Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Assignment Solution
Chapters 4, 5 & 6
Temperature & Thermodynamics | Kinetic Theory of Gases | Heat Engine & Entropy

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

CHAPTER 4: Temperature & Thermodynamics

Q1. Temperature & the Zeroth Law of Thermodynamics

Definition of Temperature
Temperature is a scalar physical quantity that measures the degree of hotness or coldness of a body.
It is a manifestation of the average kinetic energy of the particles constituting the body. The SI unit of
temperature is the Kelvin (K). Temperature determines the direction of heat flow between two bodies
in thermal contact — heat flows spontaneously from a body at higher temperature to a body at lower
temperature until thermal equilibrium is achieved.

Zeroth Law of Thermodynamics

Statement: "If two thermodynamic systems A and B are each in thermal equilibrium with a third system
C, then A and B are also in thermal equilibrium with each other."
Mathematically: If T_A = T_C and T_B = T_C, then T_A = T_B
This law establishes that temperature is a well-defined, transitive property. It underpins the concept
of a thermometer — a third body (thermometer) reaches equilibrium with a system, and its reading
tells us the system's temperature.

Practical Applications of the Zeroth Law

• Thermometry: All thermometers operate on this principle. A thermometer in thermal
equilibrium with a human body gives the body's temperature.
• Calibration of thermometers: A standard reference (e.g., triple point of water = 273.16 K) is
used to calibrate other thermometers.
• Industrial temperature control: Sensors placed in contact with industrial processes reach
thermal equilibrium and relay accurate readings.
• Meteorology: Thermometers measure atmospheric temperature by equilibrating with the
surrounding air.
• Medical diagnostics: Clinical thermometers measure body temperature based on the same
equilibrium principle.

Q2. Distinction Between Heat/Internal Energy & Heat/Temperature

Basis of Distinction Heat (Q) Internal Energy (U)

Definition Energy in transit between systems Total microscopic energy (kinetic +
due to temperature difference potential) stored within a system
Nature A process quantity (path function) A state function — depends only on
current state of system
Measurement Measured during energy transfer Measured as a property of the
system at any instant
SI Unit Joule (J) Joule (J)
Existence Exists only during transfer; cannot Always exists in every
be stored as heat thermodynamic system
Symbol Q (positive = absorbed, negative = U or E
released)

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Basis of Distinction Heat (Q) Temperature (T)

Definition Energy transferred due to A measure of average kinetic
temperature difference energy of particles
Nature Extensive property — depends on Intensive property — independent
amount of substance of amount of substance
SI Unit Joule (J) Kelvin (K)
Cause/Effect Cause — drives temperature Effect — changes as a result of heat
change transfer
Measurability Measured by calorimetry Measured directly by thermometer
Example Boiling water absorbs 2260 kJ/kg of Boiling point of water is 100°C or
heat 373 K

Q3. Thermal Expansion in Solids & Molar Specific Heat Capacity

Thermal Expansion
When a solid is heated, the interatomic distances increase due to enhanced vibrational energy of
atoms, causing the solid to expand. This is called thermal expansion.

(a) Linear Expansion

When a solid rod of original length L₀ is heated through a temperature ΔT, the increase in length ΔL
is:
ΔL = α · L₀ · ΔT ⟹ L = L₀(1 + αΔT)
where α is the coefficient of linear expansion (unit: K⁻¹). It represents fractional increase in length per
unit rise in temperature.

(b) Areal (Superficial) Expansion

For a surface of original area A₀, the change in area is:
ΔA = β · A₀ · ΔT ⟹ A = A₀(1 + βΔT)
where β = 2α is the coefficient of areal expansion. The relationship β = 2α arises because area
depends on two linear dimensions.

(c) Volumetric Expansion

For a body of original volume V₀, the change in volume is:
ΔV = γ · V₀ · ΔT ⟹ V = V₀(1 + γΔT)
where γ = 3α is the coefficient of volumetric expansion. This follows since volume depends on three
linear dimensions.

Relationship: α : β : γ = 1 : 2 : 3

Molar Specific Heat Capacity

The molar specific heat capacity (C) of a substance is defined as the amount of heat required to raise
the temperature of one mole of the substance by one degree (1 K or 1°C).
C = Q / (n · ΔT) [Unit: J mol⁻¹ K⁻¹]

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Two important molar specific heats for gases:

• Molar specific heat at constant volume (Cᵥ): Heat required per mole per degree at constant
volume. All heat goes into increasing internal energy: Q = nCᵥΔT
• Molar specific heat at constant pressure (Cₚ): Heat required per mole per degree at constant
pressure. Heat goes into both internal energy and work done: Q = nCₚΔT
Mayer's Relation: Cₚ - Cᵥ = R (where R = 8.314 J mol⁻¹ K⁻¹)

Q4. First Law of Thermodynamics

Statement
"The total energy of an isolated system is conserved. The heat energy supplied to a system equals
the sum of the increase in internal energy of the system and the work done by the system on its
surroundings."

Mathematical Form
ΔQ = ΔU + ΔW
Where:
• ΔQ = Heat absorbed by the system (positive when heat flows in, negative when heat flows
out)
• ΔU = Change in internal energy of the system (ΔU = U_final − U_initial)
• ΔW = Work done BY the system on surroundings (ΔW = ∫P dV for a gas)

For an infinitesimal process:

dQ = dU + dW = dU + P dV

Physical Interpretation
The First Law is fundamentally a statement of conservation of energy extended to thermal processes.
It tells us:
• Energy can neither be created nor destroyed; it can only change form.
• A perpetual motion machine of the first kind (one that produces work without any energy
input) is impossible.
• When heat flows into a system, it may be stored as increased internal energy (rising
temperature), converted to mechanical work (expansion), or both.
• For a cyclic process, ΔU = 0, so ΔQ = ΔW — all net heat absorbed is converted to net work
done.

Q5. Work Done in Thermodynamic Processes

General Expression for Work Done
For a gas undergoing a quasi-static process, the work done by the gas in expanding from volume V₁
to V₂ is:
W = ∫[V₁ to V₂] P dV

(a) Isothermal Process (Constant Temperature: T = constant)

For an ideal gas: PV = nRT = constant ⟹ P = nRT/V
W_iso = ∫[V₁ to V₂] (nRT/V) dV = nRT · ln(V₂/V₁)

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Alternatively, since P₁V₁ = P₂V₂:

W_iso = nRT · ln(P₁/P₂) = P₁V₁ · ln(V₂/V₁)
Key: ΔU = 0 (temperature constant), so ΔQ = W (all heat absorbed converts to work).

(b) Adiabatic Process (No heat exchange: ΔQ = 0)

For an ideal gas: PVᵞ = constant, where γ = Cₚ/Cᵥ
W_adi = (P₁V₁ - P₂V₂) / (γ - 1) = nR(T₁ - T₂) / (γ - 1)
Key: ΔQ = 0, so ΔU = −W (work done by gas comes entirely from decrease in internal energy, so gas
cools on expansion).

(c) Isochoric Process (Constant Volume: ΔV = 0)

Since volume does not change, dV = 0:
W_iso-v = ∫ P dV = 0
Key: W = 0, so from the First Law: ΔQ = ΔU (all heat absorbed goes into increasing internal energy,
raising temperature).

(d) Isobaric Process (Constant Pressure: P = constant)

W_iso-p = P(V₂ - V₁) = P·ΔV = nR(T₂ - T₁)
Key: ΔQ = ΔU + PΔV = nCₚΔT (heat input goes to both internal energy and work done by expansion).

Process Condition Work Done W ΔU ΔQ

Isothermal T = const nRT·ln(V₂/V₁) 0 =W

Adiabatic ΔQ = 0 nR(T₁−T₂)/(γ−1) = −W 0
Isochoric V = const 0 nCᵥΔT = ΔU
Isobaric P = const nRΔT = PΔV nCᵥΔT nCₚΔT

Q6. Numerical Problems — Chapter 4

Problem 1: Specific Heat
How much heat is required to raise the temperature of 5 kg of water from 20°C to 80°C? (Specific
heat of water = 4200 J kg⁻¹ K⁻¹)
Solution:
Q = mcΔT = 5 × 4200 × (80 − 20) = 5 × 4200 × 60 = 1,260,000 J = 1260 kJ

Problem 2: First Law

A gas absorbs 800 J of heat and does 300 J of work against external pressure. Find the change in
internal energy.
Solution:
ΔU = ΔQ − ΔW = 800 − 300 = 500 J
The internal energy of the gas increases by 500 J.

Problem 3: Isothermal Expansion

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

1 mole of ideal gas expands isothermally at 300 K from volume 1 L to 5 L. Find work done. (R = 8.314
J mol⁻¹ K⁻¹)
Solution:
W = nRT·ln(V₂/V₁) = 1 × 8.314 × 300 × ln(5/1)
W = 2494.2 × 1.6094 = 4015 J ≈ 4.02 kJ

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

CHAPTER 5: Kinetic Theory of Gases

Q1. Fundamental Assumptions of the Kinetic Theory of Gases

The kinetic theory of gases provides a microscopic explanation of the macroscopic properties of gases
based on the following fundamental postulates:

• A gas consists of a very large number of tiny, discrete particles called molecules.
• The molecules are perfectly rigid, identical, and perfectly elastic spheres.
• The size of a molecule is negligible compared to the average intermolecular separation —
gas molecules are treated as point masses.
• Gas molecules are in a state of random, continuous, and rapid motion in all directions with
varying speeds.
• The molecules exert no forces on each other except during collisions — there are no
intermolecular attractive or repulsive forces between collisions.
• All collisions between molecules and with the walls of the container are perfectly elastic —
kinetic energy is conserved.
• The time spent in a collision is negligible compared to the time between collisions (molecules
spend most of their time in free flight).
• The molecules obey Newton's laws of motion between collisions.
• The distribution of molecular velocities is isotropic — no preferred direction of motion. At any
instant, equal numbers of molecules move in all directions.
• Gravity is neglected; there are no external forces acting on the gas molecules.

Q2. Ideal Gas vs. Real Gas

Ideal Gas
An ideal gas is a theoretical gas that perfectly obeys all the postulates of kinetic theory and the ideal
gas equation at all temperatures and pressures:
PV = nRT
• Molecules have zero volume (point masses).
• No intermolecular forces — molecules interact only through perfectly elastic collisions.
• Internal energy depends only on temperature.

Real Gas Deviations from Ideal Behavior

Real gases deviate from ideal behavior, especially at high pressures and low temperatures, for two
main reasons:
• Non-zero molecular volume: At high pressures, molecules are packed closely — the actual
volume of molecules becomes significant. The free volume available for molecular motion is
less than V.
• Intermolecular forces: At low temperatures and high pressures, molecules are close enough
that Van der Waals attractive forces between them become significant, reducing the effective
pressure exerted on container walls.

Property Ideal Gas Real Gas

Equation PV = nRT (P + an²/V²)(V − nb) = nRT
Molecular volume Negligible Non-negligible at high P

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Intermolecular forces None Significant at low T, high P

Compressibility (Z = Always = 1 Deviates from 1
PV/nRT)
Liquefaction Cannot be liquefied Can be liquefied
Behavior at STP Approximately followed Closely approximated

Q3. Derivation of Kinetic Theory Expression: P = (1/3)ρc²

Setup
Consider N molecules of an ideal gas, each of mass m, confined in a cubical container of side L and
volume V = L³. A molecule moves with velocity components (vₓ, vᵧ, v_z) in the x, y, z directions
respectively.

Step 1: Momentum change per collision

Consider a molecule moving with x-component of velocity vₓ. When it collides elastically with the face
perpendicular to the x-axis:
Change in momentum = −mvₓ − (mvₓ) = −2mvₓ
By Newton's third law, the wall receives momentum +2mvₓ.

Step 2: Number of collisions per second

The molecule travels a distance 2L between successive collisions with the same wall.
Number of collisions per second = vₓ / 2L

Step 3: Force by one molecule

F₁ = (rate of momentum change) = (2mvₓ) × (vₓ/2L) = mvₓ²/L

Step 4: Total force by all N molecules

F_total = (m/L) × Σvₓᵢ² = (m/L) × N × <vₓ²>
where <vₓ²> is the mean square x-component of velocity.

Step 5: Mean square speed

By isotropy of molecular motion: <vₓ²> = <vᵧ²> = <v_z²>
<c²> = <vₓ²> + <vᵧ²> + <v_z²> = 3<vₓ²> ⟹ <vₓ²> = <c²>/3

Step 6: Pressure
P = F/A = F/L² = (mN<c²>) / (3L³) = (mN<c²>) / (3V)

Since total mass M = mN and density ρ = M/V:

P = (1/3)(mN/V)<c²> = (1/3)ρ<c²>

Writing c² for <c²> (mean square speed):

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

∴ P = (1/3)ρc² [Kinetic Pressure Equation]

Important Results from P = (1/3)ρc²

• Root mean square speed: c_rms = √(3P/ρ) = √(3RT/M)
• Average kinetic energy per molecule: KE = (3/2)kT, where k = R/Nₐ
• Internal energy of n moles monatomic gas: U = (3/2)nRT

Q4. Van der Waals Corrections to the Ideal Gas Equation

Van der Waals Equation of State
(P + an²/V²)(V − nb) = nRT
For n = 1 mole:
(P + a/V²)(V − b) = RT

Correction 1: Volume Correction (b)

Reason: In a real gas, each molecule occupies a finite volume. The actual free volume available for
molecular motion is less than the total container volume V.
Corrected Volume = V − nb
where b is the excluded volume per mole (called co-volume). It equals four times the actual molar
volume of the molecules. b depends on molecular size and is specific to each gas.

Correction 2: Pressure Correction (a)

Reason: Molecules in the bulk of the gas are surrounded symmetrically by other molecules —
intermolecular attractions cancel out on average. However, molecules near the wall experience a net
inward pull due to unbalanced attraction, reducing their effective impact force (pressure) on the wall.
Corrected Pressure = P + an²/V² (for n moles)
The term an²/V² is the internal pressure. The constant a measures the strength of intermolecular
attraction. Larger a means stronger intermolecular forces.

Physical Significance
• At low pressures and high temperatures: V is large, so an²/V² ≈ 0 and nb << V — the Van
der Waals equation reduces to the ideal gas equation.
• At high pressures: Molecular volume correction (b) becomes important.
• At low temperatures: Intermolecular attraction correction (a) dominates — molecules move
slowly and attractions become significant.
• The constants a and b are characteristic of individual gases and must be determined
experimentally.
• Van der Waals equation successfully predicts gas liquefaction and the critical point — things
the ideal gas law cannot explain.

Q5. Numerical Problems — Chapter 5

Problem 1: RMS Speed
Calculate the rms speed of nitrogen molecules (N₂) at 27°C. (M = 28 × 10⁻³ kg/mol, R = 8.314 J mol⁻¹
K⁻¹)

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Solution:
T = 27 + 273 = 300 K
c_rms = √(3RT/M) = √(3 × 8.314 × 300 / 28×10⁻³)
c_rms = √(7482.6 / 0.028) = √267,235.7 ≈ 516.9 m/s

Problem 2: Pressure from Kinetic Theory

A gas has density 1.25 kg/m³ and rms speed 500 m/s. Find the pressure.
Solution:
P = (1/3)ρc² = (1/3) × 1.25 × (500)² = (1/3) × 1.25 × 250000
P = 104,166.7 Pa ≈ 1.04 × 10⁵ Pa ≈ 1.03 atm

Problem 3: Average Kinetic Energy

Find the average kinetic energy of a gas molecule at 300 K. (k = 1.38 × 10⁻²³ J/K)
Solution:
KE = (3/2)kT = (3/2) × 1.38×10⁻²³ × 300 = 6.21 × 10⁻²¹ J

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

CHAPTER 6: Heat Engine & Entropy

Q1. Heat Engine — Definition, Working Principle & Diagram

Definition
A heat engine is a device that converts thermal energy (heat) into mechanical energy (work) by
operating in a cyclic process between two thermal reservoirs — a hot source at temperature T_H and
a cold sink at temperature T_C.

Essential Components
• Hot Reservoir (Source): Supplies heat Q_H to the working substance at high temperature
T_H.
• Working Substance: The medium (gas) that undergoes thermodynamic processes
(expansion, compression) to produce work. Absorbs Q_H, does net work W, and rejects
Q_C.
• Cold Reservoir (Sink): Receives rejected heat Q_C at low temperature T_C.

Working Principle
The working substance absorbs heat Q_H from the hot source, converts part of it into useful work W,
and rejects the remainder Q_C to the cold sink. By energy conservation (First Law):
Q_H = W + Q_C ⟹ W = Q_H − Q_C

Schematic Diagram of a Heat Engine

┌─────────────────────┐
│ HOT SOURCE (T_H) │
└──────────┬──────────┘
│ Q_H (heat in)
┌─────▼──────┐
│ ENGINE │──── W (Work out)
└─────┬──────┘
│ Q_C (heat rejected)
┌──────────▼──────────┐
│ COLD SINK (T_C) │
└─────────────────────┘

Thermal Efficiency
η = W/Q_H = (Q_H − Q_C)/Q_H = 1 − Q_C/Q_H

Q2. Reversible vs. Irreversible Processes

Basis Reversible Process Irreversible Process
Definition A process that can be reversed in A process that cannot be reversed —
direction by an infinitesimal change system and surroundings cannot both
in conditions, with system and return to initial states

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

surroundings returning exactly to

initial states
Equilibrium Passes through a series of quasi- Involves non-equilibrium states; driven by
static equilibrium states finite differences
Entropy change Total entropy change of universe = Total entropy change of universe > 0
0 (ΔS_universe = 0) (ΔS_universe > 0)
Efficiency Maximum possible efficiency for Always less efficient than reversible
given temperatures process
Friction/Viscosity No dissipative forces Friction, viscosity, electrical resistance
present
Speed Must be carried out infinitely slowly Occurs at finite rate
Examples Ideal Carnot cycle; slow isothermal Free expansion; heat flow through finite ΔT;
expansion of ideal gas; frictionless combustion; friction; mixing of gases
piston

Q3. Second Law of Thermodynamics — Different Formulations

1. Kelvin-Planck Statement (Engine-based)

"It is impossible to construct a heat engine that operates in a cycle and produces no effect other than
the absorption of heat from a single thermal reservoir and conversion of all this heat into work."
In other words: No heat engine can have 100% efficiency. Some heat must always be rejected to a
cold sink.

2. Clausius Statement (Refrigerator-based)

"It is impossible to construct a device that operates in a cycle and transfers heat from a colder body
to a hotter body without the expenditure of external work."
In other words: Heat cannot spontaneously flow from a cold body to a hot body. A refrigerator requires
work input.

3. Entropy Statement
"In any spontaneous process, the total entropy of the universe (system + surroundings) always
increases, or remains constant for a reversible process. It never decreases."
ΔS_universe = ΔS_system + ΔS_surroundings ≥ 0
The equality holds for reversible processes; the inequality (>) for irreversible processes.

4. Statistical Statement (Boltzmann)

"Natural processes always tend toward a state of greater disorder (higher probability). The entropy of
a system measures its statistical disorder — it always tends to a maximum."
All three statements are equivalent — violation of any one implies violation of the others.

Q4. Derivation of Efficiency of a Carnot Engine

The Carnot Cycle

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

The Carnot engine is the most efficient heat engine operating between two temperatures T_H and
T_C. It consists of four reversible steps:
• Process 1→2: Isothermal expansion at T_H — gas absorbs heat Q_H
• Process 2→3: Adiabatic (isentropic) expansion — temperature falls from T_H to T_C
• Process 3→4: Isothermal compression at T_C — gas rejects heat Q_C
• Process 4→1: Adiabatic compression — temperature rises from T_C back to T_H

Calculation of Q_H and Q_C

For the isothermal expansion (1→2) at T_H:
Q_H = nRT_H · ln(V₂/V₁)
For the isothermal compression (3→4) at T_C:
Q_C = nRT_C · ln(V₃/V₄)

Using Adiabatic Relations

For adiabatic process 2→3: T_H · V₂^(γ-1) = T_C · V₃^(γ-1)
For adiabatic process 4→1: T_C · V₄^(γ-1) = T_H · V₁^(γ-1)
Dividing these two equations:
V₂/V₁ = V₃/V₄
Therefore:
Q_H/Q_C = T_H/T_C

Carnot Efficiency
η_Carnot = 1 − Q_C/Q_H = 1 − T_C/T_H = (T_H − T_C)/T_H

This is the Carnot efficiency — the maximum possible efficiency for any heat engine operating
between T_H and T_C.

Example Calculation
A Carnot engine operates between T_H = 800 K and T_C = 300 K. Find its efficiency.
η = 1 − 300/800 = 1 − 0.375 = 0.625 = 62.5%

Q5. Why 100% Efficiency is Impossible

The impossibility of 100% efficiency of a heat engine follows directly from the Second Law of
Thermodynamics:

• Kelvin-Planck prohibition: A 100% efficient engine would convert all absorbed heat Q_H
entirely to work, with Q_C = 0. This is exactly what the Kelvin-Planck statement forbids — a
cyclic engine with a single reservoir and no heat rejection.

• Entropy argument: For 100% efficiency, Q_C = 0. The entropy decrease of the hot source is
Q_H/T_H. If no heat is rejected to the sink, entropy of universe would decrease (ΔS =
−Q_H/T_H < 0), violating the Second Law.

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

• Carnot's theorem: The maximum efficiency is η = 1 − T_C/T_H. For η = 100%, we'd need
T_C = 0 K (absolute zero) or T_H = ∞. Absolute zero is unattainable (Third Law of
Thermodynamics), and infinite temperature is physically impossible.

• Mathematical result: Even in the ideal (reversible) Carnot cycle, η = (T_H − T_C)/T_H < 1 for
any finite T_H and T_C > 0. Real engines are even less efficient due to irreversibilities
(friction, heat losses, turbulence).

• Conclusion: A perfect heat engine is thus a perpetual motion machine of the second kind —
prohibited by nature itself.

Q6. Entropy — Definition & Physical Significance

Definition
Entropy (S) is a thermodynamic state function that quantifies the unavailability of a system's energy
for performing useful work, or equivalently, the degree of disorder or randomness of the system at the
microscopic level.

Mathematical Definition (Clausius)

For a reversible process, the change in entropy is defined as:
dS = dQ_rev / T
For a finite process between states A and B:
ΔS = S_B − S_A = ∫[A to B] dQ_rev / T
SI unit: Joule per Kelvin (J K⁻¹). Molar entropy: J mol⁻¹ K⁻¹.

Physical Significance of Entropy

• Measure of disorder: Higher entropy corresponds to greater molecular disorder. A gas has
higher entropy than a liquid, which has higher entropy than a solid of the same substance.
• Direction of natural processes: Entropy tells us which way a process will spontaneously
proceed. All natural (spontaneous) processes proceed in the direction of increasing total
entropy.
• Unavailability of energy: Not all internal energy is available to do work. Entropy quantifies the
energy "wasted" or degraded into forms unavailable for mechanical work.
• Quality of energy: Low entropy implies high-grade, organized energy (like mechanical work).
High entropy implies low-grade, disorganized energy (like heat at low temperature).
• Statistical interpretation (Boltzmann): S = k · ln(Ω), where Ω is the number of microstates
corresponding to a given macrostate and k = 1.38 × 10⁻²³ J/K. Higher entropy = more
possible microstates = more disorder.

Q7. Entropy and Disorder

Entropy as a Measure of Disorder (Boltzmann's Interpretation)
S = k · ln(Ω)
where Ω (omega) is the thermodynamic probability — the number of microstates (microscopic
arrangements of molecules) consistent with a given macrostate. A state with more possible
arrangements has higher entropy.

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

Examples Illustrating Entropy and Disorder

Example 1: Mixing of Gases

Consider two different gases separated by a partition in a container. When the partition is removed,
the gases mix spontaneously. After mixing: the number of possible arrangements (microstates) of
molecules is vastly larger than before — entropy increases. The reverse process (spontaneous
unmixing) never occurs because it would require an enormous decrease in entropy.

Example 2: Melting of Ice

Ice (solid) has a regular, ordered crystalline structure with few microstates → low entropy. Water
(liquid) has molecules in random, disordered arrangements → many more microstates → higher
entropy. Melting is spontaneous (at T > 0°C) because ΔS > 0.
ΔS_melting = L_f / T_m = 334,000 / 273 ≈ 1223 J K⁻¹ kg⁻¹

Example 3: Free Expansion of a Gas

A gas confined to half a container suddenly allowed to expand to the full volume. The gas occupies
more space, molecules have more possible positions → number of microstates (Ω) increases
dramatically → entropy increases. This is irreversible — gas never spontaneously contracts back.

Example 4: Heat Flow

Heat flows from hot to cold spontaneously. Total entropy of the universe increases: entropy gained
by cold body > entropy lost by hot body (since ΔS = Q/T and T_cold < T_hot).

Example 5: Everyday Examples

• A broken egg (disordered) never spontaneously becomes whole (ordered) — entropy of the
universe would decrease.
• Ink dropped in water spreads uniformly — this increases disorder and entropy.
• A room gets messy on its own (high entropy) but needs work to tidy (reduce entropy locally,
but total increases).

Q8. Numerical Problems — Chapter 6

Problem 1: Carnot Efficiency
A Carnot engine operates between a source at 627°C and a sink at 27°C. Calculate: (a) efficiency,
(b) work done per cycle if Q_H = 5000 J.
Solution:
T_H = 627 + 273 = 900 K, T_C = 27 + 273 = 300 K
(a) η = 1 − T_C/T_H = 1 − 300/900 = 1 − 1/3 = 2/3 ≈ 66.67%
(b) W = η × Q_H = (2/3) × 5000 = 3333.3 J
Q_C = Q_H − W = 5000 − 3333.3 = 1666.7 J

Problem 2: Entropy Change — Melting

Calculate the entropy change when 200 g of ice melts at 0°C. (Latent heat of ice L = 3.34 × 10⁵ J/kg)
Solution:
T = 0°C = 273 K
Q = mL = 0.200 × 3.34×10⁵ = 66,800 J

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

ΔS = Q/T = 66,800 / 273 = 244.7 J/K

Problem 3: Entropy Change — Heat Transfer

500 J of heat flows from a body at 500 K to a body at 250 K. Find the total entropy change of the
universe.
Solution:
ΔS_hot = −Q/T_H = −500/500 = −1.0 J/K (entropy decreases for hot body)
ΔS_cold = +Q/T_C = +500/250 = +2.0 J/K (entropy increases for cold body)
ΔS_universe = ΔS_hot + ΔS_cold = −1.0 + 2.0 = +1.0 J/K > 0 ✓
The positive value confirms this is a spontaneous, irreversible process — consistent with the Second
Law.

Problem 4: Engine Efficiency

A heat engine absorbs 10,000 J from a hot reservoir and rejects 6,000 J to the cold reservoir. Find:
(a) work output, (b) efficiency.
Solution:
(a) W = Q_H − Q_C = 10,000 − 6,000 = 4,000 J
(b) η = W/Q_H = 4,000/10,000 = 0.4 = 40%

Page
 Assignment Solution: Chapters 4, 5, 6 — Thermodynamics & Kinetic Theory

SUMMARY: Key Equations Reference

Chapter Concept Key Formula

Ch.4 First Law of Thermodynamics ΔQ = ΔU + ΔW
Ch.4 Work — Isothermal W = nRT·ln(V₂/V₁)
Ch.4 Work — Adiabatic W = nR(T₁−T₂)/(γ−1)
Ch.4 Work — Isobaric W = P(V₂−V₁) = nRΔT
Ch.4 Thermal Expansion (Linear) ΔL = αL₀ΔT
Ch.4 Specific Heat Q = mcΔT
Ch.4 Mayer's Relation Cₚ − Cᵥ = R
Ch.5 Kinetic Pressure P = (1/3)ρc²
Ch.5 RMS Speed c_rms = √(3RT/M)
Ch.5 Average KE per molecule KE = (3/2)kT
Ch.5 Van der Waals Equation (P + an²/V²)(V−nb) = nRT
Ch.6 Heat Engine Efficiency η = 1 − Q_C/Q_H
Ch.6 Carnot Efficiency η_Carnot = 1 − T_C/T_H
Ch.6 Entropy Change ΔS = Q_rev/T
Ch.6 Boltzmann Entropy S = k·ln(Ω)
Ch.6 Second Law (Entropy) ΔS_universe ≥ 0

— End of Assignment Solution —

Page