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  3. Entropy and Irreversibility

Thermodynamics · JEE & NEET Physics

Entropy and Irreversibility: notes and previous year questions

Entropy as the number of ways, ΔS = Q/T, the entropy statement of the second law, ideal-gas entropy, irreversible processes and T–S diagrams.

Entropy and Irreversibility in short

  • Entropy counts the ways a state can happen: S=kln⁡ΩS = k\ln\Omega.
  • Spread-out, disordered states have more ways, so more entropy.
  • ΔS=Q/T\Delta S = Q/T at a fixed temperature, in kelvin; unit J/K.
  • The entropy of the universe never decreases; it stays constant only for reversible processes.

1Why things spread

Lift the partition and a gas spreads through a whole box; it never gathers back into one half by itself, although that would conserve energy. The reason is counting. Four molecules can share two halves in 16 ways: all on one side in 1 way, 3 and 1 in 4 ways, 2 and 2 in 6 ways. With 100 molecules, all in one half is about 1 chance in 103010^{30}; with a real gas, it never happens.

S=kBln⁡ΩS = k_B \ln \OmegaBoltzmann: Ω is the number of ways (microstates); k = 1.38 × 10⁻²³ J/K.
  • More spread out, more disordered → more ways → more entropy.
  • Entropy is in J/K, is a state function, and adds up over the parts of a system.
  • Entropy rises when ice melts, water evaporates or a gas spreads into a vacuum; it falls when water freezes, steam condenses or a gas is squeezed at constant temperature.
  • At the same temperature, liquid water has more entropy than ice.

2Entropy from heat

dS=dQrevT,ΔS=∫dQrevTdS = \frac{dQ_{\text{rev}}}{T},\quad \Delta S = \int \frac{dQ_{\text{rev}}}{T}

At constant temperature, ΔS=Q/T\Delta S = Q/T, with TT in kelvin. Heat in raises entropy; heat out lowers it; the same heat changes the entropy of a cold body more than that of a hot one. For a phase change, ΔS=mL/T\Delta S = mL/T.

3The entropy law

When 1200 J flows from a body at 400 K to one at 300 K, the hot body loses 1200/400=31200/400 = 3 J/K and the cold one gains 1200/300=41200/300 = 4 J/K: the total rises by 1 J/K. In general

ΔS=QTC−QTH>0\Delta S = \frac{Q}{T_C} - \frac{Q}{T_H} > 0

4Entropy of an ideal gas

Along a reversible path, dQ=nCv dT+P dVdQ = nC_v\,dT + P\,dV with P=nRT/VP = nRT/V. Dividing by TT and integrating:

ΔS=nCvln⁡T2T1+nRln⁡V2V1\Delta S = nC_v\ln\frac{T_2}{T_1} + nR\ln\frac{V_2}{V_1}A state function: valid between any two states, even for irreversible processes.
ΔS=nCpln⁡T2T1−nRln⁡P2P1\Delta S = nC_p\ln\frac{T_2}{T_1} - nR\ln\frac{P_2}{P_1}
ProcessΔS
IsothermalnRln⁡(V2/V1)=nRln⁡(P1/P2)nR\ln(V_2/V_1) = nR\ln(P_1/P_2)
IsochoricnCvln⁡(T2/T1)nC_v\ln(T_2/T_1)
IsobaricnCpln⁡(T2/T1)nC_p\ln(T_2/T_1)
Reversible adiabatic0 (isentropic)
Phase changemL/TmL/T

5Irreversible processes

Irreversible processes create entropy even with no heat. To find ΔS\Delta S, use any reversible path between the same two states.

ΔS=Cln⁡(T1+T2)24T1T2>0\Delta S = C\ln\frac{(T_1 + T_2)^2}{4T_1T_2} > 0Two equal bodies (heat capacity C) meeting at the average temperature; positive because (T₁ + T₂)² − 4T₁T₂ = (T₁ − T₂)².

Copper blocks at 400 K and 200 K reaching 300 K: ΔS=Cln⁡(90 000/80 000)>0\Delta S = C\ln(90\,000/80\,000) > 0.

6Carnot and T–S diagrams

In a Carnot cycle the gas gains QH/THQ_H/T_H in step 1 and loses QC/TCQ_C/T_C in step 3; the adiabatic steps change nothing. Since QC/QH=TC/THQ_C/Q_H = T_C/T_H, these cancel, and so do the reservoirs' changes: a reversible engine creates no entropy. Example: 1000 J from 400 K to a 300 K sink: hot reservoir −2.5 J/K, cold +750/300 = +2.5 J/K, universe 0.

On a T–S diagram the Carnot cycle is a rectangle: flat isothermals and upright adiabatics (ΔS = 0). Since dQ=T dSdQ = T\,dS, the area under a path is the heat, and the area inside the loop is the work:

W=(TH−TC) ΔSW = (T_H - T_C)\,\Delta S

Summary

Key ideas

  • Entropy counts the ways a state can happen: S=kln⁡ΩS = k\ln\Omega.
  • Spread-out, disordered states have more ways, so more entropy.
  • ΔS=Q/T\Delta S = Q/T at a fixed temperature, in kelvin; unit J/K.
  • The entropy of the universe never decreases; it stays constant only for reversible processes.
  • Heat flowing from hot to cold increases the total entropy.
  • A system's own entropy can fall if its surroundings gain more.
  • A reversible adiabatic process is isentropic (ΔS = 0).
  • Irreversible processes (free expansion, mixing, heat across a gap) create entropy even with Q = 0.
  • On a T–S diagram the Carnot cycle is a rectangle whose area is the work.

Every equation

Boltzmann
S=kBln⁡ΩS = k_B\ln\Omega
Clausius
dS=dQrev/TdS = dQ_{\text{rev}}/T
Fixed T
ΔS=Q/T\Delta S = Q/T
Phase change
ΔS=mL/T\Delta S = mL/T
Second law
ΔSuniverse≥0\Delta S_{\text{universe}} \ge 0
Heat flow
ΔS=Q/TC−Q/TH\Delta S = Q/T_C - Q/T_H
Ideal gas
ΔS=nCvln⁡T2T1+nRln⁡V2V1\Delta S = nC_v\ln\frac{T_2}{T_1} + nR\ln\frac{V_2}{V_1}
Isothermal
ΔS=nRln⁡(V2/V1)\Delta S = nR\ln(V_2/V_1)
Isochoric
ΔS=nCvln⁡(T2/T1)\Delta S = nC_v\ln(T_2/T_1)
Isobaric
ΔS=nCpln⁡(T2/T1)\Delta S = nC_p\ln(T_2/T_1)
Solids, liquids
ΔS=mcln⁡(T2/T1)\Delta S = mc\ln(T_2/T_1)
Two bodies
ΔS=Cln⁡(T1+T2)24T1T2\Delta S = C\ln\frac{(T_1 + T_2)^2}{4T_1T_2}
T–S work
W=(TH−TC)ΔSW = (T_H - T_C)\Delta S

Previous year questions with solutions

Real JEE and NEET questions on entropy and irreversibility. Try each one before you open the solution.

Q1NEET 2026One correct option

An electric heater supplies heat to a system at a rate of 100 W . If the system performs work at a rate of 75 J/s75\ \mathrm{J/s}, then the rate at which internal energy increases will be:

  1. A75 W
  2. B100 W
  3. C125 W
  4. D25 W
Show answer and solution

Answer: Option D

The first law holds for every second of the process, so it can be written as rates: heat in per second == rise of internal energy per second ++ work done per second.

100=dUdt+75100 = \dfrac{dU}{dt} + 75, so dUdt=25 W\dfrac{dU}{dt} = 25\ \mathrm{W}.

The trap is A, 75 W75\ \mathrm{W}, the rate of doing work, and B, 100 W100\ \mathrm{W}, the whole heating rate — as if no work were done. C, 125 W125\ \mathrm{W}, adds the work to the heat, getting the sign of WW backwards: work done BY the system is energy leaving it.

Q2JEE Main 2026One correct option

Heat is supplied to a diatomic gas at constant pressure. Then the ratio of ΔQ:ΔU:ΔW\Delta Q:\Delta U:\Delta W is ______.

  1. A2 : 3 : 5
  2. B5 : 3 : 2
  3. C2 : 5 : 7
  4. D7 : 5 : 2
Show answer and solution

Answer: Option D

At constant pressure, per mole and per kelvin: ΔQ=CP ΔT\Delta Q = C_{P}\,\Delta T, ΔU=CV ΔT\Delta U = C_{V}\,\Delta T and ΔW=R ΔT\Delta W = R\,\Delta T. For a diatomic gas CV=52RC_{V} = \dfrac{5}{2}R and CP=72RC_{P} = \dfrac{7}{2}R, so

ΔQ:ΔU:ΔW=72:52:1=7:5:2\Delta Q : \Delta U : \Delta W = \dfrac{7}{2} : \dfrac{5}{2} : 1 = 7 : 5 : 2

Check with the first law: 7=5+27 = 5 + 2.

The trap is B, 5:3:25 : 3 : 2, which is the monatomic gas (52:32:1\dfrac{5}{2} : \dfrac{3}{2} : 1). A and C list the same numbers backwards, in the order W:U:QW : U : Q — and neither passes the check that QQ is the sum of the other two.

Q3JEE Main 2026Numerical answer

A diatomic gas (γ=1.4)(\gamma =1.4) does 100 J of work when it is expanded isobarically. Then the heat given to the gas ____\_\_\_\_ J.

Show answer and solution

Answer: 350

At constant pressure W=nR ΔTW = nR\,\Delta T and Q=nCP ΔTQ = nC_{P}\,\Delta T, so QW=CPR\dfrac{Q}{W} = \dfrac{C_{P}}{R}. With γ=1.4=75\gamma = 1.4 = \dfrac{7}{5} the gas is diatomic, CP=72RC_{P} = \dfrac{7}{2}R, and QW=72\dfrac{Q}{W} = \dfrac{7}{2} (the same as γγ−1=1.40.4=3.5\dfrac{\gamma}{\gamma - 1} = \dfrac{1.4}{0.4} = 3.5).

Q=3.5×100=350 JQ = 3.5 \times 100 = 350\ \mathrm{J}: 100 J100\ \mathrm{J} goes into work and 250 J250\ \mathrm{J} into internal energy.

The trap is 250 J250\ \mathrm{J}, which is ΔU\Delta U and forgets the work itself. Another is 140 J140\ \mathrm{J}, γ×100\gamma \times 100, which treats γ\gamma as the ratio of heat to work — that ratio is CPR\dfrac{C_{P}}{R}, not CPCV\dfrac{C_{P}}{C_{V}}.

Practice questions, easy to hard

Three questions from the entropy and irreversibility practice ladder: one easy, one medium, one hard.

Q4One correct option

Two simple processes follow straight from the first law.

Constant volume (isochoric): the gas pushes nothing back, so W=0W = 0 and all the heat goes into internal energy, Q=ΔU=nCV ΔTQ = \Delta U = nC_{V}\,\Delta T.

Constant pressure (isobaric): W=p ΔV=nR ΔTW = p\,\Delta V = nR\,\Delta T (from pV=nRTpV = nRT), and Q=ΔU+W=n(CV+R) ΔT=nCP ΔTQ = \Delta U + W = n(C_{V} + R)\,\Delta T = nC_{P}\,\Delta T. So the fraction of the heat that becomes work is

WQ=RCP=1−1γ\dfrac{W}{Q} = \dfrac{R}{C_{P}} = 1 - \dfrac{1}{\gamma}

and the fraction that becomes internal energy is CVCP=1γ\dfrac{C_{V}}{C_{P}} = \dfrac{1}{\gamma}.

A monatomic ideal gas is given 500 J500\ \mathrm{J} of heat at constant pressure. How much work does it do?

  1. A300 J300\ \mathrm{J}
  2. B500 J500\ \mathrm{J}
  3. C200 J200\ \mathrm{J}
  4. D143 J143\ \mathrm{J}
Show answer and solution

Answer: Option C

For a monatomic gas CV=32RC_{V} = \dfrac{3}{2}R and CP=52RC_{P} = \dfrac{5}{2}R, so WQ=RCP=25\dfrac{W}{Q} = \dfrac{R}{C_{P}} = \dfrac{2}{5} and W=25×500=200 JW = \dfrac{2}{5} \times 500 = 200\ \mathrm{J}. The other 300 J300\ \mathrm{J} raises the internal energy.

The trap is A, 300 J300\ \mathrm{J}, which is ΔU\Delta U, not WW. B, 500 J500\ \mathrm{J}, sends all the heat into work — but the gas warms up as it expands at constant pressure. D, 143 J143\ \mathrm{J}, uses the diatomic fraction 27\dfrac{2}{7}.

Q5Numerical answer

Many processes follow pVx=constantpV^{x} = \text{constant} for some number xx — a polytropic process. x=0x = 0 is constant pressure, x=1x = 1 is isothermal, x=γx = \gamma is adiabatic. Integrating p dVp\,dV gives the work for any x≠1x \neq 1:

W=p1V1−p2V2x−1=nR(T1−T2)x−1W = \dfrac{p_{1}V_{1} - p_{2}V_{2}}{x - 1} = \dfrac{nR(T_{1} - T_{2})}{x - 1}

(With x=γx = \gamma this is the adiabatic formula you already know.)

One mole of an ideal gas is heated so that its pressure stays proportional to its volume, p=kVp = kV — that is, pV−1pV^{-1} constant, x=−1x = -1. Its temperature rises from 300 K300\ \mathrm{K} to 400 K400\ \mathrm{K}. How much work does it do, in joules? Take R=8.3 J mol−1 K−1R = 8.3\ \mathrm{J\,mol^{-1}\,K^{-1}}.

Show answer and solution

Answer: 415 J

W=nR(T1−T2)x−1=8.3×(300−400)−1−1=−830−2=415 JW = \dfrac{nR(T_{1} - T_{2})}{x - 1} = \dfrac{8.3 \times (300 - 400)}{-1 - 1} = \dfrac{-830}{-2} = 415\ \mathrm{J}.

Check by area: p=kVp = kV is a straight line through the origin, and the area under it is k(V22−V12)2=p2V2−p1V12=R ΔT2\dfrac{k(V_{2}^{2} - V_{1}^{2})}{2} = \dfrac{p_{2}V_{2} - p_{1}V_{1}}{2} = \dfrac{R\,\Delta T}{2}.

The trap is reading "pp proportional to VV" as x=+1x = +1: written as pVxpV^{x} constant, p=kVp = kV is pV−1=kpV^{-1} = k, so x=−1x = -1 (and x=+1x = +1 would divide by zero). Another is nR ΔT=830 JnR\,\Delta T = 830\ \mathrm{J}, the constant-pressure answer, twice too big.

Q6One correct option

Take logs of pVx=constantpV^{x} = \text{constant}: log⁡p=−xlog⁡V+constant\log p = -x\log V + \text{constant}. So on a graph of log⁡p\log p against log⁡V\log V, every polytropic process is a straight line, and its slope is −x-x. Reading the slope gives xx, and xx gives the heat capacity C=CV+R1−xC = C_{V} + \dfrac{R}{1 - x}.

On a graph of log⁡p\log p against log⁡V\log V, a process is a straight line of slope −γ-\gamma. Which process is it?

  1. Aisothermal
  2. Bisobaric
  3. Cadiabatic
  4. Disochoric
Show answer and solution

Answer: Option C

Slope −γ-\gamma means x=γx = \gamma: pVγpV^{\gamma} is constant, the adiabatic, with C=0C = 0.

The trap is A, isothermal, which is x=1x = 1 and slope −1-1. B, isobaric, is x=0x = 0, a horizontal line. D, isochoric, keeps log⁡V\log V fixed — a vertical line, with no finite slope at all.