Example Problem 3.

Example Problem 3.6

A sample of N2 gas undergoes a change from an initial state
described by T=200 K and Pi=5.00 bar to a final state described by
T=400 K and Pf=20.0 bar. Treat N2 as a van der Waals gas with the
parameters a=0.137 Pa m6 mol-2 and b=3.8710-5 m3 mol-1. We use
the path N2 (g, T=200 K, P=5.00 bar)N2 (g, T=200 K, P=20.0bar)
N2 (g, T=400 K, P=20.0 bar), keeping in mind that all paths will
give the same answer for U of the overall process.

Example Problem 3.6a

Example Problem 3.6

U m
dV
using the result of

m
V T
Vm ,i
Example Problem 3.5. Notice that Vm,i=3.2810-3 m3 mol-1 and
Vm,f = 7.8810-4 m3 mol-1 at 200 K, as calculated using the van
der Waals equation of state.

a. Calculate U T ,m

Vm , f

Solution
U T ,m

1
1
a

Vm ,i Vm , f

1
1

0.137 Pa m mol

3
3
3
-1
3
-1
3.28
10
m
mol
7.88
10
m
mol

132J
6

-3

Example Problem 3.6a

Example Problem 3.6

b. Calculate

Tf

U T ,m CV ,m dT using the following relationship

T
i

for CV,m in this temperature range:

CV ,m
J K 1 mol 1

2
3
T
T
T
22.50 1.187 102 2.398 105 2 1.0176 108 3
K
K
K

The ratio Tn/Kn ensure that Cv,m has the correct dimension.
Solution

Example Problem 3.6a

Example Problem 3.6

c. Compare the two contributions to Um. Can UT,m be neglected
relative to UV,m ?
Solution

UT,m is 3.1% of UV,m for this case. In this example, and for most
processes, UT,m can be neglected relative to UV,m for real gas.
Vm , f

To a good approximation U T ,m V

m ,i

U m
dV

m = 0

for real gases under most conditions. Therefore, it is sufficiently

accurate to consider U as a function of T only [U = U(T) for real
gases in processes that do not involve unusually high gas densities.

3.4

The density of liquids and solids varies only slightly with

the external pressure over the range in which these two
forms of matter are stable. This conclusion is not valid for
extremely high pressure conditions such as those in the
interior of planets and stars. However, it is safe to say that
dV for a solid or liquid is very small in most processes.
Therefore,
because V 0. This result is valid even if (U/V)T is
large.

3.4

The Variation of Enthalpy with

Temperature at Constant Pressure

For this process defined by P

= Pexternal = constant,

Because P = Pi = Pf , this
equation can be rewritten as
Figure 3.4
The initial and final states are shown for
an undefined process that takes place at
constant pressure.

3.4

The Variation of Enthalpy with

Temperature at Constant Pressure

the value of H can be

determined for an arbitrary
process at constant P in a
closed system in which only
P-V work occurs by simply
measuring qp , the heat
transferred between the
system and surroundings in
a constant pressure
process.

H qP
H
H
dH
dT
dP
T P
P T
dqP H

CP

dT T P
Tf

Tf

Ti

Ti

H P CP T dT n CP ,m T dT
H P CP T nCP ,m T

Example Problem 3.7

Example Problem 3.7

A 143.0-g sample of C(s) in the form of graphite is heated from 300
to 600 K at a constant pressure. Over this temperature range, Cp,m
has been determined to be
C p ,m

2
3
T
T
T
4
7

12
.
19

0
.
1126

1
.
947

10

1
.
919

10
J K -1 mol-1
K
K2
K3
4
T
7.800 10 11 4
K
Calculate H and qp. How large is the relative error in H if you
neglect the temperature-dependent terms in Cp,m and assume that
Cp,m maintains its value at 300K throughout the temperature
interval?

Example Problem 3.7

Solution
m
H
M

Tf

C T dT
p ,m

Ti

T
T
4

600 12.19 .1126

1
.
947
10
2
J
143.0 g
K
K d T

3
4

K
T
T
12.00g mol1 mol 300
7
11

1
.
919
10
7
.
800
10

3
4
K
K

600
2
3

T
T
5 T
12.19 0.0563 2 6.49 10 3
143.0 g
K
K
K J 46.85 kJ

4
5
T
T

12.00g mol1
8
11

4
.
789
10
1
.
56
10

4
5
K
K

300

From equation (3.28), H q p .

Example Problem 3.7

If we had assumed Cp,m =8.617 J mol K, which is the calculated

value at 300 K,
=143.0 g / 12.00 g mol-18.617 J K mol [600K-300K]=30.81 kJ
The relative error is (30.81kJ - 46.85kJ)/46.85 kJ=-34%. In this case,
it is not reasonable to assume that Cp,m is independent of temperature.

3.5 How Are Cp and Cv Related?

By first law:

U
U
U
dU dq Pext dV
dV
dV CV dT
dT
V T
V T
T V
U
(In a reversible process)
dq CV dT
dV PdV
V T
dq
U V
V
C P CV

P

dT
V T T P
T P

P V
V U
CV
P CV T

T V T P
T P V
U
P
since
T
P
V T
T V

3.5 How are Cp and Cv Related?

Express abstract partial derivatives with experimentally available

data and
2

C P CV TV

or C P ,m

CV ,m TVm

Because and are positive for ideal and real gases,

CP CV > 0

3.5 How are Cp and Cv Related?

For an ideal gas

0 and
V T

V
nR
P
P nR
T P
P

C P CV nR
The partial derivative (V/ T)p =V is much smaller for
liquids and solids than for gases. Therefore, generally
For liquids and solids

C P CV

3.6

3.6 The Variation of Enthalpy with

Pressure at Constant Temperature
H U PV

dH dU PdV VdP

H
U
CP dT
dP
C
dT

dV PdV VdP
P T
V T
U

CV dT
P dV VdP
V T

For isothermal Processes, dT=0

U
dV
H

P
V
P T V T
dP T
U
dP
since
T

P
V T
dT V
H
dP dV
dV
T
V
V
T

P T
dT V dP T
dT P

Example Problem 3.8

Example Problem 3.8

Evaluate (H/P)T for an ideal gas.
Solution

nRT

/ T nR / V and
T V V
V
V
2

RT
d
nRT
/
P
/
P
nRT
/
P

T
H
P

P
T

nR nRT
nRT nRT
V
V 0

V T
2 V
V P
P nRT
P T

Example Problem 3.8

Example Problem 3.9

Calculate the change in enthalpy when 124 g if liquid methanol
initially at 1.00 bar and 298 K undergoes a change of state to 2.50
bar and 425K. The density of liquid methanol under these
conditions is 0.791 g/cm3, and Cp,m for liquid methanol is 81.1 J K-1
mol-1.
Solution
Tf

Pf

Ti

Pi

H n CP ,m dT CdP nCP ,m T f Ti V Pf Pi
124g
81.1 J K mol
425 K-298 K
-1
32.04 g mol
-1

-1

124g
106 m3
105 Pa
2.50 bar-1.00 bar
-3
3
0.791 g cm
cm
bar
39.9 103 J+23.5 J=39.9 kJ

3.7 The Joule-Thompson Experiment

Joule-Thomson effect ()
Joule-Thomson effect
(throttling process)
1852-62James P. Joule and William
Thomson
(porous plate )

Chap 2 The First Law

Joule-Thomson coefficient,

enthalpy

47

48

Chap 2 The First Law

T
.

P H

For expansion, dp 0

if 0 , dT 0, if 0 , dT 0

Joule-Thomson expansion
49

50

Chap 2 The First Law

:
, ( P2 < P1 ).
(V2 > V1 ),:
w = P1V1 P2V2 = U2 - U1 (q = 0 )
(U2 + P2V2 ) = (U1 + P1V1 ) or H2 = H1 (isenthalpic)
: T P. Joule-Thomson coefficient: J-T

J T

T2 T1 T
lim

p 0 P P
P H
2
1

T
H
J T

P T
P H
T
H
T

P T
p H H P

H P T
H

CP
T P
T H


C P
p H T P
51

3.7 The Joule-Thompson Experiment

Joule-Thompson Experiment is an
isenthalpic process
0

V2

V1

P2 dV PV
w wleft wright PdV
1
2 2 PV
1 1
q0
U U 2 U1 w PV
2 2 PV
1 1
or
U 2 PV
2 2 U1 PV
1 1

H 2 H1

53

3.7 The Joule-Thompson Experiment

Joule-Thompson Experiment

Figure 3.5
In Joule-Thompson experiment, a gas is forced through a porous plug using a
piston and cylinder mechanism. The pistons move to maintain a constant pressure
in each region. There is an appreciable pressure drop across the plug, and the
temperature change of the gas is measured. The upper and lower figures show the
initial and final states, respectively. As shown in the text, if the piston and the
cylinder assembly forms an adiabatic wall between the system (the gases on both
sides of the plug) and the surroundings, the expansion is isenthalpic.

Chap 2 The First Law

H
H
dH
dT J T C p dp C p dT
dp
T P
P T
The modern method of measuring m is indirect, and
involves measuring the isothermal Joule-Thomson
coefficient, the quantity:
H
J T C P

p T
Which is the slope of a plot of enthalpy against
pressure at constant temperature.

55

56

 C P J T

H
H
dH
dT C P J T dp C p dT
dp
T P
P T
57

Example Problem 3.10

Example Problem 3.8

Using equation (3.43), (H/P)T=[(U/V)T+P](V/P)T+V, and

Equation (3.19), (U/V)T=T(P/T)V-P, derive an expression
giving (H/P)T entirely in terms of measurable quantities for a gas.
Solution

U
V
dH

P
V
dP T V T
P T
P
V
T
P P
V
T V
P T
V
T
V TV V V 1 T
T P

3.7 The Joule-Thompson Experiment

Joule-Thompson coefficient

J T

T
T
lim

P 0 P

H
H

H
H
dH
dT
dp
P T
T P
J T C p dp C p dT

for an isenthalpic process dH=0

H
dH CP dT
dP 0
P T
H

CP J T
P T

3.7 The Joule-Thompson Experiment

Figure 3.6

Figure 3.6
All along the curves in the figure, JT and J-T is positive to the left of
the curves and negative to the right.
To
experience
cooling upon
expansion at 100 atm, T must lie
between 50 and 150 K for H2. The
corresponding temperatures for N2
are 199 and 650 K.

Example Problem 3.11

Example Problem 3.11

Using equation (3.43), (H/P)T=[(U/V)T+P](V/P)T+V show
that J-T = 0 for an ideal gas.
Solution

J-T

CP

1 U V
H
V

P
V
CP V T P T
P T
P T

CP

V
0 P
V
P T

nRT / P

P
V
P

T
1 nRT

V 0

CP P

CP

Chap 2 The First Law

, >0, .
, H2, He. <0,
, >0, <0, .
T-P , =(T/P )H ,
(Inversion Curve).
, > 0.., <0, .
,, =0.
: , =-0.060.
TI=43 K,?

62

63

64

65

66

3.8 Liquefying Gases Using an isenthalpic Expansion (Figure 3.7)

Figure 3.7
Schematic depiction of the liquefaction
of a gas using an isenthalpic JouleThompson expansion. Heat is extracted
from the gas exiting from the
compressor. It is further cooled in the
countercurrent heat exchanger before
expanding through a nozzle. Because
its temperature is sufficiently low,
liquefaction occurs.