Chapter 2

The First Law

Unit 5 state function and exact
differentials

Spring 2009

State function and Path

function
State function
a property that is independent of how a
sample is prepared.
example : T, P, U, H
Path function
a property that is dependent on the
preparation of the state.
depends on the path between the initial
and final states
example : W, q

Example 2.7
Calculating work, heat, and internal
energy
Consider a perfect gas inside a cylinder
fitted with a piston. Let the initial state be T,
Vi and the final state be T,Vf. The change of
state can be brought about in many ways,
of which the two simplest are the following:
Path 1, in which there is free expansion
against zero external pressure;
Path 2, in which there is reversible,
isothermal expansion.
Calculate w, q, and U and Hfor each
process.

Example 2.7
Path 1 isothermal free expansion
Isothermal U=0, H=0
U=q+w = 0 q=-w
free expansion w q
Path 2 isothermal reversible expansion
Isothermal U=0, H=0
U=q+w = 0 q=-w
Vf

w nRT ln
reversible expansion
V
i
Vf

q nRT ln
Vi

Self Test 2.8

Calculate the values of q, w, and U, H for an
irreversible isothermal expansion of a perfect
gas against a constant nonzero external

Irreversible isothermal expansion

Isothermal U=0, H=0
U=q+w = 0
q=-w
Irreversible expansion w PexV q
PexV

Change in internal energy, U

Change in internal energy, U

U
T
Internal pressure

U
Constant-pressure heat capacity
CV

dU T dV CV dT

Internal pressure
The variation of the internal energy of a substance
as its volume is changed at constant temeperature.
U
T

For a perfect gas

T
For real gases
attractive force T
repulsive force T

Internal pressure
U

P
T

P
V

nRT
For ideal gas P
V
U

P
T
P T

nRT

V
T

P T

nR
P0
V

Joule experiment

Expands isothermally
against vacuum (pex=0)
w=0, q=0 so U=0
and T=0

U at constant pressure
dU T dV CV dT
U

V
T

Expansion coefficient
the fraction change in volume
with a rise in temperature
Isothermal compressibility

the fractional change in

volumewhen the pressure
increases in small amount

CV
P

1 V

V T

1 V
T

V P

E 2.32 b
The isothermal compressibility of lead at
293 K is 2.21 106 atm1. Calculate the
pressure that must be applied in order to
increase its density by 0.08 per cent.
1 V
V

V p T
Vp
V 1
p

V T

Example 2.8
Calculating the expansion coefficient
of a gas
Derive an expression for the expansion
coefficient of a perfect gas.

U at constant pressure
U

V
T

CV T V CV
P

For perfect gas

CV
P

Change in enthalpy, H

(chain relation)

Joule-Thomson
coefficient
T

= p

dH C P dp C p dT

Joule-Thomson coefficient,
T

A vapour at 22 atm and 5C was allowed to

expand adiabatically to a final pressure of 1.00
atm; the temperature fell by 10 K. Calculate the
JouleThomson coefficient, , at 5C, assuming it
remains constant over this temperature range.

T
10 K

0.48 K atm
p (1.00 22) atm

Joule-Thomson coefficient,
For perfect gases = 0
For real gases
0 gas cools on expansion
0 gas heats on expansion
Inversion temperature

Exercise 2.29a
When a certain freon used in refrigeration
was expanded adiabatically from an initial
pressure of 32 atm and 0C to a final
pressure of 1.00 atm, the temperature fell
by 22 K. Calculate the JouleThomson
coefficient, , at 0C, assuming it remains
constant over this temperature range.

T
22 K

0.71 K atm -1
p (1.00 32) atm

Joule-Thomson effect
Cooling by isenthalpic expansion
Adiabatic process q=0, U=w
Pi > P f
On the left
isothermal irreversible compression
Pi,Vi,Ti Pi,0,Ti
w1= -pi ( 0 - Vi )= pi Vi
On the right
isothermal irreversible expansion
Pf,0,Tf Pf,Vf,Tf
w2= -pf ( Vf - 0 )= -pf Vf

Joule-Thomson effect
Cooling by isenthalpic expansion
w = w1 + w2 = pi Vi - pf Vf
w = U=Uf -Ui = pi Vi - pf Vf
Uf + pf Vf = Ui + pi Vi
Hf = Hi
Joule-Thomson effect is an isenthalpic process

Isothermal Joule-Thomson
coefficient
H
T
p

C p
T

Liquefaction of gases
T

Liquefaction of gases
T

Review 1
Define internal pressure T
Prove that, for ideal gas, T = 0

Review 2
Define Expansion coefficient
Define Isothermal compressibility
T
Prove that for ideal gas
= 1/T
T= 1/p

Review 3
Define Joule-Thomsom coefficient
Prove that Joule-Thomson experiment
is an isentahlpic process.
Explain the principle of using JouleThomson effect to liquefy gases.