10pts 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.
1 0
From table A-1 we can get 𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) (i) ∆𝐺𝐺(𝑖𝑖) = −111,700 − 87.65𝑇𝑇
2
0
𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2(𝑔𝑔) (ii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −394100 − 0.84𝑇𝑇
1 0 0 0
𝐶𝐶𝐶𝐶2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) (iii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = ∆𝐺𝐺(𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖𝑖𝑖)
2
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = 282400 − 86.81𝑇𝑇
1 0
𝐻𝐻2(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) (iv) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −247500 + 55.85𝑇𝑇
2

Then combine equation (iii) and (iv), we can get

0 0 0
𝐶𝐶𝐶𝐶2(𝑔𝑔) + 𝐻𝐻2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) + 𝐶𝐶𝐶𝐶(𝑔𝑔) (v) ∆𝐺𝐺(𝑣𝑣) = ∆𝐺𝐺(𝑖𝑖𝑖𝑖) + ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖)
0
∆𝐺𝐺(𝑣𝑣) = 34900 − 30.96𝑇𝑇
0
So at temperature T=900+273 K=1173 K, ∆𝐺𝐺(𝑣𝑣) = 34900 − 30.96 ∗ 1173
0
∆𝐺𝐺(𝑣𝑣) = −1416.08 𝐽𝐽
0
∆𝐺𝐺(𝑣𝑣)
(− )
𝐾𝐾𝑃𝑃 = 𝑒𝑒 𝑅𝑅𝑅𝑅

−1416.08
𝐾𝐾𝑃𝑃 = 𝑒𝑒 (−8.3144∗1173)
𝐾𝐾𝑃𝑃 = 1.16
For the reaction (v), at the beginning there are 0.5 mol CO, 0.25 mol CO2, and 0.25 mol H2 (supposing the
total gas is 1 mol), then at the equilibrium, x mol of CO2 has reacted,

𝐶𝐶𝐶𝐶2(𝑔𝑔) + 𝐻𝐻2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) + 𝐶𝐶𝐶𝐶(𝑔𝑔)

Initially the numbers of moles are 0.25 0.25 0.5

And on the reaction, are 0.25-x 0.25-x x 0.5+x

So under the total pressure of the gas 1 atm, the partial pressure of each component is

𝑝𝑝𝐻𝐻2 = 0.25 − 𝑥𝑥
𝑝𝑝𝐻𝐻2𝑂𝑂 = 𝑥𝑥
𝑝𝑝𝐶𝐶𝐶𝐶2 = 0.25 − 𝑥𝑥
𝑝𝑝𝐶𝐶𝐶𝐶 = 0.5 + 𝑥𝑥
𝑝𝑝𝐶𝐶𝐶𝐶 𝑝𝑝𝐻𝐻2𝑂𝑂
𝐾𝐾𝑃𝑃 =
𝑝𝑝𝐻𝐻2 𝑝𝑝𝐶𝐶𝐶𝐶2
 (0.5 + 𝑥𝑥)𝑥𝑥
𝐾𝐾𝑃𝑃 =
(0.25 − 𝑥𝑥)(0.25 − 𝑥𝑥)
Then based on𝐾𝐾𝑃𝑃 = 1.16, we can get x
(0.5 + 𝑥𝑥)𝑥𝑥
1.16 =
(0.25 − 𝑥𝑥)(0.25 − 𝑥𝑥)

The solution of this equation is x=0.0678 and x=6.6822.

Then the partial pressure is

𝑝𝑝𝐻𝐻2 = 0.1822 𝑎𝑎𝑎𝑎𝑎𝑎
𝑝𝑝𝐻𝐻2𝑂𝑂 = 0.0678 𝑎𝑎𝑎𝑎𝑎𝑎
𝑝𝑝𝐶𝐶𝐶𝐶2 = 0.1822 𝑎𝑎𝑎𝑎𝑎𝑎
𝑝𝑝𝐶𝐶𝐶𝐶 = 0.5678 𝑎𝑎𝑎𝑎𝑎𝑎

10pts 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?

From table A-1 we can know that

1 0
𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) (i) ∆𝐺𝐺(𝑖𝑖) = −111,700 − 87.65𝑇𝑇
2
0
𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2(𝑔𝑔) (ii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −394100 − 0.84𝑇𝑇
1 0 0 0
𝐶𝐶𝐶𝐶2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) (iii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = ∆𝐺𝐺(𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖𝑖𝑖)
2
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = 282400 − 86.81𝑇𝑇
1 0
𝐻𝐻2(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) (iv) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −247500 + 55.85𝑇𝑇
2

Suppose we start with a mole CO2 and 1 mole H2 ,(the ratio of CO2 and H2 is a), and at the equilibrium,
1 0
𝐶𝐶𝐶𝐶2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) (iii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = 282400 − 86.81𝑇𝑇
2

Initially the numbers of moles are a

 1
And on the reaction, are a-x x (x-y)
2
At T=1600+273 K=1873 K,
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖)
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖𝑖𝑖) = 𝑒𝑒 𝑅𝑅𝑇𝑇 )
(−

282400−86.81∗1873
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖𝑖𝑖) = 𝑒𝑒 (− 8.3144∗1873
)

𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖𝑖𝑖) = 4.56 ∗ 10−4

1 0
𝐻𝐻2(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) (iv) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −247500 + 55.85𝑇𝑇
2

Initially the numbers of moles are 1

1
And on the reaction, are 1-y (x−𝑦𝑦) y
2

At T =1873 K,
∆𝐺𝐺0
(𝑖𝑖𝑖𝑖)
(− )
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 𝑒𝑒 𝑅𝑅𝑅𝑅
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖)
(− )
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 𝑒𝑒 𝑅𝑅𝑅𝑅

−247500+55.85∗1873
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 𝑒𝑒 (− 8.3144∗1873
)

𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 9.664 ∗ 103

After allowing the CO2 react by x moles and the H2 react by y moles, the number of moles of all
𝑥𝑥−𝑦𝑦
components are: 𝑛𝑛𝑐𝑐𝑐𝑐 = 𝑥𝑥, 𝑛𝑛𝑐𝑐𝑐𝑐2 = 𝑎𝑎 − 𝑥𝑥, 𝑛𝑛𝐻𝐻2𝑂𝑂 = 𝑦𝑦, 𝑛𝑛𝑜𝑜2 = ,𝑛𝑛𝐻𝐻2 = 1 − 𝑦𝑦
2
𝑥𝑥−𝑦𝑦
The total gas is 𝑛𝑛 = 1 + 𝑎𝑎 +
2

Then substitute the parameters by the number of moles of all components, we can express the partial
𝑥𝑥 𝑎𝑎−𝑥𝑥 𝑦𝑦 1−𝑦𝑦
pressure are separately, 𝑝𝑝𝐶𝐶𝐶𝐶 = , 𝑝𝑝𝐶𝐶𝐶𝐶2 =
𝑥𝑥−𝑦𝑦 𝑥𝑥−𝑦𝑦 , 𝑝𝑝𝐻𝐻2𝑂𝑂 = 𝑥𝑥−𝑦𝑦 , 𝑝𝑝𝐻𝐻2 = , 𝑝𝑝𝑂𝑂2 =
𝑥𝑥−𝑦𝑦
1+𝑎𝑎+ 1+𝑎𝑎+ 1+𝑎𝑎+ 1+𝑎𝑎+
2 2 2 2
𝑥𝑥−𝑦𝑦
2
𝑥𝑥−𝑦𝑦 .
1+𝑎𝑎+
2

Since
1
2
𝑝𝑝𝐶𝐶𝐶𝐶 𝑝𝑝𝑜𝑜2
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖𝑖𝑖) =
𝑝𝑝𝑐𝑐𝑐𝑐2
And substitute𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖𝑖𝑖) = 4.56 ∗ 10−4 ,
1
𝑥𝑥 − 𝑦𝑦 2
𝑥𝑥 2
� 𝑥𝑥 − 𝑦𝑦� � 𝑥𝑥 − 𝑦𝑦 �
1 + 𝑎𝑎 + 2 1 + 𝑎𝑎 + 2
4.56 ∗ 10−4 = 𝑎𝑎 − 𝑥𝑥 (𝑣𝑣)
𝑥𝑥 − 𝑦𝑦
1 + 𝑎𝑎 + 2
 𝑝𝑝𝐻𝐻2𝑂𝑂
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 1
2
𝑝𝑝𝐻𝐻2 𝑝𝑝𝑜𝑜2

Substitute𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 9.664 ∗ 103 ,

𝑝𝑝𝐻𝐻2𝑂𝑂
9.664 ∗ 103 = 1
2
𝑝𝑝𝐻𝐻2 𝑝𝑝𝑜𝑜2
𝑦𝑦
𝑥𝑥 − 𝑦𝑦
1 + 𝑎𝑎 + 2
9.664 ∗ 103 = 1 (𝑣𝑣𝑣𝑣)
𝑥𝑥 − 𝑦𝑦 2
1 − 𝑦𝑦 2
� 𝑥𝑥 − 𝑦𝑦� � 𝑥𝑥 − 𝑦𝑦 �
1 + 𝑎𝑎 + 2 1 + 𝑎𝑎 + 2

Also the partial pressure of oxygen is 10-7 atm, so

𝑥𝑥 − 𝑦𝑦
𝑝𝑝𝑂𝑂2 = 2
𝑥𝑥 − 𝑦𝑦
1 + 𝑎𝑎 + 2
𝑥𝑥 − 𝑦𝑦
10−7 = 2 (𝑣𝑣𝑣𝑣𝑣𝑣)
𝑥𝑥 − 𝑦𝑦
1 + 𝑎𝑎 + 2

Combine equations (v)(vi) and (vii), we can get the solutions

a =1.27596

x =0.75345

y =0.75345

So the ratio of the CO2 and H2 is 1.27596.

10pts 11.8 By establishing the equilibrium

𝑃𝑃𝑃𝑃𝑃𝑃5(𝑔𝑔) = 𝑃𝑃𝑃𝑃𝑃𝑃3(𝑔𝑔) + 𝐶𝐶𝐶𝐶2(𝑔𝑔)

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?

0
From table A-1, for reaction 𝑃𝑃𝑃𝑃𝑃𝑃3(𝑔𝑔) + 𝐶𝐶𝐶𝐶2(𝑔𝑔) = 𝑃𝑃𝑃𝑃𝑃𝑃5(𝑔𝑔) (i), we can get ∆𝐺𝐺(𝑖𝑖) = −95600 −
7.94𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 + 235.2𝑇𝑇,
0
Then for reverse reaction 𝑃𝑃𝑃𝑃𝑃𝑃5(𝑔𝑔) = 𝑃𝑃𝑃𝑃𝑃𝑃3(𝑔𝑔) + 𝐶𝐶𝐶𝐶2(𝑔𝑔) (𝑖𝑖𝑖𝑖) , ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = 95600 + 7.94𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 − 235.2𝑇𝑇

At T=500 K,
 0
∆𝐺𝐺(𝑖𝑖𝑖𝑖)
(− )
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 𝑒𝑒 𝑅𝑅𝑅𝑅

95600+7.94∗500𝐼𝐼𝐼𝐼500−235.2∗500
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 𝑒𝑒 (− 8.3144∗500
)

𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) = 0.5259

We start the reaction with a mole PCl5 and 1 mole PCl3, (the ration of PCl5 and PCl3 is a)

𝑃𝑃𝑃𝑃𝑃𝑃5(𝑔𝑔) = 𝑃𝑃𝑃𝑃𝑃𝑃3(𝑔𝑔) + 𝐶𝐶𝐶𝐶2(𝑔𝑔)

Initially the numbers of moles are a 1

And on the reaction, are a-x x+1 x

Total gas number of mole is n=a+1+x,

𝑎𝑎−𝑥𝑥 𝑥𝑥+1 𝑥𝑥
Then the partial pressure of each component is 𝑝𝑝𝑃𝑃𝑃𝑃𝑃𝑃5 = , 𝑝𝑝 = , 𝑝𝑝𝐶𝐶𝐶𝐶2 =
1+𝑎𝑎+𝑥𝑥 𝑃𝑃𝑃𝑃𝑃𝑃3 1+𝑎𝑎+𝑥𝑥 1+𝑎𝑎+𝑥𝑥

Since the partial pressure of Cl2 is 0.1 atm, 𝑝𝑝𝐶𝐶𝐶𝐶2 = 0.1 𝑎𝑎𝑎𝑎𝑎𝑎
𝑥𝑥
0.1 = (𝑖𝑖𝑖𝑖𝑖𝑖)
1 + 𝑎𝑎 + 𝑥𝑥
𝑝𝑝𝐶𝐶𝐶𝐶2 𝑝𝑝𝑃𝑃𝑃𝑃𝑃𝑃3
𝐾𝐾𝑃𝑃(𝑖𝑖𝑖𝑖) =
𝑝𝑝𝑃𝑃𝑃𝑃𝑃𝑃5
𝑝𝑝𝐶𝐶𝐶𝐶2 𝑝𝑝𝑃𝑃𝑃𝑃𝑃𝑃3
0.5259 =
𝑝𝑝𝑃𝑃𝑃𝑃𝑃𝑃5
Substitute the parameters into this equation,
𝑥𝑥 𝑥𝑥 + 1
( )(1 + 𝑎𝑎 + 𝑥𝑥 )
0.5259 = 1 + 𝑎𝑎 + 𝑥𝑥 (𝑖𝑖𝑖𝑖)
𝑎𝑎 − 𝑥𝑥
(1 + 𝑎𝑎 + 𝑥𝑥 )

Based on equations (iii) and (iv), we can get x=0.152, a=0.371

So the ratio of PCl5 and PCl3 is 0.371.

10pts 12.2 Using the standard Gibbs free energy 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.

From table A-1, we can find

0
2𝑁𝑁𝑁𝑁(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 2𝑁𝑁𝑁𝑁(𝑠𝑠) (𝑖𝑖) ∆𝐺𝐺(𝑖𝑖) = −471200 + 172𝑇𝑇
0
2𝑁𝑁𝑁𝑁(𝑙𝑙) + 𝑂𝑂2(𝑔𝑔) = 2𝑁𝑁𝑁𝑁(𝑠𝑠) (𝑖𝑖𝑖𝑖) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −506180 + 192.2𝑇𝑇

Then from 𝑁𝑁𝑁𝑁(𝑠𝑠) to𝑁𝑁𝑁𝑁(𝑙𝑙) ,

01 0
∆𝐺𝐺 0 = (∆𝐺𝐺(𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖𝑖𝑖) ),
2
 ∆𝐺𝐺 0 = 17490 − 10.1𝑇𝑇

Since ∆𝐺𝐺 0 = 𝐻𝐻𝑚𝑚 − 𝑇𝑇𝑆𝑆𝑚𝑚 ,

So 𝐻𝐻𝑚𝑚 = 17490 𝐽𝐽, 𝑆𝑆𝑚𝑚 = 10.1 𝐽𝐽/𝐾𝐾

𝐻𝐻𝑚𝑚
𝑇𝑇𝑚𝑚 =
𝑆𝑆𝑚𝑚
17490 𝐽𝐽
𝑇𝑇𝑚𝑚 =
10.1 𝐽𝐽/𝐾𝐾
𝑇𝑇𝑚𝑚 = 1732 𝐾𝐾
10pts 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.
1
From table A-1, we can get 2𝐴𝐴𝐴𝐴(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐴𝐴𝐴𝐴2 𝑂𝑂(𝑠𝑠) ∆𝐺𝐺 0 = −30540 + 66.11𝑇𝑇
2

Then for the reverse reaction, 2𝐴𝐴𝐴𝐴2 𝑂𝑂(𝑠𝑠) = 4𝐴𝐴𝐴𝐴(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) ∆𝐺𝐺 0′ = 2 ∗ (30540 − 66.11𝑇𝑇)

For reaction with solid and gas, the equilibrium constant only depends on the gas partial pressure.

𝐾𝐾𝑃𝑃 = 𝑝𝑝𝑂𝑂2
For pure oxygen, 𝑝𝑝𝑂𝑂2 = 1 𝑎𝑎𝑎𝑎𝑎𝑎

So 𝐾𝐾𝑃𝑃 = 1,
∆𝐺𝐺 0′
𝐾𝐾𝑃𝑃 = 𝑒𝑒 (− 𝑅𝑅𝑅𝑅
)

∆𝐺𝐺 0′
1 = 𝑒𝑒 (− 𝑅𝑅𝑅𝑅 )

∆𝐺𝐺 0′ = 0
Then30540 − 66.11𝑇𝑇 = 0, 5pts T=461.96 K.

For air, the oxygen partial pressure is 𝑝𝑝𝑂𝑂2 = 0.21 𝑎𝑎𝑎𝑎𝑎𝑎

𝐾𝐾𝑃𝑃 = 0.21
2∗(30540−66.11𝑇𝑇)
0.21 = 𝑒𝑒 (− 8.3144𝑇𝑇
)

The solution of this equation is 5pts T=420.66 K.

10pts 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?
3 0
2𝐶𝐶𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2 𝑂𝑂3(𝑠𝑠) (i) ∆𝐺𝐺(𝑖𝑖) = −1,110,100 + 247.3𝑇𝑇
2
1 0
𝐻𝐻2(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) = 𝐻𝐻2 𝑂𝑂(𝑔𝑔) (ii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −247,500 + 55.85𝑇𝑇
2
Then for the reaction
0
2 1 0 ∆𝐺𝐺(𝑖𝑖) 0
𝐶𝐶𝐶𝐶(𝑠𝑠) + 𝐻𝐻2 𝑂𝑂(𝑔𝑔) = 𝐻𝐻2(𝑔𝑔) + 𝐶𝐶𝐶𝐶2 𝑂𝑂3(𝑠𝑠) (iii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = − ∆𝐺𝐺(𝑖𝑖𝑖𝑖)
3 3 3
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = −122,533.33 + 26.58333𝑇𝑇

At T= 1500 K,
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖)
(− )
𝐾𝐾𝑝𝑝 = 𝑒𝑒 𝑅𝑅𝑅𝑅

−122,533.33+26.58333∗1500
𝐾𝐾𝑝𝑝 = 𝑒𝑒 (− 8.3144∗1500
)

𝐾𝐾𝑝𝑝 = 755.76
𝑝𝑝𝐻𝐻2
𝐾𝐾𝑝𝑝 =
𝑝𝑝𝐻𝐻2𝑂𝑂
1
Since the partial pressure of hydrogen is 1 atm, so 755.76 = we can get the partial pressure of
𝑝𝑝𝐻𝐻2𝑂𝑂
water is 5pts 𝑝𝑝𝐻𝐻2𝑂𝑂 = 0.001323 𝑎𝑎𝑎𝑎𝑎𝑎
0
If the pressure is above this value, ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) will become negative and the Cr oxidation will proceed. Thus,
this pressure is the maximum water pressure to which Cr can be heater without oxidizing.
0
5pts From ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) result above, the reaction is exothermic ∆H = −122,533.33 < 0.

10pts 12.6 Fe and FeO are in equilibrium with 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?
1 0
From table A-1 we can get 𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶(𝑔𝑔) (i) ∆𝐺𝐺(𝑖𝑖) = −111,700 − 87.65𝑇𝑇
2
0
𝐶𝐶(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2(𝑔𝑔) (ii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −394100 − 0.84𝑇𝑇
1 0 0 0
𝐶𝐶𝐶𝐶(𝑔𝑔) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2(𝑔𝑔) (iii) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = ∆𝐺𝐺(𝑖𝑖𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖)
2
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = −282400 + 86.81𝑇𝑇
1 0
𝐹𝐹𝐹𝐹(𝑠𝑠) + 𝑂𝑂2(𝑔𝑔) = 𝐹𝐹𝐹𝐹𝐹𝐹(𝑠𝑠) (iv) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −263700 + 64.35𝑇𝑇
2
0 0 0
For reaction 𝐹𝐹𝐹𝐹𝐹𝐹(𝑠𝑠) + 𝐶𝐶𝐶𝐶(𝑔𝑔) = 𝐹𝐹𝐹𝐹(𝑠𝑠) + 𝐶𝐶𝐶𝐶2(𝑔𝑔) (v) ∆𝐺𝐺(𝑣𝑣) = ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖𝑖𝑖)
0
∆𝐺𝐺(𝑣𝑣) = −18700 + 22.46𝑇𝑇

It is stated the Fe and FeO are in equilibrium with CO and CO2 at some ratio and at 1273K. If the
0
temperature is reduced, the reaction will go from left side to right side. Since ∆𝐺𝐺(𝑣𝑣) = −18700 +
22.46𝑇𝑇, ∆𝐻𝐻 = −18700 < 0, it is a exothermic reaction. So FeO will eventually disappear.
10pts 13.1 Air at atmosphere 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.

From table A-1, we can get

1
2𝐺𝐺𝐺𝐺(𝑙𝑙) + 𝑂𝑂2(𝑔𝑔) = 𝐶𝐶𝐶𝐶2 𝑂𝑂(𝑠𝑠) ∆𝐺𝐺 0 = −188300 + 88.48𝑇𝑇
2

At T=1500 K,
∆𝐺𝐺 0
𝐾𝐾 = 𝑒𝑒 (− 𝑅𝑅𝑅𝑅 )
−188300+88.48∗1500
𝐾𝐾 = 𝑒𝑒 (− 8.3144∗1500
)

𝐾𝐾 = 86.19
Based on textbook page 386, the equilibrium constant can be expressed by
1
𝐾𝐾 = 1
2 2
𝛼𝛼𝐶𝐶𝐶𝐶 𝑃𝑃𝑂𝑂2

Since the partial pressure of oxygen is 0.21 atm,

1
86.19 = 2
𝛼𝛼𝐶𝐶𝐶𝐶 (0.21)2

The solution of this equation is 𝛼𝛼𝐶𝐶𝐶𝐶 = 0.159

10pts 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
𝑝𝑝𝐻𝐻𝐻𝐻𝐻𝐻 = 10−5 𝑎𝑎𝑎𝑎𝑎𝑎 to form pure liquid MgCl2.

From table A-1, we can get

0
𝑀𝑀𝑀𝑀(𝑙𝑙) + 𝐶𝐶𝐶𝐶2(𝑔𝑔) = 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀2(𝑙𝑙) (𝑖𝑖) ∆𝐺𝐺(𝑖𝑖) = −603200 + 121.43𝑇𝑇
0
𝐻𝐻2(𝑔𝑔) + 𝐶𝐶𝐶𝐶2(𝑔𝑔) = 2𝐻𝐻𝐻𝐻𝐻𝐻(𝑔𝑔) (𝑖𝑖𝑖𝑖) ∆𝐺𝐺(𝑖𝑖𝑖𝑖) = −188200 − 12.80𝑇𝑇
0 0 0
Then for reaction 𝑀𝑀𝑀𝑀(𝑙𝑙) + 2𝐻𝐻𝐻𝐻𝐻𝐻(𝑔𝑔) = 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀2(𝑙𝑙) + 𝐻𝐻2(𝑔𝑔) (𝑖𝑖𝑖𝑖𝑖𝑖) ∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = ∆𝐺𝐺(𝑖𝑖) − ∆𝐺𝐺(𝑖𝑖𝑖𝑖)
0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖) = −415000 + 134.23𝑇𝑇

At T=800+273 K=1073 K, the equilibrium constant can be calculated by

0
∆𝐺𝐺(𝑖𝑖𝑖𝑖𝑖𝑖)
𝐾𝐾 = 𝑒𝑒 𝑅𝑅𝑅𝑅 )
(−
 −415000+134.23∗1073
𝐾𝐾 = 𝑒𝑒 (− 8.3144∗1073
)

𝐾𝐾 = 1.55 ∗ 1013
Also the equilibrium constant can be expressed by
𝑃𝑃𝐻𝐻2
𝐾𝐾 = 2
𝛼𝛼𝑀𝑀𝑀𝑀 𝑃𝑃𝐻𝐻𝐻𝐻𝐻𝐻

Since hydrogen is essentially 1 atm pressure 𝑃𝑃𝐻𝐻2 = 1 𝑎𝑎𝑎𝑎𝑎𝑎 and 𝑝𝑝𝐻𝐻𝐻𝐻𝐻𝐻 = 10−5 𝑎𝑎𝑎𝑎𝑎𝑎,
𝑃𝑃𝐻𝐻2
1.55 ∗ 1013 = 2
𝛼𝛼𝑀𝑀𝑀𝑀 𝑃𝑃𝐻𝐻𝐻𝐻𝐻𝐻
1
1.55 ∗ 1013 =
𝛼𝛼𝑀𝑀𝑀𝑀 (10−5 )2

Then the solution is 𝛼𝛼𝑀𝑀𝑀𝑀 = 6.4 ∗ 10−4

10pts 13.5 A CH4-H2 gas mixture at 1 atm total pressure, in which 𝑃𝑃𝐻𝐻2 = 0.957 𝑎𝑎𝑎𝑎𝑎𝑎, 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 𝑃𝑃𝐻𝐻2 in the gas mixture (at 𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 1 𝑎𝑎𝑎𝑎𝑎𝑎) have to be in order to saturate the Fe with
graphite at 1000 K?

From table A-1, we can get

0
𝐶𝐶(𝑔𝑔𝑔𝑔) + 2𝐻𝐻2(𝑔𝑔) = 𝐶𝐶𝐶𝐶4(𝑔𝑔) (𝑖𝑖) ∆𝐺𝐺(𝑖𝑖) = −91040 + 110.7𝑇𝑇

At T=1000 K,
0
∆𝐺𝐺(𝑖𝑖)
(− )
𝐾𝐾 = 𝑒𝑒 𝑅𝑅𝑅𝑅

−91040+110.7∗1000
𝐾𝐾 = 𝑒𝑒 (− 8.3144∗1000
)

𝐾𝐾 = 0.094
Also the equilibrium constant can be expressed by
𝑃𝑃𝐶𝐶𝐶𝐶4
𝐾𝐾 = 2
𝛼𝛼𝐶𝐶 𝑃𝑃𝐻𝐻2

𝑃𝑃𝐻𝐻2 = 0.957 𝑎𝑎𝑎𝑎𝑎𝑎, 𝑃𝑃𝐶𝐶𝐶𝐶4 = 1 − 𝑃𝑃𝐻𝐻2 = 0.043 𝑎𝑎𝑎𝑎𝑎𝑎

0.043
0.094 =
𝛼𝛼𝐶𝐶 (0.957)2
5pts 𝛼𝛼𝐶𝐶 = 0.5
𝑃𝑃
If it is graphite saturate with Fe,𝛼𝛼𝐶𝐶 = 1 then the equilibrium constant𝐾𝐾 = 𝛼𝛼 𝐶𝐶𝐶𝐶4
𝑃𝑃2
, with𝛼𝛼𝐶𝐶 = 1, 𝑃𝑃𝐶𝐶𝐶𝐶4 =
𝐶𝐶 𝐻𝐻2
1 − 𝑃𝑃𝐻𝐻2 and𝐾𝐾 = 0.094
 1 − 𝑃𝑃𝐻𝐻2
0.094 = 2
𝑃𝑃𝐻𝐻2

5pts The solution of this equation is 𝑃𝑃𝐻𝐻2 = 0.92 𝑎𝑎𝑎𝑎𝑎𝑎