Maxwell Relations, thermodynamic equation of state, G,A, Joule Thomson etc.
Calculation of ΔG, ΔA etc.
1. 1 mole of an ideal monoatomic gas initially at STP undergoes an irreversible isothermal expansion to 0.5atm,
thereby doing 100cal of work. Calculate the value of ΔU, ΔH, ΔG and ΔS for this process.
2. 1mole of an ideal gas at 27°C expands isothermally and reversibly from an initial volume of 2 dm3 to a final
volume of 20dm3. Calculate ΔA, ΔG and Q.
3. 1 mole of toluene is vaporized at its boiling point 111°C. The heat of vaporization at its boiling point is 363.3Jg-1.
Calculate ΔH, ΔG and ΔS for the vaporization of 1 mole of toluene.{assume the vapour to behave as an ideal gas.
Molar mass of toluene =92gmol-1]
4. Show that ΔA is greater than ΔG for melting of ice at 0°C and 1atm.
5. Show that ΔA = ΔG for an isothermal expansion involving ideal gas.
𝑎
6. The Helmoltz energy for 1 mole of a certain gas is given by 𝐴 = − − 𝑅𝑇𝑙𝑛 𝑉 − 𝑏 + 𝑓(𝑇) where a, b are
𝑉
constants. Set up an expression for pressure of a gas.
𝑎 𝑑𝐺
7. Show that for a system obeying equation of state 𝑃 + 𝑉 = 𝑅𝑇, = −𝑃
𝑉 𝑑𝑉 𝑇
8. Calculate ΔU, ΔG, ΔA and ΔS when 1 mole of water which boils at 100°C and 1 atm. Given ΔHvap = 9720 calmol-1.
𝑑𝐺
9. Establish = 𝑉, integrate it to show that ΔG = -5708Jmol-1 for an ideal gas when it expands isothermally and
𝑑𝑃 𝑇
reversibly from 1 bar to 0.1 bar at 298K. What will be the ΔG if process irreversible. Give reason.
10. If Gibbs free energy varies with temperature as G/T = a + b/T +c/T2. How will enthalpy and entropy vary with
temperature. Check whether equations are consistent with Gibbs Helmholtz equation.
11. For a reaction 1/2N2 (g) + 3/2 H2(g) = NH3(g), ΔG at 298K is -951 Jmol-1. Calculate ΔG at 1000K if ΔH is given by
ΔH (Jmol-1) = -9190-7.12T
Joule Thomson
1 2𝑎
1. The J.T coefficient for a van der waals gas is given by 𝜇𝐽𝑇 = − 𝑏 . Using this relation calculate the value of ΔH for
𝐶𝑃 𝑅𝑇
isothermal compression of 1 mole of nitrogen from 1 to 500 atmospheres at 300K, a = 0.1353Nm4mol-2, b = 0.039x10-
3m3mol-1. [3.5kJmol-1]
2. Find the expression of 𝜇𝐽𝑇 for a gas obeying the equation P(V-b) =RT. Hence calculate the 𝜇𝐽𝑇 for a such a gas at 300K
and 100 atm with 𝐶𝑃 =35.15JK-1 and b =3.92m3mol-1.
3. Find expression for 𝜇𝐽𝑇 of Euler’s gas. Hence find it value at 300K, 100 atm with CP = 35.15JK and b = 3.92m3mole-1.
𝑑𝑈
4. Show that for a gas obeying PV =RT (1+bP) following relation is true (i) = 𝑏𝑃2 and (ii) 𝜇𝐽𝑇 = 0. Comment on
𝑑𝑉 𝑇
value of 𝜇𝐽𝑇 .
5. Find the value of 𝜇𝐽𝑇 for a gas obeying P(V+ a/RT) = RT. Comment on the result.
𝑉
6. Show that 𝜇𝐽𝑇 = 𝛼𝑇 − 1
𝐶𝑃
Theory Questions
1. Show that loss in Helmoltz free energy (A) is equivalent to reversible isothermal work done by a system. And
hence obtain the condition of spontaneity with respect to A.
2. Following is the isotherm of van der waals gas below Tc,
B
C A
V
Explain the signs of CP-CV at the points A,B and C.
3. Justify/ Criticize the following statements:
(i)For a real gas, having only repulsive interactions heating occurs on Joule Thomson expansion.
(ii) The internal energy change for a Joule Thomson expansion is more than an adiabatic irreversible expansion of same
pressure and volume change.
