Chapter 1

Problem 1.1* The plot of V = V (P, T) for a gas is shown in Fig. 1.1. Determine.

the expressions of the two second derivatives of the volume of this plot. (note: the

principal curvatures of the surface are proportional to these second derivatives).

What are the signs of the curvatures? Explain.

Solution: start with the defining equations of T  and . 

 V 
   V  T assuming  T is constant
 P  T
  2V 
 2   TV > 0
2

 P T
 V 
   V assuming  is constant
 T  P
  2V 
 T2   V  0
2

  P

Since all terms in the expressions are positive (V, 2 and 2), both principal

curvatures are positive. The surface is convex.

1
Problem 1.2* The expression for the total derivative of V with respect to the

dependent variables P and T is :

 V   V 
dV    dP    dT
 P T  T  P

Substitute the values of  and  obtained in Qualitative Problem 2 into this equation

and obtain the equation of state for an ideal gas.

Solution

dV    TVdP  V dT
V 1
dV   dP  V dT
P T
dV dP dT
 
V P T
ln V  c1   ln P  c2  ln T  c3
PV  (constant)  T

The constant is nR for n moles of the ideal gas.

2
Problem 1.3* The pressure temperature phase diagram (Fig. 1.4) has no two phase

areas (only two phase curves), but the temperature composition diagram of Fig. 1.5

does have two phase areas. Explain.

Solution:

This is due to the number of components in each system. The system displayed in

Fig. 1.4 is unary and that in Fig. 1.5 is a binary. We will see more on this later in the

text.


Problem 1.4*   Calculate the value of the ratio for an ideal gas in terms of its
T

volume.

Solution:

1
 T P R
     
T 1 T V
P

  
3
Chapter 2
Problem 2.1

A monatomic ideal gas at 300 K has a volume of 15 liters at a pressure of 15 atm.

Calculate

a. the final volume of the system

b. the work done by the system

c. the heat entering or leaving the system

d. the change in the internal energy

e. the change in the enthalpy

when the gas undergoes

i. A reversible isothermal expansion to a pressure of 10 atm

ii. A reversible adiabatic expansion to a pressure of 10 atm

The constant volume molar heat capacity of the gas, cv, has the value 1.5 R.

Solution
State 1: T1  300 K V1  15 liters P1  15 atm
15 atm 15 liters
 n  9.141 liters
0.08206liter atm
300 K
deg ree mole

1 1  PV
i. After isothermal expansion to pressure 10 atm: PV 2 2

15 atm 15 liters
V2   22.5 liter
10 atm
T2  300 K P2  10 atm
Final Volume: 22.5 liters
V2 22.5
Work done by system: w  q  nT ln = 9.14  8.3144  300  ln  9244 Joules
V1 15
Heat entering or leaving the system: w  q  9244 Joules
Change in the Internal Energy of System: 0 since isothermal
Change in the Enthalpy of System: 0 since isothermal

4
Same Initial State :
T1  300 K V1  15 liters P1  15 atm n  9.14 moles

ii. After adiabatic expansion to pressure 10 atm:

5 5
 
1 1  PV
PV 3 3 15 153  10V3 3 V3  19.13 liters
PV 10 atm 19.13 liters
T3  3 3
  255 K
nR 9.14 moles  0.08206 liter atm
deg ree mole

Final Volume: 19.13 liters

Work done by system:
3
w  U  ncV (T3  T1 )  ncV (255  300) = 9.14   8.3144  45  5130 Joules
2
Heat entering or leaving the system: q  0 (adiabatic)
Change in the Internal Energy of System: U   w  5130 Joules
Change in the Enthalpy of System:
5
H  ncP (T3  T1 )  9.14   8.3144  45  8549 Joules
2

5
 Problem 2.2

One mole of a monatomic ideal gas, in the initial state T = 273 K, P = 1 atm, is

subjected to the following three processes, each of which is conducted reversibly:

a. A doubling of its volume at constant pressure,

b. Then a doubling of its pressure at constant volume,

c. Then a return to the initial state along the path P = 6.643 × 10–4V2 + 0.6667.

Calculate the heat and work effects which occur during each of the three

processes.

Solution

First we calculate the P, V and T of each step:

l  atm
1mole  0.08206  273
nRT1 mole  K
V1    22.4 l
P1 1 atm
1 atm  44.8 l
a.1  2; V2  2  V1  44.8 l T2   546 K
l  atm
0.08206
mole  K
2 atm  44.8 l
b. 2  3; V3  44.8 l P3  2 atm T3   1092 K
l  atm
0.08206
mole  K
8.3144 J
Now : 1  2; w  P(V
1 2  V1 )1  2; w  P(V
1 2  V1 )  22.4 l  atm  22.4 l  atm   2270 J
0.08206l  atm
J
q  w  U  2270 J  cV 8.3144 ( 546  273 )K  5675 J
deg  mole
J
2  3; w  0 q  U = cV 8.3144 ( 1092  546 )K  6809 J
deg  mole

1 1
3  1; w   PdV   ( 6.643 104 V 2  0.6667 )dV 
3 3

6.643 104 3

3
V1  V33   0.6667 V1  V3  
8.3144 J
=  32.35 l  atm   3278 J
0.08206l  atm

6
 J 3 J
U  cV 8.3144 ( T1  T3 )  8.3144 ( 273  1092 )K  10214 J
deg  mole 2 deg  mole
q  w  U  3278 J  10214 J  13492 J

wTotal  2270  3278  1008 J

qTotal  5675  6809  13492  1008 J

7
Problem 2.3

The initial state of a quantity of monatomic ideal gas is P= 1 atm, V= 1 liter, and T=

373 K. The gas is isothermally expanded to a volume of 2 liters and is then cooled at

constant pressure to the volume V. This volume is such that a reversible adiabatic

compression to a pressure of 1 atm returns the system to its initial state. All of the

changes of state are conducted reversibly. Calculate the value of V and the total work

done on or by the gas.

Solution

First we need to calculate the number of moles in the system

PV 1 atm  1 l
n 1 1   0.0327 moles
RT1 0.08206 l atm  373K
mole K

PV
Isothermal Expansion state 1 to 2: P2  1 1
 0.5 atm
V2

Constant pressure compression to state 3 at which:

5 5 5
PV
1 1 = PV
3
3 3
3
Thus: 1 = 0.5V 3
3
giving V3  1.52l

Now:
V2
1  2: w  nRT ln  70.3 J
V1
2  3: w  P(V3  V1 )  0.24l  atm  24.5 J

3  1: w  U  ncV ( T1  T3 )
PV 0.5atm 1.52l
T3  3 3
  283K
nR 0.0327 moles  0.08206 l atm
moleK
3
w   0.0327   8.3144( 373  283 )  37.1 J
2
Total work  70.3  24.5  37.1  8.7 J this work performed by the gas

8
Problem 2.4

Two moles of a monatomic ideal gas are contained at a pressure of 1 atm and a

temperature of 300 K. 34,166 joules of heat are transferred to the gas, as a result of

which the gas expands and does 1216 joules of work against its surroundings. The

process is reversible. Calculate the final temperature of the gas.

Solution

U  q  w   34166  1216   32950 J

3
also U  ncV T  2   8.3144  ( T2  300 )  32950 J
2
Thus T2  1620 K

9
Problem 2.5

One mole of N2 gas is contained at 273 K and a pressure of 1 atm. An addition of

3000 joules of thermal energy to the gas at constant pressure causes work to be done

during its expansion. Assume that nitrogen behaves as an ideal gas, and that the above

change of state is conducted reversibly.

a. Calculate the final temperature of the gas.

b. Calculate how much work the gas performed

c. Calculate H and U of the gas.

Solution

At the beginning: n = 1, T1 = 273 K, P1 = 1 atm : we first calculate V1.

RT1 0.08206 * 273

V1    22.4 liters
P1 1atm

7
H  3000  *8.3144* T
2
6000
a. T   103K T2  376 K
7 *8.3144

0.08206*376
V2   30.85 liters
1atm
101.32 J
b. w  PV  1atm *(30.85  22.4) liter  atm*  856 Joules
liter  atm

H  3000 Joules
c.  
U  Q  w  3000  856  2144 Joules

10
Problem 2.6

Ten moles of monatomic ideal gas, in the initial state P1 = 10 atm, T1 = 300 K, are

taken round the following cycle:

a. A reversible change of state along a straight line path on the P-V diagram to

the state P = 1 atm, T = 300 K,

b. A reversible isobaric compression to V = 24.6 liters, and

c. A reversible constant volume process to P = 10 atm.

How much work is done on or by the system during the cycle? Is this work done

on the system or by the system?

Solution 1

We first calculate the volume at 2. P1V1 = P2V2 since isothermal.

Thus V2 = 10V1.

l  atm
10 mole  0.08206  300 K
mole  deg ree
V1   24.62 l
10 atm
V2  10V1  246.2 l

The path of the cycle is shown below.

The area of the triangle is the work done by the gas going around the
11
cycle. This area

1
w ( P2  P1 )  (V2  V1 )
2
1 8.3144 J
w  (10  1)atm  (2462  24.62) l   101.01 kJ
2 0.08206 l  atm

Solution 2

Another way to solve it is the integrate the functions along their paths.

The line from 1 to 2 has the equation: P = -(0.041)*V + 11. Thus:

l  atm
10 mole  0.08206  300 K
mole  deg ree
As before V1   24.62 l
10 atm
V2  10V1  246.2 l

From 1 to 2 along P  (0.0406)V  11 we have:

V2
w   (0.0406*V  11)dV
V1

0.0406 2 246.2
= V 24.62  11 (246.2  24.62)  1219l  atm  123.48 kJ / mole
2
From 2 to 3 along P  1 we have:
8.3144 J
w  1atm  (246.2  24.62)l   22.45 kJ / mole
0.08206l  atm
Total work  123.48  22.45  101.03 kJ / mole

12
Problem 2.7

One mole of a monatomic ideal gas at 25°C and 1 atm undergoes the following

reversibly conducted cycle:

a. An isothermal expansion to 0.5 atm, followed by

b. An isobaric expansion to 100°C, followed by

c. An isothermal compression to 1 atm, followed by

d. An isobaric compression to 25°C.

The system then undergoes the following reversible cyclic process.

a. An isobaric expansion to 100°C, followed by

b. A decrease in pressure at constant volume to the pressure P atm, followed by

c. An isobaric compression at P atm to 24.5 liters, followed by

d. An increase in pressure at constant volume to 1 atm.

Calculate the value of P which makes the work done on the gas during the first cycle

equal to the work done by the gas during the second cycle.

Solution

l  atm 298K
T1  298K P1  1 atm V1 =0.08206  = 24.45l
mole  K 1atm
The First Cycle:
1  2 T2  298K P2  0.5 atm V2 =2  V1 = 48.9l
V2
Thus : w  RT ln  8.3144  298  ln 2  1717 J
V1
l  atm
0.08206  373
2  3 T3  373K P2  0.5 atm V2  mole  K  61.22l
0.5 atm
J
Thus : w  P(V3  V2 )  0.5atm( 61.27  48.9 )l 101.32  624 J
l  atm

13
 l  atm
0.8206  373K
3  4 : T4  373K P4  1 atm V4  mole  K  30.61l
1atm
V4 J
w  RT ln  8.3144  373K  ln( 0.5 )  2150 J
V3 mole  K
J
4 2 1: w  P4 (V1  V4 )  1atm  ( 24.45  30.61 )l 101.32  624 J
l  atm

Now for the second cycle:

l  atm 373K
1  2: P2  1 atm, T2  373K , V2  0.08206   30.61l
mole  K 1 atm
l  atm
w  P2 (V2  V1 )  1atm  ( 30.61  24.45 )l 101.32  624 J
mole  K
2  3 V  0, w  0
3  4 V4  24.45, P4  P
l  atm
 w  P( 24.5  30.61 ) 101.32  619 P J
mole  K
4  1: V  0, w  0

w first cycle   wsec ond cycle

1717  624  2150  624  624  619 P
P  0.3 atm

14
Problem 2.8

One mole of a monatomic ideal gas at standard temperature and pressure (STP)

undergoes the following three processes:

a. at constant Pressure the Temperature is doubled.

b. at constant Temperature the Pressure is doubled

c. the gas is returned to STP via constant volume process

Calculate U, H, q and w for each of the steps.

Solution

First calculate the values of T, V and P at the states A, B and C.

Step 1

T V P
A TA VA PA
B 2TA 2VA PA
C 2TA VA 2PA

Step 1 A B

H1  cP T  cP (2TA  TA )  cPTA

U1  H1  PA V  cPTA  PAVA  cV TA
w1  PA V  PA (2VA  VA )  PAVA  RTA
q1  U  w  CV TA  RTA  (CV  R)TA  cPTA

Step 2 BC

H 2  U 2  0 isothermal
VC RTB VC dV V
w2   dV  2 RTA   2 RTA ln C  2 RTA ln(2)
VB V V B V VB
q2  w  2 RTA ln(2)

15
Step 3 CA

U 3  cV T  cV (TA  2TA )  cV TA

H 3 = U 3  VA PA  cV TA  RTA  cPTA
RT
VA
w3   dV  0 since VC  VA
V
VC

q3  U 3  cV TA

Thus we see that for the entire process:

 U  c T  0  c T  0 as it should for a state function

i V A V A

 H  c T  0  c T  0 as it should for a state function

i P A P A

 w  RT  2 RT ln(2)  0  RT (1  2 ln(2))
i A A A

 q  c T  2 RT ln(2)  c T  RT  2 RT ln(2)  RT (1  2 ln(2))

i P A A V A A A A

w  q
i i since  U i  0

16
Problem 2.9*

M constant C
Paramagnetic salts often obey the Curie relation:   
H T T

Obtain an expression for the work needed to change the magnetization from
 
M  0 to M  M of such a material. Assume that the field and the magnetization

are parallel.

Solution

Mf Mf TM TM 2f H f M f
w H  dM    dM  
0 0 C 2C 2

TM 2f
From the equality w  we see that to get to the same M at higher temperature,
2C

more work is needed. Temperature works against the ordering of the moments.

Hf M f
From the equality w  we see that the work needed is the area under the linear
2

H vs. M plot.

17
Problem 2.10*

One mole of an ideal gas is taken on the path A B  C D A as shown in

Figure 2.7

(1) A B is a reversible isothermal expansion of the gas;

(2) B  C is a reversible adiabatic expansion of the gas;

(3) C D is a reversible isothermal compression of the gas

(4) D  A is a reversible adiabatic compression of the gas.

a. Derive expressions for U, q and w during each step in terms of Va, Vb, Vc, Vd, t1,

t2 cV and R. Determine the sign of each.

b. Determine the values of wi), qi) and Ui) in terms of Va, Vb, Vc, Vd, t1, t2

and R. Determine the sign of each.

Figure 2.7

18
Solution

Vb
(1) A  B U1  0; w1  q1  Rt2 ln( ) >0
Va
(2) B  C q2  0; U 2  cV (t 2 -t1 )  0;  w2 =U 2 so w 2 > 0
Vd
(3)C  D U 3  0; w3  q3  Rt1 ln( ) <0
Vc
(4) D  A q4  0 ; U 4  cV (t 2 -t1 ) > 0 -w4  U 4 so w 4 < 0

Vb V
SUM w i  Rt2 ln(
Va
)  Rt1 ln( d )  0
Vc
Vb V
q i Rt2 ln(
Va
)  Rt1 ln( d )  0
Vc
U  0

19
Problem 2.11*

The change in enthalpy when one mole of solid water (ice) is melted at

273 K is 6008 J.

a. Calculate the change in enthalpy when ice is melted at 298 K. Is this process

possible at 1 atm?

b. Calculate the change in enthalpy when supercooled water solidifies at 260 K.

c. Sketch the H vs. T plot for both solid and liquid water.

For this problem take the heat capacity of liquid water to be 75.44 J/k and that of solid

water to be 38 J/K over the range in temperatures of the problem. The enthalpy of

liquid water at 298 K may be set equal to zero.

Solution:

a.
273 T
H HS 2 0 (T )   cPL dT  H m   cPS dT
298 273

 75.44(273  298)  6008  38(T  273) J

 7894  38(T  273) J
T
H HL 2 0 (T )   cPLdT  75.44(T  298) J
298
Thus
H M  H L (298)  H S (298)
 0  ( 7894)  38  (298  273)
 6944 J.
Yes, ice can be superheated

b.

H fusion  H S (260)  H L (260)

H L (260)  75.44(260  298)  2866.72
H S (260)  7894  38((260  273)  8388
H fusion  ( 8388)  ( 2866.72)  5521.28 J

20
c.

21
Problem 2.12*

Three phases,  and  meet as shown in Fig. 2.8a, forming three interphase

interfaces, namely the , the  and the It can be shown that the

following holds

  /  
  /   /
sin  3 sin  2 sin 1

Using the above equation determine the equation that relates the grain boundary

grooving angle gb to the interface energy /L and the grain boundary energy .

See Fig. 2.8b.

Solution

 gb 
  /L
sin  groove sin  / L
 groove  2 / L  2
 groove  groove
sin  / L  sin(  )  sin( )
2 2
 gb  /L

                            
sin  groove  groove   
sin( )
2
using: sin(2 X )  2sin( X ) cos( X )

sin  groove  / L  groove

 gb   2  / L cos( )
 groove 2
sin( )
2

22
Chapter 3
Problem 3.1

The initial state of one mole of a monatomic ideal gas is P = 10 atm and T = 300 K.

Calculate the change in the entropy of the gas for:

(a) an isothermal decrease in the pressure to 5 atm,

(b) a reversible adiabatic expansion to a pressure of 5 atm,

(c) a constant-volume decrease in the pressure to 5 atm.

SOLUTION

0.08206 liter atm 300 K

P1  10 atm T1  300 K V1   2.462 liters
10 atm

PV
a. P2  5 atm T2  300 K V2  1 1
 2 2.462 = 4.924 liters
P2
V2 Joules
S = Rln  R ln 2  8.3144 Joules ln 2  5.76
V1 K

b. q  0 since reversible: S  0.
The work done by the gas equals the decrease in the internal energy of the gas.

PV 5 atm 2.462 liters

c. P2  5 atm V2  2.462 liters T2  2 2
  150 K
R 0.08206 liter atmK 1

T2 cal Joule 1 Joule

S = cV ln  1.5  8.3144  ln =  8.65
T1 K cal 2 K

23
Problem 3.2

One mole of a monatomic ideal gas is subjected to the following sequence of steps:

a. Starting at 300 K and 10 atm, the gas expands freely into a vacuum to triple

its volume.

b. The gas is next heated reversibly to 400 K at constant volume.

c. The gas is reversibly expanded at constant temperature until its volume is

again tripled.

d. The gas is finally reversibly cooled to 300 K at constant pressure.

Calculate the values of q and w and the changes in U, H, and S.

Solution

, ,

(a) 12 ,

(b) 23 ,

(c) 34 ,

(d)45

24
 w q
12 0 0 0 0 9.134
23 1247 2078 0 1247 3.588
34 0 0 3654 3654 9.134
45 -1247 -2078 -831 -2078 -5.980
Sum 0 0 2823 2823 15.88

25
Problem 3.3

One mole of a monatomic ideal gas undergoes a reversible expansion at constant

pressure during which the entropy of the gas increases by 14.41 J/K and the gas

absorbs 6236 joules of thermal energy. Calculate the initial and final temperatures of

the gas. One mole of a second monatomic ideal gas undergoes a reversible isothermal

expansion during which it doubles its volume, performs 1729 joules of work and

increases its entropy by 5.763 J/K. Calculate the temperature at which the expansion

was conducted.

Solution

S  S (T , P )
 S   S   S 
dS    dT    dP    dT at dP  0
 T  P  P T  T  P
c
dS gas  P dT  14.41
T
J T T
S gas  14.41  cP ln 2  2.5  8.3144  ln 2
K T1 T1
T2
Thus 2
T1

Also: qP  6236 J  cP (T2  T1 )  2.5  8.3144  (T2  T1 )

Thus (T2  T1 )  300

T1  300 T2  600

26
Problem 3.4

Calculate the change in the enthalpy and the change in entropy when 1 mole of SiC is

heated from 25°C to 1000°C. The constant pressure molar heat capacity of SiC varies

with temperature as

cp = 50.79 + 1.97 × 10–3 T – 4.92 × 106T–2 + 8.20 × 108T–3 J/moleꞏK

Solution

27
Problem 3.5

One mole of copper at a uniform temperature of 0°C is placed in thermal contact with

a second mole of copper which, initially, is at a uniform temperature of 100°C.

Calculate the temperature of the 2 mole system, which is contained in an adiabatic

enclosure, when thermal equilibrium is attained. Why is the common uniform

temperature not exactly 50°C? How much thermal energy is transferred, and how

much entropy is produced by the transfer? The constant pressure molar heat capacity

of solid copper varies with temperature as

cp = 22.64 + 6.28 × 10–3T J/moleꞏK

Solution

CP increases with increasing T. caused by withdrawing heat q from hot Cu is

less than caused by adding heat q to cold Cu.

28
Problem 3.6

A reversible heat engine, operating in a cycle, withdraws thermal energy from a high-

temperature reservoir (the temperature of which consequently decreases), performs

work w, and rejects thermal energy into a low-temperature reservoir (the temperature

of which consequently increases). The two reservoirs are, initially, at the temperatures

T1 and T2 and have constant heat capacities C1 and C2, respectively. Calculate the final

temperature of the system and the maximum amount of work which can be obtained

from the engine.

Solution

The process is said to be reversible, thus

S  0  S source  S sin k
T final dT2 T final dT1
Thus, T2
C2
T2
 
T1
C1
T1
C2 C1
T   T 
  final   1  and thus
T
 T2   final 
1
T final  T1C1T2C2  C1 C2

w  q2  q1   C2 ( T final  T2 )  C1( T final  T1 )

29
Problem 3.7*

In deriving the equation for the efficiency of a Carnot engine in Section 3.11 it was

VB VC
stated that  . Show that this equality is valid.
V A VD

Solution

Along the adibatic curve BC

PBVB  PCVC
since the gas is ideal
PBVB  RT2 and PCVC  RT1

Thus T2VB 1  TV
1 C
 1

or T21 VB  T11 VC (i)

Also, along the DA adiabatic curve

PDVD  PAVA
since the gas is ideal
PDVD  RT1 and PAVA  RT2

 1
Thus TV
1 D  T2VA 1
or T11 VD  T21 VA (ii)

T21 VB T11 VC VB VC
Dividing (i) by (ii) we obtain:  : 
T21 VA T11 VD VA VD

30
Problem 3.8*

This problem picks up from Problem 2.11. Use data from that problem for this one.

a. Calculate the change in entropy at 273 K for the freezing of water.

b. Calculate the change in entropy for the freezing of water at 260 K.

The change in enthalpy when one mole of solid water (ice) is melted at

273 K is 6008 J. Take the heat capacity of liquid water to be 75.44 J/K and that of

solid water to be 38 J/k over the range in temperatures of the problem.

Solution

The change in entropy of one mole of water on freezing at its

a. equilibrium freezing temperature is:
H L S 6008 J J
  22.01
273 273 K K

b. The freezing of water at 260 K is an irreversible process since 260 is below the

Equilibrium freezing point of water. But since entropy is a state function we

can perform a cyclic calculation as shown below:

31
S L S (260)  S S260273  S S  L (273)  S L273260  0
273 273
CS 6008 J CL
S L S (260)   P dT    P dT  0
260
T 273 K 260 T
273 6008 J 260
S L S (260)  38ln   75.44 ln 0
260 273 K 273
S L S (260)  1.85  22.01  3.68  0
J
S L S (260)  20.18
K

32
Problem 3.9*

Calculate the work performed by the Carnot cycle shown in Fig. 3.4 using the T-S

diagram of Fig. 3.9.

Solution

The area enclosed by the box in Fig.3.9 is first calculated.

Area = (t2 – t1)S

Where S = SC – SD = SB - SA

q1
 ( S B  S A )  S
t2
q2
 ( S D  SC )  ( SC  S D )  S
t1

w  q2  q1  t2 S  t1S
w  (t2  t1 ) S , the area of the box in the T-S plot

33
Chapter 4
Problem 4.1

A rigid container is divided into two compartments of equal volume by a partition.

One compartment contains 1 mole of ideal gas A at 1 atm, and the other contains 1

mole of ideal gas B at 1 atm.

a. Calculate the increase in entropy which occurs when the partition between the two

compartments is removed.

b. If the first compartment had contained 2 moles of ideal gas A, what would have

been the increase in entropy when the partition was removed?

c. and d. Calculate the corresponding increases in entropy in each of the above two

situations if both compartments had contained ideal gas A.

SOLUTION
a. After the removal of the partition, each gas doubles its volume. Thus:

SA = Rln2

SB = Rln2

Thus: STOT = 2Rln2 = Rln22 = Rln4

b. The volume occupied by the 2 moles of A doubles: SA = 2Rln2

The volume occupied by the 1 mole of B doubles: SB = Rln2

Thus: STOT = 3Rln2 = Rln23 = Rln8

c. For the case of 1 mole of A in both sides there is no change in entropy when the
partition is removed. The macrostate after the removal of the partition is identical to
the macrostate before the removal of the partition.

34
d. Double the volume of the 2 moles of A Thus: S = Rln4

Remove partition S = 0

Now return the volume of the 3 mole of the gas to the original total volume which
is 2/3 of the new volume. Hence S = 3Rln(2/3)

Thus the total change in entropy is: S = 2Rln2 + 3Rln2 - 3Rln3 = 5Rln2 – 3Rln3 =
Rln(32/27)

35
Problem 4.2

Show that, when n atoms of A and n atoms of B form a randomly mixed solution, the

fraction of the total number of distinguishable complexions which occur in the most

probable distribution decreases with increasing value of n.

SOLUTION
(2n)!
The total number of distinguishable complexions
n !n !

If n is a multiple of 4, the number of complexions in the most probable distribution is

n! n!

n n n n
  !  !   !  !
2 2 2 2
2
 
 n! 
 
  n  ! n  ! 
2 2   n !
4
    
Therefore the fraction f (n)  
(2n)!  n  
4

n !n !   2   (2n)!
!
  
This decreases with n

36
Problem 4.3

Assuming that a silver-gold alloy is a random mixture of gold and silver atoms,

calculate the increase in entropy when 10 g of gold are mixed with 20 g of silver to

form a homogeneous alloy. The gram atomic weights of Au and Ag are, respectively,

198 and 107.9.

SOLUTION
10 gm
nAu  the number of atoms of Au =  6.023 23  3.042  1022
198 gm / mole
20 gm
nAg  the number of atoms of Au =  6.023 23  1.117  1022
107.9 gm / mole
(n  nAg )!
Sconf  k B ln Au
nAu !nAg !
using Stirling's approximation we get:
Sconf  k B  (nAu  nAg ) ln(nAu  nAg )  (nAu ) ln nAu  nAg ln nAg 
Sconf  1.3805 1023  7.547  1.575  5.925 1024
Sconf  1.02 J / K

37
Problem 4.4

On the assumption that copper-nickel alloys are random mixtures of copper and nickel

atoms, calculate the mass of copper which, when mixed with 100 g of nickel, causes

an increase in entropy of 15 J/K. The gram atomic weights of Cu and Ni are,

respectively, 63.55 and 58.69.

SOLUTION
100 gm
nNi  the number of atoms of Ni =  6.023  1023  1.026  1024
58.69 gm / mole
nCu
(nNi  nCu )!
Sconf  15 J / K  k B ln
nNi !nCu !
using Stirling's approximation we get:
Sconf  15 J / K  k B  (nNi  nCu ) ln(nNi  nCu )  (nNi ) ln nNi  nCu ln nCu 
Sconf  1.3805 1023[(1.026 1024  nCu ) ln(1.026 1024  nCu )
 1.026  1024 ln(1.026  1024 )  nCu ln nCu ]
nCu  6.161 1023
6.161 1023 atoms
mass of Cu is therefore:  63.55 gm / mole  65 gm
6.023  1023 atoms / mole

38
Problem 4.5*

We saw in Sec. 4.6 (Eq. 4.20) that A  nk BT ln Z . We will see in the next chapter

 A 
that:     S . Perform the differentiation of A with respect to temperature and
 T V

obtain the relationship for the entropy of an isolated system in terms of its partition

function Z.

Solution

A   nk BT ln Z
 A   ln Z
    S   nk B ln Z  nk BT
 T V T
Thus
 ln Z
S  nk B ln Z  nk BT
T

Note that if we multiply both sides by T we obtain:

 ln Z
TS   A  nk BT 2
T
 ln Z
Thus: U  nk BT 2
T

39
Problem 4.6*

A weak magnetic field is applied to a system of up and down spins. The up spins

have a slightly lower energy state than those with down spins. This is because the up

spins are favored by the weak magnetic field. Thus

  
a. Determine the partition function for this system under the influence of the weak

magnetic field.

n
b. Determine the ratio of:  for very high temperatures and very low temperatures.
n
SOLUTION

i  
a. Z   exp( )  exp( )  exp( )
k BT k BT k BT
   
exp( ) exp( )
n k BT n k BT
 and 
n     n    
exp( )  exp( ) exp( )  exp( )
k BT k BT k BT k BT

  
exp(
) 1 
n k BT n k BT
b. at high T:   as T gets large:  1
n  
n 

exp( ) 1
k BT k BT
equal numbers of up and down

 
exp( )
n k BT  
as T  0:   exp( )
n   k BT
exp( )
k BT
The numerator of the exponental is positive: Thus as T gets small the exponential get large.
As T  0 n  n and n  0

40
Chapter 5

Problem 5.1

 S  cp
Show that   
 V  P TV 

Solution

Use the third TdS equation

cV T cp
TdS  dP  dV
 V

cp
at constant P dS  dV
TV 

 S  cp
  
 V  P TV 

 S  cp
Note: this shows that    > 0. Increasing the volume of a material
 V  P TV 

inceases the entropy of the material if  is > 0 (which is usual).

41
Problem 5.2

 S  c p βT
Show that     V
 P V T

Solution

Use the third TdS equation

cV T cp
TdS  dP  dV
 V

cV T
at constant V dS  dP
T

 S  c 
   V T
 P V T

VT 2
But cV  cP 
T
 VT 2 
c
 P  
 S   T  T cP T
     V
 P V T T

42
Problem 5.3

 A  Sβ
Show that    
 P V 

Solution

First we write the total derivative of A with the variables T and V.

 A   A 
dA    dT    dV
 T V  V T

 A   A   T 
      
 P V  T V  P V

 A   T  βT
   S and   
 T V  P V α

 A  Sβ
    T
 P V α

43
Problem 5.4

 A   S 
Show that      P
 V  P  V 

Solution

First we write the total derivative of A with the variables T and P.

 A   A 
dA    dT    dP
 T  P  P T

 A   A   T   A  1
       
 V  P  T  P  V  P  T  P αV

Next, we write the total derivative of A with the variables T and V

dA = – SdT – PdV

 A   V 
   S  P  
 T  P  T  P

 A  1
     S  PV 
 V  P V

 S 
   P
  V 

44
Problem 5.5

 H   V 
Show that    T 1  
 S V  cvβ 

Solution

 H   H 
dH    dT    dV
 T V  V T

 H   H   T 
     
 S V  T V  S V

 T  T
TdS  δqv  cv dT   
 S V cv

H = U + PV

 H   U   P 
    V  
 T V  T V  T V
 P   S 
    Maxwell 5.34
 T V  V T
 S  
   from the first TdS equation
 V T T

 H   U   S  Vα
    V    cv 
 T V  T V  V T βT

 H  T  Vα   Vα 
   cv    T 1  
 S V cv  βT   cvβT 

45
Problem 5.6

 H  cp
Show that   
 V  S cvβT

Solution

dH = TdS + VdP

 H   P 
  V  
 V  S  V  S

 P  cP
From the third TdS equation:  
 V  S cV V T


 H   cP  cP
  V  
 V  S  cV V T  cV T

46
Problem 5.7

 c   d 
Show that  p   TV   2  
 P T  dT 

Solution

 H   c p     H      H  
cp             
 T  P  P T  P  T  P T  T  P T  P
 H   S   S   V 
  T    V and     
 P T  P T  P T  T  P
 c     V  
 p    T   V 
 P T T   T  P P

  TV  V P
T
d
 V  TV  T  2V  V
dT
 d 
 TV   2  
 dT 

47
Problem 5.8

 T  T V
Show that   
 P  S cp

Solution i.

From the 2nd TdS equation we write:

TdS  0  cP dT  TV  dP
 T  TV 
  
 P  S cP

Solution ii. (from previous editions)

 S  cp  S   V 
   and        V
 T  P T  P T  T  P

 S 
 
 T   P T  αVT
  
 P  S  S  cp
 
 T  P

48
Problem 5.9

 P  cp
Show that   
 V  S cvVβT

Solution i.

From the 3rd TdS equation we write:

cV T cP
TdS  0  dP  dV
 V
cP
 P  V cP
  c  
 V  S V T VcV T


Solution ii. (from previous editions)

 S 
 
 P   V  P
   
 V  S  S 
 
 P V
 S   S 
dS    dT    dV
 T V  V T
 V 
    
 S   S   T  cv  P T c βV cvβ
 
       v 
 P V  T V  P V T  V  T αV Tα
 
 T  P
 S   S 
dS    dT    dP
 T  P  P T
 S   S   T  cp 1
      
 V  P  T  P  V  P T αV
 P  cp
  
 V  S cvVβ

49
Problem 5.10

  2G  1
Show that  2    2
 P T  A
 2
 V T

Solution

dG = – SdT + VdP

 G    2G   V 
  V and  2    
 P T  P T  P T

dA = – SdT – PdV

 A   2 A   P  1
    P and  2      2
 V T  V T  V T  G
 2
 P T

50
Problem 5.11

Joule and Thomson showed experimentally that when a steady stream of non-ideal

gas is passed through a thermally insulated tube, in which is inserted a throttle valve,

the temperature of the gas changes and the state of the gas is changed from P1, T1 to

P2, T2. Show that this process is isenthalpic. The change in T is described in terms of

the Joule-Thomson coefficient, µJ–T, as

 T 
μ J T   
 P  H

Show that

V
μ J T   1  T 
cp

and show that the Joule-Thomson coefficient for an ideal gas is zero

Solution
a. The process is adiabatic. Therefore q = 0

H  U   ( PV )   q   w  ( PV
2 2  PV
1 1)

 q  0 inssulated tube, hence it is adiabatic

work done by the gas entering the throttle = PV
1 1

work done on the gas exiting the throttle = PV

2 2

Thus : H  ( PV
1 1  PV
2 2 )  ( PV
2 2  PV
1 1)  0

 T 
b. μ J T   
 P  H

51
  H 
  
But
 T 
   P T   1  H 
   
 P  H  H  c p  P T
 
 T  P
 H   S   V 
And    T    V  T    V  TαV  V
 P T  P T  T  P
1 V
 μ J T   ( TV  V )  ( T  1)
cp cp

c. For an ideal gas

1
 , so  T  1 and μ J 1  0
T

52
Problem 5.12

Determine the values of ΔU, ΔH, ΔS, ΔA, and ΔG for the following processes. (In (c),

(d), and (e) show that an absolute value of the entropy is required).

a. The four processes in Prob. 4.1.

b. One mole of an ideal gas at the pressure P and the temperature T expands

into a vacuum to double its volume.

c. The adiabatic expansion of mole of an ideal gas from P1, T1 to P2, T2.

d. The expansion of mole of an ideal gas at constant pressure from V1, T1 to

V2 , T 2 .

e. The expansion of mole of an ideal gas at constant volume from P1, T1 to

P2 , T 2 .

Solution

a l. ΔU = ΔH = 0, ΔS = R ln 4, ΔA = ΔG = –TΔS –= RT ln 4
2. ΔU = ΔH = 0, ΔS = R ln 8, ΔA = ΔG = –RT ln 8
3. ΔU = ΔH = ΔS = ΔA = ΔH = 0
4. ΔU = ΔH = 0, ΔS = R ln(32/27), ΔA = ΔG = –RT ln(32/27)
b ΔU = ΔH = 0, ΔS = R ln(V2/V1) = R ln 2, ΔA = ΔG = –RTln 2
c ΔU = cv(T2 – T1), ΔH = cp(T2 – T1), ΔS = 0, ΔA = ΔU – S(T2 - T1),
ΔG = ΔH – S(T2 – T1)
d ΔU = cv(T2 – T1), ΔH = cp(T2 – T1), ΔS = cp ln(T2/T1),
ΔA = ΔU – (T2 – T1)S1 – T2ΔS, ΔG = ΔH – (T2 – T1)S1 – T2ΔS
e ΔU = cv(T2 – T1), ΔH = cp(T2 – T1), ΔS = cv ln(T2/T1),
ΔA = ΔU – (T2 – T1)S1 – T2ΔS, ΔG = ΔH – (T2 – T1)S1 – T2ΔS

53
Problem 5.13*

Show that the three TdS equations can be written as:

T
1. TdS  cV dT  dV
T
2. TdS  cP dT  TV  dP
T c
3. TdS  cV dP  P dV
 V

Solution

 P 
1. TdS  vV dT  T   dV
 T V

 P 
We need to obtain an expression for  
 T V

 P   T   V 
       1
 T V  V  P  P T
 P  1 V 
    T  
 T V    V    TV  T
   
 V  P  P T


TdS  cV dT  T dV
T

 V 
2. TdS  cP dT  T   dP
 T  P

54
  V 
We need an expression for  
 T  P
 V 
We know that    V
 T  P
Thus
TdS  cP dT  TV  dP

 T   T 
3. TdS  cV   dP  cP   dV
 P V  V  P

 T   T 
We need expressions for   and  
 P V  V  P

 T  T
  = see first TdS equation above
 P V 

 T  1
  
 V  P V

Thus

T c
TdS  cV dP  P dV
 V

55
Problem 5.14*

Starting from the following equation valid for a closed system, obtain the Maxwell
relations.

dH = TdS + VdP – V0MdH

Solution

 T   V 
   
 P  S ,H  S  P ,H
 V   M 
   V 0  
 H  S , P  P  S ,H
 T   M 
   V 0  
 H  S , P  S  P ,H

56
Problem 5.15*

Starting from the following equation valid for a closed system, obtain Maxwell

relations.

dA = –SdT – PdV+V0HdM

Solution

 S   P 
   
 V T , M  T V , M
 S   H 
   V 0  
 M T ,V  T  M ,V
 P   H 
   V 0  
 M V ,T  V  M ,T

57
Problem 5.16*

The cycle shown below consists of two isotherms (AB and CD) and two isobars (BC

and DA). Use the TdS equations to draw the T-S diagram for this cycle.

B C
P

A
D

Solution

Use the following TdS equations

T
1. TdS  cV dT  dV
T
2. TdS  cP dT  TV  dP
T c
3. TdS  cV dP  P dV
 V
AB from 1, at constant T, if V decreases, S decreases

BC from 3, at constant P, V increases then S increases.

From 2, at constant P if S increases T increases

C—D from 2, at constant T if P increases then S increases

D—A from 3, at constant P, if V decreases S decreases

From 2, at contant P is S decreases, T decreases.

58
59
Problem 5.17*

T cP 1  V  1  V 
Show that    , where T    and  S   
 S cV V  P T V  P  S

Hint: use the TdS equations.

Solution

Start with the First and Second TdS equations:

T
1. TdS  cV dT  dV
T
2. TdS  cP dT  TV  dP
Set S = 0 and divide 2 by 1

T
1. cV dT   dV
T
2. c P dT  TV  dP

cP TV   dP  1 
    V  T   T
cV T   dV  S V  S   S
T

60
Chapter 6
Problem 6.1

Calculate ΔH1600 and ΔS1600 for the reaction Zr(β) + O2 = ZrO2(β).

Solution

For Zr() + O2 = ZrO2() H298 = -1,101,800 J (page 653)

For Zr() + O2 = ZrO2() in the range 298- 1136K

cP =17.69 – 8.2x10-3 T-12.39x105 T-2 J/K

At 1136K Zr()Zr() H = 3900 J

For Zr() + O2 = ZrO2() in the range 1136-1478K

 cP =16.44– 1.29x10-3 T-12.39x105 T-2 J/K

At 1478K Zr()Zr() H = 5900 J

For Zr() +O2 = ZrO2() in range of 1478-1600 K

 cP =21.3– 8.82x10-3 T+1.67x105 T-2 J/K

Therefore: H1600 for Zr() +O2 =ZrO2() =-

1100800 J+17.69(1136-298)-4.14x10-3(11362-2982) +12.39x105(1/1478-1/1136)

+5900 +21.3(1600-1478) – 4.41x10-3(16002-14782) - 1.67x105(1/1600-1/1478) =

= -1,086,000 J

S298 = 50.4 – 205.1 -39 = -198.7 J/K

Thus S1600 = -193.7 +17.69ln(1136/298) -8.28x10-3(1136-298) +

6.185x105(1/11362 -1/2982) - 3900/1136 +1644xln(1478/1136) - 1.29x10-3 x(1478-

1136) + 6.1.85x105(1/14782 -1/11362) - 0.835x105(1/16002-1/14782) =

-178.5 J/k

61
Problem 6.2

Which of the following two reactions is the more exothermic?

1
1. C(graphite)  O 2( g )  CO( g ) at 1000 K
2

1
2. C(diamond)  O 2( g )  CO ( g ) at 1000 K
2

Solution

Hgraphite,1000 = 0.11(1000-298) +38.94/2x10-3(10002 – 2982) + 1.48x105(1/1000 –

1/298) – 17.38x106/3x(10003 – 298 3) =11830 J

Hdiamod, 1000 = 1500 + 9.12(1000 – 298) + 13.22x10-3/2(10002 – 2982) +

6.19x105(1/1000 – 1/298) = 12867 J

For diamond to graphite

H1000 =11830 – 12867 = - 1037 J

1
For C( graphite )  O2  CO H1
2
C( diamond )  C( graphite ) H  1037 J
1
Thus C( diamond )  O2  CO H1  1037 J
2

Thus, the oxidation of diamond is 1037 J more exothermic than the oxidation of

graphite at 1000 K on a molar basis.

62
Problem 6.3

Calculate the change in enthalpy and the change in entropy at 1000 K for the reaction

CaO(s)+ TiO2(s) = CaTiO3(s).

Solution

Change in Enthalpy
We need to calculate H1000 for each of the compounds.
From Tables A-2, A-3 and A-5

1
For Ca(  )  O2  CaO H 298  634,900 J
2
c P  9.27  9.68 103 T  6.115 105 T 2 (between 298 and 716K)
At 716K: Ca(  )  Ca(  ) H 716  900 J
1
For Ca(  )  O2  CaO between 716 and 1000K
2
c P  35  38.83 103 T  6.115  105 T 2

9.68 1 1
Thus: H1000 =  634 ,900  9.27 * ( 716  298 )  103 ( 7162  2982 )  6.115 105 (  )
2 716 298
38.83 1 1
 900  35( 1000  716 )  103 ( 10002  7162 )  6.115  105 (  )
2 1000 716
 630 ,836 J

For Ti  O2  TiO2 H 298  944, 000 J

c P  23.14  13.47  103 T  16.53  105 T 2 (between 298 and 1000K)
13.47 1 1
Thus: H1000 =  944, 000  23.14* ( 1000  298 )   103 ( 10002  2982 )  16.53 105 (  )
2 1000 298
 922 ,910 J

Thus for CaO + TiO2 = CaTiO3 we have

-922,910 + 630,836 + 933,893 + 630 ,836 = -77,820 J

63
 3
For Ca(  )  Ti  O2  CaTiO3 H 298  1,660 ,600 J
2
c P  35.09  3.78 103 T  25.485 105 T 2 (between 298 and 716K)
At 716K: Ca(  )  Ca(  ) H 716  900 J
3
For Ca(  )  Ti  O2  CaTiO3 between 716 and 1000K
2
c P  60.82  52.29 103 T  25.485 105 T 2

3.78 1 1
Thus: H1000 =  1, 660 , 600  35.09 * ( 716  298 )  103 ( 7162  2982 )  25.485 105 (  )
2 716 298
52.29 1 1
 900  60.82( 1000  716 )  103 ( 10002  7162 )  25.485 105 (  )
2 1000 716
 1, 642548 J

Thus, for CaO + TiO2 = CaTiO3,

H1000 =-1,642,458 + 922,910 + 630,836 = -88,712

Change in Entropy
We need to calculate S1000 for each of the compounds

1 205.1
For Ca(  )  O2  CaO S298  38.1  41.6  =  106.05 J /K
2 2
716 6.115 1 1 900
S1000  106.05  9.27 ln( )  9.68 103 ( 716  298 )  105 ( 2
- 2
) +
298 2 716 298 716
1000 6.115 1 1
35 ln( )  38.83 103 ( 1000  716 )  105 ( - )  94.85 J / K
716 2 1000 7162
2

For Ti  O2  TiO2 S 298  50.6  205.1  30.7  185.2 J/K

1000 22.76 16.53 1 1
Thus: S1000 =  185.2  23.14 ln( ) * 103 * ( 1000  298 )   105 (  )  175.1 J / K
298 2 2 1000 2982
2

3
For Ca(  )  Ti  O2  CaTiO3
2
3
S 298  93.7  41.6  30.7   205.1  286.25 J/K
2
716 25.485 1 1
S1000  286.25 + 35.09 ln  3.78  103 ( 716  298 )  105 ( - )
298 2 716 2982
2

900 1000 25.485 1 1

 + 60.82 ln  52.29  103 ( 1000  716 )  105 ( - ) =  265.9 J / K
716 716 2 1000 7162
2

Thus, for CaO +TiO2 = CaTiO3, S1000 =-265.9+ 94.85 + 175.1 = 4.05 J/K
64
Problem 6.4

Copper exists in the state T = 298 K, P = 1 atm. Calculate the temperature to which

the copper must be raised at 1 atm pressure to cause the same increase in

molar enthalpy as is caused by increasing its pressure to 1000 atm at 298 K. The

molar volume of Cu at 298 K is 7.09 cm3, and the volumetric coefficient of thermal

expansion is 0.501 × 10–4 K–1. These values can be taken as being independent of

pressure in the range 1–1000 atm.

Solution

State 1: P1  1 atm T1  298 K

State 2: P1  1000 atm T2  ?
Also from Taable A.2 (page 652) c P  22.64  6.28T

H  Vm ( 1   T )( P2  P1 )
l J
 7.09 103 ( 1  0.493 103 K 1  298 K )( 1000  1 )atm 101.3
mole l  atm
J
 612.6
mole

T
H   cP dT
T1

J 6.28  103 2
609.1  22.64( T  298 )  ( T  2982 )
mole 2
T  327.6 K

65
Problem 6.5

Calculate ΔH298 and ΔS298 for the following reactions:

1
a. 2 TiO+ O 2  Ti 2 O3
2

1
b. 3 Ti 2 O3  O 2  2Ti3O5
2

1
c. Ti3O5  O2  3TiO 2
2

Solution

See Table A.3

a.

1
2 TiO+ O 2  Ti 2 O3
2
H 298  H 298 (Ti 2 O3 )  H 298 (TiO)  1,521, 000  2 x(543, 000)  435kJ

1
2 TiO+ O 2  Ti 2 O3
2
1
S 298  S 298 (Ti 2 O3 )  2 xS 298 (TiO)  S 298 (O2 ) 
2
1 J
77.2  2 x34.7  x 205.1  94.75
2 K

b.

1
3 Ti 2 O3  O 2  2Ti3O5
2
H 298  2 xH 298 (Ti3O5 )  3 xH 298 (Ti 2 O3 )  355kJ

66
 1
3 Ti 2 O3  O 2  2Ti3O5
2
1
S 298  2 xS 298 (Ti3O5 )  3 xS 298 (Ti 2 O3 )  S 298 (O2 ) 
2
1 J
2x129.4  3 x77.2  205.1   75.35
2 K

c.

1
Ti3O5  O 2  3TiO 2
2
H 298  3 xH 298 (TiO 2 )  H 298 (Ti3O5 ) 
3 x(944)  (2459)  373kJ

1
Ti3O5  O 2  3TiO 2
2
1
S 298  3S 298 (TiO 2 )  S 298 (Ti3O5 )  S 298 (O2 ) 
2
1 J
3 x50.6  129.4  x 205.1  80.15
2 K

67
Problem 6.6

An adiabatic vessel contains 1000 g of liquid aluminum at 700°C. Calculate the mass

of Cr2O3 at room temperature, which, when added to the liquid aluminum (with which

it reacts to form Cr and Al3O3) raises the temperature of the resulting mixture of

Al2O3, Cr2O3, and Cr to 1600 K.

Solution

We need the value of H973 for the reaction: 2 Al  Cr2O3  2Cr  Al2O3
From Table A-3: Between 298 and 934K, the melting point of Al
H 298  1, 675, 700  1,134, 700  541, 000 J
From Table A-2: Between 298 and 934K,
c P  5.25  3.46  103 T  20.24 105 T 2 J / K
At 934 K, Al ( s )  Al (l ) H m =  10,700 J

For 2 Al (l )  Cr2O3  2Cr ( s )  Al2O3

From Table A-2: Between 934K and 973K

c P  27.43  28.22 103 T  20.24 105 T 2 J / K

Thus, for 2 Al (l )  Cr2O3  2Cr ( s )  Al2O3 at 973K we have:

934 973
H 973  H 298   cP dT  2  H MAl   cP dT
298 934

3.46 103 1 1
H 973  541, 000  5.25(934  298)  (9342  2982 )  20.24105 (  )
2 934 298
 2 10, 700
28.22 103 1 1
 27.43(973  934)  (9732  9342 )  20.24105 (  )
2 973 934
=  569,116 J

68
Now the heat required to raise the temperature of one mole of Cr2O 3 from 273 to 973K is:
973 9.3 103 1 1
298
cPCr2O3 dT  119.37(973  298) 
2
(9732  2982 )  15.65 105 ( 
973 298
)

= 80,921J
Thus there is an available sensible heat per mole of reacted Cr2O 3 of:
569,116  80921  488,195 J

To get the system to 1600K, we need to heat the Cr2O 3 , Al2O 3 and Cr from 973 to 1600K
(we assume that we need extra Cr2O 3 for the completion of the reaction)

The heat required to take one mole of Cr2O 3 from 973 to 1600K is:
1600 9.3 103 1 1
973
cPCr2O3 dT  119.37(1600  973) 
2
(16002  9732 )  15.65 105 ( 
1600 973
)

= 82,977 J
The heat required to take one mole of Al2O 3 from 973 to 1600K is:
1600 17.78 103 1 1
973
cPAl2O3 dT  106.5(1600  973) 
2
(16002  9732 )  28.53 105 ( 
1600 973
)

= 80,031 J
The heat required to take one mole of Cr from 973 to 1600K is:
1600 9.87 103 1 1
973
cPCr dT  24.43(1600  973) 
2
(16002  9732 )  3.68 105 ( 
1600 973
)

= 23,131 J
the available sensible heat to be used to increase the excess Cr2O 3 to complete the reaction is:
488,195 - 2  23,131  80, 031  361,902 J
Thus, dividing by the the number of J needed to raise one mole of Cr2O 3 from 973 to 1600K gives:
361,902 J
 4.36 excess moles of Cr2O 3
82,977 J / mole
Thus there were 2 moles of Al which reacted with 5.36 moles Cr2O 3
152 gm of Cr2O 3
Mass of Cr2O 3  5.36moles   815 gm Cr2O 3
mole
Thus 815 gm of Cr2O 3 are neceassry to add to 1000 gm of molten
Al at 973K to raise the temperature of the toal system to 1600K

69
Problem 6.7

Calculate the adiabatic flame temperature attained when methane, at 298 K, is

combusted (a) with oxygen in the molar ratio O2/CH4 = 2.0, and (b) with air in the

molar ratio air/CH4 = 9.524. Assume that CO2 and H2O are the products of

combustion. The adiabatic flame temperature is that temperature reached if all of the

heat of the oxidation reaction is used to increase the temperature of the products of the

reaction. Air is 21 molar percent O2 and 79 molar percent N2.

Solution

First we find the heat of reaction for the transformation at 298 K:

CH4 + 2O2 CO2 + 2H2O

From Table A.3 we obtain the Standard Moalr Heats of Formation of the phases;
298  393,500 J
H CO 2

H 2O
H 298  241,800 J
298  74,800 J
H CH 4

H O2982  0 J

H 298
reaction
 393,500  241,800  74,800  802,300 J
This released heat heats up the product gases from 298 to TAFT

TAFT TAFT
802,300 J   cPCO2 dT   cPH 2O dT
298 298

Heat capacities from Table A.2

 3 1 1 
 44.14  (TAFT  298)  4.52 10 (T AFT  298 )  8.54 10 ( T  298 )
2 2 5

802,300 J   AFT 
 3 1 1 
 2  [30  (TAFT  298)  5.355 10 (T AFT  298 )  0.33 10 ( T  298 )] 
2 2 5

 AFT 
This can be solved iteratively to be TAFT = 4747 K

70
The heat released at 298 from the reaction heats the product gases plus the N 2 to TAFT "
79
For every mole of O2 consumed there is moles of N 2 to be heated.
21
TAFT " TAFT " 79 TAFT " N2
802,300 J   cPCO2 dT  2   cPH 2O dT  2   cP dT
298 298 21 298
Heat capacities from Table A.2
 3 1 1 
 44.14  (TAFT "  298)  4.52  10 (T AFT "  298 )  8.54  10 ( T 
2 2 5
) 
298
 AFT " 
 3 1 1 
802,300 J   2  [30  (TAFT "  298)  5.355 10 (T AFT "  298 )  0.33 10 (
2 2 5
 )] 
 T AFT " 298 
 2  [27.87  (TAFT "  298)  2.135 103 (T 2 AFT "  2982 )] 
 
 
This can be solved iteratively to be TAFT = 2485K

71
Problem 6.8

Calculate the value of ΔG for the reaction

Si3N4 + 3 O2 = 3 SiO2(α – quartz) + 2 N2

at 800 K.

What percentage error occurs if it is assumed that Δcp for the reaction is

zero?

Solution

G800  H 800  T S800

H 298  3  910,999  744,800  1,987,900 J

J
S 298  2 191.5  3  41.5  3  205.1  113  220.8
K
cP  26.99  99.74 103 T  13.05  105  T 2

99.74
Thus : H 800  1,987,900 +26.99(800  298)  103 (8002  2982 )
2
1 1
+13.05  105  (  )  2, 005, 000 J
800 298
800
S800  220.8  26.99  ln  99.74 103 (800  298)
298
13.05 1 1 J
 10  (
5
 )  250.5
2 8002 2982 K
G800  H 800  T S800  2, 005, 000 +800  250.5
 1,805, 000 J

If, cP  0 : G800  H 800  T S800  1,987,900  800  220.8

 1,811, 000 J

1,811, 000  1,805, 000

Error 0.3%
1,805, 000

72
Problem 6.9

Determine the stoichiometric coefficients for the reaction

(3 CaO  Al2 O3  3 SiO 2 )  a (CaO  Al2 O3  SiO 2 ) 

b(CaO  Al2 O3  2 SiO 2 )  c(2 CaO  Al2 O3  SiO 2 )

and calculate ΔH298, ΔS298, and ΔG298 for the reaction.

Solution

We must perform mass alances for each of the stoichiometric compounds

Cao : 3  a  b  2c
Al2O3 : 1  a  b  c
SiO2 : 3  a  2b  c

Solving we obtain: a  3 : b  2 : c  2

Thus, the reaction is written as:

3CaO  Al2O3  3SiO2  3(CaO  Al2O3  SiO2 )  2(CaO  Al2O3  2 SiO2 )  2(2CaO  Al2O3  SiO2 )

H 298  2  (4, 223, 700)  2  (3,989, 400)  (6, 646,300)  3  (3, 293, 200)  99, 700 J

S 298  2  (202.5)  2  (198.3)  (241.4)  3  (144.8)  125.8 J / K

G298  99, 700 J  298 K 125.8 J / K  62, 210 J

73
Problem 6.10

How much heat is required to increase the temperature of 1 kg of cordierite, 2 MgOꞏ2

Al2O3ꞏ5 SiO2, from 298 K to its incongruent melting temperature of 1738 K?

Solution

The molecular weight of cordierite is: 2x40.31 + 2x101.96 + 5x60.09 = 585

cP = 626.34 + 91.21x10-3T – 200.83x105T-2 J/K mole

Thus the heat required per mole is found as :

91.21x103 1 1
 626.34(1738  298)  (17382  2982 )  200.83 x105 (  )
2 1738 298
 979.799 kJ

979799 J
The heat required for 1 kgm = x1000  1, 675 kJ
585

74
Problem 6.11*

A function    A   N , where A is the Helmholtz free energy,  is the chemical

potential and N is the number of particles in the system.

Obtain an expression for dΩ and thus determine the independent variables for this

function.

Solution

d    dA   dN  Nd 
But A  U  TS
So dA  dU  TdS  SdT   PdV  Nd   SdT
Thus d   SdT  PdV  Nd 

  (T , V ,  )

75
Problem 6.12*

(a) Given that the Helmholtz energy can be written as:

F   N system k BT ln Z

Obtain simplified expressions for both F and S of an Einstein solid.

(b) Show that the entropy approaches 0 as the temperature approaches 0 in such a

solid.

Solution

From the text we saw that Q for the Einstein solid can be written as:

 
 1 h   1 
Q  exp -   
 2 kT   1  exp   h 
  
 kT 
F = -N system k BT ln Z
3    h 
F= N system h  3N system kT ln 1  exp  
2   kT 

F   ln Z 
 = S  N sys k B lnZ  N sys kT  
T  T V

 h 
exp   
 h   kT  - N   h 
S  N system k   system k ln 1-exp   
 kT  1-exp   h    kT 
 
 kT 

Since Nsystem = 3n

As t approaches 0

 h 
exp   
 h   kT  - 3nk ln 1-exp   h 
S  3nk     
 kT  1-exp   h    kT 
 
 kT 

76
  h 
exp   
 h   kT  - 3nk ln 1-exp   h 
S  3nk     
 kT  1-exp   h    kT 
 
 kT 
 h 
exp   
 kT   0 as T  0
 h 
1-exp   
 kT 
 h 
1-exp     1 as T  0: ln 1 =0
 kT 
So S  0 as T  0

77
Problem 6.13*

Obtain an expression for the internal energy of an Einstein solid as the temperature
gets very large and differentiate it with respect to T and show that the Dulong and
Petit value for the heat capacity is attained.

Solution

3 3nhv
U' nhv 
2 h
(exp( )  1)
k BT
h h
as T   exp( ) 1
k BT k BT
3 3nhv 3
U' nhv   nhv  3nk BT
2 h
( ) 2
k BT
U '
Thus CV   3nk B  3R for one mole
T

78
Chapter 7
Problem 7.1

Using the vapor pressure-temperature relationships for CaF2(α), CaF2(β) and liquid

CaF2, calculate:

a. The temperatures and pressures of the triple points for the equilibria CaF2(α)

– CaF2(β) – CaF2(v) and CaF2(β) – CaF2(L) – CaF2(v)

b. The normal boiling temperature of CaF2

c. The molar latent enthalpy of the transformation CaF2(α) – CaF2(β)

d. The molar latent enthalpy of melting of CaF2(β)

Solution

See Table A.4

54 ,350
ln PCaF2 (  )    4.525 lnT  56.57
T
53, 780
ln PCaF2 (  )    4.525 lnT  56.08
T
50200
ln PCaF2 ( L )    4.525 lnT  53.96
T

1. At the -vapor triple point:

ln PCaF2 (  )  ln PCaF2 (  )
54 ,350 53,780
  4.525 lnT  56.57    4.525 lnT  56.08
T T
T  1,163K and PCaF2 (  )  2.52 x1010 atm

At the -Liquid-vapor triple point:

ln PCaF2 (  )  ln PCaF2 ( L )
53, 780 50 , 200
  56.08    53.96
T T
T  1689 K PCaF2  8.35 x105 atm

79
 2. The boiling point is determined from the liquid vapor pressure
temperature relationship for P = 1 atm.
50200
ln PCaF2 ( L )  0    4.525 lnT  53.96
T
Tboiling  2776 K

3.. We see from the figure below that:

H(    )  H(   v )  H( v   )

For H(v) equilibrium

54,350
ln PCaF2 (  )    4.525 lnT  56.57
T
d ln PCaF2 (  ) H(   v ) 53, 780 4.525
  
dT RT 2 T2 T
H(   v )  R( 54350  4.526T )

For H(v) equilibrium

53, 780
ln PCaF2 (  )    4.525 lnT  56.08
T
d ln PCaF2 (  ) H(   v ) 53, 780 4.525
  
dT RT 2 T2 T
H(   v )  R( 53780  4.525T )

H() = H(v) - H(v)

= 8.3144(54350 – 53780) = 4,739 Joules

80
4. We see from the figure below that:

H(   L )  H(   v )  H( v  L )

50200
ln PCaF2 ( L )    4.525 lnT  53.96
T
d ln PCaF2 H( L  v ) 50200 4.525
  
dT RT 2 T2 T
H( L  v )  R( 50200  4.525T )
H(   L )  53780  50200 )  29765 Joules

81
Problem 7.2

Calculate the approximate pressure required to distill mercury at 100°C.

Solution

See Table A.4

The saturated vapor pressure of liquid Hg is:

7611
ln P( atm )    40.795 lnT  17.168
T
At T  373K , PHg  3.55 x104 atm

Hg will be distilled at pressures below this value

82
Problem 7.3

One mole of SiCl4 vapor is contained at 1 atm pressure and 350 K in a rigid container

of fixed volume. The temperature of the container and its contents is cooled to

280 K. At what temperature does condensation of the SiCl4 vapor begin, and

what fraction of the vapor has condensed when the temperature is 280 K?

Solution

(i) Assuming ideal behavior of SiCl4, the volume of the container is found to be:

nRT
V  0.082057  350  28.72 liters and cooling causes the pressure
P
of the vapor to decrease according to:
nRT 0.082057
P  T  2.857 103 T .(Table A4)
V 28.72

The saturated vapor pressure of liquid SiCl4 is:

 3620 
P (atm)  exp    10.96 
 T 

And thus condensation begins at T given by

 3620 
2.857 10 3 T  exp    10.96 
 T 

Solving for T we obtain T = 328K.

 3620 
(ii) At 280K the saturated vapor pressure is exp    10.96   0.1396atm
 280 

And the number of moles of SiCl4 in the vapor phase

PV 0.1396  28.72
in    0.175 moles
RT 0.082057  280
The number of moles in the liquid phase is 1-0.175 =0.825 moles and thus 82.5% has

condensed.

83
Problem 7.4

The vapor pressures of zinc have been written as

15, 780
ln p (atm)    0.755ln T  19.25 (i)
T

15, 250
and ln p (atm)    1.255ln T  21.79 (ii)
T

Which of the two equations is for solid zinc?

Solution

We know that HSv > HLv

For (i )
15, 780
ln p (atm)    0.755ln T  19.25
T
d ln p H (i ) 15, 780 0.755
  
dT RT 2 T2 T
H (i )  R(15, 780  0.755T )

for (ii )
15, 250
ln p (atm)    1.255ln T  21.79
T
d ln p H (ii ) 15, 250 1.255
  
dT RT 2 T2 T
H (ii )  R (15, 250  1.255T )

Since H(i) > H(ii): (i) must be for solid zinc

84
Problem 7.5

At the normal boiling temperature of iron, Tb = 3330 K, the rate of change of the

vapor pressure of liquid iron with temperature is 3.72 × 10–3 atm/K. Calculate the

molar latent enthalpy of boiling of iron at 3330 K.

Solution

Assume that the Fe vapor behaves as an ideal gas at its normal boiling point.

Thus molar volume of Fe vapor at P = 1 atm and and T = 3330 K is calculated to be:

RT
V  0.082057 x3330  273.2 liters
P
dP H b
But  vapor
 3.72 x103 atm / K
dT TVm ( Fe )
atm
Thus : H b  3.72 x103 x 3330 K x 273.2l  3378l  atm
K
8.3144 Joules
H b  3378l  atm x  342.376 kJoules
0.082057l  atm

85
Problem 7.6

Below the triple point (–56.2°C) the vapor pressure of solid CO2 is given as

3116
ln p (atm)    16.01
T

The molar latent enthalpy of melting of CO2 is 8330 joules. Calculate the vapor

pressure exerted by liquid CO2 at 25°C and explain why solid CO2 is referred to

as “dry ice.”

Solution The triple point pressure is:

3116
ln P   16.01: P = 5.14 atm.
216.8

d ln P 3116 H S vap
We know that  2 
dT T RT 2
Thus H S vap  25907 J
H S  L  8330 J
But : H S vap  H vap  L  H L  S  0
H L vap  17577 J
For liquid CO 2
H L vap
ln P(CO2 )   constant
RT
At the triple point:
5.14 atm 17577
ln P  ln( )  constant
1 atm 216.8 R
constant = 11.39
17577
Thus at 298 K ln P (CO2liq )   11.39
8.3144 * 298

P (CO 2liq)  78.3 atm

At one atm there is never any liquid phase of CO2: hence the ice is dry

86
Problem 7.7

The molar volumes of solid and liquid lead at the normal melting temperature of lead

are, respectively, 18.92 and 19.47 cm3. Calculate the pressure which must be applied

to lead in order to increase its melting temperature by 20 centigrade degrees.

Solution

207 cm 3
The molar volume of solid Pb is  18.92
10.94 mole
207 cm 3
The molar volume of liquid Pb is  19.47
10.63 mole
cm 3
V ( S   L)  19.47  18.92  0.55
mole
H ( S   L)  4810 J
dP H ( S   L)

dT T V ( S   L)

4810 J 82.057 cm 3  atm 620

P   ln  2830 atm increase
cm 3 8.3144 J 600
0.55
mole
The new pressure is 2831 atm.

87
Problem 7.8

Nitrogen has a triple point at P = 4650 atm and T = 44.5 K, at which state the

allotropes α, β, and γ coexist in equilibrium with one another. At the triple point Vβ –

Vα = 0.043 cm3/mole and Vα – Vγ = 0.165 cm3/mole. Also at the triple point Sβ – Sα =

4.59 J/K and Sα – Sγ = 1.25 J/K. The state of P = 1 atm, T = 36 K lies on the boundary

between the fields of stability of the α and β phases, and at this state, for the

transformation of α → β, ΔS = 6.52 J/K and ΔV = 0.22 cm3/mole. Sketch the phase

diagram for nitrogen at low temperatures.

Solution

V – V = 0.043 cm3/mole

V – V = 0.165 cm3/mole

V – V = 0.165 + 0.043 = 0.208 cm3/mole

Therefore: V > VVThis means that  is the stable phase at high pressures and

 is the stable phase at low pressures.

S – S = 4.59 J/K

S – S = 1.25 J/K

S – S = 4.59 + 1.25 = 5.84 J/K

Therefore: S > SSThis means that  is the stable phase at high temperatures

and  is the stable phase at low temperatures.

88
 dP S 4.59 82.057 atm
      1053
dT V 0.043 8.3144 K
dP S 1.25 82.057 atm
      74.8
dT V 0.165 8.3144 K
dP S 5.84 82.057 atm
      277
dT V 0.208 8.3144 K

at 1 atm and 36 K
dP S 6.52 82.057 atm
      292
dT V 0.22 8.3144 K

89
Problem 7.9

Measurements of the saturated vapor pressure of liquid NdCl5 give 0.3045 atm at 478

K and 0.9310 atm at 520 K. Calculate the normal boiling temperature of NdCl5.

Solution

The vapor pressure equation is of the form:

A
ln p  B
T
A
ln(0.3045)  B
478
A
ln(0.9310)  B
520
This gives: A  6614 and B = 12.65
6614
At p = 1 atm: 0 =  12.65
Tb
Tb  523K

90
Problem 7.10*

Three allotropes  and  of a certain element are in equilibrium at its

triple point See Figure 7.19. It is known that:
Vm  Vm and Sm  S m
Determine which regions of the diagram are  and 
Explain your reasoning.

If the pressure is increased, equilibrium of the system favors the lowest molar volume

phase. Therefore  is in either region I or II of Fig. 7.19, since Vm  Vm . But at the

triple point, increasing the pressure moves equilibrium to the lowest molar volume

phase. Thus, region II is the  phase field.

If the temperature is increased, equilibrium of the system favors the phase of the

highest entropy. Therefore the  phase is in either region II or III since Sm  Sm But

at the triple point increasing the temperature moves equilibrium to the highest entropy

phase: therefore region III is the phase field for the  phase.

The phases are as they appear below

91
92
Problem 7.11*

Fig. 7.11 shows a pressure vs. temperature phase diagram for a system exhibiting two

solid state phases. Sketch the Gibbs free energy curves v. temperature for the two

solid phases and the liquid phase. Comment on the slopes of the curves.

Solution

The slopes show that the  phase has a higher entropy than the  phase both of which

have lower entropy than the liquid phase.

93
Problem 7.12*
Below is the Gibbs free energy vs. Pressure plot for three phases, solid (S) liquid (L) and
gas (V), near the triple point for the system. It is known that the molar volume of the solid
is greater than that of the liquid.
a. Label the three plots of G vs. P as S, L or V
b. Below, draw the T P plot for the material. Label the S, L and V fields and any other
points of interest. Note that the temperature is increasing in the downward direction.

It is important that the slope of the liquid / solid curve be as shown. His plot is the
normal P-T plot rotated by 900 clockwise!

94
Problem 7.13*

The Pressure Temperature phase diagram of a certain material is shown below.

Construct the Volume Temperature diagram for this substance and label all phase
fields.

Solution

95
Problem 7.14*

It can be seen from Fig. 7.7 that the metastable extensions of the two phase equilibria

go into single phase fields. At the triple point it can be seen that the stable and

metastable equilibrium curves alternate as one goes around the triple point. Show that

the metastable extensions must alternate with stable two phase curves.

Solution

Assume the curves representing the stable equilibrium and those representing the

metastable equilibrium do not alternate. Demonstrate that a contradiction arises. See

below. The metastable extension of the  curve goes into the stable  phase field.

So on the extension is the  phase stable or metastable? This ambiguity shows that

the  curve can not be extended into the single  phase field. Hence the curves must

alternate.


P

T

96
Chapter 8
Problem 8.1

Demonstrate the law of corresponding states by writing the van der Waals equation in

terms of the reduced variables. Calculate the compressibility factor for a van der

Waals fluid at its critical point and compare the result with the values obtained for

real gases at their critical points listed in Table 8.1 Calculate the value of (∂U/∂V)T for

a van der Waals fluid.

Solution

(i) For one mole of a van der Walls fluid we have:

 a 
 P  2  V  b   RT
 V 
From equation 8.26 of the text:
a 8a
Pc  2
vc  3b Tc 
27b 27 Rb
 a 
Thus:  PR Pcr  2 2  V RVcr  b   RTRTcr
 VR Vcr 
 a a  8a
 PR  2
 2 2  VR  3b  b   RTR
 27b VR 9b  27 Rb
 3 
 PR  2   3VR  1  8TR
 VR 

(ii) For a van der Waals fluid, Zcr is found to be:

a
3b
PcrVcr 27b 2 3
Zcr     0.375
RTcr 8a 8
R
27 Rb

The van der Waals fluid has a larger Zcr than the gases listed in Table 8-1

97
 dU  TdS  PdV
 U   S   P 
  T   P T   P
 V T  V T  T V
RT a
for a van der Waals fluid P   2
V  b  V
(iii)  P  R  U  RT RT RT a
Thus :    and    P   2
  V   
T V b   T   
V V b      
V b V b V
 U  a
   2
 V T V
 U 
Note : for an ideal gas, a = 0 and   0
 V T

98
Problem 8.2

n moles of an ideal gas A and (1 – n) moles of an ideal gas B, each at 1 atm pressure,

are mixed at total constant pressure. What ratio of A to B in the mixture maximizes

the decrease in the Gibbs free energy of the system? If the decrease in the Gibbs free

energy is ΔGM, to what value must the pressure be increased in order to increase the

Gibbs free energy of the gas mixture by ΔGM?

Solution

We mix n moles of A and (1-n( moles of B at constant pressure = 1 atm.

G mix  RT  n ln n  (1  n) ln(1  n) 
d G mix n
 RT  ln n  1  ln(1  n)   1)  RT ln
dn n 1
n
RT ln  0 when n  0.5
n 1
Thus the maximum change occurs when nA  nB  0.5
(note: the second derivative of G mix is negative)

Increasing the pressure from 1 atm to P atm increases the free energy by:
G  RT ln P
1 1
 G mix  RT ln P  RT ln 2
2 2
Thus : P  2  1.44atm

99
Problem 8.3

You are responsible for the purchase of oxygen gas which, before use, will be stored

at a pressure of 200 atm at 300 K in a cylindrical vessel of diameter 0.2 meters and

height 2 meters. Would you prefer that the gas behaved ideally or as a van der Waals

fluid? The van der Waals constants for oxygen are a = 1.36 liters2ꞏatmꞏmole–2 and b =

0.0318 liter/mole.

Solution

Assume the best result for you is that the tank holds less gas and therefore is less

expensive.

The volume of the tank is calculated as:

Vtan k   r 2 h  3.14  (0.1) 2  2  0.06284m3  62.84l

PV 200atm  62.84l
For an ideal gas: n    511 moles
RT 0.08206 l  atm  300 K
mole  K

For an van der Waals

 an 2 
 P   V  nb   nRT
 V2 
 1.36  n 2  l  atm
gas:  200atm  2 
(62.84  0.318  n)  n  0.08206  300 K
 (62.84 l )  mole K
solving this yields : n  565 moles

Thus it is less expensive to fill the tank if the behavior of the gas is ideal

100
Problem 8.4

The virial equation of state for n-butane at 460 K is Z = 1 + A/V + B/V2 in which A =

–265 cm3/gꞏmole and B = 30,250 cm6/gꞏmole2. Calculate the work required to

reversibly compress 1 mole of n-butane from 50 to 100 atm at 460 K.

Solution

cm3
The virial equation of state with the volume in is :
mole
265 30250
Z  1 
V V2
 1 265 30250 
P (atm)  82.057  460    2  
V V V3 
at P1  50atm this gives V1  394.6cm3
at P2  100atm this gives V2  176.9cm3

2 2 1 265 30250 
Thus, w   PdV  RT    2  dV
1

1 V V V3 
 V  1 1  30250  1 1 
w  RT  ln 2  265      2  2  
 V1  V2 V1  2  V2 V1  
 176.9  1 1  30250  1 1 
w  8.3144  460  ln  265      
 394.6  176.9 394.6  2  176.9 394.62  
2

w  1385 J

101
Problem 8.5

For sulfur dioxide, Tcr = 430.7 K and Pcr = 77.8 atm. Calculate

a The critical van der Waals constants for the gas

b The critical volume of van der Waals SO2

c The pressure exerted by 1 mole of SO2 occupying a volume of 500 cm3 at 500 K.

Compare this with the pressure which would be exerted by an ideal gas occupying the

same molar volume at the same temperature.

Solution

a 8a
Pc  Tc 
27b 2 27 Rb
8a
Tc 27 Rb 8b
 
Pc a R
2
27b
T R 430.7  0.08206
Thus b  c   0.0567 l / atm
Pc 8 77.7  8
l2 l2
a  27b 2 Pc  27  0.0567  77.8atm  6.77
atm 2 atm  mole2

l
(ii ) V  3b  0.170
mole

l2
6.77
RT a 0.08206  500 atm  mole 2  65.5atm
(iii ) Pvdw   2  atm 
V b V 0.5  0.0567 0.52 l
RT 0.08206  500
Pideal   atm  82.1 atm
V 0.5

102
Problem 8.6

One hundred moles of hydrogen gas at 298 K are reversibly and isothermally

compressed from 30 to 10 liters. The van der Waals constants for hydrogen are a =

0.2461 liters2ꞏatm mole-2 and b = 0.02668 1/mole, and in the range of pressure 0–

1500 atm, the virial equation for hydrogen is PV = RT (1 + 6.4 × 10–4 P). Calculate

the work that must be done on the system to effect the required change in volume and

compare this with the values that would be calculated assuming that (1) hydrogen

behaves as a van der Waals fluid and (2) hydrogen behaves as an ideal gas.

Solution

For this problem, n = 100 moles, T = 298K, V1 = 30 l, V2 = 10 l

Using the Virial equation of state:

PV  nRT (1  6.4 104 P )
w   PdV
1 1 dP
V  nRT (  6.4 104 ) and dV  nRTd    nRT 2
P P P
P2 dP P
Thus : w   nRT  nRT ln 1
P1 P P2
Now : PV  6.4  104 nRTP  nRT : P (V  6.4 104 )  nRT
nRT
P
(V  6.4  104 nRT )
100  0.08206  298
Thus : P1   86atm
30  6.4 104 100  0.08206  298
100  0.08206  298
P2   290atm
10  6.4 104 100  0.08206  298

P1 86
Thus : w  nRT ln  100  8.3144  298ln  301kJ
P2 290

103
Using the van der Waal equation of state:
nRT n2 a l  atm l
P  2 and a  0.2461 and b  0.02668
V  nb V mole mole
 nRT n a
2
 V  nb  2  1 1 
w   PdV     2 dV  nRT ln  2   n a  
 V  nb V   V1  nb   V2 V1 
 
 
 10  100  0.02668  8.3144  1 1 
w  100  8.3144  298  ln    100  0.2461
2
 
 30  100  0.02668  0.08206  10 30 
 
 
w  309kJ

Using the Ideal gas equation of state :

V 10
w  nRT ln 2  100  8.3144  298ln
V1 30
w  272kJ

104
Problem 8.7

Using the virial equation of state for hydrogen at 298 K given in Problem 8.6,
calculate:
a. The fugacity of hydrogen at 500 atm and 298 K

b. The pressure at which the fugacity is twice the pressure

c. The change in the Gibbs free energy caused by a compression of 1 mole of

hydrogen at 298 K from 1 to 500 atm

What is the magnitude of the contribution to (c) caused by the nonideality of

hydrogen?

Solution

The virial equation of state for one mole of hydrogen is:

PV  nRT (1  6.4 104 P)
PV
(a ) Z   1  6.4 104 P Z  1  6.4 104 P
RT

f P Z 1
But ln   6.4  104 500  0  0.3194
P 0 P
f
 exp(0.3194)  1.376 so : f  1.376  500  688atm
P

f f
(b) if  2, then ln  ln 2  6.4 104 ( P  0) (see above)
P P
ln 2
Thus, P   1083atm
6.4  104

1
(c) G   VdP and V  RT [  6.4  104 ]
P
P2
G  RT ln  RT  6.4 104  ( P2  P1 )
P1
 500  4
G  8.3144  298   ln   8.3144  298  6.4 10  (500  1)
 1 
G  15400J + 790J = 16190J
Thus the contribution due to the non ideal behavior is 790J

105
Problem 8.8*

Show that the truncated Kammerlingh Onnes virial equation:

PV B '(T )
 1
RT V
reduces to P(V - b’) = RT, and find the expression for b’ .

Solution

PV
 RT
 B '(T ) 
1  
 V 
1
if V  B '(T ) then using the expansion  1  x for x  1
1 x
 B '(T ) 
PV 1    P V  B '(T )  RT
 V 

so b' = B '(T )

106
Problem 8.9*

Fig. 8.8 shows an isothermal variation, with pressure, of the volume of a van der

Waals gas at a temperature below its critical temperature. Redraw this Figure and

below it sketch the Helmholtz free energy vs. Volume plot. Be sure to indicate

important points on the A vs. V plot.

Solution

dAT   PdV
 A 
    P so the slope should always be < 0
 V T
  2 A   P 
 2    and there are two extrema in P vs V.
 V T  V T
Thus there are two points where A vs. V changes its curvature.
Also the common tangent delineates the molar volumes of the
equilibrium phases.

107
Problem 8.10*

Obtain a simplified expression for the total derivative of the pressure for an van der

Waals’gas.

Solution

 P   P 
dP    dT    dV
 T V  V T

RT a
P  for a van der Waals' gas
(V  b) V 2

 P  R
   for a van der Waals' gas
 T V V  b
 P  RT 2a
    3 for a van der Waals' gas
 V T (V  b) V
2

R RT 2a
Thus, dP  dT  (  3 )dV
V b (V  b) V
2

R RT
This reduces to dP = dT  2 dV if a = 0 and b = 0
V V

108
Problem 8.11*

Obtain a simplified expression for the total derivative of the pressure for a gas that

obeys the truncated Kammerlingh Onnes virial equation:

PV B '(T )
 1
RT V

Solution

 B '(T )  RT
P  1  
 V  V
 P  R B '(T ) R RT  B 
     2 
 T V V V2 V  T 

 P  RT 2 B ' RT
   2 
 V T V V3
 R B '(T ) R RT  B '(T )    RT 2 B '(T ) RT 
dP     2    dT   2  dV
V  T   
2
V V V V3

R RT
which reduces to dP = dT  2 dV if B'(T) = 0
V V

109
Problem 8.12*

Derive an expression for Zcr of a van der Waals gas.

Solution

The equation of state for the van der Waals fluid is

RT a
P  2
v b v

Where P is the pressure in Pa

R is the gas constant (8.314 Joule/K)
v is the molar volume of the gas (m3)
a and b are empirical constants that vary from gas to gas.

To calculate Zcr we must obtain: Pcr, vcr and Tcr

At the critical pressure and volume, the critical isotherm has a horizontal inflection:
 P   2 P 
   2  0
 v TC  v TC

 P  RT 2a
    3 0
 v TC  v  b v
2

 2P  2 RT 6a
 2   0
 v TC  v  b 
3
v4
Solving we get:
8a a
v Critical  3b; RTCritical  ; Pcritical 
27b 27b2

a
3b
Pcr vcr 27b 2 3
Z cr   
RTcr 8a 8
27b

110
Problem 8.13*

The ideal entropy of mixing of a binary solution is given as:

S mix   R ( X A ln X A  X B ln X B )

a. Sketch the entropy of mixing vs. XB.

b. Calculate (using the expression for the ideal entropy of mixing) the ideal entropy of
mixing at B = 0.25

c. Calculate the slope of this curve at XB = 0.25

d. Calculate the partial molar entropy of component B for the composition XB = 0.25

e. Calculate the partial molar entropy of component A for the composition XB = 0.25

f. Show that your answers in d and e are consistent with your answer in c.

Solution

111
 S mix   R ( X A ln X A  X B ln X B )
b. 4.56 J/Mol
S mix   R ln 2

Smix   R( X A ln X A  X B ln X B )
c. dS mix 9.13 J/Mol
  R[ln X B  ln X A )   R( ln 3)  R ln 3
dX B

d. S B   R (ln X B )  R ln 4 11.52 J/Mol

3
e. S A   R (ln X A )  R ln( ) 2.39 J/Mol
4

dS mix
f.  R ln 3 11.52-2.39 = 9.13 J/Mol
dX B
S mix  S B  S A  R (ln 4  ln 3  ln 4)  R ln 3

112
Chapter 9
Problem 9.1

One mole of solid Cr2O3 at 2500 K is dissolved in a large volume of a liquid

Raoultian solution of Al2O3 and Cr2O3 in which X Cr2O3  0.2 and which is also at

2500 K. Calculate the changes in enthalpy and entropy caused by the addition. The

normal melting temperature of Cr2O3 is 2538 K, and it can be assumed that the

S m,Al2O3  S m,Cr2O3 .

Solution

From Table A-5 of the text:

107500 J J
H MAl2O3  107500 J : thus S MAl2O3   46.25
2324 K K
J
By the assumption of the problem:S MCr2O3  S MAl2O3  46.25
K
J
Thus : H MCr2O3  TMCr2O3  S MCr2O3  2538 K  46.25  117382 J
K
Cr2O3 ( s )  Cr2O3 (l ) H MCr2O3  117382 J
Cr2O3 (l )  Cr2O3 (insolution) H Mideal  0
Thus, H Total  117382 J

J
Cr2O3 ( s )  Cr2O3 (l ) S MCr2O3  46.25
K
J
Cr2O3 (l )  Cr2O3 (insolution) S Mideal   R ln X Cr2O3  8.3144  ln 0.2  13.38
K
J J J
Thus, STotal  46.25  13.38  59.63
K K K

113
Problem 9.2

When 1 mole of argon gas is bubbled through a large volume of an Fe–Mn melt of

XMn = 0.5 at 1863 K evaporation of Mn into the Ar causes the mass of the melt to

decrease by 1.50 g. The gas leaves the melt at a pressure of 1 atm. Calculate the

activity coefficient of Mn in the liquid alloy.

Solution

From Table A.4 of the text:

The saturated vapor pressure of liquid Mn at 1863K is calculated to be:
 33440 
exp    3.02 ln1863  37.68   0.0493atm
 1863 
1.5 g
The number of moles removed was:  0.0273 moles
54.94 g / mole

nMn 0.0273
The partial pressure of the Mn in the gas mixture    0.0266
nMn  nAr  1  0.0273
pMn 0.0266
Thus : aMn  0
  0.539
pMn 0.0493
aMn 0.539
Now:  Mn    1.08
X Mn 0.5

114
Problem 9.3

The variation, with composition, of GXS for liquid Fe–Mn alloys at 1863 K is listed

below.

a. Does the system exhibit regular solution behavior?

XS XS
b. Calculate G Fe and G Mn at XMn = 0.6.

c. Calculate AGM at XMn = 0.4.

d. Calculate the partial pressures of Mn and Fe exerted by the alloy of XMn =

0.2.

XMn 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

GXS joules 395 703 925 1054 1100 1054 925 703 395

Solution

G XS
(a) If regular wrt G XS the calulated values of   should be constant.
X Fe X Mn
1 9 G iXS
 average   i  4395 J  10 J . Thus regular.
9 1 X Fe X i Mn
(note that this could have been predicted by the symmetry of the table
G XS (.1Mn)  G XS (.9 Mn) : G XS (.2 Mn)  G XS (.8Mn) : etc.

XS  X B2
(b) G A  RT ln  A and  A  exp( )
RT
XS XS
Thus : G A   X B2  G Fe   X Mn
2
= 4395  0.62  1582 J
XS
 G Mn   X Fe
2
= 4395  0.42  703 J

115
(c) G mix
 RT ( X A ln X A  X B ln X B )   X A X B
G mix
 8.3144 1863(0.6 ln 0.6  0.4 ln 0.4)  4395  0.4  0.6  9370 J

(d ) We need to obtain the activities of Fe and Mn at X Mn  0.2

 X B2  X Fe
2
 4395  0.82 
 A  exp( ) : Thus,  Mn  exp( )  exp    1.2
RT RT  8.3144  1863 
aMn   Mn X Mn  1.2  0.2  0.24
33440
0
Now from Table A.4: pMn  exp(  3.02  ln1863  37.68)  0.0493 atm
1863
 pMn  aMn  pMn
0
 0.24  0.0493  0.018

 X B2  X Mn
2
 4395  0.22 
 A  exp( ) : Thus,  Fe  exp( )  exp    1.011
RT RT  8.3144  1863 
aFe   Fe X Fe  1.011 0.8  0.809
45390
0
From Table A.4: pFe  exp(  1.27  ln1863  23.93)  4.55 105 atm
1863
 pFe  aFe  pFe
0
 0.809  4.55  105  3.68  105 atm

116
Problem 9.4

Calculate the heat required to form a liquid solution at 1356 K starting with 1 mole of

Cu and 1 mole of Ag at 298 K. At 1356 K the molar heat of mixing of liquid Cu and

liquid Ag is given by ΔHM = –20,590XCuXAg.

Solution

The Cu and the Ag must be heated from their solid state at 298K to their liquid state at

1356K. Use data from Table A.2 of the text.

1356
H Cu   cPCu dT  H mCu
298

6.28 103
22.64  (1356  298)   (13562  2982 )  12970 J  42, 420 J
2

1234 1356
H Ag   cPAg dT  H mAg  H mAg   cPAg ( l ) dT
298 1234

8.54 103 1 1
=21.3  (1234-298) +  (12342  2982 )  1.51105 (  )
2 1234 298
11, 090  30.5  (1356  1234)  41, 260 J

For the two moles of the solution we have: H M  2  ( 20,590  0.52 )  10300 J

Thus : The total heat required is 42, 420 J  41, 260 J  10,300 J  73380 J

117
Problem 9.5

Melts in the system Pb–Sn exhibit regular solution behavior. At 473°C aPb = 0.055 in

a liquid solution of XPb = 0.1. Calculate the value of  for the system and calculate

the activity of Sn in the liquid solution of XSn = 0.5 at 500°C.

Solution

From equation 9.64 and 9.65 of the text:

  X B2    X A2 
 A  exp   and  B  exp  
 RT   RT 

aPb 0.055
at 473 0 C:  Pb    0.55
X Pb 0.1
8.3144  746  ln 2
Thus :    4578 J
0.92

4578  0.52
at 500 0 C: ln  Sn   0.178
8.3144  773
Thus : aSn  0.5  exp(0.178)  0.418

118
Problem 9.6*
a. Calculate the values of G B and aB for an alloy of XB = 0.5 at 1000 K assuming the
solution is ideal.

b. Calculate the values of G B and aB for an alloy of XB = 0.5 at 1000 K that is a

regular solution with a H mixing  16,628* X A * X B .

Solution
M M
a. For ideal and regular solutions G M ( X B  0.5)  G A  G A

G M ,id ( X B  0.5)   RT S M ( X B  0.5)

1 1 1 1
 8314 * ( ln  ln )  5763J
2 2 2 2

G B  RTa B  5763J
5763
a B ( X B  0.5)  exp(  )  0.5
8314

b..
1 1 1 1
G M ,reg (0.5)  16,626  8314 * ( ln  ln )
2 2 2 2
1 1 1 1 1
=16,626 *  8314 * ( ln  ln )
4 2 2 2 2
 1609 J

G B  RTaB  1609 J
1609
aB  exp( )  0.844
8314

119
Problem 9.7*

A regular solution exhibits a miscibility gap. Sketch the activity of XB vs. XA at a

temperature within the miscibility gap.
Denote regions where Henry’s law is obeyed and where Raoults’ law is obeyed if
applicable.

Solution

XA

120
Problem 9.8

Tin obeys Henry’s law in dilute liquid solutions of Sn and Cd and the Henrian activity


coefficient of Sn, γSn , varies with temperature as

840

ln γSn   1.58
T

Calculate the change in temperature when 1 mole of liquid Sn and 99 moles of liquid

Cd are mixed in an adiabatic enclosure. The molar constant pressure heat capacity of

the alloy formed is 29.5 J/K.

Solution

We must determine HMix and equate that to -cPT (since the entropy change in the

enclosure is zero.

Mix R ln  Sn
 H Sn   8.3144  840  6984 J
1
 
T 
Mix Mix
H Mix ( per mole)  X Sn  H Sn  X Cd  H Cd
Now since Sn obeys Henries law, Cd obeys Raoult's law on the same range of composition
Mix
Thus :  H Cd  0
H Mix ( per mole)  0.01 (6984 J )  69.84 J
Thus : cP  T  H Mix  69.84 J
69.84 J
and thus T   2.37 K
J
29.5
K

121
 Problem 9.9

Use the Gibbs-Duhem equation to show that, if the activity coefficients of the

components of a binary solution can be expressed as

1 1
ln γ A  1 X B   2 X B2   3 X B3  
2 3

and

1 1
ln γ B  β1 X A  β 2 X A2  β3 X A3  
2 3

over the entire range of composition, then α1 = β1 = 0, and that, if the variation can be

represented by the quadratic terms alone, then α2 = β2.

Solution

1 1
ln γ A  1 X B   2 X B2   3 X B3  
2 3
X A d ln γ A  1 X A dX B   2 X A X B dX B   3 X A X B2 dX B  
1 1
ln γ B  β1 X A  β 2 X A2  β3 X A3  
2 3
and remembering that dX A  dX B
 X B d ln γ B  β1 X B dX B  β 2 X B X A dX B  β3 X B X A2 dX B  

The Gibbs  Duhem relation gives : X A d ln  A  X B d ln  B and for up to quadratic terms:

1 X A dX B   2 X A X B dX B  β1 X B dX B  β 2 X B X A dX B

Now equating term by term over all values of composition :

first term 1 X A dX B  β1 X B dX B
This can only happen if 1  β1  0
second term  2 X A X B dX B  β 2 X B X A dX B
This can only happen if  2  β 2

122
Problem 9.10

The activity coefficient of Zn in liquid Zn–Cd alloys at 435°C can be represented as

ln γ Zn  0.875 X Cd
2
 0.30 X Cd
3

Derive the corresponding expression for the dependence of ln γCd on composition and

calculate the activity of cadmium in the alloy of XCd = 0.5 at 435°C.

Solution

ln γ Zn  0.875  X Cd
2
 0.30  X Cd
3

d ln γ Zn  1.75  X Cd dX Cd  0.90  X Cd
2
dX Cd
X Zn d ln γ Zn  X Cd d ln γ Cd  0
X Zn
 d ln γ Zn  d ln γ Cd
X Cd
X Zn
  (1.75  X Cd dX Cd  0.90  X Cd
2
dX Cd )  d ln γ Cd
X Cd
1.75  X Zn dX Cd  0.90  X Cd X Zn dX Cd  d ln γ Cd
1.75  X Zn dX Zn  0.90  (1  X Zn ) X Zn dX Zn  d ln γ Cd
(1.75  0.9)  X Zn dX Zn  0.90  X 2 Zn dX Zn  d ln γ Cd
0.85  X Zn dX Zn  0.90  X Zn
2
dX Zn  d ln γ Cd
0.425  X Zn
2
 0.30  X Zn
3
 ln γ Cd

at X Cd  0.5, X Zn  0.5 : 0.425  0.52  0.30  0.53  1.154  ln γ Cd

aCd   Cd X Cd  1.154  0.5  0.577

123
 Problem 9.11

The molar excess Gibbs free energy of formation of solid solutions in the system Au–

Ni can be represented by

 T 
G XS  X Ni X Au (24,140 X Au  38, 280 X Ni  14, 230 X Au X Ni ) 1  J
 2660 

Calculate the activities of Au and Ni in the alloy of XAu = 0.5 at 1100 K.

Solution

XS  G XS 
Use the expression: G Au ( X Au  .5)  G XS ( X Au  .5)  (1  X Au )  
 X Au  X Au .5
 T 
G XS  X Ni X Au (24,140 X Au  38, 280 X Ni  14, 230 X Au X Ni ) 1  J
 2660 
for X Au =0.5 and at 1100 K
G XS  X Au =0.5   4055 J
 T 
G XS  (1  X Au ) X Au (24,140 X Au  38, 280(1  X Au )  14, 230 X Au (1  X Au )) 1  J
 2660 
 T 
G XS  ( X Au
2
 X Au
3
)24,140  ( X Au  X Au
3
 2 X Au
2
)38, 280  ( X Au
2
 X Au
4
 2 X Au
3
)14, 230  1  J
 2660 
 G XS   T 
    (2 X Au  3 X Au
2
)24,140  (1  3 X Au
2
 4 X Au )38, 280  (2 X Au  4 X Au
3
 6 X Au2
)14, 230  1  
 X Au  X .5
Au
 2660 
for X Au =0.5 and at 1100 K
 G XS 
   3535
 X Au  X Au .5
XS  G XS 
Thus : G Au ( X Au  .5)  G XS ( X Au  .5)  (1  X Au )    4055  1036  3019 J
 X Au  X Au .5
XS
G Au ( X Au  .5)  RT ln  Au  3019 J
 3019 
 Au  exp    1.39 and a Au =X Au   Au  0.5 1.39  0.695
 8.3144  1100 

G XS  X Au =0.5   4055 J  RT [ X Au ln  Au  X Ni ln  Ni ]
 Ni  1.75 aNi =X Ni   Ni  0.5 1.75  0.87

124
Problem 9.12*

The activities of liquid iron-copper solutions at 1550 °C as a function of composition

are shown in Fig. 9.9. Sketch the activity coefficients as a function of composition at

this temperature.

Solution

125
Problem 9.13* Use the equation: G XS  b(T  TC ) 2  c 4 to derive the following

T 1/2
equation for  = (T): eq  (1  )
TC

(Hint: see Qualitative Example Problem 1. Also use the Third Law of

Thermodynamics to set  = 1 at T = 0).

Solution

G XS  b(T  TC ) 2  c 4
G XS
 0 for equilibrium

G XS
 2b(T  TC )  4c 3  0

b(T  TC )
Thus   0 and  2   are extrema
2c

By taking the second derivative  = 0 can be shown to be a maximum when T< Tc

and the other two extrema are minima when T< Tc.

b(T  TC )
2  
2c
at T = 0,   1 (by the third law)
2c T
Thus : TC  which leads to  2  (1  )
b TC

126
Problem 9.14*

It has been found that in a certain solution the activity aA = XA over a certain range of

composition. Determine the relationship between aB = XB over the same range of

composition.

Solution

aA  X A
d (ln a A )  d (ln X A )
X Ad (ln a A )  X B d (ln a B )  0 Gibbs Duhem
XA X dX B
Thus : d (ln a2 )   d (ln a A )   A d (ln X A ) 
XB XB XB
integrating: ln a2  ln X 2  ln  where  is a constant
Thus, aB   X B   B X B
This is Henry's law.

127
Problem 9.15*
All regular solutions with positive heats of mixing have the same value of the activity of its
components (A or B) at the critical point of the miscibility gap.
a. Calculate this activity.

b. Plot aB vs. XB for a regular solution at TC for a miscibility gap.

c.
Solution

Another way

G B  Gmix (0.5)  H mix  T Smix 


=  RT  ln 2  RT ln aB
4

But: T  TC 
2R
1
 ln 2  ln aB  0.1935
2
aB  0.824

128
Problem 9.16*.

At a certain temperature, T the A-B system exhibits regular solution behavior. The
activity coefficient of A is given by:
ln( A )  b(1  X A ) 2 , where b is a constant at the given T
Compute the corresponding equation for the variation of B with composition at the
same temperature. Be sure to state justification for the steps of your solution.

Solution

ln  A  b(1  X A ) 2
Gibbs  Duhem
X Ad G A  X B d G B  0
d G A  RTd ln a A  RTd ln( A X A )
X A d ln  A  X B d ln  B  0
XA X
d ln  B   d ln  A   A (2bX B (dX A )
XB XB
B

 d ln  B  ln  B  bX A2  b(1  X B ) 2
1

129
Chapter 10
Problem 10.1

CaF2 and MgF2 are mutually insoluble in the solid state and form a simple binary

eutectic system. Calculate the composition and temperature of the eutectic melt

assuming that the liquid solutions are Raoultian. The actual eutectic occurs at

X CaF2  0.45 and T = 1243 K.

SOLUTION

See Table A.5 for data

We define X CaF2  X
For the CaF2 liquidus line:
H M
G 0M  H M  T S M  H M  T   RT ln X
TM
G 0M  31200  18.45T  8.3144T ln X
For the MgF2 liquidus line:
H M
G 0M  H M  T S M  H M  T   RT ln(1  X )
TM
G 0M  58160  37.86T  8.3144T ln(1  X )

Solving these equations simultaneously we obtain for the intersection of the liquidus

lines:

T = 1317 K and X = 0.53

The experimentally determined values for the eutectic are:

T = 1243 K and X = 0.45.

130
Problem 10.2

Gold and silicon are mutually insoluble in the solid state and form a eutectic system

with a eutectic temperature of 636 K and a eutectic composition of XSi = 0.186.

Calculate the Gibbs free energy of the eutectic melt relative to (a) unmixed liquid Au

and liquid Si, and (b) unmixed solid Au and solid Si.

1338  636 
At 636 K Gm , Au  12, 600   6, 611 J
 1338 
1658  636 
and Gm ,Si  50, 200   30,943 J
 1685 

(note: this solution uses 1685 K for melting point of Si. See Table A.5)

SOLUTION

1338  636 
At 636 K we have for Au: GM0  12600   6611J
 1338 
1658  636 
For Si we have: GM0  50200   31252 J
 1685 

a. See Figure: G M  ab  (0.186  31252  0.814  6611) J  11038 J

b. GM = 0

131
Problem 10.3

Al2O3, which melts at 2324 K, and Cr2O3, which melts at 2538 K form complete

ranges of solid and liquid solutions. Assuming that S m ,Cr2O3  S m ,Al2O3 , and that the

solid and liquid solutions in the system Al2O3–Cr2O3 behave ideally, calculate

a. The temperature at which equilibrium melting begins when an alloy of

X Al2O3  0.5 is heated

b. The composition of the melt which first forms

c. The temperature at which equilibrium melting is complete

d. The composition of last-formed solid

SOLUTION

From Table A.5 we get:

107,500
GM0 ( Al2O3 )  107,500  T  107,500  T  5.563
2324
GM0 ( Al2O3 ) 12929
  5.563
RT T

Since S M0 ( Al2O3 )  S M0 (Cr2O3 )  5.563 we can calculate

GM0 (Cr2O3 )  2538  5.563  14,119 J

Thus:

GM0 (Cr2O3 )  117,391  T  5.563

GM0 (Cr2O3 ) 14119
  5.563
RT T

a. The solidus temperature, T, at X Al2O3  0.5 is given by Eq. 10.4

132
 GCr


1  exp(  2O3
)
X Al2O3  0.5  RT
G Al 2O3 GCr


exp(  )  exp(  2O3

)
RT RT
14119
1  exp(  5.563)
0.5  T
12929 14119
exp(   5.563)  exp(   5.563)
T T

The solution to which is T = 2418K

b. Since the solutions are assumed to be ideal:

X Al2O3 (liquidus ) 12929

 exp(   5.563)
X Al2O3 ( solidus ) T
12929
X Al2O3 (liquidus )  0.5  exp(   5.563)  0.621
T

c. The liquidus temperature, T at X Al2O3  0.5 is given by Eq. 10.5

 GCr 
2O3
 G Al 2O3
1  exp(  )  exp(  )
 RT  RT
X A( l ) 
G Al 2O3 GCr

2O3
exp(  )  exp(  )
RT RT
14119 12929
(1  exp(   5.563))  exp(   5.563)
X Al2O3  0.5  T T
12929 14119
exp(   5.563)  exp(   5.563)
T T

The solution to which is T = 2444K

d. The corresponding solidus composition is:

14119
1  exp( 
 5.563)
X Al2O3 ( solidus )  T  0.38
12929 14119
exp(   5.563)  exp(   5.563)
T T

133
Problem 10.4

Na2OꞏB2O3 and K2OꞏB2O3 form complete ranges of solid and liquid solutions and the

solidus and liquidus show a common minimum at the equimolar composition and T =

1123 K. Calculate the molar Gibbs free energy of formation of the equimolar solid

solution from solid Na2OꞏB2O3 at 1123 K, assuming that the liquid solutions are ideal.

SOLUTION

See Table A.5

Using equation 10.1 and see Figure below

 1240  1123 
GM0 , Na2OB2O3  67000     6322 J
 1240 
 1220  1123 
GM0 ,K2OB2O3  62800     4993 J
 1220 
G M (from liquids)  8.3144  1123  0.5ln(0.5)  0.5ln(0.5)   6472  ac
ab  0.5  6322  0.5  4993  5658 J

G M (from solids)  bc  6472  5658  814 J

134
 Problem 10.5

SiO2, which melts at 1723°C, and TiO2, which melts at 1842°C, are immiscible in the

solid state, and the SiO2–TiO2 binary system contains a monotectic equilibrium at

1794°C, at which temperature virtually pure TiO2 is in equilibrium with two liquids

containing mole fractions of SiO2 of 0.04 and 0.76. If, for the purpose of simple

calculation, it is assumed that the compositions of the two liquids are X SiO2  0.24

and X SiO2  0.76 and that the liquid solutions are regular in their behavior, what is the

value of l and at what temperature does the liquid immiscibility gap disappear?

SOLUTION

For a regular solution:

G M  RT ( X A ln X A  X B ln X B
G M X
 RT (ln B )   (1  2 X B )  0
X B XA
Thus : at 2067 :
0.24
8.3144  2067  ln   (1  2  0.24)
0.76
 =38,096 J

 38,096 J
For a regular solution, Tcr =   2, 291 K
2R J
2  8.3144
K

135
Problem 10.6

The binary system Ge–Si contains complete solid and liquid solutions. The melting

temperatures are Tm,Si = 1685 K and Tm,Ge = 1210 K, and H m ,Si  50, 200 J . At

1200°C the liquidus and solidus compositions are, respectively, XSi = 0.32 and XSi =

0.665. Calculate the value of H m ,Ge assuming

a. That the liquid solutions are ideal.

b. That the solid solutions are ideal.

Which assumption gives the better estimate?

The actual value of H m ,Ge at Tm,Ge is 36,900 J.

SOLUTION (see also Quantitative Problem 2)

First calculate Gm ,Si (1473)

Assume constant heat capacity of the range of temperatures and use Eq.10.1
 T T 
Gm ,Si (T )  H m ,Si (T )  m , Si 
 T
 m, Si 
 1685  1473 
Gm ,Si (1473)  50, 200    6316 J
 1685 

The equation of the solidus curve is obtained from Eq. (10.4) as

136
  Gm , Si 
1  exp  
 RT 
X Ge,(solidus),T 
 Gm ,Ge   Gm , Si 
exp    exp  
 RT   RT 
 6316 
1  exp  
0.335   8.3144  1473 
 Gm ,Ge   6316 
exp    exp  
 8.3144  1473   8.3144  1473 
From this we get: Gm ,Ge  7197 J

Again assume constant heat capacity of the range of temperatures and use Eq.10.1
 T T 
Gm ,Ge (T )  H m ,Ge (T )  m,Ge 
 T
 m,Ge 
Gm ,Ge (1473)
H m ,Ge (1473)   33,111 J
 1210  1473 
 
 1210 

From the liquidus:

 Gm ,Ge    Gm ,Si  
exp   1  exp  
 RT    RT  
X Ge,(liquidus),T 
 Gm ,Ge   Gm ,Si 
exp    exp  
 RT   RT 
 Gm ,Ge    6316 
exp   1  exp  
 8.3144 1473    8.3144  1473  
0.68 
 Gm ,Ge   6316 
exp    exp  
 8.3144  1473   8.3144  1473 
From this we obtain: Gm ,Ge  4679 J

4679 J
H m ,Ge (1473)   21,527 J
 1210  1473 
 
 1210 

The estimate from the solidus is closer to the experimental value.

137
Problem 10.7
CaO and MgO form a simple eutectic system with limited ranges of solid solubility.
The eutectic temperature is 2370°C. Assuming that the solutes in the two solid
solutions obey Henry’s law with γ CaO in MgO = 12.88 and  MgO


SOLUTION

At 2300 0C aCaO (  )  aCaO ( )

(1  X 1 )  6.23(1  X 2 ) eq. 1

aMgO ( )  aMgO (  )
12.88  X1  X 2 eq. 2

Solving the above two equations simultaneously we obtain:

X1  X CaO  0.066
X 2 = X CaO  0.85

138
Problem 10.8*

A metatectic binary phase diagram displays the following invariant transformation on

cooling:

 +L

Sketch such a phase diagram and then draw free energy curves of mixing just below,

at and just above the invariant temperature.

Solution

139
Problem 10.9*
The free energy of mixing of a regular solution is given by:

Gmix  a0 X A X B  RT [ X A ln X A  X B ln X B ]
and a0  24,943 Joules/mole

a. Plot Gmix vs. XB at 1400, 1500 and 1600 K.

1400 K 1500 K 1600 K

Gmix
b. Plot vs. XB at the same
X B
temperatures as (a). Plot of the first derivative for
1400K. The first and third zeros
are the minima of free energy
plot: they give the compositions
of the two phases in equilibrium.
The maximum in this plot and the
minimum give us the spinodals

140
 Plot of the first derivative for
1500K. Only one zero for this
plot at 0.5. In fact when it passes
through zero the curve has zero
slope. This demonstrates that this
is the critical temperature.

Plot of the first derivative for

1600K.The zero value is the
minimum in free energy vs. XB
plot (0.5)

c. Determine the critical temperature for this alloy. Show work.

From the answers above we estimate TC to 1500 K.

Or, since a regular solution we calculate it to be TC = a0/2R = 1500 K

141
Problem 10.10*.
A certain solid solution of A and B has a Gmix
xs
as follows:

Gmix
xs
 Gmix  Gmix
id
 X B X A [a1 X A  a2 X B ]  RT [ X A ln X A  X B ln X B ]
Where a1 = 12,500 Joules/mole and a2 = 5500 Joules/mole

a. Plot Gmix
xs
at T = 500 and 700 K

b. Sketch the T vs. XB phase diagram of this alloy

c. Determine the critical temperature and composition of this alloy.

Solution

200

0
0 0.2 0.4 0.6 0.8 1 1.2
-200

-400
Series1

-600

-800

-1000

-1200

Plot of Gmix
xs
ve. XB at 500 K, showing that a miscibility gap will exist in the T vs.
XB phase diagram with TC being less than XB = 0.5.

142
 500

0
0 0.2 0.4 0.6 0.8 1 1.2

-500

Series1
-1000

-1500

-2000

-2500

Plot of Gmix
xs
ve. XB at 700 K, showing that 700 K is above TC.

b. Plot will be asymmetric with TC less than XB = 0.5

 2 Gmix
xs

c. A graphical way of doing this is to plot X B vs. XB and see what T has the
2

 2 Gmix
xs

curve just touching the 0 ordinate. Below is the X B2 vs. XB for 700 K

143
 10000
9000
8000
7000
6000
5000
4000
3000
2000
1000 Series1
0 Series2
-1000 0 20 40 60 80 100 120
-2000
-3000
-4000
-5000
-6000
-7000
-8000
-9000
-10000

This is above TC.

 2 Gmix
xs

The 600 K plot shows two crossings of the X B2 = 0. Hence T < TC.

10000
9000
8000
7000
6000
5000
4000
3000
2000
1000 Series1
0 Series2
-1000 0 20 40 60 80 100 120
-2000
-3000
-4000
-5000
-6000
-7000
-8000
-9000
-10000

By trying various values of T, TC can be found to be 607.5 K and the composition of

the critical point is XB = 0.35

144
Problem 10.11*.

The phase diagram of an alloy that has a eutectoid transformation is shown in

Fig.10.33 (below).

a. Sketch the Gibbs free energy curves for this alloy at T = T’.

b. Show that the  solvus must enter the  two phase field (as

shown by the arrow).

Solution
The common tangent of  and  below TE intersects the  free energy
curve to the right of E.

145
Problem 10.12*

A eutectoid phase diagram is shown in Fig. 10.33. Draw the phase diagram that

would result if for some reason it were impossible to form the  phase.

SOLUTION

A possible diagram is shown below. Note that the  curve is the same as the one in
Fig.10.28a until the temperature where the eutectoid temperature was. is reached. It
then is extrapolated to 0 K. The 0 K phases present are and 

146
Chapter 11
Problem 11.1

A gas mixture of 50% CO, 25% CO2, and 25% H2 (by volume) is fed to a furnace at

900°C. Determine the composition of the equilibrium CO–CO2–H2–H2O gas if the

total pressure of the gas in the furnace is 1 atm.

Solution

We first must find the value of G1173

0
of the reaction:

CO2 + H2 = H2O + CO

1
(i ) CS  O2  CO G 0  111, 700  87.65T
2
(ii ) CS  O2  CO2 G 0  394,100  0.85T
1
(iii ) H 2  O2  H 2 O G 0  247,500  55.85T
2

if we subtract (ii )  (i ) from (iii ) we obtain:

H 2  CO2  H 2 O  CO G 0  34,900  30.96T
which at 1173K yields: G1173
0
 34,900  30.96 1173  1416 J

1414
Thus : K P  exp( )  1.156
8.3144  1173

CO2 + H2 = H2O + CO

Initial # of moles 0.25 0.25 0 0.5

# after reaction 0.25 - X 0.25 - X X 0.5 +X

147
For PT  1atm
pH 2O  pCO X (0.5  X )
KP   1.156 
pCO2  pH 2 (0.25  X ) 2

Solving : X  0.0676

 X CO2  X H 2  0.25  0.0676  0.182

X CO  0.5  0.0676  0.568
X H 2O  0.0676

148
Problem 11.2

How much heat is evolved when 1 mole of SO2 and ½ mole of O2, each at 1 atm

pressure, react to form the equilibrium SO3–SO2–O2 mixture at 1000 K and 1 atm

pressure?

Solution

From Section 11.6 we get:

1
SO2  O2  SO3 G 0  94, 600  89.37T
2
G1000
0
=  94, 600  89.37 1000  5230 J
5230
K P ,1000  exp( )  1.876
8.3144 1000

1
SO2  O2 = SO3
2
1
initial moles 1 0
2
1 1
upon reaction 1-x  x x
2 2

1 1 1
The total number of moles in the system is:1-x +  x + x = (3  x)
2 2 2
ni
and pi  P
nTotal
1 1
 x
(1  x) 2(1  x) 1 x x 2x
 pSO2  P P : pO2  2 2 P  P : pSO3   P
1 (3  x ) 1 (3  x ) 1 (3  x )
(3  x) (3  x) (3  x)
2 2 2
1
pSO3 x(3  x) 2
K P ,1000   1.876  1 : x  0.463
pSO2 pO2
(1  x) (1  x)
2

For the formation of one mole of SO3 : H  H 0  94, 600 J

For the formation of 0.463 mole of SO3 : H  (0.463)  (94, 600)  43,800 J evolved

149
Problem 11.3

A CO2–CO–H2O–H2 gas mixture at a total pressure of 1 atm exerts a partial pressure

of oxygen of 10-7 atm at 1600°C. In what ratio were the CO2 and H2 mixed to produce

the gas with this oxygen pressure?

Solution

The ratio of CO2 to H2 is set as the unknown a.

CO2  H 2  H 2O  CO
initial moles a 1 0 0
after reaction ax 1 x x x

The O 2 comes from the decomposition of the water

1
H 2  O2  H 2O G1873
0
 142,892 J
2
142,892 pH 2O x
For this reaction: K P  exp( )  9660 = 
8.3144 1873 pH 2  pO2 (1  x)103.5
1/2

This yields x  0.753

1
Now for the reaction: CO  O2  CO2 G1873 0
 119,805 J
2
119,805 pCO2 ax
For this reaction: K P  exp( )  2193  = 
8.3144 1873 pCO  pO2 x 103.5
1/2

This gives: a  1.275 which is the ratio to be determined.

150
 Problem 11.4

Lithium bromide vapor dissociates according to LiBr(g) → Li(g) + ½ Br2,(g). At

what temperature does the partial pressure of Li reach the value of 10–5 atm

when the gas is heated at a constant total pressure of 1 atm?

Solution

1
LiBr  Li  Br2
2
initial moles a 0 0
1
after reaction 1 x x x
2

x
At PTotal  1 atm :  105  x  105
p Li 
1
1 x
2
1 x 1 5
 pLiBr  1 pBr2  x  0.5 10
1 2
1 x
2
1
pBr2 2  p Li 1
Thus : K P   (0.5 105 ) 2 105  2.236 108
pLiBr

1
For the reaction: LiBr  Li  Br2 G 0  333900  42.09T
2
 333,900  42.09T  8
K P  exp    2.236 10
 8.3144  T 

Thus, T  1771 K

151
 Problem 11.5

When SO3 is decomposed at the constant pressure P and T = 1000 K, the partial

pressure of O2 in the equilibrium gas is 0.05 atm. What is the pressure P? If the

pressure of this equilibrated gas is increased to 1 atm, to what value must the

temperature be decreased to produce a gas mixture in which pO2  0.05 atm?

Solution

From Section 11.6 we get:

1
SO3 = SO2  O2 G 0  94, 600  89.37T
2
G1000 = 94, 600  89.37 1000  5230 J
0

5230
K P ,1000  exp( )  0.533
8.3144  1000
pSO2  2 pO2 and pSO3  PTotal  pSO2  pO2  PTotal  3  pO2

1 1
pO22  pSO2 (0.05) 2  2  0.05
K P  0.533  
pSO3 ( PTotal  0.15)
This gives; PTotal  0.192 atm

1
(0.05) 2  2  0.05
If PTotal  1 atm, K P   0.0263
(1  0.15)

G 0  94, 600  89.37T  8.3144T  ln 0.0263

which gives: T  791 K

152
Problem 11.6

For the dissociation of nitrogen according to

N2 = 2N

∆G° = 945,000 – 114.9T J

Calculate:

a. The equilibrium partial pressure of N in nitrogen gas at 3000 K and a total

pressure of 1 atm

b. The total pressure of the gas, at 3000 K, at which the partial pressure of

N2 is 90% of the total pressure

Solution

(i) For the reaction: N 2  2 N at 300 K we have:

G 3000
0
 945, 000  114.9T  600,300 J
600,300 p2 pN2
 K P  exp( )  3.53 1011  N 
8.3144  3000 pN2 1  pN
pN  5.94 106 atm

(ii) PTotal = pN2 + pN  0.9 PTotal +0.1PTotal

pN2  0.1PTotal  0.01

2

But K P  3.53 1011   =  PTotal

pN 2 0.9 PTotal 0.9

 PTotal  3.18 109 atm

153
Problem 11.7

Ammonia gas is heated to 300°C. At what total pressure is the mole fraction of N2 in

the equilibrium gas mixture equal to 0.2. Calculate the standard enthalpy change and

the standard entropy change for the reaction

3 1
H 2( g )  N 2( g )  NH 3( g )
2 2

at 300°C.

Solution

(i) For the reaction: 3H 2( g )  N 2( g ) = 2NH3( g )

From Table A.1 GT0  87030  25.8  T  ln T  31.7  T : G 573
0
 25, 022
 25022 
and therefore K P ,573  exp    191
 8.3144  573 
Since pH 2  3 pN2 thus: x H 2  3 xN2
Thus, xN2  0.2, x H 2  0.6 and x NH3  1  0.2  0.6  0.2

2
pNH ( xNH3  P ) 2 0.22
K  191  3
 
pN2  pH3 2 x N 2  P  ( xH 2  P ) 3 0.2  0.63  P 2
P  13.3 atm

(ii) For the reaction: 3H 2( g )  N 2( g ) = 2NH 3( g )

G T0  87030  25.8T ln T  31.7T
G T0
 ST0  25.8ln T  25.8  31.7 S5730
 221.4 J / K
T
H 573
0
 G573
0
 T S573
0
 25, 022  573  (221.4)  101,840 J

3 1
Thus, for the reaction: H 2( g )  N 2( g ) = NH 3( g )
2 2
101,840
H 573
0
  50,920 J
2
221.4
S573
0
 =  110.7 J / K
2

154
Problem 11.8

By establishing the equilibrium

PCl5(g) = PCl3(g) + Cl2(g)

at 500 K in a mixture of PCl5 and PCl3 a gas is obtained at 1 atm total pressure in

which the partial pressure of Cl2 is 0.1 atm. In what ratio were PCl5 and PCl3 mixed to

obtain this equilibrium gas?

Solution

From Table A.1 we obtain:

GT0  95, 600  7.94  T  ln T  235.2  T for the reaction:
PCl3( g )  Cl2( g )  PCl5( g )
G500
0
 95, 600  7.94  500  ln 500  235.2  T  2, 672 J
2, 672
Thus : K P ,500  exp( )  1.90
8.3144  500
PCl3 + Cl2 = PCl5
initial moles a 0 1
upon reaction ax x 1 x

Here, nTotal  a  x  1
x
At: PTotal  1 atm pCl2   0.1 (i)
a  x 1
pPCl5 (1  x)  (a  x  1)
K P ,500  1.90   (ii)
pPCl3  pCl2 x  (a  x)
Solving (i) and (ii) simultaneously, we obtain: a  2.692 and x  0.410

PCl3
Therefore :  a  2.692
PCl2

155
Problem 11.9

Air and hydrogen are mixed in the ratio 1:4 and are heated to 1200 K. Calculate the

partial pressures of H2 and O2 in the equilibrium gas at 1 atm pressure and at 10 atm

pressure. Air contains 21 volume percent O2.

Solution

We use the basis as 100 moles of H 2 plus air

nH 2 =20 and nair  80 or nO2  0.21 80  16.8 and nN2  0.79  80  63.2

1
H 2  O2  H 2O GT0  247,500  55.85T
2
G1200
0
 247,500  55.85 1200  180, 480 J
180, 480 pH 2O
K P ,1200  exp( )  7.178 107 
8.3144 1200 1
pH 2  pO22

nH 20 2nH 2  2nH 2O
  1.1905 
nO 16.8 2nO2  nH 2O
nO 16.8 2nO2  nH 2O 2nO2  nH 2O
  0.2658  
nN 63.2 2  63.2 126.4

Therefore :
2nO2  nH 2O  0.2658 126.4  33.6
2nH 2  2nH 2O  33.6 1.1905  40

Therefore : nH 2O  20  nH 2  33.6  2nO2

1
2nO2  6.8  nH 2
2
nTotal  nH 2O  nH 2  nO2   nN2
 1  1
 
nTotal  20  nH 2  nH 2   6.8  nH 2   63.2  90  nH 2
 2  2
1
n n 2
H 2O Total
K P ,1200  7.178 107  1 1
n n P
H2
2
O2
2

156
For P  1 atm
1
 1 2
n n
1
2
H 2O Total
 20  n 
H2  90  nH 2 
 2 
7.178 10  7
1 1
 1
n n P 2 2  1 2
H2 O2 nH 2   6.8  nH 2 
 2 
7
Thus : nH 2  9.43 10 moles
nO2  6.8 moles and nTotal  90 moles
nH 2 9.43 107 moles
pH 2   PTotal   1.05 108 moles
nTotal 90
6.8
and pO2  PTotal  0.0756 atm
90

For P  10 atm
1
 1 2
n n
1
2
H 2O Total
 20  n 
H2  90  nH 2 
 2 
7.178 10  7
1 1
 1
n n P 2 2  1 2
H2 O2 nH 2   6.8  nH 2  10
 2 
7
Thus : nH 2  2.98 10 moles
nO2  6.8 moles
nH 2 2.98 107 moles
pH 2   PTotal   10  3.31108 moles
nTotal 90
6.8 6.8
and pO2  PTotal  10  0.756 atm
90 90

157
Problem 11.10

One mole of each of hydrogen, iodine vapor, and HI gas are allowed to react at 1500

K and P = 1 atm. Calculate the mole fractions of H2, I2, and HI in the equilibrium

mixture. The temperature is then changed to that value at which pHI in the equilibrated

gas is five times pH2 . What is this temperature?

Solution

For the reaction: H 2  I 2  2 HI , GT0  8,370  17.65  T

G1500
0
 8,370  17.65 1500  34,845 J
2
34,845 pHI
K P ,1500  exp( )  16.345 
8.3144 1500 pH 2  p I 2

H2  I2  2 HI
before reaction 1 1 1
after reaction 1-x 1-x 1 2x
Thus, nTotal  3

1  2 x 
2

(i ) K P ,1500  16.345  : This gives: x  0.504

(1-x)  (1-x)
 1  x   1  0.504 
xH 2  xI 2      0.165
 3   3 

xHI 
1  2 x   1  2  0.504   0.669
3 3

(5 pH 2 ) 2
(ii ) For : pHI  5 pH 2 : K P ,1500   25  8,370  17.65  T
 
2
pH 2
G1500
0
 8,370  17.65 1500  34,845 J  8,370 1500  ln 25

This gives: T  918 K

158
Problem 11.11*
Consider the reduction of Magnetite by CO to form pure iron:

Fe3O4 ( s )  4CO ( g )  3Fe( s )  4CO2 ( g )

Calculate the partial pressure of CO and CO2 in terms of the equilibrium constant KP
for the reaction at any temperature, T.

SOLUTION

Assume the activity of the solids to be unity and that the gases behave as ideal gases.
3 4 4
a Fe aCO pCO
KP  2
4
 4
2

a Fe3O4 aCO pCO

1
pCO2
K P4 
pCO
Also the total pressure is 1 atmosphere:
pCO2  pCO  1

Solving the two equations simultaneously:

1
1 K P4
pCO  1
pCO2  1
( K  1)
4
P ( K P4  1)

159
Problem 11.12*

It is known that at 300 K the value of KP for a certain reaction is 1012. For the

reaction H0 is 100 kJ/mole.

a. Determine if this reaction is favorable at 800 K and estimate KP (800K). Explain.

b. The actual value of KP (800) is 35. Explain any discrepancy from your estimate.

SOLUTION

First, estimate KP at 800 K.

 K (800 K )  H 0  1 1 
ln  P    
 K P (300 K )  R  300 800 
 K (800 K )  100000  1 1 
ln  P      25.06
 K P (300 K )  8.3144  300 800 
K (800 K )
Thus P  exp( 25.06)
K P (300 K )
K P (800 K )  K P (300 K ) exp( 25.06)  13.12

Since the value is greater than unity the reaction is possible at 800 K,

b. The above method assumed there was no temperature dependence of H0 over the

span of 500 K.

160
Problem 11.13.

Sketch the natural log of KP vs. 1/T for the cases of 

      aH0 < 0 S0 < 0

b.H0 < 0 S0 > 0

c.H0 > 0 S0 > 0

d.H0 > 0 S0 < 0

161
Chapter 12
Problem 12.1

To what temperature must MgCO3 be heated in an atmosphere containing a partial

pressure of CO2 of 10–2 atm to cause decomposition of the carbonate?

SOLUTION

MgO  CO2  MgCO3

from Table A-2 GT0  117600  170  T  RT ln pCO 2
pCO2  102 atm
 117600  170  T  8.3144T ln102
which gives T  565 K

162
Problem 12.2

Using the standard Gibbs free energies of formation of NiO from solid Ni and liquid

Ni, calculate the melting temperature, molar heat of melting, and the molar entropy of

melting of nickel.

SOLUTION

(i ) 2 Ni ( s)  O2  2 NiO GT0 =  471, 200  172T J

(ii ) 2 NiO( s)  O2  2 Ni (l ) GT0 =  506,180  192.2T J

Subtracting (ii) from (i):we get:

2 Ni ( s )  2 Ni (l ) GT0 =+34,980  20.2T J

34,980
Thus: Tmelting  = 1731 K
20.2
34980
H melting
0
 = 17,490 J (+ since endothermic)
2
20.2 J
Smelting
0
= =10.1
2 K

163
Problem 12.3

Calculate the temperature at which pure Ag2O decomposes to Ag metal and O2 gas

when heated in (1) pure oxygen at 1 atm pressure, and (2) in air.

SOLUTION

1
2 Ag  O2  Ag 2O
2
GT  30,540  66.11T J
0

For pO2 (eq)  1atm

1
 30,540  66.11T   RT ln 1
0
p 2
pO2 ( eq )

T  462 K

For pO2 (eq)  0.21atm

1 1
30,540  66.11T   RT ln 1
 8.3144  T  ln(0.21)
2
p 2
pO2 ( eq )

T  421K

164
Problem 12.4

Determine the maximum pressure of water vapor in wet hydrogen at 1 atm pressure in

which chromium can be heated without oxidation occurring at 1500 K. Is the

oxidation of Cr by water vapor exothermic or endothermic?

SOLUTION

3
For 2Cr  O2  Cr2O3 GT0  1,110,100  247.3  T
2
G1500
0
 739,150 J
3
For 3H 2O  3H 2  O2 GT0 = 742,500  167.55  T
2
G1500
0
 491,175 J
Adding the above equations gives:
2Cr  3H 2O  Cr2O3 + 3H 2 GT0 =  367, 600  79.75  T
G1500
0
 247,975 J
pH2O
G10500  247,975 J  1500 K  8.3144  3  ln
pH 2
pH2O
 1.32 103 atm pH 2  1 atm pH2O  1.32 103 atm
pH 2

Thus, for 2Cr  3H 2O  Cr2O3 + 3H 2

GT0 =  367, 600  79.75  T  H 0  T S 0
H 0    367, 600
EXOTHERMIC

165
Problem 12.5

A mixture of argon gas and hydrogen gas at 1 atm total pressure is passed through a

reaction vessel containing a mixture of liquid Sn and liquid SnCl2 at 900 K. The

composition of the gas leaving the vessel is 50% H2, 7% HCl, and 43% Ar. Has

equilibrium been attained between the gas phase and the liquid phases in the vessel?

SOLUTION

For SnCl 2 (l )  Sn(l )  Cl2 (g) GT0  333, 000  118.4  T

G1500
0
 226,440 J
For H 2  Cl2  2 HCl GT0 =  188, 200  12.8  T
G1500
0
 199720 J
Adding the above : SnCl2 (l )  H 2  Sn(l )  2 HCl (g)
G1500
0
 26, 720 J
26, 720 p2
K P  exp( )  0.028  HCl
8.3144  900 pH 2

2
pHCl 0.07 2
In the exit gas   0.0098.
pH 2 0.5
Since this is less than K P , equilibrium has not been attained.

166
Problem 12.6

Fe and FeO are in equilibrium with a gas mixture of composition 71.8% CO– 28.2%

CO2 at 1273 K. Which of the two solid phases disappears if the composition of the

gas is held constant and the temperature of the system is decreased?

SOLUTION

1
For Fe  O2  FeO GT0  263, 700  64.35  T J
2
1
For CO2  O2  CO GT0  282, 400  86.81 T J
2
Adding the above two reaction:
Fe  CO2  FeO  CO GT0  18, 700  22.46  T J

As written, the reaction is endothermic

Decreasing the temperature thus shifts the reaction to the left.
Thus the pressure of CO is lowered and that of CO2 is increased

Thus, if we decrease the temperature at constant pressure of both CO and CO2 the FeO
phase will disappear.

167
Problem 12.7

Calculate the vapor pressure of Mg exerted at 1400°C by the system in which the

reaction equilibrium

4MgO(s) + Si(s) = 2Mg(g) + Mg2SiO4(s)

is established.

SOLUTION

For 2MgO  SiO2  Mg 2SiO 4 GT0  67, 200  4.31 T J

G1673
0
 67, 200  4.31 1673  59,989 J
For 2MgO(s)  O2  2Mg ( g ) GT0  1, 459, 200  408  T J
G1673
0
 1, 459, 200  408  1673 =776,616 J
For Si  O2  SiO2 GT0  907,100  175  T J
G1673
0
 907,100  175 1673 J  614,325

For : 4 MgO  Si  2 Mg (v)  Mg 2 SiO4 we only need to add all three of the above
equations : G1673
0
 59,989  776,616  614,325  102,302 J
102,302
K P  exp( )  p 2 Mg( v ) pMg( v )  2.53 102 atm
8.3144 1673

168
Problem 12.8

One gram of CaCO3 is placed in an evacuated rigid vessel of volume 1 liter at room

temperature, and the system is heated. Calculate (1) the highest temperature at which

the CaCO3 phase is present, (2) the pressure in the vessel at 1000 K, and (3) the

pressure in the vessel at 1500 K. The molecular weight of CaCO3 is 100.

SOLUTION

For the reaction: CaO  CO2  CaCO3 G T0  168, 400  144  T

 168, 400 144  20, 254
Thus, ln pCO2       17.32 (i)
 8.3144  T 8.3144  T
1g
One gram of CaCO3   0.01 moles
g
100
mole
All of the CaCO3 is depleted when the gas phase CO2 is composed of 0.01 moles.
nRT 0.01 0.  T
pCO2    8.2057 104  T (ii)
V 1

(a) Solving equations (i) and (ii) simultaneously gives: T  1166 K and pCO2  0.96
This is the highest temperature that the solid can CaCO3 exist under the given conditions

(b) At 1000K, equation (i) gives: pCO2  0.053 atm

(c ) At 1500K, equation (ii) gives: pCO2  1.23 atm

169
Problem 12.9

Calculate the total pressure p SO3  pSO2  pO2  exerted by equilibrated CoO and

CoSO4 at 1223 K.

SOLUTION

For the reaction: CaO  SO3  CaSO4 G T0  227,860  165.3  T

G1223
0
 227,860  165.3  1223  25, 698 J
 227,860 165.3  2
Thus, pSO3  exp      7.99 10 atm (i)
 8.3144 1223 8.3144 

1
For the reaction: SO3  SO2 + O 2 G T0  94, 600  89.37  T
2
1
pSO2  pO22
G 0
1223  94, 600  89.37 1223  14, 699 J  8.3144 1223  ln
pSO3
1
pSO2  pO22 1
 4.244 and pSO2  pO2
pSO3 2

1
pSO2  (0.5 pSO2  ) 2
Thus 4.244 
7.99  102
pSO2  0.612
pO2  0.306
pSO3  0.08
Total Pressure = 1 atm

170
Problem 12.10

A gas mixture initially containing 90% CO, 0.4% COS, and 9.6% inert constituents

(by volume) is passed over sponge iron at 1000 K to remove sulfur by the following

reaction: COS(g) + Fe(s) = CO(g) + FeS(s)

(1) Assuming that the effluent gas is in equilibrium with Fe and FeS, calculate the

percentage of sulfur removed from the gas by reaction with the sponge iron. (2)

Calculate the partial pressure of S2 in the effluent gas.

SOLUTION

1 1
For (i) C ( s )  O2  S 2  COS GT0  202,800  9.96  T J
2 2
G1000
0
 202,800  9.96 1000  212, 760 J
1
(ii) Fe( s )  S 2  FeS GT0  150, 200  52.55  T J
2
G1000
0
 150, 200  52.55 1000  97,650J
1
(iii) C ( s )  O2  CO GT0  111, 700  87.65  T J
2
G1000
0
 111, 700  87.65 1000  199,350 J

For COS  Fe( s )  CO  FeS ( s ) we sum (ii )  (iii )  (i )

G1000
0
 84, 220 J
 84, 220  pCO
Thus : K P  exp    2.5130 10 
4

 8.3144  1000  pCOS

COS  Fe  CO  FeS
before reaction 0.4 90
after reaction 0.4  x 90  x

pCO 90  x
(a) 2.5130  104   : solving we get x  0.3964
pCOS 0.4  x
0.3964
Thus, the % of S removed is: 100  99.1
0.4

1
(b) For CO  S 2  COS : we sum (i )  (iii ) : G10000
 13, 410 J
2
 13, 410  pCOS (0.4  0.3964)
Thus : K P  exp    5.017  
 8.3144 1000 
1 1
pCO  pS22 (90  0.3964)  pS22
Thus, pS2  6.3 1011 atm

171
Problem 12.11

An Ar–H2O gas mixture of pH2O  0.9 atm (Ptotal = 1 atm) is passed over solid CaF2,

as a result of which CaO forms according to

CaF2(s) + H2O(g) = CaO(s) + 2HF(g)

The reaction proceeds to equilibrium and solid CaO and solid CaF2 are mutually

immiscible. When the gas flow rate (measured at 298 K and 1 atm pressure) over the

sample is 1 liter per minute, the measured rates of weight loss of the sample are 2.69

× 10–4 and 8.30 × 10–3 grams per hour at 900 and 1100 K, respectively. Use these data

to calculate the variation of ΔG° for the above reaction with temperature. The atomic

weights are

O = 16, F = 19, and Ca = 40.08.

SOLUTION

CaF2  H 2O( g )  CaO  2 HF ( g )

molecular weight 78.08 56.08
Thus a loss of 22 g produces 2HF and consumes 1 H 2O
1 1
A loss of one g produces = 0.0909 moles HF and consumes = 0.0455 moles of H 2O
11 22

At 900 K for one hour there was a loss of 2.69  104 g :

This produces (0.0909*2.69  104 )  2.44 105 moles of HF
It consumes (0.0455* 2.69  104 )  1.22  105 moles of H 2O

The number of moles of H 2O which passed over the solid is found by the ideal gas law to be:
p H 2 0 V 0.9atm  60l
nH 2 0    2.208 moles
RT l  atm
0.082057  298K
mole  K
The loss of 1.22  105 moles of H 2O is insignificant.
The pressure of the HF is found to be:
l  atm
2.44  105 moles  0.082057  298K
pHF  mole  K  9.94 106 atm
60l
p HF  9.94 10 
2 6 2

K 900    1.09 1010

pH 2O 0.9
G900
0
 8.3144  900  ln 1.09  1010   171,596

172
At 1100 K for one hour there was a loss of 8.3  103 g :
This produces (0.0909*8.3 103 )  7.545  104 moles of HF

The pressure of the HF is found to be:

l  atm
7.545 104 moles  0.082057  298K
pHF  mole  K  3.075 104 atm
60l
p HF  3.075 10 
2 4 2

K 900    1.051107
pH 2O 0.90
G900
0
 8.3144  1100  ln 1.051 107   146,959 J

Now G T0  A  BT
146,959 J  A  B 1100
171,596 J  A  B  900

Thus we obtain : A  282, 449 J and B  123 J / K

173
Problem 12.12

Magnetite (Fe3O4) is reduced to sponge iron (Fe) in a continuous reactor operating at

800 K using methane gas (CH4) as the reducing agent. The gaseous reaction product

leaving the reactor at a total pressure of 1 atm is a mixture of CO, CO2, H2, and H2O

with a negligible methane content. The gas is at equilibrium with the Fe–Fe3O4

mixture in the reactor. Calculate the consumption of methane as moles of methane

used per mole of Fe produced.

SOLUTION

For 3Fe  2O2  Fe3O4 GT0  1,102, 200  307.4  T

G 800
0
 1,102, 200  307.4  800  856, 280 J
 2  8.3144  800  ln pO2 (eq )
pO2 in the exit gas is thus: 1.111028 atm

For H 2  2O2  H 2 O GT0  247,500  55.85  T

G 800
0
 247,500  55.85  800  202,820 J
pH 2O
 202,820 J  8.3144  800  ln 1
pH 2  p 2
O2

pH 2O pH 2O 1

1
 1.748  10
13
and thus  1.748 10  1.1110
13

28 2
 0.1842 (i)
pH 2
pH 2  p 2
O2

For 2CO  O2  2CO2 GT0  564,800  173.62  T

G 800
0
 564,800  173.62  800 J  425,904 J
pCO2
 425,904 J  8.3144  800  ln 1
pH 2  pO22
pCO2 pCO2 1

1
 8.02  1013 and thus  8.02 1013  1.111028  2  0.845 (ii)
pH 2
pH 2  p 2
O2

174
Now : pH 2  pH 2O  pCO  pCO2  1 atm (iii)

All of the carbon and hydrogen in the gass came from the CH 4
nC 1 pCO  pCO2
 
nH 4 2 pH 2  2 pH 2O
Therefore : pH 2  pH 2O  2 pCO  2 pCO2 (iv)

Solving equations (i ) through (iv) similtaneously gives :

pH 2 = 0.5662 atm
pH 2O  0.1003 atm
pCO = 0.1806 atm
pCO2 = 0.1528 atm
All of the carbon came from the CH 4  0.1806  0.1528  0.3334 moles

3
Thus there was 0.3334 moles of CH 4 per  0.5865  0.5398 moles of Fe
4

Thus : 0.76 moles of CH 4 was consumed per mole of Fe produced.

175
Problem 12.13

Three equations for the oxidation of Mg according to

Mg + ½O2(g) = MgO(s) are ∆G° = –604,000 – 5.36T ln T + 142.0T J (i)

∆G° = –759,800 – 13.4T ln T + 317T J (ii)

∆G° = –608,100 – 0.44T ln T + 112.8T J (iii)

One of these expressions is for the oxidation of solid Mg, one is for the oxidation of

liquid Mg, and one is for the oxidation of gaseous Mg. Determine which equation is

for which oxidation and calculate the melting and normal boiling temperature of Mg.

SOLUTION

To solve this problem we will apply the Gibbs-Helmholtz equation (5.38) to each of

the above reactions and then use the following inequalities to determine which of the

equations belong to the various states Mg.

H Mg
0
( gas )  H Mg ( liquid )  H Mg ( solid )
0 0

176
  G 0 
 
 T    H
0

T T2
GI0 604, 000
For equation I :   5.36 ln T  142.0
T T
 GI0 
 
 T   604, 000  5.36   H I
0

T T2 T T2
H I0  604, 000  5.36T
GII0 759,800
For equation II :   13.4 ln T  317
T T
 GI0 
 
 T   759,800  13.4   H II
0

T T2 T T2
H I0  759,800  13.4T

GIII
0
608,100
For equation III :   0.44 ln T  112.8
T T
 GI0 
 
 T   608,1000  0.44   H III
0

T T2 T T2
H I0  608,1000  0.44T
H Mg
0
( gas )  H Mg ( liquid )  H Mg ( solid )
0 0

Thus : II is for the oxidation of gaseous Mg

Thus : III is for the oxidation of liquid Mg
Thus : I is for the oxidation of solid Mg

The melting temperature is where GMg

0
( liquid )  GMg ( solid )
0

GIII
0
 GI0 Thus, TM , Mg  930 K
The boiling temperature is where GMg
0
( liquid )  GMg ( gas )
0

GIII
0
 GII0 Thus, TB , Mg  1372 K

177
Problem 12.14

200 grams of liquid zinc are placed in a crucible at 1030 K. Two moles of air are

bubbled through the liquid zinc, and the gas comes to equilibrium with the liquid

before leaving the system. If the total pressure of the gas remains constant at 0.8 atm

throughout the process, how many grams of metallic zinc are left in the crucible? The

atomic weights of Zn and O are, respectively, 65.38 and 16.

SOLUTION

178
 1
For the reaction: Zn(v)  O2 ( g )  ZnO( s) G T0  460, 200  198T
2
G1030  460, 200  198 1030  256, 620
0

460, 200 1
 K1030  exp( )  9.9  1012 
8.3144 1030 1
pZn  pO22
The saturated vapor pressure of Zn (from Table A.4)
15, 250
0
ln pZn (atm)    1.255ln T  21.79
T
Thus, at 1030K: pZn 0
 0.1787(atm)
2
 1  25
and pO2     3.2  10 (atm)
 9.9  10  0.1787 
12

Two moles of air:  0.42 moles of O2  1.58 moles of N 2

Thus : 0.42 moles O2  0.84 moles of Zn  0.84 moles of ZnO
g
0.84 moles of Zn  0.84  65.38  54.92 grams moles of Zn oxidized to ZnO
mole

1.58 moles of N 2 at 1030K and PTotal  0.8(atm)

 pN2  0.8  0.179  0.621(atm)
1.58  0.082057  1030
Now : pN2V  nN2 RT : Thus Vgas   215 liters
0.621
0.179  215
pZnV  nZn RT : Thus nZn   0.455 moles of Zn
0.082057  1030
0.455 moles of Zn  0.455  65.38  29.78 grams of Zn
Thus, 29.78 grams of Zn evaporated so the remaining Zn
in the liquid is 200  54.9  29.8  115.3 g

179
Problem 12.15

Methane gas is burned with twice the amount of stoichiometric air (i.e, the initial ratio

of CH4 and O2 in the mixture is 0.25), and the combustion gas produced, in which the

concentration of methane is negligible, is used to calcine CaCO3 in an isothermal

furnace. The gas and the solids are at 1080 K and the pressure of the gas is maintained

constant at 1 atm. How many moles of CaCO3 are decomposed per mole of CH4

burned?

SOLUTION

79
CH 4  4O2  4  N 2  CO2  2 H 2O  2O2  15.05 N 2
21
nTotal  20.05 moles
1
In the gas; pCO2   0.0499( atm)
20.05
For the reaction: CaO  CO2  CaCO3 G T0  168, 400  144T
Thus: G1080
0
 168, 400  144  1080  12,880  8.3144  1080  ln pCO2

pCO2  0.238. The decomposition of x moles of CaCO3 produces x moles of CO2

and increases the pressure of CO2 from 0.0499 to 0.238

1 x
Thus, 0.238  : x  4.95
20.05  x

Thus, 4.95 moles of CaCO3 are decomposed per mole of CH 4 that is burned.

180
Problem 12.16

Mercuric oxide (HgO) is placed in a vessel which is then evacuated, filled with

nitrogen, and heated to 600 K, at which temperature it is observed that the total

pressure in the vessel is 2 atm. Calculate the mole fractions of O2 and Hg vapor in the

gas phase.

SOLUTION

1
HgO( s)  Hg (v)  O2
2
GT  152, 200  207.2T (see Table A-1)
0

G600
0
 27,880 J
1
27,880
Thus, K  exp( )  3.74 103  pHg  pO22
8.3144  600 K
1
1  pHg  2
But, pO2  pHg Thus 3.74 103  pHg   
2  2 

1
pHg  0.0303 pO2  pHg  0.0151 pN2  2  .0303  .0151  1.95
2

0.0303 0.0151
X Hg   0.0151 X O2   0.005
2 2

181
Problem 12.17

In Fig. 12.17 the line AB, which represents the equilibrium

FeO(s) + CO(g) = Fe(s) + CO2(g)

intersects the carbon deposition line at the point A (T = 972 K, pCO(s) = 0.595 atm,

pCO2  0.405 atm, P = 1.000 atm). At what total pressure does the point of

intersection of the lines occur at 1000 K, and what are the values of the partial

pressures of CO and CO2 in this state?

SOLUTION

For the reaction FeO  CO  Fe  CO2 we need to add the following two reactions:
1
(a) FeO  Fe  O2 G T0  263, 700  64.35T
2
1 564,800 173.62
(b) CO  O2  CO2 GT0    T see section 12.6
2 2 2
Adding (a) +(b) FeO  CO  Fe  CO2 GT0  18, 700  22.46T
pCO2
GT0  18, 700  22.46T   RT ln
pCO
18,700 22.46 pCO2
Thus, at the total pressure PT :  = ln
8.3144  T 8.3144 pCO
2, 249 pCO2 ( P  pCO )
(i )  2.70  ln  ln Total  0.46
T pCO pCO
For the reaction: C  CO2  2CO
2
pCO
G 0 = 170, 700  174.5  T =  RT ln
pCO2
2
170, 700 174.5 pCO
(ii )    20.53  20.99  ln  0.46 at 1000 K
8.3144  T 8.3144 PTotal  pCO
( PTotal  pCO )
Solving (i)  0.63
pCO
2
pCO
(ii)  1.58
PTotal  pCO

PTotal  1.68 atm pCO  1.03 atm pCO2  1.68  1.03  0.65 atm

182
Chapter 13
Problem 13.1

Air at atmospheric pressure is blown over a Cu-rich copper-gold liquid solution at

1500 K. If only the copper is oxidized (to form pure solid Cu2O), calculate the

minimum activity of Cu which can be obtained in the solution.

Solution

1
For the reaction: 2Cu (l )  O2  Cu2O
2
GT  188,300  88.48T J
0

1
G1500
0
 188,300  88.48  1500  55,580 J  RT ln aCu
2
 pO22
1
 55,580 
 aCu
2
 (0.21) 2  exp     0.0116
 8.3144 1500 

aCu  0.159

183
Problem 13.2

Magnesium can be removed from Mg–Al liquid solution by selectively forming the

chloride MgCl2. Calculate the activity of Mg in the liquid Mg–Al system which can

be achieved at 800°C by reacting the solution with an H2–HCl gas mixture containing

hydrogen at essentially 1 atm pressure and pHCl = 10–5 atm to form pure liquid MgCl2.

Solution

For the reaction: Mg (l )  O 2  MgCl2 GT0  603, 200  121.43T J

G1073
0
 603, 200  121.43  1073 J  472,906 J
For the reaction: H 2 Cl 2  2 HCl ( g ) GT0  188, 200  12.8T J
G1073
0
 188, 200  12.8  1073 J  201,934 J

 Mg  2 HCl  MgCl2  H 2  472,906  201,934  270,971 J

aMg  pHCl
2

G1073
0
 270,971 J  RT ln
pH2 2
aMg  pHCl
2
270,971 14
aMg  (105 ) 2
 exp( )  6.44 10 
pH2 2 8.3144  1073 1

aMg  6.44  104

184
Problem 13.3

The partial pressure of oxygen in equilibrium with pure liquid lead and pure liquid

lead oxide at 1200 K is 2.16 × 10–9 atm. When SiO2 is added to the liquid PbO to

form a lead silicate melt the oxygen pressure in equilibrium with pure liquid lead and

the silicate melt is decreased to 5.41 × 10–10 atm. Calculate the activity of PbO in the

lead silicate melt.

Solution

1
For the reaction: Pb(l )  O 2  PbO(l )
2
aPbO 1
For the aPbO  1: K1200  1
 1
 21517
aPb  pO2 1   2.16  10 
2 9 2

1
In the lead silicate, aPbO  K1200 1   5.4110 
10 2
 0.5
aPbO  0.5

185
Problem 13.4

Copper, present as an impurity in liquid Pb, can be removed by adding PbS to the Cu–

Pb alloy and allowing the exchange reaction

2Cu(s) + PbS(s) = Cu2S(s) + Pb(l)

to come to equilibrium.

The solid sulfides are mutually immiscible, Pb is insoluble in solid Cu, and the Cu

liquidus, below 850°C, can be represented by

3500
log X Cu    2.261
T

where XCu is the solubility of Cu in liquid Pb. If Cu obeys Henry’s law in liquid Pb,

calculate the extent to which Cu can be removed from liquid Pb by this process at

800°C. Would the extent of purification of the lead be increased by increasing or by

decreasing the temperature?

Solution

186
 1
For the reaction: Pb(l )  S 2  PbS GT0  163, 200  88.03T J (i)
2
1
For the reaction: 2Cu(s)  S 2  Cu2 S GT0  131,800  30.79T (ii)
2

Subtracting reaction (i) from reaction (ii)

2Cu(s)  PbS  Cu2 S  Pb(l ) GT0  31, 400  57.24T J
G1073
0
 31, 400  57.24  1073 J  30,019 J   RT ln K
30, 019 a
K  exp( )  28.93  2Pb ( l )
8.3144 1073 aCu ( s )
3500
(  2.261) 1
At 1073K , X Cu (liquidus )  10 1073
 0.0998   Cu   10.02
0.0998
aCu ( s )  10.02 X Cu and aPb  (1  X Cu )

(1  X Cu )
28.93  which gives: X Cu  0.018
10.02 X Cu 
2

At 1123K
3500
(  2.261) 1
X Cu (liquidus )  10 1123
 0.139   Cu   7.19
0.139
aCu ( s )  7.19 X Cu and aPb  (1  X Cu )
(1  X Cu )
28.93  which gives: X Cu  0.0255
 7.19 X Cu 
2

Thus the extent of prification is increased by decreasing the temperature.

187
Problem 13.5 A CH4–H2 gas mixture at 1 atm total pressure, in which pH2  0.957

atm, is equilibrated with an Fe–C alloy at 1000 K. Calculate the activity of C with

respect to graphite in the alloy. What would the value of pH2 in the gas mixture (at

Ptotal = 1 atm) have to be in order to saturate the Fe with graphite at 1000 K?

Solution

For the reaction: 2H 2  C  CH 4 GT0    91, 040  110.7T J

G1000
0
   91, 040  110.7 1000 J  19, 660  RT ln K
19, 660 pCH 4 1  0.957
 K  exp( )  9.4 102  
8.3144 1000 aC  pH 2  0.957 2  aC
2

 aC  0.5

For Fe saturated with C: aC  1 and PTotal  1

pCH 4 pCH 4
9.4  102   which gives :
aC  pH2 2 1  (1  pCH 4 ) 2

pH 2  0.92 and pCH 4  0.08

188
Problem 13.6

Calculate the activity of FeO in an FeO–Al2O3–SiO2 melt below which the FeO

cannot be reduced to pure liquid iron by a CO–CO2 mixture of pCO pCO2  105 at

1600°C.

Solution

For FeO(l ) : GT0  232, 700  45.13T : G1873

0
 232, 700  45.13 1873  148,172 J
For CO : GT0  111, 700  87.65T : G1873
0
 111, 700  87.65 1873  275,868 J
For CO2 : GT0  394,100  0.84T : G1873
0
 394,100  0.84 1873  395, 673 J

For the reaction: Fe(l )  CO2  FeO (l )  CO

G1873
0
   148,172  275,868  395, 673  28366 J   RT ln K
aFeO  pCO aFeO
K  6.18   105
aFe  pCO2 1
 aFeO  6.18 105

189
Problem 13.7

A piece of iron is to be heat-treated at 1000 K in a CO–CO2–H2O–H2 gas mixture at 1

atm pressure. The gas mixture is produced by mixing CO2 and H2 and allowing the

equilibrium CO2 + H2 = CO + H2O to establish. Calculate (a) the minimum H2/CO2

ratio in the inlet gas which can be admitted to the furnace without oxidizing the iron,

(b) the activity of carbon (with respect to graphite) in the equilibrated gas of this

initial minimum H2/CO2 ratio, (c) the total pressure to which the equilibrated gas

would have to be raised to saturate the iron with graphite at 1000 K, and (d) the effect,

on the partial pressure of oxygen in the equilibrated gas, of this increase in total

pressure.

Solution

(i ) For CO : GT0  111, 700  87.65  T : G1000

0
 111, 700  87.65 1000  199,350 J
For CO2 : GT0  394,100  0.84  T : G1000
0
 394,100  0.84 1000  394,940 J
For H 2O : GT0  247,500  55.85  T : G1000
0
 247,500  55.85 1000  191, 650 J
For FeO( s ) : GT0  263, 700  64.35  T : G1000
0
 263, 700  64.35 1000  199,350 J

For the reaction: CO  FeO  CO2  Fe : G1000

0
 394,940  199,350  199,350  3, 760 J
pCO2 3, 760
K   exp( )  0.636
pCO 8.3144 1000
For the reaction: H 2  FeO  H 2O  Fe : G1000
0
 191, 650  199,350  7, 700 J
pH 2 O 7, 700
K   exp( )  0.396
pH 8.3144  1000
2

For the reaction: CO2  H 2  CO  H 2O : pCO  pH 2O

190
Now : pCO  pCO2  pH 2  pH 2O  1 atm
pH 2 O
pCO  0.636  pCO   pH 2O  1 atm
0.396
1
pCO  [1  0.636   1] =1:  pCO  0.1938
0.396
pH 2O  pCO  0.1938
pH 2 O 0.1938
pH 2    0.4894
0.396 0.396
pCO2  0.636  pCO  0.636  0.1938  0.1233
These sum to 1 atm. This gas is in equilibrium with Fe and FeO

CO2
We mix CO2 and H 2 in the ratio x
H2

CO2  H 2  CO  H 2O
before reaction x 1 0 0
after reaction x  a 1 a a a
a
 pCO 
1 x
a
pH 2 O 
1 x
1 a
pH 2 
1 x
xa
pCO2 
1 x
xa
pCO2 xa
For equilibrium with Fe and FeO :  0.636   x 
1
pCO a a
1 x
pH 2 O a
Also,  0.396  :
pH 2 1 a
x  a x  0.2837 CO2
Thus, a  0.2837 and from the above: 0.636    x  0.4641 
a 0.2837 H2

1
For the reaction: Fe  O2  FeO GT0  263, 700  64.35  T
2
1
G1000
0
 263, 700  64.35 1000  199,350 J  RT ln pO2
2
pO2 ( Fe / FeO)  1.494 1021 atm

CO2
Now we choose a ratio of  0.4641 to see how that affects the equilibrium.
H2
We choose x  1

191
 CO2  H 2  CO  H 2O
before reaction 1 1 0 0
after reaction 1 a 1 a a a
a
 pCO  pH 2O 
2
1 a
pCO2  pH 2O 
2
For the reaction: CO2  H 2  CO  H 2O : we get G1000
0
from the following:
(i ) CO  FeO  CO2  Fe : G1000
0
 3, 760 J
(ii) H 2  FeO  H 2O  Fe : G1000
0
 7, 700 J
pCO  pH 2O
G1000
0
 (ii )  (i )  3940 J   RT ln
pCO2  pH 2
3940 a2
Thus : exp  0.6226  which gives a  0.441
 8.3144 1000  (1  a ) 2

a 1 a pCO2
pCO   0.2205 and pCO2   0.2796 Thus:  1.268
2 2 pCO
1
Now for the reaction CO  O2  CO2
2
 564,800   173.62 
G1000
0
     1000  195,590
 2   2 
1 1

 195,590  pCO2  1  2  1 2
Thus, K1000  exp    1.64  1010
     1.268  
 8.3144 1000  pCO  pO2   pO2 
This gives: pO2  5.93  1011 atm. This is greater than the value obtained above
for pO2 = 1.494  1021atm for the equilibrium of Fe / FeO. Thus increasing the value
pCO2
of the ratio of gives more oxygen in the gas, so we should leave that ratio at 0.4641.
pH 2

(ii) We need G1000

0
for C  CO2  2CO
(a) C  O2  CO2 G1000
0
 394,100  0.84 1000  394,940 J
(b) 2C  O2  2CO G1000
0
 2  111, 700  2  87.65 1000  398, 700 J
2
p
(b)  (a)  C  CO2  2CO G1000
0
 3760 J   RT ln CO

p 2
CO2 C a
2 2
p 0.1938
 CO
 1.572  which gives aC  0.194
2
p
CO2  aC 0.1233  aC
0.19382 P
(iii ) If the aC =1, and the pressure P : 1.572  : P = 5.16atm
0.1233 1
pCO2 pH 2O
(iv) The values of : and are not functions of the total pressure, P
pCO pH 2
192
Problem 13.8

An Fe–Mn solid solution containing XMn = 0.001 is in equilibrium with an FeO–MnO

solid solution and an oxygen-containing gaseous atmosphere at 1000 K. How many

degrees of freedom does the equilibrium have? What is the composition of the

equilibrium oxide solution, and what is the partial pressure of oxygen in the gas

phase? Assume that both solid solutions are Raoultian in their behavior.

Solution

(i ) P  F  C  2 : C = 3 (Mn, Fe and O), P = 3 (metal, oxide, gas)  F = 2

At a fixed temperature, T, there is only one degree of freedom.

1
(ii ) For the reaction Mn  O2  MnO : G1000 0
 388,900  76.32 1000  312,580 J
2
1
For the reaction Fe  O2  FeO : G1000 0
 263, 000  64.35 1000  199,350 J
2
X MnO
 312,580  1
exp  
K Mn X  p
 8.3144 1000   exp  113, 230   821215  Mn O2  X MnO  X Fe
2
  
K Fe  199,350   8.3144 1000  X FeO X Mn  X FeO
exp   1
 8.3144  1000  X Fe  pO22
X MnO  X Fe (1  X FeO )(1  0.001)
 : Thus, X FeO  1.22 103
X Mn  X FeO (0.001) X FeO

 199,350  X FeO 1.22  103

(iii ) K Fe  exp    2.587 10 
10

 8.3144  1000 
1 1
X Fe  pO22 0.999  pO22
Which gives pO2  2.23 1027 atm

193
Problem 13.9

The elements A and B, which are both solid at 1000°C, form two stoichiometric

compounds A2B and AB2, which are also both solid at 1000°C. The system A–B does

not contain any solid solutions. A has an immeasurably small vapor pressure at

1000°C, and, for the change of state, B(s) = B(v)

∆G° = 187,220 – 108.80T J

The vapor pressure exerted by an equilibrated AB2–A2B mixture is given by

11, 242
log p (atm)    6.53
T

and the vapor pressure exerted by an equilibrated A–A2B mixture is given by

12, 603
log p (atm)    6.9
T

From these data, calculate the standard Gibbs free energies of formation of A2B and

AB2.

Solution

pB
aB for the A2 B  AB2 mixture is first found. aB 
pB0
11, 242
The vapor pressure in the A2 B  AB2 mixture : log p (atm)    6.53 : p (atm)  5 103
T
Find the vapor pressure of B at 1273: G1273
0
 187, 220  108.8*1273  48, 718 J
G1273
0
pB0  exp( )  0.01
RT
p 5 103
Thus, aB  B0   0.5
pB 0.01

Now, from the G M plot: ab  RT ln aB  7,336 J

194
Now, from the G M plot: ab  RT ln aB  7,336 J

We now find the Activity of B in in the A2 B  A mixture :

12603
The vapor pressure in the A2 B  A mixture : log p (atm)    6.9 : p (atm)  103
1273
pB 103
Thus, aB    0.1
pB0 0.01
Now, from the G M plot: ac  RT ln aB  24,371 J

24,371
By similar triangles we obtain: ed   8123 J
3

For 2 A  B  A2 B : G 0  3  ed  24,371 J

ed  ab
gf   7730 J
2

For A  2 B  AB2 : G 0  3  gf  23,190 J

195
Problem 13.10

For the change of standard state V(s) = V(1 wt% in Fe)

∆Go = – 15,480 – 45.61T J

Calculate the value of γ V at 1600°C. If a liquid Fe–V solution is equilibrated with

pure solid VO and a gas containing pO2  4.72 1010 atm, calculate the activity of V

in the liquid solution (a) with respect to solid V as the standard state, (b) with respect

to liquid V as the standard state, (c) with respect to the Henrian standard state, and (d)

with respect to the 1 wt% in iron standard state.

Solution

 V0  55.85
(a ) V( S )  V (1wt %) : G1873
0
 15, 480  45.61 1873  101, 282  RT ln :   V0  0.14
100  50.94

1 1
V( S )  O2  VO( S ) : G1873
0
 424, 700  80.04 1873  274, 785   RT ln 1
2
a  pO22
 274, 785 
1 exp  
(b) Since p  4.72 1010 :
2
a ( S )   8.3144 1873   103
O2
4.72 1010

H M0 22,840
V( S )  V ( L): G 0  H M0  T S M0 : but S M0   :
TM 2193
22,840
G 0  22,840  1873   3,333 J
2193
1
V ( L )  O2  VO( S ) G1873
0
 274, 785  3,333  278,118 J
2
1
(c)  278,118 J   RT ln 1
: a ( L )  8.07 104
a ( L )  pO22
0.001
a ( L )  hV   V0   hV   7.13 103
0.14

hV (1%) 50.95 100

  91.24
hV 55.85

(d) hV (1%)  91.24  7.13 103  0.65

196
Problem 13.11

When an Fe–P liquid solution is equilibrated at 1900 K with solid CaO, solid

3CaOꞏP2O5 and a gas phase containing pO2  1010 atm, the activity of P in the iron,

with respect to the 1 wt% in Fe standard state, is 20. Given that

G1900

K  564, 600 J for

3CaO(s) + P2O5(g) = 3CaO∙P2O5(s)

and G° = –122,200 – 19.22T J for

1
P2( g )  P(1 wt% in Fe)
2

calculate G1900

K for the reaction

5
P2( g )  O 2( g )  P2O5( g )
2

Solution

For the reaction: 3CaO( s )  P2O5 ( g )  3CaO P2O5 ( s) G1900

0
 564, 600 J
564, 600 1
K  exp( )  3.325  1015  : pP2O5  3  1016 atm
8.3144 1900 pP2O5

1
For the reaction: P2 ( g )  P(1wt %) G1900 0
 122, 200  19.22 1900  158, 680 J
2
158, 680 h a 20
K  exp( )  2.303  104  P1%  P1  1 :  pP2 =7.539  107 atm
8.3144 1900
pP22 pP22 pP22

5
Therefore for : P2 ( g )  O2  P2O5 ( g )
2
pP2O5 3  1016
K 5
 5
 3.99 1015
pP2  pO22 7.539 10  10  2
 7 10

Thus : G1900
0
  RT ln K  8.3144  1900  ln  3.99 1015   567,500 J

197
Problem 13.12

Liquid iron, contained in an Al2O3 crucible under a gaseous atmosphere of

pO2  3  1012 atm at 1600°C, contains its equilibrium contents of dissolved oxygen

and aluminum. To what value must be pO2 be raised in order that solid hercynite

(FeOꞏAl2O3) appears in equilibrium with the melt and with solid Al2O3? What is the

activity of Al (with respect to the 1 wt% in Fe standard state) in this state? How many

degrees of freedom does this equilibrium have at 1600°C? Given

1
O 2( g )  O(1wt% in Fe) G   111, 070  5.87T J
2

Al,(l) = Al(1 wt% in Fe) ∆G° = – 43,100 – 32.26T J

FeO  Al2 O3( s )  Fe( l )  O(1wt% in Fe)  Al 2 O3( s )

G   146, 230  54.35T J

Solution

From the given, we get:

Al (1wt %)  Al (l ) G1873
0
 103,523 J
1
O(1wt %)  O2 ( g ) G1873
0
 122, 064 J (i)
2
3
2 Al (l )  O 2 = Al2 O3 : From Table A.1 we get:G1873
0
 1, 687, 200  326.8 1873  1, 075,104 J
2
 2 Al (1wt %)  3O(1wt %)  Al2 O3 G1873 0
 501,865 J
G1873
0
 501,865 = 8.3144  1873  2.303 log[O]3  [ Al ]2
 for saturation with Al2O3  14  3log[O]  2 log[ Al ] (ii)
FeO  Al 2 O3  Fe(l )  [O1wt % ]  Al2O3 G 0
1873  146, 230  54.35 1873  44, 432 J
44, 432 J  8.3144  1873  ln[O1wt % ] :
[O1wt % ]  5.77 102 wt.%
1
pO22
 (i )122, 064   RT ln :  pO2  5.18 1010 atm
[O1wt % ]
and from (ii) [ Al ]  7.215  106

For the phase rule: C = 3 (Al,Fe,O), P = 4 (metal, Al2O3 , FeO  Al 2 O3 and gas)
Thus: F = C + 2  P = 3  2  4  1, which was specified by the given temperature of 1873K.

198
Problem 13.13

UC2 can be equilibrated with UC and C at high temperature and can be equilibrated

with U2C3 and C at lower temperatures. Calculate the maximum and minimum

temperatures at which UC2 can exist.

Solution

U  C  UC GT0  102,900  5.02T

2U  3C  U 2 C3 GT0  236,800  25.1T
U  2C  UC2 GT0  115,900  10.9T

Thus : UC  C  UC2 GT0  13, 000  5.88T

This equals 0 at T = 2,211 K.

At T > 2,211 K, UC2 is metastable with respect to UC  C

U 2C3  C  2UC2 GT0  5, 000  3.3T

This equals 0 at T = 1.515 K.
At T < 1,515 K, UC2 is metastable with respect to U 2C3  C

Thus,UC2 is the equilibrium phase between 1,515 and 2,211 K

199
Problem 13.14

In the Pigeon process for the production of magnesium, dolomite (CaOꞏMgO) is

reduced by silicon to form magnesium vapor and 2CaOꞏSiO2. Calculate the

equilibrium pressure of magnesium vapor produced by this reaction at 1200°C. The

Gibbs free energy of formation of dolomite from CaO and MgO is small enough that

it can be ignored.

Solution

2 MgO  Ca  Si  2 Mg  2CaO  SiO2 (i)

2CaO  SiO2  2CaO  SiO2 G1473

0
 118,800  11.3  1473  135, 445 J (ii )
2 MgO  O2  2 Mg (v) G 0
1473 =2  (729,600  204  1473) = 858,216 J (iii)
Si  O2  SiO2 G1473
0
 907,100  175  1473  649,325 J (iv)

Therefore : G1473
0
of 2 MgO  Ca  Si  2 Mg  2CaO  SiO2 is found by (iii)  (iv)  (ii)
G 0
1473  858,216+(  649,325)  (135, 445)  73446 J   RT ln pMg
2

 pMg  0.05atm

200
Problem 13.15

What is the minimum value that the activity of MgO can have in MgOꞏAl2O3 at

1000°C?

Solution

For the reaction: MgO  Al2O3  MgO  Al2O3

aMgO Al2O
GT0  35,560  2.09T : G1273
0
 38, 220   RT ln
aMgO  a Al2O 3
The minimum value of the activity of MgO in MgO  Al2O3 occurs when the it is saturated with
Al2O3 , and here a Al2O3  1.
38, 220
Thus, aMgO  exp( )  0.027
8.3144 1473

201
Problem 13.16

A mixture of ZnO and graphite is placed in an evacuated vessel and heated to 1200 K.

Calculate the partial pressures of Zn, CO, and CO2 that are developed.

Solution

For the reaction ZnO  C  Zn  CO : GT0  348,500  285.7T  5, 660 at 1200 K

5, 660 J   RT ln pZn  pCO : pZn  pCO  0.567

For 2 ZnO  C  2 Zn(v)  CO2 : GT0  526,300  396.8T  50,140 at 1200 K

50,140 J   RT ln pZn
2
 pCO2 : 2
pZn  pCO2  6.57  103

nZn pZn
In the gas phase, 1 :  pZn  pCO  2  pCO2
nO pCO  pCO2
Thus :  
pZn  pCO  pCO  2  pCO2 pCO  0.567

 
2
And : 2
pZn  pCO2  pCO  2  pCO2 pCO2  6.57 103

which gives : pCO  0.74atm pCO2  0.013atm pZn  0.766atm

202
Problem 13.17

An assemblage of solid CaO, MgO, 3CaOꞏAl2O3, and liquid Al exerts an equilibrium

vapor pressure of Mg of 0.035 atm at 1300 K. Write the equation for the appropriate

reaction equilibrium. Calculate the standard Gibbs free energy of formation of

3CaOꞏAl2O3 from CaO and Al2O3 and the activity of Al2O3 in CaO-saturated

3CaOꞏAl2O3 at 1300 K.

Solution

The equilibrium equation is:

3CaO  2 Al (l )  3MgO  3Mg (v)  3CaO  Al2O3 for which:
5
Kp 3
Mg  0.035  4.288  10
3

G1300
0
 8.3144 1300 ln  4.288 105  J  108, 700 J

3CaO  2 Al (l )  3MgO  3Mg (v)  3CaO  Al2O3 G1300

0
 108, 700 J
3
Al2O3  O2  2 Al (l ) G1300
0
 1, 262,360 J
2
3
3Mg (v)  O2  3MgO G1300
0
 1,393, 200 J
2
add the above three equations anf obtain:
3CaO  Al2O3  3CaO  Al2O3 G1300
0
 22,140 J

 with aCaO Al2O3  aCaO  1

1
 22,140 J   RT ln so a Al2O3  0.129
a Al2O3

203
Problem 13.18

An iron-carbon melt containing 0.5 wt% C is prepared in an alumina crucible under

an atmosphere of pCO = 1 atm at 1600°C. Calculate the equilibrium concentrations of

O and Al in the melt (a) ignoring all solute-solute interactions and (b) considering the

solute-solute interactions. The interaction coefficients are listed in Table 13.1.

Solution

(i ) ignoring solute/solvent interactions

2[ Al ]  2 Al (l ) G1873
0
 2, 670, 045 J
3
3[O]  O G1873
0
 366,193 J
2
 2[ Al ]  3[O]  Al2O3 G1873
0
 501,864 J  RT ln[% Al ]2  [%O]3

 2 log[% Al ]  3  log[%O ]  13.996 (i)

1
C  O2  CO G1873
0
 275,868 J
2
1
[O ]  O G1873
0
 122, 064 J
2
[C ]  Cgr G1873
0
 56,552 J
pCO
[C ]  [O]  CO G1873
0
 97, 250 J   RT ln
[%C ][%O]
for : pCO  1atm : log[%C]  log[%O]=  2.716 J (ii)
 log[%O]=  2.716  log0.5  2.414 and therefore [%O]  0.00385
13.996  3  (2.414)
from (i ) above: log[%Al]   3.377 J :[%Al]  0.00042
2

204
(ii ) including interactions

eq.(i) becomes 2 log[hAl ]  3  log[hO ]  13.996 J

eq.(ii) becomes log[h C ]  log[h O ]=  2.716 J

log f C   CC [C ]   CO [O]   CAl [ Al ]

log f O   OO [O]   OC [C ]   OAl [ Al ]
log f Al   AlAl [ Al ]   AlC [C ]   AlO [O]

where :  CC  22 102  OO  20 102  AlAl  4.8 102

 CO  9.7 102  OC  13 102  AlC  11102
 CAl  4.8 102  OAl  94 102  AlO  160 102

 2[log f Al  log[ Al ]]  3  [log f O  log[O]]  13.996 J

or 2{ AlAl [ Al ]   AlC [C ]   AlO [O]  log[ Al ]}  3{ OO [O]   OC [C ]   OAL [ Al ]  log[O]}  13.996 J

Also: logf C  log[C ]  logf O +log[O]=  2.716 J

 CC [C ]   CO [O]   CAl [ Al ]  log[C ]   OO [O]   OC [C ]   OAl [ Al ]  log[O]  2.716 J

 2{4.8 102 [ Al ]  11102 [C ]  160 102 [O]  log[ Al ]}

 3{20 102 [O]  13 102 [C ]  94 102 [ Al ]  log[O]}  13.996 J
and 22  102 [C ]  9.7 102 [O]  4.8 102 [ Al ]  log[C ] 
 20 102 [O]  13 102 [C ]  94 102 [ Al ]  log[O]  2.716 J

When [C ]  0.5 we get: %Al  0.000541 %O  0.00351

205
Problem 13.19

It is required that PbO be eliminated from an ore containing PbO, PbS, and PbSO4 by

converting it to PbS or PbSO4 by reaction with an SO2–O2 gas. Although the pressure

of O2 in the gas can vary within wide limits, the partial pressure of SO2 may not be

higher than 0.5 atm. Calculate the maximum temperature at which it can be

guaranteed that the PbO phase will be eliminated.

Solution
1
1
For : PbO( s )  SO2  O2  PbSO4 : GT0  401, 200  261.5T  RT ln pSO2  pO22
2
401, 200 261.5 1
  ln pSO2  ln pO2
8.3144  T 8.3144 2
48, 253 1
  31.45  ln pSO2  ln pO2 (i)
T 2
1

3 pO22
For : PbO( s )  SO2  PbS  O2 : GT0  407, 200  80.6T   RT ln
2 pSO2
407, 200 80.6 3
  ln pO2  ln pSO2
8.3144  T 8.3144 2
48,975 3
  9.69  ln pO2  ln pSO2 (ii)
T 2
96,506
With pSO2  0.5atm, (i) becomes ln pO2    63.59 (iii)
T
32, 650
(ii) becomes ln pO2    5.998 (iv)
T
1
(iii) and (iv) intersect at =9.02 104 and ln pO2  23.46
T

Since PbO is not stable if T > 1108 K it is therefore the maximum temperature at

which it is eliminated.

206
Problem 13.20

Cementite, Fe3C, is metastable with respect to carbon-saturated a-iron and graphite at

950 K and 1 atm pressure. Given that the molar volumes of α-Fe, graphite, and Fe3C

at 950 K are, respectively, 7.32, 5.40, and 23.92 cm3/mole, calculate the pressure, at

950 K, at which Fe3C is in equilibrium with carbon-saturated α-Fe and graphite. At

what temperature, at 1 atm pressure, is carbon-saturated γ-Fe and graphite in

equilibrium with cementite?

Solution

For the reaction 3Fe( )  C  Fe3C : G T0  29, 040  28.03T

G 950
0
 29, 040  28.03  950  2411 J
cc
VFe  7.32
mole
cc
Vgr  5.4
mole
cc
VFe3C  23.92
mole

cc
V  23.92  5.4  3  7.32  3.44
mole

cc 8.3144
Equilibrium occurs at the pressure at which: 2411 J  3.44  ( P  1)atm 
mole 82.057

P  6917 atm

207
Problem 13.21

An experiment is being conducted on an equilibrated mixture of CaO and CaCO3

contained in a closed vessel at 1200 K. The mixture is contaminated by iron in the

form of hematite (Fe2O3). The contaminant would not be harmful to the experiment if

it occurred as either wustite (FeO) or as cementite (Fe3C). The necessary changes in

the chemical form of the contaminant can be effected by admitting CO gas to the

vessel. Calculate the allowable limits of pCO in the vessel for the occurrence of the

contaminant (a) as wustite and (b) as cementite.

Solution

(a ) wustite
CaO  CO 2  CaCO3 : G1200
0
 3340  8.3144 1200 ln pCO
2

pCO  1.398 atm

2

pCO
For : 3FeO  CO2  Fe3O4  CO G1200
0
 4348  8.3144 1200 ln
pCO
2

pCO
For equilibrium between FeO / Fe3O4  0.647
pCO
2

pCO  0.647  pCO  0.647 1.398 = 0.904 atm

2

Thus, for FeO to be stable pCO  0.904 atm

pCO
For : Fe  CO2  FeO  CO G1200
0
 8252  8.3144 1200 ln
pCO
2

p
 CO  2.287 pCO  2.287  pCO  2.287 1.398 = 3.196 atm
pCO 2
2

Thus, for FeO to be stable 3.196 > pCO  0.904 atm

208
(b) cementite
pCO
For : 3Fe( )  2CO  Fe3C  CO2 G1200
0
 36686  8.3144 1200 ln 2

pCO 2
pCO
For equilibrium between Fe / Fe3C 2
 0.0253
pCO 2
1
 p
 
2 1

pCO 
CO 2  
=
1.398  2 =7.43 atm

 0.0253   0.0253 
 

pCO 2
For : C  CO2  2CO G1200
0
 38, 492  8.3144 1200 ln
pCO
2

pCO 2
  47.4 pCO  47.4  pCO  47.4 1.398 = 8.14 atm
pCO 2
2

Thus, for Fe3C to be stable 8.14 > pCO  7.43 atm

209
Problem 13.22

A Cu–Au alloy of XCu = 0.5 is being annealed at 600°C in deoxidized argon. The

argon is deoxidized by being passed over heated pure copper turnings prior to its

admission to the annealing furnace. The solid Cu–Au system is virtually regular in its

solution behavior, with a molar Gibbs excess free energy of mixing given by

GXS = – 28,280XCuXAu J

Assuming that equilibrium is attained in the deoxidizing furnace, calculate the

maximum temperature at which the deoxidizing furnace can be operated without

causing oxidation of the copper in the Cu–Au alloy being annealed.

Solution
1
1
2Cu  O2  Cu2O GT0  162,200+69.24  T  G873
0
 101, 753 J  RT ln pO22  aCu
2

2
1
pO22  aCu
2
 8.16(3)  107
28, 280  0.52
  28, 280 J RT ln  Cu  X Au
2
 ln Cu    0.974
8.3144  873
  Cu  0.378 and aCu  0.378  0.5  0.1888.
The oxygen pressure for the equilibrium between the Cu-Au alloy and Cu 2O is :
2
 8.16(3) 107  10
pO2     5.24  10 atm
 0.1888 

1
1
2Cu  O2  Cu2O GT0  162,200+69.24  T  8.3144  T ln(5.24  1010 ) 2
2
Solving this for T we get T = 1026 K. This is the temperature at which 5.24 1010 atm
is the oxygen pressure required for equilibrium between Cu and Cu2O.
Thus,1016 K is the maximum temperature that the deoxidizing furnace can be operated
without causing oxidation of the alloy.

210
Problem 13.23

In a dew-point experiment a Cu–Zn alloy is placed in one end of an evacuated and

closed tube, and is heated to 900°C. When the other end of the tube is cooled to 740°

C Zn vapor begins to condense. Calculate the activity of Zn in the alloy relative to

pure zinc.

Solution

15, 250
At 740 0C  1013 K 0
ln pZn   1.255ln(1013)  21.79
1013
,1013 K  0.142 atm
0
pZn

15, 250
At 900 0C  1173 K 0
ln pZn   1.255ln(1173)  21.79
1173
,1173 K  0.923 atm
0
pZn

0.142
 a Zn (in the alloy)   0.154
0.923

211
Problem 13.24

A crucible containing 100.0 g of silver at 1000°C is placed in the reaction chamber of

a Sieverts’s apparatus. The chamber is evacuated and filled with 50 cm3 (STP) of

argon, which measures the dead volume of the chamber. An external manometer reads

the pressure of argon as 0.9 atm. The chamber is re-evacuated and filled with oxygen,

and it is found that 251.5 cm3 (STP) are required to produce a gas pressure of 0.9 atm

in the chamber. Calculate the solubility of O in the Ag (as atom percent) and calculate

the value of the Sieverts’s law constant at 1000°C.

Solution

The number of moles of Ar required to fill the chanber:

1 50
nAr   2.232 103
82.057  273
The number of moles of O 2 required to fill the chanber:
1 251.5
nO2   1.123 102
82.057  273
 The number of moles of O 2 dissolved in the liquid Ag is:
1.123 102  2.232 103  8.995 10 3 : 8.995 103  32  0.288 grams of O
0.288
Thus, wt % of oxygen = 100  0.287
100  0.288

2  8.995 103
Mole fraction O  X O   0.0190
3 100
2  8.995  10 
107.87
107.87
atomic % oxygen =0.0287  =1.9
16

1 [O] 1.9
For O2 ( g )  [O] k 1
  2.0
2 0.9
p2
O2

212
Problem 13.25

Silicon and manganese are commonly used together as deoxidizers for liquid steel. At

1600°C,

[Mn](1wt % in Fe)  [O](1wt% in Fe)  MnO( s ) K  23.5

[Si](1wt% in Fe)  2[O](1wt% in Fe)  SiO 2( s ) K  27,840

The values of the equilibrium constants show that SiO2 is considerably more stable

than MnO. Why, then, is a mixture of Mn and Si more effective as a deoxidizing

agent than Si alone? The activities of MnO and SiO2, with respect to solids as the

standard states in MnO–SiO2 melts at 1600°C, are shown in Fig. 13.37.

Solution

213
Using Si alone produces solid SiO2 , ( with an activity = 1) as the deoxidation product.
Thus, with 0.01 wt% Si, the oxygen content is:
1 1
 aSiO2  2  1 2
[O]       0.06
 K Si [% Si ]   27840  [% Si ] 

Using Si + Mn produces a liquid Mn silicate as the deoxidation product, which if saturated with
Mn gives aSiO2  0.02.
Thus, with 0.01 wt% Si, the oxygen content is:
1 1
 aSiO2  2  0.02 2
[O]       0.0085
 K Si [% Si ]   27840  0.01 

The Mn content required to satuate MnO is calculated as:

aMnO 1
[%Mn] =   5.0
K Mn  [%O] 23.5  0.0085

214
Chapter 14
Problem 14.1

The EMF of the galvanic cell

Pb( s ) PbCl2( s ) HCl(aqueous) AgCl( s ) Ag ( s )

where all of the components are present as pure solids in contact with an HCl

electrolyte, is 0.490 volts at 25°C and, at that temperature, the temperature coefficient

of the EMF is –1.84 × 10–4 volts/degree. Write the cell reaction and calculate the

Gibbs free energy change and the change in entropy for the cell reaction at 298 K.

Solution

At the anode: Pb  Pb 2  2e

At the cathode: Ag   e   Ag

 The reaction is: Pb  2 AgCl  2 Ag  PbCl2

G 0   zF  0  2  96, 487  0.490  94,560 J

 0 J
S 0  zF  2  96, 487  (1.84 104 )  35.5
T K

215
Problem 14.2

At 298 K, the EMF of the cell

Pb | PbCl2 | Hg2Cl2 | Hg
is +0.5357 volts and the temperature coefficient of the EMF is 1.45 × 10–4
volts/degree. Calculate (a) the maximum work available from the cell at 298 K per
mole of Pb reacted, (b) the change in entropy for the cell reaction, and (c) the heat
absorbed by the cell at 298 K per mole of Pb reacted when the cell is operating
reversibly.
The Hg electrode in the cell is replaced by an Hg–X alloy in which XHg = 0.3 and
where X is inert. The EMF of the cell at 298 K is found to increase by 0.0089 volts.
Calculate (d) the activity of Hg in the alloy at 298 K.

Solution

(a ) G 0   zF  0  2  96, 487  0.5357  103, 400 J

 0 J
(b) S 0  zF  2  96, 487  (1.45  104 )  27.98
T K
J
(c) q  T S 0  298  27.98  8338 J / mole
K

RT
 0  2
ln aHg
zF
For the cell reaction: Pb  Hg 2Cl2  PbCl2  2 Hg
RT 8.3144  298
 0   2
ln aHg  0.0089  2
ln aHg
zF 2  96, 487

aHg  0.707

216
Problem 14.3

The solid-state electrochemical cell

 Pt  , O2 (gas at pO 2
) CaO  ZrO 2 Fe FeO, (Pt)

is built to measure the partial pressure of oxygen in gases. Write an equation relating

the oxygen pressure and temperature of the gas to the EMF to the cell.

Solution

( Pt )O2 ( gas at p O2 ) CaO  ZrO2 Fe FeO, ( Pt )

anode cathode
1
O 2  O2 (at pO2 )  2e  FeO  2e   Fe  O 2
2

RT pO2 ( anode )
  ln
zF pO2 ( eq. Fe / FeO )

1 1
For : Fe  O2  FeO G T0  263, 700  64.35T   RT ln pO2 ( eq. Fe / FeO )
2 2
RT RT
  ln pO2 ( anode ) + lnpO2 ( eq.Fe / FeO )
zF zF

RT RT  2  263, 700 2  64.35 

Now lnpO2 ( eq.Fe / FeO )   
zF zF  RT R 
RT RT
Thus,    ln pO2 ( anode ) + lnpO2 ( eq.Fe / FeO ) 
zF zF
 2.154  105 lnpO2 ( eq. Fe / FeO )  1.3665  3.334  104

46, 620   63, 440

or, lnpO2 ( eq. Fe / FeO )    15.48
T T

217
Problem 14.4

The EMF of the cell

Ag ( s ) AgCl( s ) Cl2( g ,1 atm) , Pt

is found to be

ℰ(volts) = 0.977 + 57 × 10–4 (350 – t) – 4.8 × 10–7 (350 – t)2

in the temperature range = 100°–450°C. Calculate the value of Δcp for the cell

reaction.

Solution

  0.977  5.7 104  350  5.7 104 t  4.8 107 (350)2  4.8 107  350  2t  4.8 107  t 2
d 4 7 7 4 4 7
 5.7 10  4.8 10  350  2  2  4.8 10 t  2.34 10 2.34 10  9.6 10 t
dt

d
S  zF  1 96487   2.34 104  9.6  107 t   22.57  0.0926  (T  273)
dt
T in K
d S cP J
 cP  0.0926  T
dt T K

218
Problem 14.5

A galvanic cell is set up with electrodes of solid aluminum and solid aluminum-zinc

alloy and an electrolyte of molten AlCl3–NaCl. When the mole fraction of Al in the

alloy electrode is 0.38, the EMF of the cell is 7.43 millivolts at 380°C, and the

temperature coefficient of the EMF is 2.9 × 10–5 volts/degree. Calculate (a) the

activity of Al in the alloy, (b) the partial molar entropy of mixing of Al in the alloy,

and (c) the partial molar enthalpy of mixing of Al in the alloy.

Solution

Al AlCl3  NaCl Al  Zn

cell reaction: Al  Al in Al  Zn
M
(a ) G Al   zF   3  96487  7.43 103  2150 J  RT ln a Al
at 380 0C , a Al  0.673

M d J
(b)  S Al  zF  3  96, 487  2.9 105  8.39
dT K

M M M
(c)  H Al  G Al  T  S Al  2150  653  8.39
M
 H Al  3329 J

219
Problem 14.6

By measuring the EMFs of cells of the type

Ni(s) | NiO(s) | CaO–ZrO2 | Cu(l) containing dissolved oxygen

it has been established that eOO in liquid copper at 1363 K is –0.16 and that the

standard Gibbs free energy change for

1
O 2( g )  [O]1wt% in Cu
2

is ΔG° = -74,105 + 10.76T J. If the EMF of such a cell is 0.222 volts at 1363 K,

calculate (a) the activity of oxygen in the liquid copper cathode with respect to a

standard state of oxygen gas at 1 atm pressure, (b) the activity of Cu2O in the cathode

metal with respect to Cu-saturated pure solid Cu2O, (c) the weight percentage of

oxygen dissolved in the copper cathode, (d) the maximum solubility of oxygen in

liquid copper at 1363 K.

Solution

220
 Ni ( s ) NiO( s) CaO  ZrO2 Cu (l )  O
pO2 ( low)
RT pO ( low) pO2 (low)
1)   0.222   ln 2 :   5.206  104
4F pO2 ( high ) pO2 ( high )
For 2 Ni  O2  2 NiO GT0  471, 200  172  T  236, 764  RT ln pO2 (low)
pO2 ( low)  8.44  1010 atm and
8.44 1010
pO2 ( high )  activity of the O rel to pO2  1atm   1.622 106
5.206 104

1
2) For 2Cu (l )  O2  Cu2O(l ) : GT0  188,300  88.48  T
2
1
G1363
0
   67, 702 J  RT ln pO2 :  pO2  6.47  106 atm
2
1
1.622  106  2
 aCuO  6 
 0.5
 6.47 10 

1
3) O2  [O](1wt %) G1363
0
   59, 439 J  RT ln K
2
1
h
K  189.6  O1 : hO  189.6  1.622  106  2  0.241
pO22
log hO  eO0 [%O ]  log[%O]

0.617  0.16[%O]  log[%O ] :

[%O]  0.266

1
6 2
4) hO (at saturation with O) =189.6  [6.47  10 ]  0.42

 log hO (saturation) =  0.3167  0.16[%O]  log[%O]

[%O]saturation  0.602

221
Problem 14.7

Calculate the conditions under which an aqueous solution of [Pb2+] = 1 mole/liter is

in equilibrium with metallic Pb and solid PbO at 298 K. Is any other lead ion present

in significant concentration in this solution?

Species G298K

J
PbO( s ) 189,300
Pb(2m ) 24,310
Pb(4m ) 302,500

HPbO 2( m) 339, 000
2
PbO3( m ) 277,570
PbO 44(m ) 28, 210
H 2 O(l ) 237,190

Solution

For PbO  2 H   2e  Pb  H 2O

G 0  237,190  189,300  47,890 J
47,890
 0   0.248
2F
RT 1
   0.248  ln  0.248  0.0591log[ H  ]  0.248  0.0591 pH
2F  2
1
[H ]
For Pb 2  2e   Pb G 0  24,310 J
24,310
 0    0.126
2F
RT 1
   0.126  ln  0.126  0.02957  log[[ Pb 2 ]]
2F [ Pb 2 ]
With [ Pb 2 ]  1,   0.126 volts
0.126  0.248
and the pH   6.33
0.0591

For Pb 4  2e   Pb 2  24,310  302,500 =  326,810 J

326,810
 0   1.693
2F
RT [ Pb 2 ] [ Pb 2 ]
   1.693  ln  1.693  0.02957 log
2F [ Pb 4 ] [ Pb 4 ]
[ Pb 2 ]
At   0.126 log  3.27 1061
[ Pb 4 ]
and with [ Pb 2 ]  1, [ Pb 4 ]  3.05  1061

222
 For 3H   HPbO2  Pb 2  2 H 2O
[ Pb 2 ]
G 0  159, 690   RT ln
[ HPbO2 ]  [ H  ]3
[ Pb 2 ]
 27.99  log  3 pH
[ HPbO2 ]
At pH  6.33 and [ Pb 2 ]  1, [ HPbO2 ]  109

For PbO32  6 H   2e   Pb 2  3H 2O
G 0  458,311 and  0  2.375
RT [ Pb 2 ] [ Pb 2 ]
   2.375   ln  2.375  0.02957 log  0.1774 pH
2F [ PbO32 ]  [ H  ]6 [ PbO32 ]
At   0.126, pH  6.33 and [ Pb 2 ]  1
[ PbO32 ]  2.5 1047

For PbO44  8H   2e  Pb 2  4 H 2O

G 0  944,860 J and  0  4.896
RT [ Pb 2 ] [ Pb 2 ]
   0.126  4.896  ln  4.896  0.0296 log  0.236  6.33
2F [ PbO44 ]  [ H  ]8 [ PbO44 ]
With [ Pb 2 ]  1
[ PbO44 ]  5.6 10221

223
 Problem 14.8

Aluminum can be produced by electrolysis of Al2O3 dissolved in molten

cryolite, 3NaFꞏA1F3. If inert electrodes are used in an electrolysis cell and the

cryolite is saturated with Al2O3 at 1000°C, what is the decomposition voltage of

the Al2O3? The Hall-Heroult process for electrolysis of Al2O3 uses graphite as

the anode material, and the gas which is evolved at the anode is essentially pure

CO2 at 1 atm pressure. Calculate the decomposition voltage of Al2O3 in an

Al2O3-saturated 3NaFꞏAlF3 electrolyte at 1000°C in the Hall-Heroult cell.

Solution

3
For 2 Al (l )  O2  Al2O3 ( s ) GT0  1, 687, 200  326.8T
2
G1273  1, 687, 200  326.8 1273  1, 271,183 J
0

1, 271,183
 0   2.196 volts
6F

3 3
For 2 Al (l )  CO2  Al2O3 ( s)  C we add the following reactions
2 2
3
2 Al (l )  O2  Al2O3 ( s) GT0  1, 687, 200  326.8T
2
3 3 3 3
CO2  C  O2 GT0   394,100  0.84T 
2 2 2 2
3 3
adding 2 Al (l )  CO2  Al2O3 ( s )  C GT0  1, 096, 050  328.06T
2 2
G1273  1, 096, 050  328.06 1273  678, 430 J
0

678, 430
 0   1.17 volts
6F

224
Problem 14.9

At 298 K the solubility of Cl2 in H2O, under a partial pressure of Cl2 = 1 atm, is

0.0618 molal. Calculate the standard Gibbs free energy of formation of an aqueous

solution of chlorine and calculate the change in the Gibbs free energy to form a

solution of chlorine which is 0.01 molal. Ideal solution behavior can be assumed.

Solution

1 [Cl ]
For Cl 2 ( g )  [Cl ] K 1
 0.0618
2
p 2
Cl2

G 0  8.3144  298  ln  0.0618   6897 J

For [Cl ]1mole =[Cl ].01mole G 0  6,897  11, 410  4,513 J

1
Thus, adding Cl 2 ( g )  [Cl ].01mole
2

225
Chapter 15

Problem 15.1*.

2-4 Landau Case

The excess Gibbs free energy as a function of order parameter for a solution is written

as:

G XS  Gord  Gdis  a (T  TC ) 2  C 4
where Gdis is the free energy of the disordered phase and a and C are positive constants.
a. Obtain an expression for the excess entropy of the equilibrium ordered phase as a
function of temperature.

Solution
G XS  Gord  Gdis  a (T  TC ) 2  C 4
a (T  TC ) G XS
First we obtain eq2   by setting 0
2C 
and solving for eq .
a 2 (T  TC ) 2
G XS  a (T  TC )eq2  Ceq4  
4C
G XS 2a 2 (T  TC )
  S XS  
T 4C
a 2
(T  T )
S XS  C
2C
(valid only at T  TC )

SXS is negative since it is the excess entropy over and above the disordered entropy!

226
b. Determine the value of CP = CPord -Cpdis at the transition temperature TC.

Solution
 S 
CP  T  
 T  P
a 2 (T  TC )
Thus, since S ord  Sdis 
2C
S ord S dis a 2
 
T T 2C
S S T a2
TC ord -TC dis  C
T T 2C
2
TCa
P -C P 
Cord 0
dis

2C
2C
and since TC  : CordP -C P  a
dis

The heat capacity is of the ordered phase is larger than that of the disordered phase since
some thermal energy must be used to disorder the ordered phase on heating.

227
Problem 15.2*
2-4-6 Landau case:

The Gibbs energy as a function of order parameter for a solution is written as:
G  a (T  TC ) 2  C 4  E 6

For this case assume C < 0 and a and E are positive.

a. Find the non-zero value of the order parameter of the solution that has the
same Gibbs Energy as that of the disordered solution.

SOLUTION

G XS of the disorderd phase  0. Thus G of the ordered phase also  0

G
If equilibrium obtains:  0. Thus we have 2 equations to solve:


G  a (T  TC ) 2  C 4  E 6  0
G
 0  2a (T  TC )  4C 3  6 E 5  a (T  TC ) 2  C 4  E 6

solving these two equations:
2a (T  TC )
on eliminating E we obtain:  0 and  2  
C
C
on eliminating a (T  TC ) we get   0 and  2  
2E
2a (T  TC ) C
Thus:   (note for part d that 4AE = C2 )
C 2E
2
C
T  TC 
4aE

228
b. Sketch the Gibbs Energy vs.  curve for the temperature in question in (a). This
temperature can be called T0.

c. Determine if the transformation for this alloy is first order. Explain.

Solution
C2
Since there are two phases at T  TC  with the same Gibbs energy and both are
4aE
minima, this is a first order transformation. This value of T can be called T0 in line with
the way we have defined T0 in the text.

d. Calculate the heat of transformation, ΔH0, for this disorder / order transformation in
terms of a, η0 and Ttr, where η0 is the order parameter at the equilibrium transition
temperatureTtr.

Solution
H  T0 S XS
S  Sordered  Sdisordered
 G XS 
 T     S T0 
XS

 T0
G XS  a (T  TC )02  C04  E06
 G XS 
 T   a0    S T0
2 XS

 T0
H  T0a02  0
 C 
H  T0a    0 since C < 0)
 2E 

e. What is the significance of the sign of ΔHtr for this transformation?

It is an Exothermic transformation

229
Problem 15.3*

A 2-4 Landau case:

Using the equation: G XS ( )  a (T  T0 ) 2  C 4

show that the excess enthalpy for the Landau model with B = 0 and C > 0 is:

a (T 2  TC2 )
H XS 
2 TC

Solution

TC  T T
From Eq.5.10 that eq   1
2

TC TC

2C
TC  T TC 
Inserting  
2
eq and a into G XS ( )  a (T  T0 ) 2  C 4
TC

a (TC  T ) 2
G XS  
2TC
G XS a (TC  T )
and  S XS  
T TC
a (TC  T ) 2 Ta (TC  T )
H XS  G XS  TS XS   
2TC TC
a (TC2  2TTC  T 2 ) 2 aTTC  2 aT 2
H XS   
2TC 2TC
a (T 2  TC2 )
H XS 
2TC

It can be seen that

dH XS aT
 CPXS 
dT TC
at TC CPXS  a

230
Problem 15.4*

A solid is held at high temperature until equilibrium is attained. Its surface displays

grooves as shown in Fig. 15.19.

a. Write an expression for the relationships between the grain boundary energy of 1

and 2.

SOLUTION

See problem 2.12*

12
 gb/12  2  / 2 cos( )
1
2

b. Which grain boundary has the largest energy: 1/2 or 2/3?

SOLUTION

The one with the smallest groove angle. Hence 1/2

12
 gb/12 2  / cos( 2 )
1 2

 gb/23 2 23
 / cos( )
2 2
2

c. If ij goes to  what is the value of the grain boundary energy?

SOLUTION


 gb/i  j  2  / cos( ij )  0
i j
2

d. If ij goes to 0 what is the value of the grain boundary energy?

SOLUTION


 gb/i  j  2  / cos( ij )  2  /
i j
2 i j

231
Problem 15.5*.

Small cylindrical particles has been observed to nucleate in certain alloys system.

a. What values of r and l will minimize the energy barrier to the formation of these

particles.

b. What surface energies favor the formation of long thin cylinders? Explain

1 is the surface energy of the circular face

2 is the surface energy along the length of the cylinder.

Note: assume the volume of the particle is constant.

V=πr 2l=constant
S.E.=Surface Energy = 2πr 2 1  2 rl 2
V 2 r 2 V 2 2
S .E .  2πr 2 1  2
 2πr 2 1 
πr πr
d ( S .E .) 2
 0  4πr 1  V 22
dr πr
r* 1 2
 for small  1 large r
l * π 1

Long rod for small 2 or large 1

Thin disc for large 2 or small 1

232
Problem 15.6*
A 2-6 Landau case

The Gibbs energy of a phase can be written in terms of its order parameter as:
G  a (T  TC ) 2  E 6
where a > 0 and b > 0

a. What is the temperature T0 where the disordered phase has the same Gibbs
Energy as the equilibrium ordered phase? Show work.

Solution
G  0 for   0 (disordered)
for the ordered phase G  0  a (T  TC ) 2  E 6
a (T  TC )
or  4  
E
G
Also since in equilibrium:  0  2a (T  TC )  6 E 5

a (T  TC )
or  4  
3E
For both to be true: T0  TC

b. What is the value of the order parameter at T0?

0: that is, the phase is just beginning to order
c. Is this a first order or higher order phase transition? Explain.
Must be a higher order transition
d. Show mathematically that for T < TC, the disordered phase is unstable.

G  a (T  TC ) 2  E 6
G
 2a (T  TC )  6 E 5

 2G
 2a (T  TC )  30 E 4  2a (T  TC ) for   0
 2
 2G
Thus  2a (T  TC )  0 for T  TC
 2
Therefore unstable (a maximum)

233