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8.

Applications of thermodynamics

8.1 Surface tension

The wire of length L is pulled to increase the area of the film


A A + dA
Work done to the system
dW = - dA

: Surface tension (force/length)

We can take analogy to the system of liquid-vapour at equilibrium

When the volume is increased, V , V

Liquid-surface at equilibrium
The properties of the molecules at the surface are taken to be different from those in the bulk
of the liquid
When the surface area is increased, more molecules from the bulk of the liquid will be added
to the surface

If the temperature is not changed during the process,

will not be changed

This implies that heat must be added to the system


dQ = dA

where : heat per unit surface area added, and

dT

= T

Consider isothermal process,


dW = dA
dQ = dA

Internal energy :

d
U
dU = dQ dW = ( + )dA

= + = T
dT
A T

Lets say we start from

A = 0 (U = 0)

dU = T dT dA
0
0

U = T
A
dT

Here U is the surface energy


U
d
= T
A
dT

Define heat capacity for constant A


d
d 2
d 2 d
U
= AT

CA =
= A
2
2

T
dT
dT
dT
A

dT

Specific heat capacity :

d 2
CA
= T 2
cA =
A
dT

F
Helmholtz function : U = F T

T V

Compare

U = T
A
dT

Entropy:

d
F
S =

= A
T
dT

Specific entropy :

s=

d
dT

F=A

[nota: V A]

8.2 Vapour pressure of liquid drop


A freely suspended liquid drop assume spherical

(2r)

(Pi - Pe) r2
Consider one half of the drop,
Net force :

(Pi - Pe) r2

Surface tension force :

(2r)

(Pi - Pe) r2 = (2r)

Pi Pe =

2
r

Pi = Pe +

2
r

At thermodynamic equilibrium, Pe = P, the vapour pressure

internal pressure

Pi = P +

2
r

This is the internal pressure of a liquid drop with radius r

8.3 Blackbody radiation


A blackbody is an object that absorp 100% radiation energy that is impinged onto it, and
the radiation energy density emitted from it, u is expressed by Stefan Law

u = T 4

(energy per unit volume)

= 7.56 10-16 J m-3 K-4


Total internal energy :

Stefan constant

U = uV = T4 V

U
3
CV =
= 4VT
T V
T
T
1
4
S = CV dT = 4VT 2 = VT 3
Entropy :
3
0T
0
4
1
Helmholtz function :
F = U TS = VT 4 VT 4 = VT 4
3
3
1

1
G = F + PV = VT 4 + T 4 V = 0
Gibbs function :
3

Heat capacitr for V unchanged :

8.4

Magnetic material
Work :

dW = - , dM

where

, is the external magnetic field strength


M is the magnetic moment

When the magnetic material (paramagnetic) is placed into magnetic field, its potential
energy is

Ep = - , M
Hence, the total energy : E = U - , M

[H = U + PV]

dE = dU -, dM - Md,
TdS equation :

TdS = dU + dW
= dE + , dM + Md, - , dM
= dE + Md,

Compare with PVT system :

TdS = dH VdP

In general, in our study of the thermodynamics of magnetism, we can take analogy of


PVT system :
Magnetic material

,
M
E
C,

PVT
P
V
H
CP

CM=

T M

U
CV =

T V

F = E - TS

F = U - TS