Assignment 3: Due 4 Sep 2023 before midnight

1. Consider the processes (x, y) : (0, 0) → (1, 1) shown in the following plots :

(a) Calculate the change in the function f (x, y) = xy for the two processes by integrating df over the paths shown.

Ans. df = d(xy) = ydx + xdy

(1,1) (1,1) (1,1) R1 1
y2
First process : x = y =⇒ ∆f =
R R R
df = ydx + xdy = 2 ydy = 2. 2 =1
(0,0) (0,0) (0,0) 0 0
(1,1) (1,0) (1,0) (1,1) (1,1)
Second process : ∆f =
R R R R R
df = ydx + xdy + ydx + xdy = 0 + 0 + 0 + 1 = 1
(0,0) (0,0) (0,0) (1,0) (1,0)

(b) Is df an exact or an inexact dierential? Ans. df is an exact dierential.

(c) Calculate the change in the quantity g dened by dg = ydx for the two processes by integrating dg over the paths.
(1,1) R1 1
y2
Ans. First process : x = y =⇒ ∆g = 1
R
ydx = ydy = 2 = 2
(0,0) 0 0
(1,0) (1,1)
Second process : ∆g =
R R
ydx + ydx = 0 + 0 = 0
(0,0) (1,0)

(d) Is dg an exact or an inexact dierential? Ans. dg is an inexact dierential.

(e) Which of the two : f and g , should be called a state function and which one a path function? Why?

Ans. Change in value of f in a process is independent of path, whereas change in value of g depends on path. Hence, f

should be called a state function and and g a path function.

2. Assuming U = CV T for a perfect gas, nd (i) the internal energy per unit mass and (ii) the internal energy per unit volume,

in terms of mass density, pressure and the heat capacity ratio γ .

Ans. Let m be the mass of one molecule, then density, ρ = NA m

V and pV = NA kB T =⇒ p
ρ = kB T
m

Cp Cp −CV
γ= CV =⇒ γ − 1 = CV = R
CV per mole.

or, per mole CV = γ−1 ;

R
∴ U = CV T = RT
γ−1 = NA kB T
γ−1

∴ internal energy per unit mass ũ = U

mNA = kB T 1
m . γ−1 = ρp . γ−1
1

internal energy per unit volume= ũ.ρ = p

γ−1

3. For a van der Waals gas, obtain an expression for the coecient of thermal expansion, α. The isothermal compressibility of a
 
substance is dened as κT = − V1 ∂V∂p .Why is the negative sign there? Show that κT R = α(Vm b), where Vm is the molar
T

volume.

Ans. α = 1 ∂V 1 1


V ∂T = V
p ( ∂V
∂T
)p
We want the value of κT to be positive. But, volume decreases on increasing pressure, i.e., if dp > 0, then dV < 0. Hence, it

is convenient to dene the quantity with a negative sign in front of the derivative.
 n2 a 2n2 a
For a van der Waals gas, p = nRT
V2 . Dierentiating both sides by V and keeping p const., nRT ∂T


V nb − V nb ∂V p
− V3 =0

1 1 RV 2 (V −nb)
∴α= V . T 2na = RT V 3 −2na(V −nb)2
V nb − RV 3 (V −nb)
 
V 2 (V −nb)2
κT = − V1 ∂V
∂p = −V 1
∂p = − V1 . 1
2a = nRT V 3 −2n2 a(V −nb)2
T ( ∂V )T − (VnRT
−nb)2
+ 2n
V3

∴ κT
α = V −nb
nR =⇒ κT R = α(Vm b)
( ∂V
∂p )T
− V1
 
alternatively, κT
α = = − ∂p 1. ∂V = ∂T ∂p
( ∂T )p
∂V1
V ( ∂V )T ( ∂T )p V
 
nRT n2 a (V −nb)p ∂T (V −nb)p
p= V nb − V2 =⇒ T = nR + f (V ) =⇒ ∂p = nR
V

∴ κT R = α(Vm b).

4. A sample of liquid water supercooled to −10o C placed in a thermally insulated compartment undergoes a spontaneous

crystallisation to form a mixture of ice and liquid water. Calculate q, w, ∆T, ∆U, ∆H, ∆S for the process.

Ans. thermally insulated compartment, ∴ q = 0

∵ spontaneous crystallisation and the nal state has liquid water along with ice,

∴ nal temperature = 0o C and ∆T =10◦

Let us say there are n moles of water in the sample.

volume of water= n×18

ρ , where ρ =density of liq. water.

let us consider the path : water (l, −10o C)−→ water (l, 0o C)−→ mixture of water(l)+ice, 0o C

There is some decrease in volume in the rst step due to anomalous expansion and in the second step there is an increase in

volume (11 volumes of water become 12 volumes of ice)

∴ ∆V ≈ 0 (water freezes to a greater volume of ice) and the only work is mechanical, ∴ w ≈ 0

For the rst step, ∆U = nCV,m,water × 10 and for the second step, part of the sample freezes releasing enough heat, (∆U =

∆H − p∆V , p const) so that the ∆U in the rst step is canceled (∵ only part of liq. water freezes).

∴ ∆U for the entire process= 0

for the rst step: ∆H ≈ ∆U > 0 (p const) and say n1 moles freeze, then for the second step, ∆H = −n1 ∆fus,m H

∆H for the entire process≈ 0 if the insulation is well maintained

∆Ssys for the rst step (calculated for a reversible path)

273
T ≈ 0.075.n. ln 263 = 0.075 × 0.037.n = 0.0028.n kJ/K > 0.
Cp,m,water dT 273
R
=n
263
n1 ∆fus,m H n1 ∆fus,m H
For the second step, ∆Ssys = 272 =− 272 272 n1 = −0.022.n1 kJ/K
= − 6.02

overall ∆Ssys is a sum of the two terms and we expect it to be negative.

∆Suniverse > 0 ∵ it is spontaneous crystallisation.

the change in chemical potential (Gibbs' free energy) drives the process, ∵ ∆G = ∆H − T ∆S

As long as ∆G < 0, the freezing continues and it stops when it reaches the value 0.