CC IV — STATISTICAL MECHANICS

Section A — 2 Mark Questions & Answers

AVC College (Autonomous) | I [Link]. Physics | Semester II

UNIT I — PHASE TRANSITIONS

Q1. What are Thermodynamic Potentials?

Thermodynamic potentials are state functions describing the thermodynamic state of a system. They are:
Internal Energy U, Enthalpy H = U + PV, Helmholtz Free Energy F = U - TS, and Gibbs Free Energy G = U
+ PV - TS. Each is minimized at equilibrium under different constraints.

Q2. What is Phase Equilibrium?

Phase equilibrium is the condition where two or more phases coexist in thermodynamic equilibrium. At
equilibrium, temperature, pressure and chemical potential are equal in all phases: µ1 = µ2 = µ3. The system
shows no tendency to change phase.

Q3. State Gibbs Phase Rule.

Gibbs phase rule: F = C - P + 2, where F = degrees of freedom, C = number of components, P = number of
phases. Example: For pure water at triple point, F = 1 - 3 + 2 = 0 (invariant point — T and P fixed).

Q4. What is a Phase Transition?

Phase transition is the transformation of a system from one phase to another at specific temperature and
pressure. Examples: solid to liquid (melting), liquid to gas (boiling), normal to superconducting. It involves
change in symmetry and thermodynamic properties.

Q5. What is Ehrenfest's Classification?

Ehrenfest classified phase transitions based on discontinuity in derivatives of Gibbs free energy G. First
order: first derivatives (S, V) are discontinuous — latent heat present. Second order: first derivatives
continuous, second derivatives (Cp, κ) discontinuous — no latent heat.

Q6. What is a First Order Phase Transition?

First order transition shows discontinuity in first derivatives of G: entropy S = -(∂G/∂T)P and volume V =
(∂G/∂P)T are discontinuous. Characteristics: latent heat L = T∆S ≠ 0, volume change ∆V ≠ 0, two phases
coexist. Examples: melting, boiling.

Q7. What is a Second Order Phase Transition?

Second order transition has continuous first derivatives of G but discontinuous second derivatives: heat
capacity Cp = -T(∂2G/∂T2)P and compressibility κ are discontinuous. No latent heat, no volume change.
Examples: ferromagnetic transition, superconductivity, lambda transition in He.

Q8. State the Third Law of Thermodynamics.

Third Law (Nernst): The entropy of a perfect crystalline substance approaches zero as temperature
approaches absolute zero. Mathematically: S → 0 as T → 0 K. Consequence: absolute zero is unattainable
in a finite number of steps.
Q9. What is an Order Parameter?
Order parameter η characterizes the degree of order across a phase transition. η = 0 in disordered phase
(T > Tc) and η ≠ 0 in ordered phase (T < Tc). Examples: magnetization M for ferromagnet, density
difference (ρL - ρG) for liquid-gas transition.

Q10. What are Critical Indices?

Critical indices (exponents) characterize power-law behavior of physical quantities near the critical point Tc.
Key exponents: β (order parameter: η ∝ (Tc-T)^β), γ (susceptibility: χ ∝ |T-Tc|^-γ), α (heat capacity: Cv ∝
|T-Tc|^-α), ν (correlation length: ξ ∝ |T-Tc|^-ν).

Q11. What is Landau's Theory of Phase Transition?

Landau theory expands Gibbs free energy in powers of order parameter η near Tc: G = G0 + a(T)η2 +
b(T)η4. Here a(T) = a0(T-Tc) changes sign at Tc. Minimizing G gives η ∝ (Tc-T)^(1/2) below Tc, predicting
mean field critical exponent β = 1/2.

Q12. What is Scale Transformation?

Scale transformation (renormalization group) studies how physical systems behave at different length
scales near the critical point. Near Tc, correlation length ξ → ∞ making the system self-similar (fractal-like).
It explains universality: different systems share same critical exponents if they have same symmetry and
dimension.

UNIT II — STATISTICAL MECHANICS AND THERMODYNAMICS

Q1. What is Statistical Mechanics?

Statistical mechanics connects microscopic properties of individual atoms/molecules to macroscopic
thermodynamic properties of matter. It uses probability theory and statistics to derive thermodynamic
quantities (pressure, temperature, entropy) from the mechanical behaviour of a large number of particles.

Q2. What is a Microstate?

A microstate is a specific microscopic configuration of a system — the exact positions and momenta of all
particles at a given instant. For quantum systems, it is a specific quantum state. A macrostate corresponds
to an enormous number of microstates with the same macroscopic properties (T, P, V).

Q3. What is Phase Space?

Phase space is a 6N-dimensional mathematical space where each point represents a unique microstate of
an N-particle system — 3N position coordinates (q) and 3N momentum coordinates (p). The time evolution
of the system traces a trajectory in phase space called the phase trajectory.

Q4. What is a Microcanonical Ensemble?

Microcanonical ensemble represents an isolated system with fixed energy E, volume V and number of
particles N (E, V, N = constant). All accessible microstates with energy E are equally probable. Entropy is
defined as S = kB ln Ω, where Ω is the number of microstates.

Q5. What is Entropy in Statistical Mechanics?

Boltzmann defined entropy as S = kB ln Ω, where Ω is the number of accessible microstates and kB = 1.38
× 10^-23 J/K is Boltzmann's constant. This connects microscopic disorder (number of microstates) to
macroscopic thermodynamic entropy. Maximum entropy corresponds to thermodynamic equilibrium.

Q6. What is Liouville's Theorem?

Liouville's theorem states that the phase space density (distribution function) f(q,p,t) is conserved along
phase trajectories: df/dt = 0, or ∂f/∂t + {f, H} = 0, where {f, H} is the Poisson bracket with Hamiltonian H. This
means phase space volume is conserved under Hamiltonian dynamics.

Q7. What is the Connection between Statistics and Thermodynamics?

The bridge between statistics and thermodynamics: Entropy S = kB ln Ω (Boltzmann), Temperature 1/T =
∂S/∂E, Pressure P = T(∂S/∂V), Free energy F = -kBT ln Z where Z is partition function. All thermodynamic
quantities derivable from partition function Z = Σ exp(-Ei/kBT).

Q8. What is Entropy of an Ideal Gas (Sackur-Tetrode)?

Entropy of an ideal gas from microcanonical ensemble (Sackur-Tetrode equation): S = NkB[ln(V/N) +
(3/2)ln(4πmE/3Nh2) + 5/2]. This gives entropy as extensive quantity, correctly accounting for
indistinguishability of particles. Entropy increases with V, E and N as expected.

Q9. What is Gibbs Paradox?

Gibbs paradox: When two identical ideal gases mix, classical statistics predicts entropy increase ∆S = 2NkB
ln 2, which is wrong — mixing identical gases should not increase entropy. The paradox is resolved by
treating identical particles as indistinguishable, dividing the partition function by N! (quantum correction).

Q10. What is Entropy of Mixing?

When two different ideal gases mix at constant T and P: ∆Smix = -NkB Σ xi ln xi, where xi is mole fraction of
component i. For equal amounts: ∆Smix = NkB ln 2 per component (positive — spontaneous mixing). For
identical gases, ∆Smix = 0 (no entropy of mixing — Gibbs paradox resolution).

Q11. What is the Specification of States of a System?

For a classical system: state specified by positions (q1...qN) and momenta (p1...pN) of all N particles — a
point in 6N-dimensional phase space. For quantum system: state specified by quantum numbers (n1,
n2...nN). In quantum mechanics, states are discrete and countable, resolving classical infinities.

Q12. What are the Foundations of Statistical Mechanics?

Key postulates: (1) Ergodic hypothesis — time average equals ensemble average. (2) Equal a priori
probability — all microstates with same energy equally probable. (3) Thermodynamic quantities are
ensemble averages of mechanical quantities. These postulates connect mechanics to thermodynamics
through probability theory.

UNIT III — CANONICAL AND GRAND CANONICAL ENSEMBLES

Q1. What is a Canonical Ensemble?

Canonical ensemble (NVT ensemble) represents a system in thermal contact with a heat reservoir at
temperature T, with fixed N, V, T. Energy can fluctuate but T is fixed. The probability of a microstate with
energy Ei is given by Boltzmann factor: Pi = exp(-Ei/kBT) / Z, where Z is the partition function.

Q2. What is the Partition Function?

Partition function Z = Σi exp(-Ei/kBT) is the sum over all microstates of Boltzmann factors. It is the central
quantity in statistical mechanics. All thermodynamic properties derivable from Z: F = -kBT ln Z, E = -∂(ln
Z)/∂β, S = kB(ln Z + βE), where β = 1/kBT.

Q3. What is a Grand Canonical Ensemble?

Grand canonical ensemble (µVT ensemble) represents a system in contact with both heat reservoir (T
fixed) and particle reservoir (µ fixed), with fixed µ, V, T. Both energy and particle number can fluctuate.
Grand partition function: Ξ = Σ(N,i) exp(-β(Ei - µN)). Used for quantum gases.

Q4. What is Chemical Potential µ?

Chemical potential µ = (∂F/∂N)T,V is the change in free energy when one particle is added at constant T
and V. In grand canonical ensemble, µ controls the average number of particles. At equilibrium between
systems: µ1 = µ2. For ideal gas: µ = kBT ln(n/nQ) where nQ is quantum concentration.

Q5. What is Liouville's Theorem?

Liouville's theorem states that the phase space probability density f(q,p,t) is conserved: df/dt = ∂f/∂t + {f,H} =
0. This means phase space volume element dqdp is conserved under Hamiltonian evolution. It is
fundamental to statistical mechanics — justifies use of equilibrium ensembles and ergodic hypothesis.

Q6. What is Density of States?

Density of states g(E) gives the number of quantum states per unit energy interval at energy E. For 3D ideal
gas: g(E) = (4πV/h3)(2m)^(3/2) E^(1/2). Partition function Z = ∫g(E)exp(-βE)dE. Density of states is crucial
for calculating thermodynamic properties of quantum systems.

Q7. What are Energy Fluctuations?

In canonical ensemble, energy fluctuates about the mean value . Mean square fluctuation: <(∆E)2> = kBT2
Cv, where Cv is heat capacity. Relative fluctuation: <(∆E)2>^(1/2)/ ∝ 1/√N → 0 for large N. Justifies treating
canonical and microcanonical ensembles as equivalent for large systems.

Q8. What are Density Fluctuations?

In grand canonical ensemble, particle number N fluctuates about mean . Mean square fluctuation: <(∆N)2>
= kBT(∂/∂µ)T,V. Relative fluctuation ∝ 1/√ → 0 for large systems. Near critical point, density fluctuations
diverge — responsible for critical opalescence phenomenon.

Q9. What is a Phase Space Trajectory?

Phase space trajectory is the path traced by a representative point (q1...qN, p1...pN) in 6N-dimensional
phase space as the system evolves in time under Hamiltonian equations of motion. For isolated system,
trajectory lies on constant energy surface. Ergodic hypothesis: trajectory covers entire energy surface over
time.

Q10. How are Statistical Quantities Calculated from Partition Function?

From partition function Z(β,V,N) with β=1/kBT: Average energy = -∂(ln Z)/∂β. Helmholtz free energy F =
-kBT ln Z. Entropy S = -(∂F/∂T)V = kB(ln Z + β). Pressure P = -(∂F/∂V)T = kBT(∂ ln Z/∂V)T. Heat capacity Cv
= ∂/∂T. Chemical potential µ = -(∂F/∂N)T,V.
Q11. What is the Grand Potential?
Grand potential Ω = F - µN = -kBT ln Ξ, where Ξ is grand partition function. From grand potential: average
number = -(∂Ω/∂µ)T,V, pressure P = -(∂Ω/∂V)T,µ, entropy S = -(∂Ω/∂T)V,µ. Grand potential is natural
thermodynamic potential for grand canonical ensemble (µ, V, T fixed).

Q12. What is the Boltzmann Factor?

Boltzmann factor exp(-Ei/kBT) gives the relative probability of finding a system in microstate i with energy Ei
when in thermal equilibrium at temperature T. Higher energy states less probable. Ratio of probabilities:
Pi/Pj = exp(-(Ei-Ej)/kBT). Foundation of canonical ensemble and Maxwell-Boltzmann statistics.

UNIT IV — CLASSICAL AND QUANTUM STATISTICS

Q1. What is Maxwell-Boltzmann Statistics?

Maxwell-Boltzmann (MB) statistics applies to classical distinguishable particles with no restriction on
occupation numbers. Average occupation: ni = gi exp(α-βEi), where α=µ/kBT and β=1/kBT. Valid for dilute
gases at high T. Gives Maxwell speed distribution for ideal gas. Particles distinguishable and any number
can occupy same state.

Q2. What is Fermi-Dirac Statistics?

Fermi-Dirac (FD) statistics applies to identical indistinguishable fermions (half-integer spin: electrons,
protons, neutrons) obeying Pauli exclusion principle. Average occupation: ni = 1/[exp((Ei-µ)/kBT) + 1].
Maximum occupation = 1 per state. At T=0, all states below Fermi energy EF filled, above empty.

Q3. What is Bose-Einstein Statistics?

Bose-Einstein (BE) statistics applies to identical indistinguishable bosons (integer spin: photons, He-4
atoms) with no restriction on occupation. Average occupation: ni = 1/[exp((Ei-µ)/kBT) - 1]. Any number of
bosons can occupy same state. At low T, macroscopic occupation of ground state occurs (BEC).

Q4. What is the Density Matrix?

Density matrix ρ = Σi pi|psi_i)(psi_i| describes quantum statistical systems where state is not pure but a
statistical mixture. For canonical ensemble: ρ = exp(-βH)/Z. Expectation value of observable A: [A] = Tr(rho
x A). Diagonal elements give state populations; off-diagonal give coherences.

Q5. What is an Ideal Fermi Gas?

Ideal Fermi gas is a system of non-interacting fermions. At T=0: all states below Fermi energy EF =
(h2/2m)(3π2n)^(2/3) filled (ground state). Fermi energy ~ few eV for electrons in metals. Properties: finite
zero-point energy, Fermi pressure, linear heat capacity Cv = (π2/2)NkB(T/TF) at low T.

Q6. What is Degeneracy of Fermi Gas?

Fermi gas is degenerate when T << TF (Fermi temperature, TF = EF/kB ~ 10^4-10^5 K for metals). In
degenerate regime: quantum effects dominate, Pauli exclusion important, heat capacity Cv ∝ T (linear,
much less than classical 3NkB/2). Electrons in metals are highly degenerate at room temperature.

Q7. What is Bose-Einstein Condensation (BEC)?

BEC occurs when identical bosons macroscopically occupy the ground state below critical temperature Tc =
(h2/2πmkB)(n/2.612)^(2/3). Below Tc, fraction in ground state: N0/N = 1-(T/Tc)^(3/2). First observed in Rb
atoms (1995, Nobel Prize 2001). Superfluid He-4 is related phenomenon.

Q8. What is Planck's Radiation Formula?

Planck's radiation formula gives energy density of blackbody radiation: u(ν) = (8πhν3/c3) × 1/[exp(hν/kBT) -
1]. Derived using Bose-Einstein statistics for photons (µ=0). Limits: Wien's law (hν >> kBT): u ∝ ν3
exp(-hν/kBT); Rayleigh-Jeans (hν << kBT): u ∝ ν2T. Resolves ultraviolet catastrophe.

Q9. What is an Ideal Bose Gas?

Ideal Bose gas is a system of non-interacting bosons. Grand partition function: ln Ξ = -Σk
ln[1-exp(-β(Ek-µ))]. Chemical potential µ ≤ 0 always (for µ=0, condensation begins). Equation of state: PV =
(2/3)E (same form as classical). Below Tc, pressure independent of volume (condensate doesn't contribute
to pressure).

Q10. What are Statistics of Indistinguishable Particles?

For indistinguishable particles, wave function must be symmetric (bosons) or antisymmetric (fermions)
under particle exchange. Bosons: ψ(1,2) = ψ(2,1) — any occupation. Fermions: ψ(1,2) = -ψ(2,1) — Pauli
exclusion, max one per state. Distinguishability fundamentally changes statistical counting.

Q11. What is the Fermi Energy?

Fermi energy EF is the energy of the highest occupied state at T = 0 K. For free electrons: EF =
(h2/2m)(3π2n)^(2/3), where n = N/V is electron density. For copper: EF ≈ 7 eV, TF ≈ 80,000 K. Chemical
potential µ(T) ≈ EF[1 - (π2/12)(T/TF)2] at low temperatures.

Q12. What is the difference between MB, FD and BE Statistics?

MB Statistics: classical, distinguishable particles, any occupation, valid at high T/low density. FD Statistics:
fermions (spin 1/2), indistinguishable, max 1 per state (Pauli), occupation = 1/(e^((E-µ)/kT)+1). BE
Statistics: bosons (integer spin), indistinguishable, any occupation, occupation = 1/(e^((E-µ)/kT)-1). All three
agree at high T (classical limit).

UNIT V — REAL GAS, ISING MODEL AND FLUCTUATIONS

Q1. What is Cluster Expansion?

Cluster expansion is a systematic method to account for interactions in real gases. Partition function
expanded as series in density n: PV/NkBT = 1 + B2(T)n + B3(T)n2 + ..., where B2, B3... are virial
coefficients. Each term corresponds to clusters of 2, 3... interacting particles. Valid for moderate densities.

Q2. What is the Virial Equation of State?

Virial equation: P/kBT = n + B2(T)n2 + B3(T)n3 + ..., where n=N/V, B2, B3 are second, third virial
coefficients. B2(T) = -1/2 ∫[exp(-u(r)/kBT) - 1]4πr2 dr, where u(r) is pair potential. At Boyle temperature TB,
B2=0 and gas behaves ideally. Van der Waals constants related to B2.

Q3. What is the Second Virial Coefficient?

Second virial coefficient B2(T) accounts for two-body interactions: B2 = -1/2 ∫f(r)d3r, where f(r) =
exp(-u(r)/kBT) - 1 is Mayer f-function. For hard sphere gas: B2 = 2πσ3/3 (positive, repulsive). For van der
Waals gas: B2 = b - a/kBT. B2 < 0 at low T (attraction dominates), B2 > 0 at high T.

Q4. What is the Ising Model?

Ising model is a mathematical model of ferromagnetism. N spins on lattice, each spin Si = ±1. Hamiltonian:
H = -J Σ Si Sj - h Σi Si, where J is exchange coupling (J>0: ferromagnet), h is external field, denotes nearest
neighbours. Exactly solvable in 1D and 2D. Shows phase transition in 2D and 3D.

Q5. What is Mean-Field Theory of Ising Model?

Mean-field theory replaces interaction with each neighbor by average field: H_eff = zJm + h, where z =
number of neighbours, m = = mean magnetization. Self-consistent equation: m = tanh(β(zJm + h)). Critical
temperature: Tc = zJ/kB. Mean field exponents: β=1/2, γ=1, exact in d>4 dimensions.

Q6. What is the Exact Solution of 1D Ising Model?

1D Ising model exactly solvable using transfer matrix method. Partition function: Z = λ1^N + λ2^N, where
λ1,2 = exp(βJ)[cosh(βh) ± √(sinh2(βh) + exp(-4βJ))]. No phase transition in 1D at T > 0 (Tc = 0). Correlation
length: ξ = -1/ln(tanh(βJ)) → ∞ only as T → 0.

Q7. What is Brownian Motion?

Brownian motion is the random motion of a particle suspended in fluid, caused by thermal fluctuations from
molecular collisions. Observed by Robert Brown (1827). Mean square displacement: = 2Dt, where D =
kBT/6πηr (Einstein relation, 1905). D is diffusion coefficient, η viscosity, r particle radius. Random walk in
3D.

Q8. What is Langevin's Theory?

Langevin equation for Brownian particle: m(dv/dt) = -γv + F(t), where γ = 6πηr is friction coefficient and F(t)
is random force with =0, =2γkBT δ(t-t'). Solution gives: velocity autocorrelation = (kBT/m)exp(-γt/m). Mean
square displacement = 2kBTt/γ = 2Dt at long times.

Q9. What is the Fluctuation-Dissipation Theorem?

Fluctuation-dissipation theorem connects equilibrium fluctuations to dissipation (response to perturbation).
For Brownian motion: D = kBT/γ (Einstein relation). General form: χ''(ω) = (ω/2kBT)S(ω), where χ''(ω) is
imaginary part of response function and S(ω) is power spectral density of fluctuations. Links noise to
friction.

Q10. What is the Fokker-Planck Equation?

Fokker-Planck equation describes time evolution of probability distribution P(x,t) for a Brownian particle:
∂P/∂t = -∂(A·P)/∂x + (1/2)∂2(B·P)/∂x2, where A is drift coefficient and B is diffusion coefficient. For free
Brownian particle: ∂P/∂t = D∂2P/∂x2 (diffusion equation). Solution: Gaussian spreading with = 2Dt.

Q11. What are Space-Time Dependent Fluctuations?

Space-time dependent fluctuations described by correlation function G(r,t) = <δρ(0,0)δρ(r,t)>, where δρ = ρ -
<ρ> is density fluctuation. Fourier transform gives dynamic structure factor S(q,ω). Near critical point,
correlation length ξ → ∞ causing critical opalescence. Fluctuation-dissipation theorem relates S(q,ω) to
response function.

Q12. What are Transport Phenomena?

Transport phenomena involve flow of conserved quantities (mass, momentum, energy) due to gradients.
Diffusion: J = -D∇n (Fick's law). Thermal conduction: Q = -κ∇T (Fourier's law). Viscosity: σ = -η(∂v/∂x).
Transport coefficients D, κ, η related to microscopic fluctuations via Green-Kubo relations: D = ∫dt.
Fluctuation-dissipation theorem applies.

All 5 Units — Section A Complete | Good Luck for your Exam! ■