3

The First Law: the machinery

Solutions to exercises
Discussion questions
E3.1(b)

The following list includes only those state functions that we have encountered in the first three
chapters. More will be encountered in later chapters.
Temperature, pressure, volume, amount, energy, enthalpy, heat capacity, expansion coefficient,
isothermal compressibility, and JouleThomson coefficient.

E3.2(b)

One can use the general expression for T given in Justification 3.3 to derive its specific form for
a van der Waals gas as given in Exercise 3.14(a), that is, T = a/Vm2 . (The derivation is carried
out in Example 5.1.) For an isothermal expansion in a van der Waals gas dUm = (a/Vm )2 . Hence
Um = a(1/Vm,2 1/Vm,1 ). See this derivation in the solution to Exercise 3.14(a). This formula
corresponds to what one would expect for a real gas. As the molecules get closer and closer the molar
volume gets smaller and smaller and the energy of attraction gets larger and larger.

E3.3(b)

The solution to Problem 3.23 shows that the JouleThomson coefficient can be expressed in terms
of the parameters representing the attractive and repulsive interactions in a real gas. If the attractive
forces predominate then expanding the gas will reduce its energy and hence its temperature. This
reduction in temperature could continue until the temperature of the gas falls below its condensation
point. This is the principle underlying the liquefaction of gases with the Linde Refrigerator which
utilizes the JouleThomson effect. See Section 3.4 for a more complete discussion.

Numerical exercises
E3.4(b)

E3.5(b)
E3.6(b)

A function has an exact differential if its mixed partial derivatives are equal. That is, f (x, y) has an
exact differential if




f
f
=
y x
x y


f
f
2 2
= 3x y
= 6x 2 y
and
(a)
x
y x


f
f
Therefore, exact.
= 2x 3 y and
= 6x 2 y
y
x y


f
f
s
= te + 1 and
= es
(b)
s
t s


f
f
= 2t + es and
Therefore, exact.
= es
t
s t
dz =
(a)
(b)

z
z
dx
2x dy
dx +
dy =

x
y
(1 + y)2
(1 + y)3

dz =

z
z
dx +
dy = (3x 2 2y 2 ) dx 4xy dy
x
y

2z
=
(3x 2 2y 2 ) = 4y
yx
y
2z

and
=
(4xy) = 4y
xy
x

THE FIRST LAW: THE MACHINERY

E3.7(b)

dz =

45

z
z
dx +
dy = (2xy + y 2 ) dx + (x 2 + 2xy) dy
x
y

2z

=
(2xy + y 2 ) = 2x + 2y
yx
y
2z
2
=
(x + 2xy) = 2x + 2y
xy
x











Cp

H
2H
H
=
=
p T
p T p
pT T p T p
T



H
Because
= 0 for a perfect gas, its temperature derivative also equals zero; thus
p T



Cp
= 0.
p T


(U +pV )



V
(H /V )p
(U/V )p + p
H
p
p
=
=
=
= 1+
U p
(U/V )p
(U/V )p
(U/V )p
(U/V )p
and

E3.8(b)

E3.9(b)

E3.10(b)

E3.11(b)

E3.12(b)



p
p
dp =
dV +
dT
V T
T V






dp
1 p
1 p
d ln p =
dV +
dT
=
p
p V T
p T V



p
in terms of the isothermal compressibility T
We express
V T







 1

1 V
p
p
1
T =
= V
so
=
V p T
V T
V T
T V



p
in terms of T and the expansion coefficient =
We express
T V










(V /T )p
p
T
V
p
= 1 so
=
=
T V V p p T
T V
(V /p)T



dV

1
1
dT
+
=
so d ln p =
pV T
pT
pT
V





U
3
= 0 by direct differentiation
nRT so
U=
2
p T
 
 
H = U + pV = 23 nRT + nRT = 25 nRT ,



H
= 0 by direct differentiation
so
p T







1
V
V
V
nRT
nR
=
=
V =
=
V
T p
p
T p
p
T



V
1
1

=
=
V
T
T

1
V


V
T p

INSTRUCTORS MANUAL

46



V
nRT
V
= 2
p T
p T
p




1
1
nRT
=
2
T =
V
p
p

T =

E3.13(b)

E3.14(b)

1
V



The JouleThomson coefficient is the ratio of temperature change to pressure change under
conditions of isenthalpic expansion. So



T
10 K
T
= 0.48 K atm1

=
=
(1.00 22) atm
p H
p






Um
dUm
dVm
dT +
Um = Um (T , Vm )
dUm =
Vm
T Vm
dT = 0 in an isothermal process, so

a
Um
dVm = 2 dVm
Vm T
Vm

1
Vm2
Vm2
22.1 L mol1
a
dVm
a

22.1 L mol
Um =
dUm =
dVm = a
=
2
2
Vm
1.00 L mol1
Vm1
Vm1 Vm
1.00 L mol1 Vm

dUm =

a
a
21.1a
+
=
= 0.95475a L1 mol
1
1
22.1 L mol
1.00 L mol
22.1 L mol1

a = 1.337 atm L2 mol2

Um = (0.95475 mol L1 ) (1.337 atm L2 mol2 )
= (1.2765 atm L mol

) (1.01325 10 Pa atm

1 m3
103 L

= 129 Pa m3 mol1 = 129 J mol1

RT
a
w = pex dVm and p =
2 for a van der Waals gas
Vm b V m




a
RT
dVm +
dVm = q + Um
so w =
Vm b
Vm2
Thus

22.1 L mol1

22.1 L mol1
RT

dVm = +RT ln(Vm b)

q=+
1
1.00 L mol1
Vm b
1.00 L mol
= +(8.314 J K1 mol1 ) (298 K)


22.1 3.20 102
ln
1.00 3.20 102
= +7.7465 kJ mol1
w = 7747 J mol1 + 129 J mol1 = 7618 J mol1 = 7.62 kJ mol1

THE FIRST LAW: THE MACHINERY

E3.15(b)

47

The expansion coefficient is




V  (3.7 104 K 1 + 2 1.52 106 T K2 )
1 V
=
=
V
V T p
=

V  [3.7 104 + 2 1.52 106 (T /K)] K 1

V  [0.77 + 3.7 104 (T /K) + 1.52 106 (T /K)2 ]

[3.7 104 + 2 1.52 106 (310)] K 1

= 1.27 103 K 1
0.77 + 3.7 104 (310) + 1.52 106 (310)2
Isothermal compressibility is



V
1 V
V
so p =

T =
V p T
V p
V T
A density increase 0.08 per cent means V /V = 0.0008. So the additional pressure that must be
applied is
=

E3.16(b)

p =
E3.17(b)

0.0008
= 3.6 102 atm
2.21 106 atm1

The isothermal JouleThomson coefficient is


H
= Cp = (1.11 K atm1 ) (37.11 J K 1 mol1 ) = 41.2 J atm1 mol1
p T
If this coefficient is constant in an isothermal JouleThomson experiment, then the heat which must
be supplied to maintain constant temperature is H in the following relationship
H /n
= 41.2 J atm1 mol1
p

so

H = (41.2 J atm1 mol1 )n p

H = (41.2 J atm1 mol1 ) (12.0 mol) (55 atm) = 27.2 103 J

E3.18(b)

The JouleThomson coefficient is


T
T
T
4.5 K
=

= 3.4 102 kPa

so p =
=
p H
p

13.3 103 K kPa1

Solutions to problems
Assume that all gases are perfect and that all data refer to 298 K unless stated otherwise.

Solutions to numerical problems

P3.1


1 atm
= 2.18 1011 Pa1
T = (2.21 10 atm )
1.013 105 Pa
For the change of volume with pressure, we use







V
1 V
dV =
dp[constant temperature] = T V dp
T =
p T
V p T
6

V = T V p

[If change in V is small compared to V ]

p = (1.03 10 kg m3 ) (9.81 m s2 ) (1000 m) = 1.010 107 Pa.

3

INSTRUCTORS MANUAL

48

Consequently, since V = 1000 cm3 = 1.0 103 m3 ,

V (2.18 1011 Pa1 ) (1.0 103 m3 ) (1.010 107 Pa)
= 2.2 107 m3 ,

or

0.220 cm3 .

For the change of volume with temperature, we use








1 V
V
dT [constant pressure] = V dT
=
dV =
T p
V T p
V = V T [if change in V is small compared to V ]
(8.61 105 K 1 ) (1.0 103 m3 ) (30 K)
2.6 106 m3 ,

or

2.6 cm3

Overall, V 2.8 cm3 V = 997.2 cm3

Comment. A more exact calculation of the change of volume as a result of simultaneous pressure
and temperature changes would be based on the relationship






V
V
dV =
dp +
dT = T V dp + V dT
p T
p p
This would require information not given in the problem statement.
P3.5

Use the formula derived in Problem 3.25.

Cp,m CV ,m = R
which gives =

1
(3Vr 1)2
=1

4Vr3 Tr

Cp,m
CV ,m + R
R
=
=1+
CV ,m
CV ,m
CV ,m

In conjunction with CV ,m = 23 R for a monatomic, perfect gas, this gives

= 1 + 23
Vm
Vm
T
27RbT
, Tr =
(Table 1.6) with a =
=
=
Vc
3b
Tc
8a
4.137 L2 atm mol2 and b = 5.16 102 L mol1 (Table 1.6). Hence, at 100 C and 1.00 atm,
RT
where Vm
= 30.6 L mol1
p

For a van der Waals gas Vr =

Vr

30.6 L mol1
= 198
(3) (5.16 102 L mol1 )

Tr

(27) (8.206 102 L atm K1 mol1 ) (5.16 102 L mol1 ) (373 K)

1.29
(8) (4.317 L2 atm mol2 )

Hence
[(3) (198) (1)]2
1
=1
= 1 0.0088 = 0.9912,

(4) (198)3 (1.29)

 
(1) + 23 (1.009) = 1.67

= 1.009

THE FIRST LAW: THE MACHINERY

49

Comment. At 100 C and 1.00 atm xenon is expected to be close to perfect, so it is not surprising
that differs only slightly from the perfect gas value of 53 .
P3.7

See the solution to Problem 3.6. It does not matter whether the piston between chambers 2 and 3 is
diathermic or adiabatic as long as the piston between chambers 1 and 2 is adiabatic. The answers
are the same as for Problem 3.6. However, if both pistons are diathermic, the result is different. The
solution for both pistons being diathermic follows.
See Fig. 3.1.

Diathermic piston

Diathermic piston

Figure 3.1

Initial equilibrium state.

n = 1.00 mol diatomic gas in each section
pi = 1.00 bar
Ti = 298 K
For each section
nRTi
(1 mol) (0.083 145 L bar K1 mol1 ) (298 K)
Vi =
=
pi
1.00 bar
= 24.8 L
Vtotal = 3Vi = 74.3 L = constant
Final equilibrium state. The diathermic walls allow the passage of heat. Consequently, at equlibrium
all chambers will have the same temperature T1 = T2 = T3 = 348 K. The chambers will also be at
mechanical equlibrium so
p1 = p2 = p3 =

(n1 + n2 + n3 )RT1
Vtotal

(3 mol) (0.083 145 L bar K1 mol1 ) (348 K)

74.3 L
= 1.17 bar = p2 = p3

The chambers will have equal volume.

INSTRUCTORS MANUAL

50

Vtotal
= Vi = 24.8 L = V1 = V2 = V3
3
 
U1 = n1 CV T1 = n1 25 R T1
 
= (1 mol) 25 (8.314 51 J K 1 mol1 ) (348 K 298 K)
V1 =

U1 = 1.04 kJ = U2 = U3
Utotal = 3 U1 = 3.12 kJ = Utotal

Solutions to theoretical problems

P3.11

dw =








w
w
w
dx +
dy +
dz
y x,z
z x,y
x y,z

dw = (y + z) dx + (x + z) dy + (x + y) dz
This is the total differential of the function w, and a total differential is necessarily exact, but here
we will demonstrate its exactness showing that its integral is independent of path.
Path a
dw = 2x dx + 2y dy + 2z dz = 6x dx
(1,1,1)
1
dw =
6x dx = 3
(0,0,0)

Path b
dw = 2x 2 dx + (y 1/2 + y) dy + (z1/2 + z) dz = (2x 2 + 2x + 2x 1/2 ) dx
(1,1,1)
1
2
4
(2x 2 + 2x + 2x 1/2 ) dx = + 1 + = 3
dw =
3
3
0
(0,0,0)
Therefore, dw is exact.
P3.12

U = U (T , V )









U
U
U
dU =
dT +
dV = CV dT +
dV
T V
V T
V T
For U = constant, dU = 0, and













dV
V
U
U
U
dV or CV =
=
CV dT =
V T
V T dT U
V T T U
This relationship is essentially the permuter [Relation 3, Further information 1.7].

P3.13

H = H (T , p)









H
H
H
dH =
dT +
dp = Cp dT +
dp
T p
p T
p T
For H = constant, dH = 0, and



H
dp = Cp dT
p T








H
dT
T
= Cp
= Cp
= Cp = Cp
p T
dp H
p H
This relationship is essentially the permuter [Relation 3, Further information 1.7].

THE FIRST LAW: THE MACHINERY

P3.16

51

The reasoning here is that an exact differential is always exact. If the differential of heat can be shown
to be inexact in one instance, then its differential is in general inexact, and heat is not a state function.
Consider the cycle shown in Fig. 3.2.

4
A
Isotherm at
B
2

Isotherm at

Isotherm at

Figure 3.2
The following perfect gas relations apply at points labelled 1, 2, 3 and 4 in Fig. 3.2.
(1) p1 V1 = p2 V2 = nRT ,

(2) p2 V1 = nRT  ,

Define T  = T T  , T  = T  T
Subtract (2) from (1)
nRT  + nRT = p2 V1 + p1 V1
V1 (p1 p2 )
RT
Subtracting (1) from (3) we obtain

giving T  =

T  =

V2 (p1 p2 )
RT

Since V1 = V2 , T  = T 
qA = Cp T  CV T  = (Cp CV ) T 
qB = CV T  + Cp T  = (Cp CV ) T 

P3.18

giving qA =
qB and q(cycle) = qA qB = 0.

Therefore dq = 0 and dq is not exact.
a
RT

p = p(T , V ) =
Vm b Vm2






p
p
dp =
dT +
dV
T V
V T

(3) p1 V2 = nRT 

INSTRUCTORS MANUAL

52

In what follows adopt the notation Vm = V .


p
R
;
=
T V
V b

then, dp =

R
V b


p
RT
2a
=
+ 3
V T
(V b)2
V

RT
2a

dT +
V3
(V b)2


dV

Because the van der Waals equation is a cubic in V ,

of the permuter.


V
is more readily evaluated with the use
T p

 
p

R
T V
V
RV 3 (V b)
V b
=
=   = 
p
T p
RT V 3 2a(V b)2
RT 2 + 2a3
V
T

For path a
T2 ,V2
T1 ,V1

For path b
T2 ,V2
T1 ,V1

(V b)


V2 
R
RT2
2a

dp =
+ 3 dV
dT +
(V b)2
V
T1 V1 b
V1


R
RT2
1
RT2
1
=
2
(T2 T1 ) +

a
V1 b
(V2 b) (V1 b)
V22
V1


RT1
RT2
1
1
=
+
a
2
2
V1 b V 2 b
V2
V1
T2

V2 


T2
RT1
R
2a

dp =
+ 3 dV +
dT
2
(V b)
V
V1
T1 V2 b


RT1
RT1
1
R
1
=

a
(T2 T1 )
2 +
V2 b
V 2 b V1 b
V22
V1


RT1
RT2
1
1
=
+
a
2
V1 b V 2 b
V22
V1

Thus, they are the same and dp satisfies the condition of an exact differential, namely, that its integral
between limits is independent of path.
P3.20

p = p(V , T )
Therefore,






p
n2 a
p
nRT
dp =
2 [Table 1.6]
dV +
dT with p =
V T
T V
V nb
V







p
V 2nb
n2 a
nRT
2n2 a
p

+
=
+
=
V T
V nb
V nb
(V nb)2
V3
V3



p
p
n2 a
nR
= +
=
T V
V nb
T
TV2

THE FIRST LAW: THE MACHINERY

53

Therefore, upon substitution

  2 


  2 



p dV
n a
p dT
n a
dV
dT
dp =
+
+
+
(V 2nb)

3
2
V nb
V

nb
T
T
V
V




(n2 a) (V nb)/V 3 p
p + n2 a/V 2
=
dV +
dT
V nb
T

=

a(Vm b)/Vm3 p
Vm b


dVm +

p + a/Vm2
T


dT

Comment. This result may be compared to the expression for dp obtained in Problem 3.18.
P3.21

nRT
n2 a
2 (Table 1.6)
V nb
V



 p 
na
Hence T =
(V nb)
(V nb) +
nR
RV 2
p=


T
V nb
Vm b
1
=
=
= 
p
nR
p V
R
T






p
V
T
For Eulers chain relation, we need to show that
= 1
p V V T T p









T
p
V
1
Hence, in addition to
and
[Problem 3.20] we need
= 
T
p V
V T
T p


which can be found from

 p 
2na
T
na

(V nb)
=
+
V p
nR
RV 2
RV 3





T
2na
=
(V nb)

V nb
RV 3

V p

Therefore,



T
p V



p
V T

V
=
T p

 

p
T
p V V T
 
T
V p




 

2n2 a
T
2na
(VnRT
+
(V nb)
+
2
3
3
V nb
nb)
V
RV
 

 

=
= 
T
2na
T
2na
V nb RV 3 (V nb)
V nb RV 3 (V nb)
= 1


P3.23

Cp = T

V nb
nR


V
T
V =   V [Relation 2, Further information 1.7]
T
T p
V
p


T
2na
T

=
(V nb) [Problem 3.21]
V p
V nb RV 3

INSTRUCTORS MANUAL

54

Introduction of this expression followed by rearrangement leads to

Cp =

(2na) (V nb)2 nbRT V 2

V
RT V 3 2na(V nb)2
RT V 3
to simplify the appearance of the expression
2na(V nb)2

Then, introducing =

Cp =

1 nb
V
1


V =


1 Vbm
1

For xenon, Vm = 24.6 L mol1 , T = 298 K, a = 4.137 L2 atm mol2 , b = 5.16 102 L mol1 ,
b
5.16 102 L mol1
nb
=
=
= 2.09 103
V
Vm
24.6 L mol1
=

(8.206 102 L atm K1 mol1 ) (298 K) (24.6 L mol1 )3

= 73.0
(2) (4.137 L2 atm mol2 ) (24.6 L mol1 5.16 102 L mol1 )2

Therefore, Cp =

1 (73.0) (2.09 103 )

(24.6 L mol1 ) = 0.290 L mol1
72.0

Cp = 20.79 J K1 mol1 [Table 2.6], so

=

0.290 103 m3 mol1

0.290 L mol1
=
1
1
20.79 J K mol
20.79 J K1 mol1

= 1.393 105 K m3 J1 = 1.393 105 K Pa1

= (1.393 105 ) (1.013 105 K atm1 ) = 1.41 K atm1
The value of changes at T = T1 and when the sign of the numerator 1
is positive). Hence
b
= 1 at T = T1
Vm


that is, T1 =

2a
Rb

or

RT1 bV 3
=1
2na(V nb)2 Vm

nb
changes sign ( 1
V

implying that T1 =

2a(Vm b)2
RbVm2







b 2
b 2
27
1
Tc 1
=
Vm
4
Vm

2a
(2) (4.137 L2 atm mol2 )
=
= 1954 K
Rb
(8.206 102 L atm K1 mol1 ) (5.16 102 L mol1 )
2

5.16 102
= 1946 K
and so T1 = (1954 K) 1
24.6

For xenon,

Question. An approximate relationship for of a van der Waals gas was obtained in Problem 3.17.
Use it to obtain an expression for the inversion temperature, calculate it for xenon, and compare to
the result above.

THE FIRST LAW: THE MACHINERY

P3.25

55

2 T V
Cp,m CV ,m =
[3.21] = T V
T



p
nR
=
[Problem 3.20]
T V
V nb



V
1
V =
= 
T
T p


p
[Justification 3.3]
T V

V p

Substituting,
 
p
T T
Cp,m CV ,m =   V
T

so

V p


2na
T
T

=
(V nb) [Problem 3.21]
V p
V nb RV 3

Substituting,
Cp,m CV ,m =

nRT
(V nb)

T
(V nb)

2na
RV 3

(V nb)

= nR

with =

2na
RT V 3

1

(V nb)2

For molar quantities,

Cp,m CV ,m = R

with

2a(Vm b)2
1
=1

RT Vm3

Now introduce the reduced variables and use Tc =

8a
, Vc = 3b.
27Rb

After rearrangement,
1
(3Vr 1)2
=1

4Tr Vr3
For xenon, Vc = 118.1 cm3 mol1 , Tc = 289.8 K. The perfect gas value for Vm may be used as any
1
error introduced by this approximation occurs only in the correction term for .

Hence, Vm 2.45 L mol1 , Vc = 118.8 cm3 mol1 , Tc = 289.8 K, and Vr = 20.6 and Tr = 1.03;
therefore
1
(61.8 1)2
= 0.90,
=1

(4) (1.03) (20.6)3

and

P3.27

giving 1.1

Cp,m CV ,m 1.1R = 9.2 J K1 mol1






Vm
1 H
1
T
(a)
=
=
Vm [Justification 3.1 and Problem 3.24]
Cp p T
Cp
T p
RT
+ aT 2
Vm =
p



R
Vm
= + 2aT
T p
p

INSTRUCTORS MANUAL

56

=
=

1
Cp

aT 2
Cp

RT
RT
+ 2aT 2
aT 2
p
p


p
(b)
CV = Cp T Vm
T V





p
Vm
= Cp T
T p T V
RT
But, p =
2


 Vm aT
p
R
RT (2aT )
=

T V
(Vm aT 2 )2
Vm aT 2
R
2aRT 2
=
+
(RT /p) (RT /p)2
2ap 2
p
= +
T
R
Therefore



 
R
p
2ap 2
CV = Cp T
+ 2aT
+
p
T
R




  
2apT
2apT
p
RT
= Cp
1+
1+

p
R
R
T



2apT 2
CV = Cp R 1 +
R

Solutions to additional problems

P3.29

(a) The JouleThomson coefficient is related to the given data by

= (1/Cp )(H /p)T = (3.29 103 J mol1 MPa1 )/(110.0 J K1 mol1 )
= 29.9 K MPa1
(b) The JouleThomson coefficient is defined as
= (T /p)H ( T / p)H
Assuming that the expansion is a JouleThomson constant-enthalpy process, we have
T = p = (29.9 K MPa1 ) [(0.5 1.5) 101 MPa] = 2.99 K