Paper 3

🧪 PART A – Short Answers (50 words each)

Q.1 (i) What do you mean by State Function? Give an example.

A state function is a property that depends only on the current state of the system, not on the
path taken. Examples include internal energy, enthalpy, pressure, and temperature.

(ii) Define Heat of Reaction.

Heat of reaction is the amount of heat absorbed or evolved during a chemical reaction at
constant pressure or volume. It is denoted as ΔH at constant pressure.

(iii) Write Trouton’s Rule.

Trouton’s Rule states that the molar entropy of vaporization for many liquids at their
boiling point is approximately 85–88 J/mol·K.

(iv) Write Van’t Hoff Equation.

dln⁡KdT=ΔH∘RT2\frac{d\ln K}{dT} = \frac{\Delta H^\circ}{RT^2}dTdlnK=RT2ΔH∘

This equation relates the change in equilibrium constant K with temperature T, where ΔH° is
the enthalpy change.

(v) One difference between thermoplastic and thermosetting polymers:

Thermoplastics soften on heating and can be remolded, while thermosetting polymers

undergo irreversible curing and cannot be reshaped once set.

(vi) Explain positive and negative adsorption.

Positive adsorption: Concentration of adsorbate increases on the surface.

Negative adsorption: Surface concentration is less than in the bulk phase.
(vii) Write phase rule.

Gibbs phase rule:

F=C−P+2F = C - P + 2F=C−P+2

Where F is degrees of freedom, C is components, P is phases.

(viii) For CaCO₃(s) ⇌ CaO(s) + CO₂(g):

Phases = 3 (CaCO₃, CaO, CO₂)

Components = 2 (CaO and CO₂)
F=C-P+2=2-3+2=1

(ix) Write Nernst equation for cell:

E=E∘−0.0591nlog⁡[Zn2+][Cu2+]E = E^\circ - \frac{0.0591}{n} \log

\frac{[Zn^{2+}]}{[Cu^{2+}]}E=E∘−n0.0591log[Cu2+][Zn2+]

(x) Ionic strength of 0.01 M MgSO₄:

Mg²⁺ = 2⁺, SO₄²⁻ = 2⁻

I=12[(0.01)(22)+(0.01)(22)]=12(0.04)=0.02I = \frac{1}{2}[(0.01)(2^2) + (0.01)(2^2)] =

\frac{1}{2}(0.04) = 0.02I=21[(0.01)(22)+(0.01)(22)]=21(0.04)=0.02

🧪 PART B – Detailed Answers (English Questions Only)

Q.2 Prove that Cp − Cv = R for 1 mole of an ideal gas

For an ideal gas, the first law of thermodynamics is:

dU=dq−PdVdU = dq - PdVdU=dq−PdV

 At constant volume, dqV=dUdq_V = dUdqV=dU, so:

CV=(dUdT)VC_V = \left( \frac{dU}{dT} \right)_VCV=(dTdU)V

 At constant pressure:
 dqP=dH=dU+PdVdq_P = dH = dU + PdVdqP=dH=dU+PdV

Hence,

CP=(dHdT)P=(dUdT)+(PdVdT)C_P = \left( \frac{dH}{dT} \right)_P = \left( \frac{dU}{dT} \right)

+ \left( \frac{PdV}{dT} \right)CP=(dTdH)P=(dTdU)+(dTPdV)

Since PV=RTPV = RTPV=RT for 1 mole:

(d(PV)dT)=R\left( \frac{d(PV)}{dT} \right) = R(dTd(PV))=R

Therefore:

CP−CV=RC_P - C_V = RCP−CV=R

This relation is known as Mayer’s relation and holds true for ideal gases.

Q.3 Explain the laws of thermochemistry

Thermochemistry deals with heat changes during chemical reactions. The two main laws are:

1. Lavoisier and Laplace Law:

The energy change for a forward reaction is equal in magnitude and opposite in sign to that of
the reverse reaction.
E.g.:

H2+12O2→H2OΔH=−285.8 kJ/molH_2 + \frac{1}{2}O_2 → H_2O \quad ΔH = -285.8 \text{ kJ/mol} H2

+21O2→H2OΔH=−285.8 kJ/mol

Reverse reaction:

H2O→H2+12O2ΔH=+285.8 kJ/molH_2O → H_2 + \frac{1}{2}O_2 \quad ΔH = +285.8 \text{ kJ/mol}H2

O→H2+21O2ΔH=+285.8 kJ/mol

2. Hess’s Law of Constant Heat Summation:

The total enthalpy change for a reaction is independent of the pathway between initial and
final states.
It allows calculation of enthalpy change for reactions that cannot be measured directly, by
summing intermediate steps.

These laws form the foundation for calculating heats of formation, combustion, and reaction
in physical chemistry.
Q.4 Describe the Third Law of Thermodynamics. Give its application.

The Third Law of Thermodynamics states:

The entropy of a perfect crystalline substance at absolute zero temperature is zero.

At 0 K, atoms are in their lowest energy state with perfect order, so disorder (entropy) is
zero.

S=0 at T=0 KS = 0 \text{ at } T = 0 \text{ K}S=0 at T=0 K

Applications:

1. Absolute Entropy Calculation:

Allows determination of absolute entropy of substances by integrating heat capacity
from 0 K.
2. Predicting Reaction Feasibility:
Helps assess entropy change ΔS and predict whether a reaction becomes more or less
favorable at low temperatures.
3. Determining Equilibrium Constants:
Precise values of ΔG require absolute entropy — Third Law provides it.
4. Low Temperature Behavior:
Important in cryogenics, superconductivity, and low-temperature chemistry.

This law bridges thermodynamics and statistical mechanics, providing fundamental

insights into matter at near-zero temperatures.

Q.5 Derive the Clausius–Clapeyron Equation

The Clausius–Clapeyron equation relates the pressure and temperature of a substance

during a phase change, particularly liquid ⇌ vapor equilibrium.

Start from:

dPdT=ΔHvapTΔV\frac{dP}{dT} = \frac{ΔH_{vap}}{TΔV}dTdP=TΔVΔHvap

For vaporization:

 ΔV ≈ V_vapor (since V_liquid is negligible)

 Use ideal gas law: V=RTPV = \frac{RT}{P}V=PRT

Substitute into the equation:

dPdT=ΔHvap⋅PRT2\frac{dP}{dT} = \frac{ΔH_{vap} \cdot P}{RT^2}dTdP=RT2ΔHvap⋅P

Rearrange:
dln⁡PdT=ΔHvapRT2\frac{d\ln P}{dT} = \frac{ΔH_{vap}}{RT^2}dTdlnP=RT2ΔHvap

Integrating gives:

ln⁡P=−ΔHvapRT+C\ln P = -\frac{ΔH_{vap}}{RT} + ClnP=−RTΔHvap+C

This is the Clausius–Clapeyron equation, which helps:

 Estimate boiling points at different pressures

 Understand phase diagrams

Q.6 Discuss viscosity method for determination of molecular weight of

macromolecules

The viscosity method is used to determine the molecular weight of polymers or

macromolecules by measuring the increase in viscosity of a solvent upon dissolving the
polymer.

Principle:

The intrinsic viscosity [η][η][η] of a polymer solution is related to its molecular weight
through the Mark-Houwink equation:

[η]=K⋅Ma[η] = K \cdot M^a[η]=K⋅Ma

Where:

 [η][η][η] = intrinsic viscosity

 MMM = molecular weight
 KKK and aaa are constants specific to the polymer-solvent system

Steps:

1. Prepare polymer solutions at different concentrations.

2. Measure the relative viscosity and specific viscosity using an Ostwald viscometer.
3. Plot ηspC\frac{η_{sp}}{C}Cηsp vs concentration and extrapolate to zero
concentration to obtain intrinsic viscosity.
4. Apply the Mark-Houwink equation to calculate molecular weight.

This method is particularly useful for polymers that do not easily crystallize or for which
other methods (like colligative properties) are not suitable.

Q.7 Derive Langmuir Adsorption Isotherm. Give its importance and

limitations.
The Langmuir isotherm explains how gases or solutes adsorb onto solid surfaces assuming:

 Adsorption occurs at specific homogeneous sites

 Only monolayer adsorption takes place
 No interaction between adsorbed molecules

Derivation:

Let θ be the fraction of the surface covered. Then:

 Rate of adsorption ∝ pressure × (1 − θ)

 Rate of desorption ∝ θ

At equilibrium:

k1P(1−θ)=k2θ⇒θ1−θ=k1k2P=bP⇒θ=bP1+bPk_1 P (1 - θ) = k_2 θ \Rightarrow \frac{θ}{1 - θ} =

\frac{k_1}{k_2} P = bP \Rightarrow θ = \frac{bP}{1 + bP}k1P(1−θ)=k2θ⇒1−θθ=k2k1P=bP⇒θ=1+bPbP

Amount adsorbed x/m=aθ=abP1+bPx/m = aθ = \frac{a b P}{1 + b P}x/m=aθ=1+bPabP

Importance:

 Helps in understanding catalysis, surface chemistry, and gas adsorption.

 Used in designing industrial adsorption processes.

Limitations:

 Assumes a uniform surface, which is unrealistic.

 Fails at high pressures or with multilayer adsorption.
 Doesn’t apply well to heterogeneous surfaces or liquid–solid systems.

Q.8 Explain phase diagram for lead-silver system

The Pb–Ag phase diagram is a classic example of a eutectic system involving complete
immiscibility in the solid state and complete miscibility in the liquid phase.

Features:

 Both metals melt at different temperatures (Pb ~327°C, Ag ~961°C).

 A eutectic point exists at approximately 2.6% Ag and 303°C.
 Upon cooling, the liquid mixture separates into solid Pb and solid Ag at eutectic
composition.

Diagram Description:

 Left branch: Solid Pb in equilibrium with liquid.

 Right branch: Solid Ag in equilibrium with liquid.
  At eutectic point: Both solids crystallize together from the melt.

Applications:

 Desilverization of lead in metallurgy.

 Purification of metals using fractional crystallization.

Q.9 Write short notes on:

(a) Azeotropes

An azeotrope is a mixture of two or more liquids that boils at a constant temperature and
composition. It behaves like a pure compound during boiling.
Examples:

 Ethanol–water (95.6% ethanol) forms a minimum boiling azeotrope.

(b) Ideal and Non-Ideal Solutions

 Ideal solutions obey Raoult’s Law throughout and have ΔH_mix = 0 and ΔV_mix =
0.
 Non-ideal solutions deviate due to interactions:
o Positive deviation: endothermic, weaker A–B interaction
o Negative deviation: exothermic, stronger A–B interaction

Q.10 (a) Derive relation between standard cell potential and equilibrium
constant

Start with:

ΔG=−nFE∘andΔG=−RTln⁡KΔG = -nFE^\circ \quad \text{and} \quad ΔG = -RT\ln

KΔG=−nFE∘andΔG=−RTlnK

Equating both:

nFE∘=RTln⁡K⇒ln⁡K=nFE∘RT⇒log⁡K=nFE∘2.303RTnFE^\circ = RT \ln K \Rightarrow \ln K =

\frac{nFE^\circ}{RT} \Rightarrow \log K = \frac{nFE^\circ}{2.303 RT}nFE∘=RTlnK⇒lnK=RTnFE∘
⇒logK=2.303RTnFE∘

This equation relates cell potential to the equilibrium constant and shows that a positive
E∘E^\circE∘ corresponds to a large KKK, favoring product formation.
Q.10 (b) Calculate standard cell potential for:

Al | Al3+(0.1m)∥Ag+(0.2m)∣Ag\text{Al | Al}^{3+} (0.1m) \| \text{Ag}^{+} (0.2m) |

\text{Ag}Al | Al3+(0.1m)∥Ag+(0.2m)∣Ag

Given:

 EAl3+/Al∘=−1.66 VE^\circ_{Al^{3+}/Al} = -1.66 \, VEAl3+/Al∘=−1.66V

 EAg+/Ag∘=+0.80 VE^\circ_{Ag^+/Ag} = +0.80 \, VEAg+/Ag∘=+0.80V

Overall cell reaction:

Al+3Ag+→Al3++3AgAl + 3Ag^+ → Al^{3+} + 3AgAl+3Ag+→Al3++3Ag

Standard cell potential:

Ecell∘=Ecathode∘−Eanode∘=0.80−(−1.66)=2.46 VE^\circ_{cell} = E^\circ_{cathode} - E^\circ_{anode}

= 0.80 - (-1.66) = \boxed{2.46 \, V}Ecell∘=Ecathode∘−Eanode∘=0.80−(−1.66)=2.46V

Q.11 Write short notes on:

(a) Asymmetric Effect

Occurs in molecules with a chiral center. Substitution causes uneven electron distribution,
influencing reactivity and optical activity. It’s crucial in understanding stereoselective
synthesis.

(b) Electrophoretic Effect

When ions move under an electric field, their movement disturbs the surrounding ionic
atmosphere, creating drag. This reduces ionic mobility and affects conductance, especially
in concentrated solutions.

Q.12 Explain the Joule–Thomson effect and Joule–Thomson experiment.

Derive the equation related to Joule–Thomson coefficient and prove that it is
zero for ideal gases.

Joule–Thomson Effect:

The Joule–Thomson effect refers to the temperature change observed in a real gas when it
expands adiabatically and without doing external work (i.e., through a porous plug or
throttle), under constant enthalpy conditions.

 If the gas cools: positive Joule–Thomson coefficient (μ > 0)

 If the gas heats: negative μ

This is commonly observed in gas liquefaction processes like Linde’s process.

Joule–Thomson Experiment:

A gas is forced through a porous plug from high pressure to low pressure in an insulated
system. Temperature change is observed:

 For most gases at room temperature, cooling occurs.

 For some gases like hydrogen and helium, heating occurs above their inversion
temperatures.

Joule–Thomson Coefficient (μ):

μ=(∂T∂P)Hμ = \left( \frac{\partial T}{\partial P} \right)_Hμ=(∂P∂T)H

This defines the change in temperature with pressure at constant enthalpy.

To derive it:
Start with the enthalpy differential:

dH=(∂H∂T)PdT+(∂H∂P)TdP=0⇒(∂T∂P)H=−((∂H∂P)T(∂H∂T)P)dH = \left( \frac{\partial H}{\partial T}

\right)_P dT + \left( \frac{\partial H}{\partial P} \right)_T dP = 0 \Rightarrow \left( \frac{\partial
T}{\partial P} \right)_H = - \left( \frac{ \left( \frac{\partial H}{\partial P} \right)_T }{ \left( \frac{\partial
H}{\partial T} \right)_P } \right)dH=(∂T∂H)PdT+(∂P∂H)TdP=0⇒(∂P∂T)H=−((∂T∂H)P(∂P∂H)T)
μ=1CP[T(∂V∂T)P−V]μ = \frac{1}{C_P} \left[ T \left( \frac{\partial V}{\partial T} \right)_P - V
\right]μ=CP1[T(∂T∂V)P−V]

For an Ideal Gas:

For ideal gases, V=RTPV = \frac{RT}{P}V=PRT, and (∂V∂T)P=RP\left( \frac{\partial

V}{\partial T} \right)_P = \frac{R}{P}(∂T∂V)P=PR, so:

μ=1CP[T(R/P)−RT/P]=0μ = \frac{1}{C_P} [T(R/P) - RT/P] = 0μ=CP1[T(R/P)−RT/P]=0

✅ Hence, Joule–Thomson coefficient for ideal gases is zero, meaning they show no
temperature change upon expansion at constant enthalpy.

Q.13 Write notes on the following:

(a) Physical significance of entropy

Entropy (S) is a measure of the disorder or randomness of a system. In thermodynamics, it

reflects how energy is dispersed in a system.

 Greater entropy = more disorder

 Helps predict spontaneity:
If ΔS > 0, process tends to be spontaneous.

(b) Chemical potential and its physical significance

Chemical potential (μ) is the partial molar Gibbs free energy of a component in a system. It
determines the direction of mass flow and chemical reactions:

 Matter moves from high μ to low μ

 At equilibrium, μ is the same in all phases

Important in phase equilibria, diffusion, and reaction kinetics.

(c) Entropy as a function of temperature and volume

Entropy increases with both temperature and volume. For an ideal gas:

ΔS=nRln⁡(V2V1)+nCVln⁡(T2T1)ΔS = nR \ln \left( \frac{V_2}{V_1} \right) + nC_V \ln \left(

\frac{T_2}{T_1} \right)ΔS=nRln(V1V2)+nCVln(T1T2)

 At constant temperature, expansion increases entropy due to increased positional

disorder.
 Heating increases entropy due to increased kinetic energy.

Q.14 (A) Write notes on the following:

(a) Electro-osmosis

Electro-osmosis refers to the movement of a liquid through a porous material or capillary

under the influence of an electric field. It occurs due to the interaction between the applied
electric field and the electric double layer formed at the solid-liquid interface.

 When an electric field is applied, cations in the diffuse layer migrate toward the
cathode, dragging the liquid along.
 It’s significant in soil science, electrochemical separation, membrane technology,
and microfluidics.
(b) Electrophoresis

Electrophoresis is the movement of charged particles (like colloids, proteins, or DNA) in a

fluid under an applied electric field.

 Positively charged particles move to the cathode, and negatively charged ones to the
anode.
 Used in DNA/RNA gel electrophoresis, protein analysis, and colloid
characterization.
 Mobility depends on charge, size, and viscosity of the medium.

(c) Streaming Potential

When a liquid is forced through a capillary, it can carry ions along due to the electric
double layer at the surface. This movement creates a potential difference between the two
ends, known as streaming potential.

 It is a type of electrokinetic phenomenon.

 Used to determine zeta potential, which reflects particle surface charge — crucial in
colloid stability studies.

Q.14 (B) Calculate the number average molecular weight for a polymer
having two monomers in equal number. Molar masses = 102 and 103.

Since the number of molecules of each monomer is equal:

Mn=Σ(ni⋅Mi)Σni=102+1032=102.5 g/molM_n = \frac{Σ (n_i \cdot M_i)}{Σ n_i} = \frac{102 + 103}{2} =

\boxed{102.5 \text{ g/mol}}Mn=ΣniΣ(ni⋅Mi)=2102+103=102.5 g/mol

Q.15 Draw and discuss the phase diagram of ferric chloride–water system.

The FeCl₃–H₂O system shows the interaction between hydrated salts and water. The phase
diagram includes:

 Eutectic points
 Congruent melting compounds (e.g., FeCl₃·6H₂O)
 Multiple solid hydrates

Key Features:

 FeCl₃·12H₂O, FeCl₃·7H₂O, and FeCl₃·6H₂O are common hydrates.

 Each has a distinct melting point and composition, appearing as peaks or breaks in
the diagram.
  At the eutectic composition, the solution freezes into a mixture of ice and salt
hydrate.

Applications:

 Used in hydration studies, cooling systems, and formulating freeze-resistant

solutions.

Q.16 (A) Describe the calomel electrode. How is pH calculated using it?

The calomel electrode is a reference electrode based on the redox reaction of mercury and
mercurous chloride (Hg₂Cl₂).

Construction:

 Mercury at the bottom

 Paste of calomel (Hg₂Cl₂) and KCl solution
 Saturated KCl provides stable potential

Half-cell reaction:

Hg2Cl2(s)+2e−⇌2Hg(l)+2Cl−Hg_2Cl_2(s) + 2e^- ⇌ 2Hg(l) + 2Cl^-Hg2Cl2(s)+2e−⇌2Hg(l)+2Cl−

Standard potential:

 ~0.241 V (saturated KCl)

Use in pH Measurement:

It is used with a glass electrode in a pH meter. The measured potential difference (emf)
correlates with [H⁺] via the Nernst equation:

E=E∘−0.0591nlog⁡[H+]⇒pH=E−E∘0.0591E = E^\circ - \frac{0.0591}{n} \log[H^+] \Rightarrow pH =

\frac{E - E^\circ}{0.0591}E=E∘−n0.0591log[H+]⇒pH=0.0591E−E∘

Q.16 (B) Calculate the pH for a cell with E = 0.445 V at 298 K

Let’s assume the cell is:

Hydrogen electrode∥H+(unknown)∥Calomel\text{Hydrogen electrode} \| \text{H}^+ (unknown) \|

\text{Calomel}Hydrogen electrode∥H+(unknown)∥Calomel

Using the Nernst equation:

E=ECalomel∘−0.0591⋅pHE = E^\circ_{Calomel} - 0.0591 \cdot \text{pH}E=ECalomel∘−0.0591⋅pH

Given:

 E = 0.445 V
 ECalomel∘=0.241 VE^\circ_{Calomel} = 0.241 \, VECalomel∘=0.241V

0.445=0.241−0.0591⋅pH⇒0.204=−0.0591⋅pH⇒pH=−0.2040.0591≈−3.450.445 = 0.241 - 0.0591 \cdot

\text{pH} \Rightarrow 0.204 = -0.0591 \cdot \text{pH} \Rightarrow \text{pH} = -\frac{0.204}{0.0591}
\approx \boxed{-3.45}0.445=0.241−0.0591⋅pH⇒0.204=−0.0591⋅pH⇒pH=−0.05910.204≈−3.45

Since pH cannot be negative for a standard aqueous solution, re-check:

The positive sign may be reversed:

pH=0.2040.0591≈3.45\text{pH} = \frac{0.204}{0.0591} \approx \boxed{3.45}pH=0.05910.204≈3.45

✅ Final Answer: pH = 3.45