ans. It is because Zn has completely filled ‘4s’ orbital which is stable.
(b) Why is 3rd ionization enthalpy of Mn high?
Ans. It is because after losing 2 electrons, it becomes 3d5 which is more stable.
(c) Why is Cr3+ more stable than Cr2+?
Ans. It is because Cr3+(t2g3 ) half-filled orbitals are more stable than Cr2+(3d4).
(d) Why is E° Mn2+ /Mn = –1.18V?
Ans. It is due to low enthalpy of atomization, sublimation enthalpy, ionization
enthalpy.
OR
(d) Why is E ° Cu2+/Cu= +0.34V?
Ans. It is due to high ionization enthalpy and low hydration enthalpy

54
Coordination compounds
Gist of chapter
Coordination compounds
The compounds in which a metal atom/ion is surrounded by a definite
number of ligands by coordinate bonds.
They do not ionize into simple ions in aq. solution.
Ex: K4[Fe(CN)6]
Double salts
When two salts in their stochiometric ratio crystallize together from their
saturated solution.
They get ionized into all constituting ions. Ex: potash alum, Mohr salt
Coordination entity
Paricle involving metal atom/ion with definite no of ligands. [Fe(CN)6]4-
Coordination polyhedra
The geometry of the complex entity is called Coordination polyhedral.
[Cu(NH3)4]2+ ------square planar

Ligand
Species that provide a pair of electrons to the central metal atom/ion by
coordinate bond. They act as Lewis bases in complexes NH3 , H2O, en
Types of ligands
Monodentate ligands: Only one donar atom, surround metal by one
coordinate bond. Ex: NH3, H2O, CN-1
Bidentate ligands: Two donar atom, surround metal by two coordinate
bonds. Ex: SO42-, en, C2O42-
Polydentate ligands: More than two donar atom, surround metal by one
coordinate bond. Ex: EDTA4-
Ambident ligands: Two donar atom but attached with only one at a time:
CN1- and NC1-
Coordination number
Number of monodentate or equivalent ligands surrounding the metal in a
complex. [Fe(CN)6]4- ………….coordination number is 6
Homoleptic and hetroleptic complexes
When all ligands surrounding metal are same-----homoleptic complex
[Fe(H2O)6] SO4 ------------ all six ligands are same water molecules
When all ligands surrounding metal are not same-----heteroleptic complex.
[Fe(H2O)3(NH3)3] SO4 ----- Two different type of ligands

55
Nomenclature of Coordination Compounds
Cation is written first followed by anion.
While writing name of coordination sphere ligands are named first followed by
central metal atom.
To indicate number of ligands prefix di, tri, tetra, penta, hexa, hepta etc are
used. If ligands itself involve such prefixes in its name then prefix bis, tris,
tetrakis, and so on are used to indicate number of ligands.
While writing name of central metal atom: -
(i) If coordination sphere is cation name of metal atoms written as such: Fe –
Iron, Au – Gold, Cu – Copper, Cr – Chromium, Ag – Silver.
(ii) If, coordination sphere is anion suffix ‘ate’ is used to write name of central
metal atom. Such as: Fe – Ferrate, Hg – Mercurate, Cu – Cuperate, Ag –
Argentate, Au – Aurate, Pd – Peladate, Cr - Chromate
After writing name of central metal atom its oxidation number is indicated in
perantheses’()’.
Valance bond theory of coordination compound
Write electronic configuration of metal atom/ion
Observation Prediction
C.N. of metal If 4 --- dsp2/sp3 hybridization
If 6--- d2sp3/sp3d2 hybridization
Inner d- orbital is /are vacant dsp2----C.N.=4 d2sp3---
C.N=6
Inner- d orbital is/are not C.N=4 dsp2-ligand is CN-1 or CO
vacant but can be vacated by (Strong ligand) sp3- weak ligand
pairing of electrons C.N=6 d2sp3-ligand is CN-1 or CO
(Strong ligand)sp3d2 weak ligand
Inner d- orbitals are not C.N=4 sp3-weak ligand (SFL /
vacant and can’t be vacated WFL)
by pairing of e- C.N=6 sp3d2- weak ligand (SFL
/WFL)
dsp2-hybridization Sq. planar
sp3-hybridization Tetrahedral
d sp /sp d -hybridization
2 3 3 2
Octahedral
Presence of unpaired e- paramagnetic
Unpaired electron absent Diamagnetic
Magnetic moment µspin only=√𝑛(𝑛 + 2)
[Co(H2O)6] 3+
[Co(NH3)6]3+

 Sp3d2 hybridization
 Paramagnetic in nature  d2sp3 hybridization
 Outer sphere complex  Inner sphere complex
 Octahedral complex  Diamagnetic in nature
High spin complex Low spin complex Octahedral
[Ni Cl4]2- complex
[Ni(CO)4]

56
 Sp3 hybridization
 Sp3 hybridization
 Low spin
 Paramagnetic in nature
 Diamagnetic in nature
 Tetrahedral complex
Tetrahedral complex
CRYSTAL FIELD theory of coordination compound
The d- orbitals of metal split into two sets of orbitals due to electronic interaction
between ligands and metal depending upon the crystal field produced by the
ligands around the metal.

COLOUR OF THE COMPLEXES

The d-d transition of electrons in visible region causes colouration in the
complexes.

Application of coordination compound

a) Biological System:
i) Chlorophyll – complex of Mg
ii) Hemoglobin – complex of Fe
iii) Vitamin B-12 – complex of Co

B) Metallurgy:
i) Extraction of Au, Ag, by cyanide
ii) Refining of Ni by Mond’s process
Refining of Zr by Van Arkel process.
C) Quantitative Analysis:
Estimation of hardness of water Ca2+ and Mg2+ are estimated by complexomatric
titration using EDTA.
d) Black& White Photography:
In black and white photography the film is fixed by washing with hypo solution
which dissolves the undecomposed AgBr
e) As medicines: Cisplatin -Cancer Treatment EDTA [Used toremove heavy
metal poison
57
2-Marks Questions
Q1. [NiCl4]2– is paramagnetic while [Ni(CO)4] is diamagnetic though both are
tetrahedral. Why?
Ans.In [Ni(CO)4], Ni is in zero oxidation state whereas in [NiCl4]2– it is in +2 oxidation
state. In the presence of strong ligand, CO, the unpaired d-electrons of Ni pair up but
Cl– being weak ligand is unable to pair up the unpaired electrons.

Q2. A solution of [Ni(H2O)6]3+ is green but a solution of [Ni(CN)4]2– is

colourless. Explain.
Ans. H2O being a weak ligand is unable to pair the unpaired electrons in Ni2+. So d-d
transition is possible in the complex [Ni(H2O)6]3+. Hence it is coloured. But CN– being a
strong ligand paired the unpaired electrons in Ni2+. So d-d transition is not possible in
the complex [Ni(CN)4]2–. Hence it is colourless.
Q3. When a co-ordination compound CoCl3.4NH3 is mixed with AgNO3, 1 mole
of AgCl is precipated per mole of the compound. Write
a) structural formula of the complex. b) IUPAC name of the complex.
Ans. (a) [Co(NH3)4Cl2]Cl (b) Tetraamminedichloridocobalt(III) chloride.
Q4. For the complex [Fe(CN)6]4-, write the hybridization, magnetic character
and spin type of the complex.
Ans.Hybridization: d2sp3, magnetic character: Diamagnetic, spin: Low spin complex
Q5. Distinguish between Double salt and Coordination compound.
Double Salt Coordination Compound
1. They completely dissociate into simple 1. They do not dissociate into simple ions
ions when dissolved in water. when dissolved in water
2. They give the tests for the constituent 2. They does not give tests for the
ions. constituent ions.
3. Ex. FeSO4.(NH4)2 SO4.6H2O(Mohr’s salt) 3. Ex. K4[Fe(CN)6]

Q6. Explain Homoleptic and Heteroleptic complexes with example.

Ans. The complex in which metal atom is bound to only one type of ligand is
called homoleptic complex. Ex. [Ni(CO)4]
The complex in which metal atom is bound to more than one type of ligand is
called heteroleptic complex.
Ex. [Co(NH3)4Cl2]+
Q7. The hexaaquamanganese(II) ion contains five unpaired electrons
while the hexacynomanganes(II) ion contain one unpaired electron.
Explain

Ans: In hexaaquamanganese(II) ion the ligand H2O is a weak field ligand and
so can not cause pairing of electrons in 3d orbital while in hexacynomanganes(II)
ion the ligand CN- is a strong field ligand so it causes the pairing of electron in
the 3d orbital

58
Q8 The Spin magnetic moment of [MnBr4]2- is 5.9 BM .Predict the
geometry of the complex ion?

Ans: Since coordination number of Mn2+ ion is 4 it will either sp3 with
tetrahedral shape or dsp2 with square planar shape but it is tetrahedral as d
orbital will occupy by the presence of 5 unpaired electrons.
Q 9. What do you meant by chelate ligands &ambidentate ligands ?
Ans: When di or polydentateligands uses its two or more donor atoms to bind a
single metal ionis called chelate ligand.eg ethylene diamine.
Ambidentate ligands: ligands which can ligate through two different donor
2

sites.eg NO
3-MARKS-QUESTIONS
Q1.Write IUPAC names of the following coordination compounds:
a) [Fe(CN)6] 4– b) K2 [PdCl4] c) [Co(NH3)4Cl(NO2)]Cl
Ans. a) Hexacyanoferrate(II)ion b) Potassium tetrachloridopalladate(II)
c) Tetraamminechloridonitro-N-cobalt(III) chloride
Q2.Write the formulas for the following co-ordination compounds:
a) Tetraammineaquachloridocobalt(III) chloride
b) Potassium tetrahydroxozincate(II)
c) Potassium trioxalatoaluminate(III)
Ans. a) [Co(NH3)4(H2O)Cl]Cl2 b) K2 [Zn(OH)4] c) K3 [Al(C2O4)3]
Q3. Write IUPAC names of the following coordination compounds:
a)[Pt(NH3)2Cl(NO2)] b) K3 [Cr(C2O4)3] c) [CoCl2(en)2]Cl
a) Diamminechloridonitrito-N-Platinum(II)
a) Potassium trioxalatochromate(III)
b) Dichloridobis(ethane-1,2-diammine)cobalt(III) chloride
Q4. Write the name, structure and the magnetic behavior of the
following complex:[Ni(CO)4]
Ans. Tetracarbonylnickel(0), tetrahedral, diamagnetic
Q5. Write the name, structure and the magnetic behavior of the
following complex: [Co(NH3)4Cl2]Cl
Ans. Tetraamminedichloridocobalt(III) chloride, octahedral, diamagnetic
5 _MARKS QUESTIONS :
Q1.Discuss the nature of bonding in the following coordination entities
on the basis of valence bond theory: (i) [Fe(CN)6]4− (ii) [FeF6]3− (iii)
[Co(C2O4)3]3− (iv) [CoF6]3−
(i) [Fe(CN)6]4−
2+
In the above coordination complex, iron exists in the +II oxidation state. Fe :
6
Electronic configuration is 3d
2+
Orbitals of Fe ion:

59
As CN− is a strong field ligand, it causes the pairing of the unpaired 3d electrons.

Since there are six ligands around the central metal ion, the most feasible
hybridization is d2sp3. d2sp3 hybridized orbitals of Fe2+ are:

6 electron pairs from CN− ions occupy the six hybrid d2sp3orbitals. Then,

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:

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
orbital. Hence, the most feasible hybridization is sp3d2.
sp3d2 hybridized orbitals of Fe are:

Hence, the geometry of the complex is found to be octahedral.

(iii) [Co(C2O4)3]3−

Cobalt exists in the +3 oxidation state in the given complex. Orbitals of Co 3+

ion:

Oxalate 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 either sp3d2 or
60
d2sp3hybridization.
sp3d2 hybridization of Co3+:

The 6 electron pairs from the 3 oxalate ions (oxalate anion is a bidentate ligand)
occupy these sp3d2 orbitals.
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:

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:

Hence, the geometry of the complex is octahedral and paramagnetic.

I. Read the given passage and answer the questions that follow:
Complex compounds play an important role in our daily life. Werner’s theory of
complex compounds says every metal atom or ion has primary valency
(oxidation state) which is satisfied by negatively charged ion which are ionisable
secondary valency (coordination number) is non-ionisable, satisfied by ligands
(+ve / –ve/ neutral) but having lone pair. Primary valency is non-directional,
secondary valency is directional. Complex
compounds are name according to IUPAC system. Valence bond theory helps in
determining shapes of complexes based on hybridization, magnetic properties,
outer or inner orbital complex. EDTA is used to treat lead poisoning, Cisplatin
61
as anticancer agents. Vitamin B12 is complex of cobalt. Hemoglobin, oxygen
carrier is complex of Fe2+ and chlorophyll essential for photosynthesis is complex
of Mg2+ .
(a) What is the oxidation state and coordination number of Ni in [Ni(CO)4]?
Ans. Zero and four
(b) One mole of CrCl3. 6H2O reacts with excess of AgNO3 to yield 2 mole
of AgCl. Write formula of complex. Write IUPAC name also.
Ans. [Cr(H2O)5Cl]Cl2.H2O, Penta aqua chloride chromium (III) chloride
(c) Name the hexadentate ligand used for treatment of lead poisoning.
Ans. EDTA4– (ethylene diamine tetra acetate)
(d) What is hybridization of [CoF6]3– ? [Co = 27].
Give its shape and magnetic properties.
Ans. sp3d2 , octahedral, paramagnetic. It is outer orbital complex.
(e) Out [Fe(CO)5], [Fe(C2O4)3]3–, [Fe(H2O)6]3+,[Fe(CN)6]3– which is most stable
Ans. [Fe(CO)5] is most stable because CO is strongest ligand.
2. Observe the diagram of splitting of d-orbitals in octahedral field and answer
the questions based on the diagrams and related studied concepts.

a) What is crystal field splitting energy?

Ans: The energy difference between the two sets of d-orbitals is called crystal
field splitting energy denoted by ▲0
(b) Why dx2–y2, dz2 have higher energy than dxy, dyz, dzx orbitals in octahedral
crystal field?
Ans: The orbitals dx2y2, dz2 lying in the direction of ligands, will experience
greater repulsion and their energies will be raised relative to their positions in
symmetrical field as compared to orbitals dxy, dyz, dzx lying in between the axis
away from the approach of ligand.
62
(c) What is relationship between (CFSE) Δ0 and strength of ligand?
Ans. Greater the (CFSE) Δ0, more will be strength of ligand.
(d) What is electronic configuration of d5 ion if Δ0< P?
Ans. t2g 3 eg2
OR
(d) What is spectrochemical series?
Ans. The series in which ligands are arranged in increasing order of magnitude
of crystal field splitting energy (Δ0) is called spectrochemical series.

3.Read the passage given below and answer the following questions:
Werner, a Swiss chemist in 1892 prepared and characterised a large number of
coordination compounds and studied their physical and chemical behaviour. He
proposed that, in coordination compounds, metals possess two types of
valencies, viz. primary; valencies, which are normally ionisable and secondary
valencies which are non-ionisable. In a series of compounds of cobalt (III)
chloride with ammonia, it was found that some of the chloride ions could be
precipitated as AgCI on adding excess of AgNO3 solution in cold, but some
remained in solution. The number of ions furnished by a complex in a solution
can be determined by precipitation reactions. The measurement of molar
conductance of solutions of coordination compounds helps to estimate the
number of ions furnished by the compound in solution.

(i)Why the complex [Co(NH3)3CI3] does not give precipitate with silver nitrate
solution
Ans. The given complex is non-ionisable.
(ii) The complex [Co(NH3)4Cl2]Cl will give precipitate corresponding to how
many mol of AgCl with AgNO3 solution.
Ans. It ionises as [Co(NH3)4Cl2]+ + Cl– ,so it will give ppt.of 1 mol of AgCl..
(iii) What is the secondary valency in [CrCl2CH2O)4]Cl· 2H2O.
Ans.6
(iv) CoCl3·3NH3 is not conducting while CoCl3·5NH3 is conducting. Why?
Ans.: The complex of CoCl3·3NH3 is [ CoCl3(3NH3)3] while that of CoCl3·5NH3 is
[CoCl3(3NH3)5]Cl2.

4.Read the passage given below and answer the following questions:
For understanding the structure and bonding in transition metal complexes, the
magnetic properties are very helpful. Low spin complexes are generally
diamagnetic because of pairing of electrons, whereas high spin complexes are
usually paramagnetic because of presence of unpaired electrons. Larger the
number of unpaired electrons, stronger will be the paramagnetism. However
63
magnetic behaviour of a complex can be confirmed from magnetic moment
measurement.
Magnetic moment μ=n(n+2)−−−−−−−√ B.M. μ=n(n+2) B.M. where
n = number of unpaired electrons. Greater the number of unpaired electrons,
more will be the magnetic moment.

(i) Both [Cr(H2O)6]2+ and [FeH2O)6]2+ have same magnetic moment. Why?

Ans.: Number of unpaired electrons in Cr2+ and Fe2+ are same.

(ii) [Fe(H2O)6]SO4 is paramagnetic. Why?

Ans. The Fe in [Fe(H2O)5NO]SO4 has three unpaired electrons.

(iii): [Co(en)3]3+ is diamagnetic. '

Ans. It is an inner orbital complex.( en is a strong field ligand, therefore,
pairing of electrons will take place.

(iv) [Ni(CN)4]2- is diamagnetic complex.

Reason: It involvesd sp2 hybridisation and there is no unpaired electron.

64
ALDEHYDES KETONES AND CARBOXYLIC ACIDS
NAMED REACTION

ROSENMUND REACTION

GATTERMAN KOCH

CLEMMENSON’S REACTION

ETARD REACTION

STEPHAN’S REACTION

CANNIZZARO REACTION

WOLF KISHNER REACTION

O
i) NH2-NH2
C H3C CH2 CH3
H3C CH3 ii) KOH / Ethylene glycol / 
ALDOL CONDENSATION’

CROSS ALDOL

HELL VOLHARD ZELINSKY

DECARBOXYLATION CH3COONa + NaOH)CaOCH4 + Na2CO3

FRIEDAL AND CRAFT ACYATION

65
DISTINGUISH BY SINGLE CHEMICAL TEST
Examples Reagents Test performed by
(i) Propanal and Propanone (i) Tollens reagents (i) Propanal
(ii) Acetophenone and Benzophenone (ii) Iodoform test (ii) Acetophenone
(iii) Phenol and Benzoic acid (iii) FeCl3 Test (iii) Phenol
(iv) Benzoic acid and Ethyl benzoate (iv) NaHCO3 Test (iv) Benzoic acid
(v) Pentan-2-one and Pentan-3-one (v) Iodoform test (v) Pentan-2-one
(vi) Benzaldehyde and Acetophenone (vi) Iodoform test (vi) Acetophenone
(vii) Ethanal and Propanal (vii) Iodoform test (vii) Ethanal
(viii) Benzoic acid and Ethyl benzoate (viii) NaHCO3 test (viii) Benzoic acid
Important Reasoning Question
Question Answer
Cyclohexanone forms cyanohydrin in good yield Due to steric hinderance and decrese
but 2,2,6-trimethylcyclohexanonedoes not. in the electrophilicity of Carbony
carbon by +I alkyl group
There are two –NH2 groups in semicarbazide. Due to resonance Lone pair of –NH2
However, only one is involvedin the formation of group decrese the eletrophilicity of
semicarbazones. carbonyl carbon.
During the preparation of esters from a carboxylic due to reversible reaction
acid and an alcohol in presence of an acid catalyst,
the water or the ester should be removed as soon
as it is formed.
Carboxylic acids are stronger acids than phenols. than Phenoxide ion due to Carboxylate
ion is more stabledispersionof -ve
Charge on higher electronegative
element
Aromatic carboxylic acids do not undergo Friedel – COOH group is m- directing-
Crafts reaction
Ethanal is more reactive towards nucleophilic Due greater +I effect and steric
addition reactions than propanone. hinderance in propanone
Ethanoic acid is a stronger acid than ethanol. carboxylate ion are more stable than
alkoxide ion
Monochloroethanoic acid has a higher pKa value Due to greater –I effect of two Cl atom
than dichloroethanoic acid in dichloroethanoc acid than
Monochloroacetic acid
The aldehydes & ketones undergo a no. of addition Due to polarity of carbonyl group
reactions Carbon become more electrophilic

Ethanoic acid is weaker acid than benzoic acid due to –I effect of Sp2 hybridized
carbon atom of phenyl group
Although phenoxide ion has more number of Carboxylate ion is more stable than
resonating structures than carboxylate ion, Phenoxide ion due to delocalisation of
carboxylic acid is a stronger acid than phenol. ve Charge on higher electronegative -
Why? element
CONVERSIONS (SINGLE STEP)
Question REAGENTS
(i) Hexan-1-ol to hexanal (i) C5H5NH+CrO3Cl-(PCC)
(ii) Cyclohexanol to cyclohexanone (ii) Anhydrous CrO3
(iii) p-Fluorotoluene to p- (iii) CrO3 in presence of acetic anhydride/1.
fluorobenzaldehyde CrO2Cl2 2. HOH
(iv) Ethanenitrile to ethanal (iv) (Diisobutyl) aluminium hydride (DIBAL-
(v) Allyl alcohol to propenal H)
(vi) But-2-ene to ethanal (v) PCC
66
(vii) Butan-1-ol to butanoic acid (vi) O3/H2O-Zn dust
(viii) Cyclohexene to hexane-1,6-dioic acid (vii) CrO3 - H2SO4
(ix) Butanal to butanoic acid. (viii) KMnO4- H2SO4
(ix) Tollens reagents
CONVERSIONS
(i) Propanone to
Propene

(ii) Benzoic acid to

Benzaldehyde

(iii) Ethanol to 3-
Hydroxybutanal

(iv) Benzene to m-
Nitroacetophenone

(v) Benzaldehyde to
Benzophenone
(vi) Bromobenzene to
1-Phenylethanol

(vii) Benzaldehyde to
3-Phenylpropan-1-ol

(viii) Benzaldehyde to
α Hydroxy
phenylacetk acid
(ix) Benzoic acid to m-
nitrobenzyl alcohol

Arrengement order(Decresing/Increasing)
In order of- Questions Answers
(i) In increasing order of CH3CH2CH2CHO, CH3CH2CH2CH3 ,H5C2-O-
boiling points: CH3CH2CH2CH2OH, H5C2-O-C2H5, C2H5
CH3CH2CH2CH3 ,CH3CH2CH2CHO,CH3CH2C
H2CH2OH
(ii) decreasing order Acetaldehyde, Acetone, Di-tert-
reactivity towards HCN butyl ketone, Methyl tert-butyl Acetaldehyde, Acetone,
ketone Di-tert-butyl ketone,
Methyl tert-butyl ketone
(iii) In increasing order of CH3CH2CH(Br)COOH,CH3CH(Br)CH
acid strength 2COOH, (CH3)2CHCOOH, (CH3)2CHCOOH,
CH3CH2CH2COOH CH3CH2CH2COOH,
67
CH3CH(Br)CH2COOH,CH3
(iv) In increasing order of Benzoic acid,4-Nitrobenzoicacid, CH2CH(Br)COOH
acid strength 3,4 Dinitro benzoic acid,4-
Methoxybenzoic acid 4-Methoxybenzoic acid,
(v)increasing order of their Ethanal, Propanal, Propanone, Benzoic acid, 4-
reactivity in nucleophilic Butanone. Nitrobenzoic acid, 3,4-
addition reactions Dinitrobenzoic acid,
Benzaldehyde, p-Tolualdehyde, p- Butanone , Propanone ,
(vi) increasing order of Nitrobenzaldehyde, Propanal ,Ethanal
reactivity in nucleophilic Acetophenone.
addition reactions Acetophenone , p-
(vii) increasing order of Tolualdehyde ,
their boiling points. CH3CHO, CH3CH2OH, CH3OCH3, Benzaldehyde , p-
CH3CH2CH3 Nitrobenzaldehyde.
CH3CH2CH3 < CH3OCH3 <
CH3CHO < CH3CH2OH

68
Predict the products of the following reactions:
Questions Answers

WORD PROBLEM
(i) An organic compound (A) with molecular formula C8H8O forms an orange-red
precipitate with 2,4-DNP reagent and gives yellow precipitate on heating with
iodine in the presence of sodium hydroxide. It neither reduces Tollens’ or
Fehlings’ reagent, nor does it decolourise bromine water or Baeyer’s reagent.
On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having
molecular formula C7H6O2. Identify the compounds (A) and (B) and explain the
reactions involved.
Answers :- (A) Acetophenone (B) Benzoic Acid

69
(ii) An organic compound with the molecular formula C9H10O forms 2,4-DNP
derivative, reduces Tollen’s reagent, and undergoes Cannizzaro reaction. On
vigorous oxidation, it gives 1,2-benzenedicarboxylic acid. Identify the
compound.

(iii) An organic compound (A) (molecular formula C8H16O2) was hydrolysed with
dilute sulphuric acid to give a carboxylic acid (B} and an alcohol (C). Oxidation
of (C) with chromic acid produced (B). (C) on dehydration gives but-l-ene. Write
equations for the reactions involved.

(iv) An organic compound contains 69-77% carbon, 11-63 % hydrogen and rest
oxygen. The molecular mass of the compound is 86. It does not reduce Tottens’
reagent but forms an addition compound with sodium hydrogensulphite and
give positive iodoform test. On vigorous oxidation, it gives ethanoic and
propanoic acid. Write the possible structure of the compound.

70
(v) An organic compound ‘A’ which has characteristic odour, on treatment with
NaOH forms two compounds ‘B’ and ‘C’. Compound ‘B’ has the molecular
formula C7H8O which on oxidation with CrO3 gives back compound ‘A’.
Compound ‘C’ is the sodium salt of the acid. ‘C’ when heated with soda lime
yields an aromatic hydrocarbon ‘D’. Deduce the structures of ‘A’, ‘B’, ‘C’ and
‘D’.

(vi) Two moles of organic compound ‘A’ on treatment with a strong base gives two
compounds ‘B’ and ‘C’. Compound ‘B’ on dehydrogenation with Cu gives ‘A’
while acidification of ‘C’ yields carboxylic acid ‘D’ with molecular formula of
CH2O2. Identify the compounds A, B, C and D and write all chemical reactions
involved.

71
Two Marks Questions
1. Complete each synthesis by giving the missing material, reagent or products ::-

2. Give a chemical test to distinguish the following pairs:

(A) Phenol and benzoic acid (B) Benzaldehyde and acetophenone
Ans (A):_Phenol give sthe FeCl3 test while Benzoic acid not
Ans(B):-Acetophenone gives iodoform test but benjaldehyde not
3. Account for the following:-
(A) Chloroacetic acid is a stronger acid than acetic acid
(B) Carboxylic acids do not give the reactions of carbonyl group.
Ans A):-In Cl-CH2COOH, -I effect of Cl stabilizes the CH2COO- ion while in
CH3COOH +I-effect of methyl group destabilizes CH2COO- ion so chloacetic
acid is stronger acid than acetic acid.
Ans(B):-In the resonating structures of carboxylic acids and carbonyls, the
carbonyle carbon of carboxylic acid is less electropositive than that in
carbonyls so carboxylic acids do not give reactions of carbonyle group.
4. Arrange the following
(A):-C6H5COOH, FCH2COOH, NO2CH2COOH in the decreasing order of
acidic character
(B):-Ethanal, Propanal, propanone and butanone in increasing order of
nucleophilic addition reactions
Ans(A):- NO2CH2COOH> FCH2COOH> C6H5COOH
Ans(B):-,Butanone < propanone< Propanal < Ethanal
5. An organic compound A with molecular formula C8H8O gives positive DNP and
iodoform test. It does not reduce Tollen’s reagent and does not decolorise
bromine water also. On oxidation with chromic acid it gives a carboxylic acid B
with molecular formula C7H6O2. Deduce the structures A and B.
Ans:-Since A does not give Tollen’s test but gives iodoform test and 2,4
DNP test so it should have CH3 and CO group

72
O O
CH3 OH
H2CrO4

(A) (B)

6. Explain nucleophilic addition reactions of aldehydes and ketones followed by

elimination of a water molecule.

Ans:-

Three marks questions

1. Explain the following
(A) Formation of acetals
(B) Reactivity comparison of methanal and ethanal
(C)Effect of electron withdrawing group upon acidity of carboxylic acids

Ans:-
(B) The reactivity of carbonyl compounds is due to the polarity of carbonyl
group, in ethanal methyl group decreases the polarity of carbonyl group
by +I effect hence the reactivity of ethanal is less than that of methanal.
(C)The presence of EWG increases the stability of the carboxylate anion which
is formed by donation of proton, hence the presence of EWG increases the
strength of acid.
2. Explain the following
(A) Addition of NaHSO3 to aldehydes and ketones.
(B) Addition of HCN to aldehydes and ketones.
(C)Decarboxylation of carboxylic acids.
Ans:-(A)

73
(B) (C)

3. Explain the following:

(A) Formic acid is more acidic than acetic acid.
(B) Carboxylic acids are more acidic than phenols.
(C)Benzoic acid is more acidic than acetic acid.
Ans:-(A) In acetic acid +I effect of methyl group destabilises the carboxylate
anion formed by donation of proton while in formic acid no any group is
present which can destabilizes the carboxylate anion, hence formic acid is
more strong than acetic acid.
(B) Carboxylate anion has two oxygen atoms in its resonating structures while in
resonating structures of Phenol there is only one oxygen atom so negative
charge in carboxylate anion is spread upon two O atoms so it is more stable
than phenoxide anion in which the negative charge is situated upon only one
O atom.
(C)In Benzoic acid the negative charge of carboxylate anion is in conjugation with
benzene ring hence involved in resonance so carboxylate anion of benzoic acid
is more stable than that of acetic acid, and +I effect of methyl group in acetic
acid also makes it weaker acid.
FIVE MARKS QUESTION

74
Q3. Predict the product when cyclohexanecarbaldehyde reacts with
following reagents :
(i) C6H5MgBr followed by H30+ (ii) Tollen’s reagent
(iii) Semicarbazide in the weakly acidic medium
(iv) Excess of ethanol in the presence of acid
(v) Zinc amalgam and Cyclohexanecarbaldehyde Semicarbazide

75
ALDEHYDES , KETONES & CARBOXYLIC ACIDS
CASE BASED QUESTIONS
(a) The aldehydes and ketones undergo nucleophilic addition reactions. A nucleophile
attacks the electrophilic carbon atom of the polar carbonyl group from a direction
approximately perpendicular to the plane of sp 2 hybridised orbitals of carbonyl
carbon . The hybridisation of carbon changes from sp 2 to sp 3 in this process, and a
tetrahedral alkoxide intermediate is produced. This intermediate captures a proton
from the reaction medium to give the electrically neutral product. The net result is
addition of Nu– and H+ across the carbon oxygen double bond.
1. Though carboxylic acid contains C=O group but it do not give nucleophilic addition
reactions, why?
2. How will you convert ethanal to lactic acid?
3. Arrange the following compounds in their increasing order of reactivity towards
nucleophilic addition reactions- C6H5CHO, HCHO, CH3CHO, CH3COCH3
4. Complete the following reactions-
(a) CH3CHO + C2H5OH →
(b) CH3CHO+ NaOH (Dil) →
ANSWER-
1. Because electrophilicity on carbon atom of COOH group is not present due to
resonance.
𝐻𝐶𝑁 𝐻2𝑂/𝐻+
2. CH3CHO → CH3CH(OH)CN → CH3CH(OH)COOH
3. C6H5CHO < CH3COCH3 < CH3CHO < HCHO
76
4.
(a) CH3CHO + C2H5OH → CH3-CH(OH)-OC2H5
𝐻𝐸𝐴𝑇𝐼𝑁𝐺
(b) CH3CHO+ NaOH (Dil) → CH3-CH(OH)-CH2-CHO → CH3-CH=CH-CHO

(b) Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids at
room temperature with unpleasant odours. The higher acids are wax like solids and
are practically odourless due to their low volatility. Carboxylic acids are higher boiling
liquids than aldehydes, ketones and even alcohols of comparable molecular masses.
Carboxylic acids are weaker than mineral acids, but they are stronger acids than
alcohols and many simple phenols (pKa is ~16 for ethanol and 10 for phenol). In
fact, carboxylic acids are amongst the most acidic organic compounds you have
studied so far.
1. Ethanoic acid forms dimer in vapour state, justify.
2. Why carboxylic acids have higher boiling points than that of aldehydes & ketones
of comparable molecular masses, why?
3. Though phenoxide ion has more number of resonating structures than
carboxylate ion but phenol is weaker acid than carboxylic acids, why?
4. Arrange the following compounds in their increasing order of pKa-
(i) HCOOH, C6H5COOH, CH3COOH
(ii) BrCH2COOH, ClCH2COOH , FCH2COOH
ANSWER-
1. Due to formation of intermolecular hydrogen bond.
2. Due to formation of intermolecular hydrogen bond.
3. In carboxylate ion charge separation is among same atoms i.e. oxygen atoms
whereas in phenoxide ion it is among different atoms i.e. oxygen and carbon
atoms hence carboxylate ion is more stable and carboxylic acids are stronger
acids.
4.
(i) C6H5COOH> CH3COOH > HCOOH
BrCH2COOH >ClCH2COOH > FCH2COOH

AMINES
Hoffmann Ammonolysis reaction: Hoffmann bromamide
degradationreaction

Gabriel phthalimide synthesis: Coupling Reaction:

77
Sandmeyer reaction: Gatterman reaction:

Diazotisation: Prepared by M R Choudhary 8469113570

Carbylamine reaction:

NAME REACTION
-:Hinsberg test:-To distinguish 10 20 30 Amine

DISTINGUISH BY SINGLE CHEMICAL TEST

Examples Reagents Test performed by
(i) Methylamine and dimethylamine Carbyl amine test Methylamine
(ii) Secondary and tertiary amines Hinsberg reagent Secondary amines
(iii) Ethylamine and aniline Azo dye test Aniline
(iv) Aniline and benzylamine Azo dye test Aniline
(v) Aniline and N-methylaniline. Carbyl amine test Aniline
Important Reasoning Question

Question Answer
Why pH of reaction should be carefully amonia derivated get protenated in acidic
controlled while preparing ammonia medium so nucleophilic attack on CO group
derivatives of carbonyl compound? would not possible
pKb of aniline is more than that of Due to delocalisation of lone pair of electron
methylamine. of N aton in aniline it is less basic and have
higher value of PKb
Ethylamine is soluble in water whereas aniline due to formation of H bonding by ethyl amine
is not.
Methylamine in water reacts with ferric RNH2 + H2O-RNH3+ +OH
chloride to precipitate hydrated ferric oxide.
-FeCl3 + 3OH-Fe(OH)3+ +3Cl
Although amino group is o– and p– directing in due to formaton of anilinium ion under stron
aromatic electrophilic substitution reactions, acidic condition
aniline on nitration gives a substantial amount
of m-nitro aniline.
Aniline does not undergo Friedel-Crafts Due to formation of salt
reaction.
Diazonium salts of aromatic amines are more Due to resonance
stable than those of aliphatic amines.
78
Gabriel phthalimide synthesis is preferred for due to only one replacable H in phthalamide
synthesising primary amines.
Why cannot aromatic primary amines be Aromatic 1oamines cannot be prepared by
prepared by Gabriel phthalimide synthesis? this method because aryl halides do not
undergo nucleophilic substitution with the
anion formed by phthalimide.
Why are amines less acidic than alcohols of Due to less electronegativity of N
comparable molecular masses?
Why do primary amines have higher boiling Due to Intermolecular H bonding
point than tertiary amines?
Why aliphatic amines stronger are bases than Due to delocalisation of lone pair of electron
aromatic amines? of N atom in aromatic amine

CONVERSIONS
Question REAGENTS
(i) Benzene into aniline

(ii) Benzene into N,N-

dimethylaniline

(iii) Cl-(CH2)4-Cl into

Hexane -1,6- diamine

(iv) 3-Methylaniline into 3-

nitrotoluene

(v) Aniline into 1,3,5-

Tribromo benzene

(v) Ethanoic acid into

methanamine
(vi) Ethanamine into
methanamine

(vii) Nitromethane into

dimethylamine
(viii) Nitrobenzene to
benzoic acid

79
(ix) Benzoic acid to aniline

Arrengement order(Decresing/Increasing)
In order of- Questions Answers
(i) In decreasing order of the C2H5NH2, C6H5NHCH3, C2H5NH2, C6H5NHCH3,
pKb values: (C2H5)2NH and C6H5NH2 (C2H5)2NH and C6H5NH2
(ii) In increasing order of C6H5NH2, C6H5N(CH3)2,C6H5NH2, C6H5N(CH3)2,
basic strength: (C2H5)2NH and CH3NH2 (C2H5)2NH and CH3NH2
(iii) In increasing order of Aniline, p-nitroaniline and p-
Aniline, p-nitroaniline and p-
basic strength: toluidine toluidine
(iv) In decreasing order of C2H5NH2, (C2H5)2NH, (C2H5)3N
basic strength in gas phase: C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of and NH3
boiling point: C2H5OH, (CH3)2NH, C2H5NH2 C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of
solubility in water: C6H5NH2, (C2H5)2NH, C6H5NH2, (C2H5)2NH, C2H5NH2.
C2H5NH2.

WORD PROBLEM
A colourless substance ‘A’ (C6H7N) is sparingly soluble in water and gives a water
soluble compound ‘B’ on treating with mineral acid. On reacting with CHCl 3 and
alcoholic potash ‘A’ produces an obnoxious smell due to the formation of
compound ‘C’. Reaction of ‘A’ with benzenesulphonyl chloride gives compound
‘D’ which is soluble in alkali. With NaNO2 and HCl, ‘A’ forms compound ‘E’ which
reacts with phenol in alkaline medium to give an orange dye ‘F’ Identify
compounds ‘A’ to ‘F’

Two Marks Questions

1 Write the short note on reductive amination reactions?

AN When aldehydes or ketones react with ammonia imines is formed. These imines give
S the primary amine by catalytic reduction.

RCHO + NH3 RCH=NH RCH2NH2

2 How will you form quaternary ammonium salt from haloalkane?
AN When haloalkanes heated with an ethanolic solution of ammonia in a sealed tube at
S 1000C .

RX + NH3 RNH2 R2NH R3 N R4+NX-

Haloalkane P. amine S. Amine T. Amine

Quaternary Ammonium salt
3 Why is aniline a weaker base than methylamine?
AN Aniline and methylamine both have nitrogen with lone pair of electron. In aniline the
S phenyl group is electron attracting. It tend to decrease the electron density on
nitrogen atom and hence decreases electron releasing tendency of nitrogen. While
80
in methylamine CH3- group is electron repelling in nature. It tends to increase the
electron density on the nitrogen atom and helps in electron releasing tendency of
nitrogen. So, the aniline is a weaker base than methylamine.
4 Arrange the following in increasing order of basic strength: -
(i) Triethylamine, ethylamine and ammonia.
(ii) p-nitroaniline, aniline and p-toludine.
AN (i) Ammonia < Triethylamine < Ethylamine
S (ii) Aniline < p-nitroaniline < p-toludine.
5 Can we prepare aniline by Gabriel-phthalimide reaction?
AN We can not prepare aniline by Gabriel-phthalimide reaction because this preparation
S requires the reaction of pot. Phthalimide with chlorobenzene or bromobenzene. But
aryl halides do not give nucleophilic substitution reaction at ordinary condition in
laboratory.
6 Arrange the following in increasing order of their basic strength
C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
AN C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
S
7 Complete the following reactions:
(i) CH3NH2 + C6H5COCl ………… + ……..
(ii) C6H5NH2 + (CH3CO)2O ………. + ……….
AN (i) CH3NH2 + C6H5COCl CH3NHCOC6H5 + HCl
S
(ii) C6H5NH2 + (CH3CO)2O C6H5NH-COCH3 + CH3COOH
8 How will you distinguish between cyanides and isocyanides?
AN Properties Cyanide Isocyanides
S 1.Solubility in 1. Soluble in water 1. Sparingly soluble in water.
water 2. Pleasant smell 2. Highly unpleasant smell
2.Odour 3. Give acid on hydrolysis 3. Give primary amines and
3.Hydrolysis with acid and alkalies formic acid on hydrolysis with
4. Reduction 4. Give primary amine on dil. Acids.
complete reduction. 4. Give secondary amines on
complete reduction.
9 Why is NO2 group called an ambident group?
AN Nitro group can attach itself through two different atoms, i.e., through O atom and
S N atom. Thus, nitro group is an ambident group
Three Marks Questions
1 Predict the products of and balance the following reactions:

(i) C2H5NO2 ………

(ii) C2H5-O-N=O ……… + …….. + ………..

(iii) C6H5 NO2

…….. ………
AN
(i) C2H5NO2 C2H5NH2 + 2H2O
S
(ii) C2H5-O-N=O C2H5OH + NH3 + H2 O

(iii) C6H5 NO2 m-C6H4(NO2)2 H2N.C6H4.NO2

2 Account for the following :-
(i) Pkb of aniline is more than that of methylamine.
81
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii)Why has aniline a weak basic nature than aliphatic amines?
AN Ans: (i) aniline has an electron withdrawing phenyl group so it is the weaker base
S than ammonia. Methyl group in methylamine is electron donating group so it is
stronger base than ammonia.
(ii)ethyl group in ethylamine is comparatively a small group and causes no hindrance
in formation of hydrogen bonding and hence it is soluble in water.
(iii) Due to resonance in aniline
3 (i) Arrange the following in the order of basicity in aqueous solution
(Me)3N, MeNH2, (Me)2NH, NH3
(ii) Complete and name the following reactions:

AN (i) Arrange the following in the order of basicity in aqueous solution

S
NH3＜ (Me)3N, ＜ MeNH2,＜ (Me)2NH,

(ii)(a)

(ii)(b)
4 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
a compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of
molecular formula C6H7N. Write the structures and IUPAC names of the compounds
A, B, C.
AN
S

AN NaCN NaOH
S H3C I H3C N H3C NH2 H3C NH2
OH- hydrolysis O
Br2

82
FIVE MARKS QUESTIONS
1

i) In aniline, the lone pair of electrons on N atom is in resonance with benzene ring.
Hence, it cannot be easily donated to an acid. This decreases its basicity. In methyl
amine, the +I effect of methyl group increases the electron density on N atom so that
the lone pair of electrons on N atom can be easily donated to an acid. Hence,
methylamine is more basic than aniline. Higher is the basicity, lower is the pKb and vice
versa.
(ii) Ethylamine is soluble in water whereas aniline is not. With increase in the molecular
weight, the solubility decreases. Aniline has higher molecular weight than ethylamine.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
Due to the +I effect of −CH3 group, methylamine is more basic than water. Therefore,
in water, methylamine produces OH− ions by accepting H+ ions from water. OH− ions
react with ferric chloride to precipitate hydrated ferric oxide.
(iv)In aniline NH2 increases e density at o- and p- positions due to +R effect. But when
it is nitrated by nitrating mixture, a substantial amount of m-nitro aniline is formed.
But in acidic medium (Nitrating mixture - HNO3(c) + H2SO4(c)).
NH2 + H+ ⇌NH3+ is e− withdrawing group and so is m - directing. So gives larger
amount of m- nitroaniline.
(v) Aniline does not undergo Friedel craft's reactions because the reagent AlCl3 (the
Lewis acid which is used as a catalyst in friedel crafts reaction), being electron
deficient acts as a Lewis base.
2.

Answers

83
AMINES
CASE BASED QUESTIONS
(a) Amines constitute an important class of organic compounds derived by
replacing one or more hydrogen atoms of ammonia molecule by alkyl/aryl
group(s). In nature, they occur among proteins, vitamins, alkaloids and
hormones. Synthetic examples include polymers, dye stuffs and drugs. Two
biologically active compounds, namely adrenaline and ephedrine, both
containing secondary amino group, are used to increase blood pressure.
Novocain, a synthetic amino compound, is used as an anaesthetic in dentistry.
Benadryl, a well known antihistaminic drug also contains tertiary amino group.
Amine can be prepared by a numbers of ways.
1. Can aniline be prepared by Gabriel phthalimide synthesis, justify?
2. What happens when Acetamide treated with NaOBr?
3. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating
forms compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of
molecular formula C6H7N. Write the structures and IUPAC names of compounds
A, B and C.
Answer- 1. No, aniline can not be prepared by Gabriel phthalimide synthesis because
to prepare aniline by this method chlorobenzene is required which do not undergo
SN reactions under normal conditions.
𝑁𝑎𝑂𝐵𝑟
2. CH3-CO-NH2 → CH3-NH2
3. A- C6H5COOH- Benzene carboxylic acid B- C6H5CONH2- Benzamide
C- C6H5NH2 – Aniline (Benzenamine)
(b) The reaction of amines with mineral acids to form ammonium salts shows that
these are basic in nature. Amines have an unshared pair of electrons on nitrogen
atom due to which they behave as Lewis base. Basic character of amines can be
better understood in terms of their Kb and pKb values.
1. Aniline is weaker base than ammonia, why?
2. Tertiary amines becomes less basic than secondary amines in solution, justify.
3. Aqueous solution of methyl amine gives brown ppt with neutral FeCl3 , why?
4. Arrange the following amines in their increasing order of basic nature in gas
phase and in solution- (CH3)3N , (CH3)2NH, CH3NH2
Answer- 1. Because in aniline lone pair of electron is involved in resonance.
2. Due to steric hindrance of bulkier alkyl group of tertiary amine lone pair can
not be donated easily.
3. Methyl amine reacts with water to give OH- ion which reacts with Fe3+ ion to
form brown ppt of Fe(OH)3.
4. In gas phase- CH3NH2 < (CH3)2NH <(CH3)3N
In solution - CH3NH2 < (CH3)3N <(CH3)2NH

84
Kendriya Vidyalaya Sangathan, Ahmedabad Region
Sample question paper (2021-22)
Term II Class XII Chemistry Theory (043)
Max. Marks: 35 Time: 2 hrs
**************************************************************
General instructions:
1. There are 12 questions in this question paper.
2. Section A - Q. No.1 to 3 are very short answer questions carrying 2 marks each.
3. Section B - Q. No.4 to 11 are short answer questions carrying 3 marks each.
4. Section C - Q. No.12 is case based question carrying 5 marks.
5. All questions are compulsory.
6. There is no overall choice. However, internal choices have been provided.
7. Use of log tables and calculators is not allowed
SECTION A
1 Give names of the reagents to bring about the following transformations: 2
(a) Hexan-1-ol to hexanal (b) Cyclohexanol to cyclohexanone
2 (i) Write one function of salt bridge 2
(ii) How much charge is required for changing 1 mol of Al3+ to Al?
3 Which acid of each pair shown here would you expect to be stronger? 2
(a) CH3COOH or CH2FCOOH (b) CH2FCOOH or CH2ClCOOH
SECTION B
4 Arrange the following in increasing order of property specified: 3
(i) Aniline, ethanamine, 2-ethylethanamine (solubility in water)
(ii) Ethanoic acid, ethanamine, ethanol (boiling point)
(iii)Methanamine, N, N- dimethylmethanamine and N- methylmethanamine (basic
strength in aqueous phase)
OR
(i) Give a chemical test to distinguish between N-methyl Ethan amine and N,N-
dimethyl Ethan amine.
(ii) Write the reaction for catalytic reduction of nitrobenzene followed by reaction
of product so formed with bromine water.
(iii) Out of butan-1-ol and butan-1-amine, which will be more soluble in water and
why?
5 Answer the following questions: 1+2
a. [Ni(H2O)6 ] 2+ (aq) is green in colour whereas
[Ni(H2O)4 en)]2+(aq)is blue in colour , give reason in support of your answer .
b. Write the formula and hybridization of the following compound: tris(ethane-1,2–
diamine) cobalt(III) sulphate
OR
In a coordination entity, the electronic configuration of the central metal ion is t2g 3
eg 1
a. Is the coordination compound a high spin or low spin complex?
b. Draw the crystal field splitting diagram for the above complex.
6 Explain giving reasons: 3
(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.
7 An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate with 1+2
2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of
sodium hydroxide. It neither reduces Tollens’ or Fehling’s reagent, nor does it decolourise
bromine water or Baeyer’s reagent. On drastic oxidation with chromic acid, it gives a

85
carboxylic acid (B) having molecular formula C 7H6O2. Identify the compounds (A) and (B)
and explain the reactions involved.
8 (i)Define the terms – (a) Brownian movement (b) Electrophoresis? 2+1
(ii)State Hardy- Schulze rule?
9 What happens when reactions: a. N-ethylethanamine reacts with benzenesulphonyl 1x3
chloride. =3
b. Benzylchloride is treated with ammonia followed by the reaction with
Chloromethane.
c. Aniline reacts with chloroform in the presence of alcoholic potassium hydroxide.
OR
(i)Write structure of following (i) Aminobut -2- ene
(ii)A compound (X) having formula C3H7 NO reacts with Br2 in the presence of NaOH
to give another compound (Y). Compound (Y) reacts with HNO2 to form ethanol and
N2 gas . Identify (X) and (Y) . Write the reaction involved. 1+2
=3
10 What is the cell potential for the cell at 250C 3
Cr / Cr3+ 0.1 M] //Fe2+ (0.01M) /Fe E0 cr+/cr = -0.74V ; E0 Fe2+/Fe = - 0.44V.
11 What is the lanthanoid contraction? What are its causes and consequences? 1+2
OR
What is the general valance configuration of f-block elements? [1]
What is the composition of mischmetal? Give its one use. [2]
SECTIONC
12 Rate law: Rate law or rate equation is the expression which relates the rate of reaction with 1+1
concentration of the reactants. The constant of proportionality ‘k’ is known as rate constant. +3
The rate law states that the rate of reaction is directly proportional to the product of molar =5
concentration of reactants and each concentration is raised to some power which may or
may not be equal to stoichiometric coefficients of reacting species. Rate = k[A]m [B]n  Rate
constant: Rate constant is also called specific reaction rate. When concentration of both
reactants are unity (one), then the rate of reaction is known as rate constant. It is denoted
by ‘k’.
Order of reaction: Order is defined as the sum of powers of concentration of the reactants in
the experimentally derived rate equation or rate law expression. Order of reaction is
experimentally determined and is not written from the balanced chemical equation. Order of
reaction can be whole number, zero or fractional.
First order reaction: The rate of reaction is directly proportional to the first power of the
concentration of reacting substance. i.e., Rate = k[A] 1 .
Rate constant of the first order reaction is
k = 2.303/t log (a /a -x )- where ‘a’ is initial concentration and
(a – x) is the concentration after time ‘t’. Unit of ‘k’ is s–1 or min–1
(i) For a reaction A + B → P, the rate is given by Rate = k[A] [B]2
(a) How is the rate of reaction affected if the concentration of B is doubled?
(b) What is the overall order of reaction if A is present in large excess?
(ii) A first order reaction takes 30 minutes for 50% completion. Calculate the time required
for 90% completion of this reaction. (log 2 = 0.3010)

86
Answer key
Section A
1 Names of the reagents to bring about the following transformations: 1x2
a) Hexan-1-ol to hexanal-PCC =2
b) Cyclohexanol to cyclohexanone-K2Cr2O7/H2SO4

2 ii) Any One function of salt bridge -To connect to half-cells, to maintain electroneutrality 2
iii) Charge required for changing 1 mol of Al3+ to Al----
3F i,e. 3x96500C.

3 Stronger acid in pair (a) CH2FCOOH (b) CH2FCOOH 1x2

=2
SECTION B
4 Arrange the following in increasing order of property specified: 1x3
i) Aniline, 2-ethylethanamine ethanamine =3
(solubility in water)
ii) ethanamine, ethanol, Ethanoic acid (boiling point)
iii) n N, N- dimethylmethanamine , Methanamine, N- methylmethanamine (basic strength in
aqueous phase)
OR
iv) Chemical test to distinguish between N-methyl Ethan amine and N,N-dimethyl Ethan amine. -
Hinsberg Test

N,N-dimethyl Ethan amine will not react with benzenesulphonyl chloride & N-methyl Ethanamine will react
to give a ppt. which is insoluble in alc.KOH.

v) the reaction for catalytic reduction of nitrobenzene followed by reaction of product so formed
with bromine water.

Sn/HCl Br2/H2O
C6H5NO2  C6H5NH2  2,4,6TRIBROMOANILINE

vi) Out of butan-1-ol and butan-1-amine, Butan1-ol is more soluble in water because the H bond
formed is more strong.
5 Answer the following questions: 1+2
2+
a. [Ni(H2O)6 ] (aq) is green in colour whereas
[Ni(H2O)4 en)]2+(aq)is blue in colour

The colour of coordination compound depends upon the type of ligand and dd transition taking place . H2O
is weak field ligand , which causes small splitting , leading to the d-d transition corresponding green colour
, however due to the presence of ( en ) which is strong field ligand , the splitting is increased . Due to the
change in t2g -eg splitting the colouration of the compound changes from green to blue.

(b)Formula of the compound is [Co(H2NCH2CH2NH2 )3]2 (SO4)3 The hybridisation of the compound is:
d2sp3
OR
5. In a coordination entity, the electronic configuration of the central metal ion is t 2g 3 eg 1
a)As the fourth electron enters one of the eg orbitals giving the configuration
t2g 3eg 1 ,which indicates ∆o < P hence forms high spin complex.

b) the crystal field splitting diagram for the above complex.

Correct diagram.

1+1
+1

87
6 i) Transition metals and many of their compounds show paramagnetic behaviour due to presence
of unpaired electrons.
ii) The enthalpies of atomisation of the transition metals are high because of strong bonding.
iii) The transition metals generally form coloured compounds due to presence of unpaired electrons
d-d transition is possible.
7 Compound A-Acetophenone C6H5COCH3
As it is methyl ketone it gives iodoform testbut does not respond to Tollen’s or fehling’s reagent.
Compound B – Benzoic acid
Reaction needed.
8 (i) (a) Brownian movement: - The continuous zig-zag movement of particles in a colloidal 2+1
solution is called Brownian movement.
(b) Electrophoresis: - The movement of particles under an applied electric potential is called
electrophoresis.
(ii) According to Hardy- Schulze rule- The greater the valence of the flocculating ion added,
the greater is its power to cause precipitation
9 (a)When N-ethylethanamine reacts with benzenesulphonyl chloride , N,N-diethylbenzenesulphonamide is 1x3
formed. =3
b)When benzylchloride is treated with ammonia , Benzylamine is formed which on reation with
Chloromethane yields a secondary amine , N-methylbenzylamine .
c)When aniline reacts with chloroform in the presence of alcoholic potassium hydroxide , phenyl
isocyanides or phenyl isonitrile is formed .
OR
(i) structure of (i) Aminobut -2- ene
CH2(NH2)CH=CHCH3
(ii) NaOH/Br2 HNO2 1+2
CH3CH2CONH2  CH3CH2NH2  CH3CH2OH +N2 =3
(X) (Y)
10 What is the cell potential for the cell at 250C
Cr / Cr3+ 0.1 M] //Fe2+ (0.01M) /Fe E0 cr+/cr = -0.74V ;
E0 Fe2+/Fe = - 0.44V. [3]
The cell reaction is 2 Cr + 3 + Fe2+ + 6e- → 2 Cr3+ + 3Fe
Nernst Equation –
Ecell = ( E0 Fe2+/ Fe- E0 Cr 3+ /Cr ) - 0.059 /6 log[Cr+3]/Fe+2]
= (0.30) -0.01log(10 -4 )
= (0.30) -0.01x4
=0.30-0.04 =0.26 V
11 Lanthanoid contractions – The cumulative effect of the regular decrease in size or radii of Lanthanoid with 3
increase in atomic number is called Lanthanoid contraction.
Causes - The shape of f orbitals is diffused. They have poor shielding effect due to which the effective
nuclear charge increase with increase in atomic number. This causes a decrease in atomic radii
Consequences – Due to Lanthanoid contraction- 1. Radii of the members of the third transition series is
similar to those of second transition series. 2. It becomes difficult to separate Lanthanoids.
OR
The general electronic configuration of f-block elements is
(n-2) f 1-14 (n-1) d 0-1 ns2
Mischmetall is an alloy of a Lanthanoid metal and iron and traces of S, C, Ca & Al. It is used in Magnesium
based alloy to produce bullets, shell and lighter Flint. [2] 1+2
SECTIONC
12 (i) A + B → P Rate = k[A] [B]2 1+1
(a) When concentration of B is doubled it means concentration of B becomes 2 times. Thus, Rate = k[A] 1 [2B]2 = k[A] +3
[4B ]2 So, the rate becomes 4 times. =5
(b) Order of reaction is the number of molecules whose concentration alters after the reaction. If A is present in excess
i.e., its concentration is unaffected. So, rate depends only on the concentration of B. as k = [B]2 Thus, the reaction is
of second order.
(ii) For the 1st order reaction: k = 2.303/t log (a/ a -x)
Ans. 5.98 x10 3 sec
88
Kendriya Vidyalaya Sangathan, Ahmedabad Region
Sample question paper -2(2021-22)
Term II Class XII Chemistry Theory (043)

Max. Marks: 35 Time: 2 hrs

******************************************************
General instructions:
1. There are 12 questions in this question paper.
2. Section A - Q. No.1 to 3 are very short answer questions carrying 2 marks each.
3. Section B - Q. No.4 to 11 are short answer questions carrying 3 marks each.
4. Section C - Q. No.12 is case based question carrying 5 marks.
5. All questions are compulsory.
6. There is no overall choice. However, internal choices have been provided.
7. Use of log tables and calculators is not allowed
SECTION A
1 Draw the structure of the following – 1x2=2
i) I,2–Ethanedioc acid
ii) Pent-3-ene -2-one
2 The conversion of molecule X to Y follows second order kinetics. If 2
concentration of X is increased to three times, how will it affect the rate of
formation of Y?
3 Give Reasons :- 1x2=2
i)Carboxylic acids do not give characteristic reactions of carbonyl group.
ii) Formal dehyde does not undergo aldol condensation
SECTION B
4 i) Why do amines behave as nucleophiles? 1x3=3

ii) What is the role of pyridine in the acylation reaction of amines?

iii) What is the role of HNO3 in the nitrating mixture used for nitration
of benzene
OR
Account for the following:
(i) Aniline gets coloured on standing in air for a long time.
(ii) MeNH2 is stronger base than MeOH.
(iii) The presence of a base is needed in the ammonolysis of alkyl
halides.
5 1+2
Write the formulas for the following coordination compounds:
(i) tetraamminediaquacobalt(III) chloride
(ii) potassium tetracyanidonickelate(II)
(iii) tris (ethane-1, 2-diamine) chromium(III) chloride
OR
Write IUPAC names of the following coordination compounds:
(i) [(Co(NH3)6Cl3)]
(ii) [Co(NH3)5Cl]Cl2
(iii) K3[Fe(CN)6]
6 The elements of 3d transition series are given as:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:
(a) Which element has the highest m.p. and why?
(b) Which element is a strong oxidising agent in +3 oxidation state and why?
89
c) Which element is soft and why?
7 a)Arrange the following compounds in increasing order of their reactivity in 2+1
nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde,
Acetophenone
b)Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
8 Write three differences between physisorption and chemisorption. 3
9 Write short notes on the following: 1x3=3
(i) Carbylamine reaction
(ii) Diazotisation
(iii) Hofmann’s bromamide reaction
OR
(i)Coupling reaction
(ii)Ammonolysis
(iii) Acetylation

10 The half-life for radioactive decay of C-14 is 5730 years. An archaeological 3

artifact containing wood had only 80% of the C-14 found in a living tree.
Estimate the age of the sample.
11 Give reasons: (a) Among transition metals, the highest oxidation state is 1+2
exhibited in oxoanions of a metal.
(b) Ce4+ is used as an oxidising agent in volumetric analysis.
(c) Zn2+ salts are white while Cu2+ salts are blue.
OR
Account for the following: (i) Mn2O7 is acidic whereas MnO is basic. (ii) Though
copper has completely filled d-orbital (d10) yet it is considered as a transition
metal.
(iii) Eu2+ is a strong reducing agent.
SECTIONC
12 Redox reactions play an important role in chemistry. Whenever a redox 1x5=5
reaction takes place directly in a single beaker, chemical energy in the form of
heat is produced. By suitable means, it is possible to bring about the redox
reactions indirectly so as to convert the chemical energy into electrical energy.
A device used to convert the chemical energy produced in a redox reaction into
electrical energy is called an electrochemical cell. If a redox reaction is allowed
to take place in such a way that oxidation half reaction takes place in one
beaker and the reduction half reaction in another beaker, the electrons given
out by the former will be taken by the latter and the current will flow. The two
portions of the cell are called half cells. The values of standard redox potential
(Eo ) of two half cell reactions decides in which way the reaction will proceed.
A redox reaction is feasible when the substance having higher reduction
potential gets reduced and the one having lower reduction potential gets
oxidised. For example, In Daniel cell, zinc goes into solution and copper gets
deposited.
a.
i) Formulate the galvanic cell in which the following reaction takes place: Zn(s)
+ 2Ag+ (aq)  Zn2+(aq) + 2Ag(s)
ii). Is it safe to stir AgNO3 solution with a copper spoon? Why or why not?
Given: Eo Ag+/Ag = 0.80 volt and Eo Cu2+/Cu = 0.34 volt.
b.
i)Two half cell reactions of an electrochemical cell are given below: MnO4 – (aq)
+ 8H+ (aq) + 5e – Mn2+(aq) + 4H2O(l),
90
Eo = +1.51 V Sn2+(aq) Sn4+(aq) + 2e – , Eo = +0.15 V
Construct the redox reaction from the two half cell reactions and predict if this
reaction favours formation of reactants or products shown in the equation.

ii). State the factors that influence the value of cell potential of the following
cell: Mg(s)|Mg2+(aq) || Ag+ (aq)|Ag(s)
iii). Can Eo cell or ∆rGo for cell reaction ever be equal to zero?

ANSWER KEY
SECTION A
1 i) 1,2–Ethaneodioc acid --CH2(COOH)-CH2(COOH) 1x2=2
ii) Pent-3-ene -2-one -- CH3COCH=CHCH3
2 2
Rate = k [X] 2
r1 = k [X] 2 ...(i)
r2 = k [3X] 2 ...(ii)
Dividing (ii) by (i),
r2 = 9r1
Thus, rate of formation of Y will increase by nine times.
3 i)Carboxylic acids do not give characteristic reactions of carbonyl group 1x2=2
because it is involved in resonance & is not free to give carbonyl group
reactions
ii). Formal dehyde does not undergo aldol condensation due to absence of
alpha H.
SECTION B
4 a)(i)Due to the presence of a lone pair of electrons on nitrogen atom, 1x3=3
amines behave as nucleophiles.
(ii) Pyridine and other bases are used to remove the side product, i.e.,
HCl from the reaction mixture.
(iii)HNO3 acts as a base in the nitrating mixture and provides the
electrophile NO2+.
OR
b) (i) Due to electron-donating effect (+R-effect) of —NH2 group, the
electron density on the benzene ring increases. As a result, aniline is easily
oxidised on standing in air for a long time to form coloured products.
(ii) Nitrogen is less electronegative than oxygen therefore lone pair of
electrons on nitrogen is readily available for donation. Hence, MeNH2 is
more basic than MeOH
(iii) To remove HX formed so that the reaction shifts in the forward
direction.
5 Formulas of the coordination compounds: 1x3=3
Ans. (i) [Co(NH3)4(H2O)2]Cl3
(ii) K2Ni[(CN)4]
(iii) [Cr(en)3]Cl 3
OR
IUPAC names of the following coordination compounds:
(i) hexaamminecobalt(III) chloride
(ii) pentaamminechloridocobalt(III) chloride
(iii) potassium hexacyanoferrate (III)
6 (i) (a) Cr, the highest melting point of Cr is attributed to the involvement 1x3=3
of greater number of electrons(5) from 3d in addition to 4s electrons in
interatomic metallic bonding.
91
(b) Mn, because the change from Mn3+ (d4 ) to Mn2+ (d5 ) results in the
half filled configuration which has extra stability.
(c) Zn, in Zn (3d10 4s 2) all the electrons present in d-orbitals are paired
and hence metallic bonds present in it are weak. That is why, it is soft
7 a)(i) The reactivity in nucleophilic addition reactions increases in the order: 1x3=3
Butanone < Propanone < Propanal < Ethanal
(ii)the required order is as follows: Acetophenone < p-Tolualdehyde <
Benzaldehyde < p-Nitrobenzaldehyde
b) CH3CH2CH3 < CH3OCH3 < CH3CHO< CH3CH2OH
8 Physisorption 3
It arises because of van der Waals’ forces. It is not specific in
nature.
It is reversible in nature.
It depends on the nature of gas. More easily liquefiable gases are
adsorbed readily.
Enthalpy of adsorption is low (20-40 kJ mol–1) in this case..
Low temperature is favourable for adsorption. (vii) No appreciable
activation energy is needed. (viii) It results into multimolecular layers
on adsorbent surface under high pressure.
Chemisorption
It is caused by chemical bond formation.
It is highly specific in nature
It is irreversible
It also depends on the nature of gas. Gases which can react with the
adsorbent show chemisorption.
Enthalpy of adsorption is high (80-240 kJ mol–1) .
It decreases with increase of temperature. High temperature is
favourable for adsorption. It increases with the increase of temperature.
High activation energy is sometimes needed.
It results into unimolecular layer (Any3 points)
9 (i) Carbylamine reaction 1x3=3
(ii) Diazotisation
(iii) Hofmann’s bromamide reaction
OR
(i)Coupling reaction
(ii)Ammonolysis
(iii) Acetylation
Correct equations

10 Radioactive decay follows first order kinetics. 3

Steps
Calculate K from t ½
K= 0.693/t 1/2
Cal t using formula
k = 2.303/t log [A0/A]
= 1845 years (approx.)
11 a) In these oxoanions the oxygen atoms are directly bonded to the 1+2
transition metal. Since oxygen is highly electronegative, the oxoanions
bring out the highest oxidation state of the metal.
b) Ce4+ has the tendency to attain +3 oxidation state which is more stable
and so it is used as an oxidising agent in volumetric analysis.

92
c) Zn2+ ion has all its orbitals completely filled whereas in Cu2+ ion there is
one half-filled 3d-orbital. Therefore, due to d-d transition Cu2+ has a
tendency to form coloured salts whereas Zn2+ has no such tendency.
OR
(i) Mn has +7 oxidation state in Mn2O7 and +2 in MnO. In low oxidation
state of the metal, some of the valence electrons of the metal atom are not
involved in bonding. Hence, it can donate electrons and behave as a base.
On the other hand, in higher oxidation state of the metal, valence electrons
are involved in bonding and are not available. Instead effective nuclear
charge is high and hence it can accept electrons and behave as an acid.
(ii) Copper exhibits +2 oxidation state wherein it will have incompletely
filled d-orbitals (3d9), hence a transition metal.
(iii) This is because Eu2+ tends to change to Eu3+ as +3 is the common
oxidation state of lanthanoids.
SECTIONC
12 a) 1+1+3
i) The cell is represented as Zn(s) | Zn2+(aq) | | Ag+ (aq) | Ag(s) =5

ii) No, it is not safe to stir AgNO3 solution with copper, because copper is
more reactive than Ag and can displace Ag from AgNO3 solution.
b)
i)The redox reaction will be 2MnO4 – (aq) + 16H+ (aq) + 5Sn2+(aq)
2Mn2+(aq) + 5Sn4+(aq) + 8H2O(l) Eo Cell = Eo Cathode – Eo Anode = 1.51
V – 0.15 V = 0.36 V, i.e., it will be positive. Hence, reaction will favour
formation of products.

ii)The factors that influence the value of cell potential are concentration of
Mg2+ and Ag+ ions in the solution and temperature.

iii)No, E o cell or ∆rGo for cell reaction can never be zero.

∆Go = – nFEo .Eo is never zero hence ∆Go will also be not equal to zero.

********************************************************************
*********

93