Final exam CL207/CL250/CL255 [Total 40 points]

1. Binary azeotropic mixture. [Total 16 points]

Ethanol and water form an azeotrope at a pressure of 1 atm. The following 𝑇 − 𝑥 − 𝑦 data (at 1 atm) is
available:
Table 1. T-x-y data for vapor-liquid equilibrium involving ethanol and
𝒙 𝒚 𝑻 (°𝑪)
water.
0 0 100
0.019 0.17 95.5
0.0721
0.0966
0.3891
0.4375
89
86.7
T-x-y plot
0.1238 0.4704 85.3 Temperature (degree celcius) 100
0.1661 0.5089 84.1
0.2337 0.5445 82.7 95
0.2608 0.558 82.3 90
0.3273 0.5826 81.5
0.3965 0.6122 80.7 85
0.5079 0.6564 79.8
0.5198 0.6599 79.7
80
0.5732 0.6841 79.3 75
0.6763 0.7385 78.74
0.7472 0.7815 78.41 70
0.8943 0.8943 78.3 0 0.2 0.4 0.6 0.8 1
0.98 0.98 78.3 Mole fraction x,y
1 1 78.3
A plot showing the T-x-y data is also provided.
𝐵
The parameters for the Antoine equation (log10 𝑃𝑖𝑠𝑎𝑡 = 𝐴 − 𝑇+𝐶) are (units of 𝑃 is bar and 𝑇 is K)

A B C
Ethanol 5.24677 1598.673 -46.424
Table 2. Antoine parameters for ethanol and water.
Water 5.08354 1663.125 -45.622

a. Starting with an equilibrium relation for vapor and liquid coexistence, proceed to find the value of the
activity coefficient 𝛾1 and 𝛾2 when 𝑥 = 1.9% ethanol. State any assumptions. [3 points]
Explain whether the activity coefficients can be used for vapor or liquid or both phases. [1 point]

The activity coefficient can be used only for liquid phase. The vapor phase is assumed to be ideal.
𝑣𝑎𝑝 𝑦𝑖 𝑃
At equilibrium, 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖 (𝑇)𝛾𝑖 . Therefore, 𝛾𝑖 = 𝑣𝑎𝑝 . Here 𝑇 = 95.5 + 273.15 = 368.65 𝐾.
𝑥𝑖 𝑃𝑖 (𝑇)

1598.673
𝑣𝑎𝑝
For component 1 (ethanol): 𝑥1 = 0.019, 𝑦1 = 0.17, 𝑃1 (368.65 𝐾) = 10(5.24677−368.65−46.424) = 1.9294 𝑏𝑎𝑟.
𝑣𝑎𝑝
For component 2 (water): 𝑥2 = 1 − 0.019 = 0.981, 𝑦1 = 1 − 0.17 = 0.83, 𝑃2 (368.65 𝐾) =
1663.125
(5.08354− )
10 368.65−45.622 = 0.861 𝑏𝑎𝑟.
1
 𝑦1 𝑃 0.17×1.013 𝑦2 𝑃 0.83×1.013
This gives us 𝛾1 = 𝑣𝑎𝑝 = 0.019×1.9294 = 4.7 and 𝛾2 = 𝑣𝑎𝑝 = 0.981×0.861 = 1.
𝑥1 𝑃1 𝑥2 𝑃2

b. Similarly, find the activity coefficients when 𝑥 = 98% ethanol. [2 points]

Here 𝑇 = 78.3 + 273.15 = 351.45 𝐾.

𝑣𝑎𝑝
For component 1 (ethanol): 𝑥1 = 0.98, 𝑦1 = 0.98, 𝑃1 (351.45 𝐾) = 1.013 𝑏𝑎𝑟.
𝑣𝑎𝑝
For component 2 (water): 𝑥2 = 0.02, 𝑦1 = 0.02, 𝑃2 (351.45 𝐾) = 0.442 𝑏𝑎𝑟.
𝑦1 𝑃 1.013 𝑦2 𝑃 1.013
This gives us 𝛾1 = 𝑣𝑎𝑝 = 1.013 = 1 and 𝛾2 = 𝑣𝑎𝑝 = 0.442 = 2.29.
𝑥1 𝑃1 𝑥2 𝑃2

c. According to the two-constant Margules equation for a binary mixture 1-2, the activity coefficient of the
individual species is given by

𝑅𝑇 ln 𝛾1 = (𝑎 + 3𝑏)𝑥22 − 4𝑏𝑥23 and 𝑅𝑇 ln 𝛾2 = (𝑎 − 3𝑏)𝑥12 + 4𝑏𝑥13 .

There are two unknowns 𝑎 and 𝑏 which can be determined using two infinite dilution activity coefficients.
In parts (a) and (b) you have determined total 4 activity coefficient values. Which two activity coefficients
will you use to determine the unknown parameters? Provide explanation. [2 point]

One should use the 𝛾1 when 𝑥1 → 0 and the 𝛾2 when 𝑥2 → 0. These are called the infinite dilute activity coefficients.

d. Now use the two chosen activity coefficients to obtain the parameters 𝑎 and 𝑏 in the model for the
activity coefficients in part a. State any assumptions made. [2 points]

𝐽
𝑅𝑇 ln 𝛾1 = 8.314 (368.65 𝐾) × ln 4.7 = 4743.2 = (𝑎 + 3𝑏)0.9812 − 4𝑏(0.981)3
𝑚𝑜𝑙. 𝐾
= 0.9624 𝑎 + 2.8871 𝑏 − 3.7763 𝑏 = 0.924 𝑎 − 0.8892 𝑏
𝐽
𝑅𝑇 ln 𝛾2 = 8.314 (351.45 𝐾) × ln 2.9 = 3111 = (𝑎 − 3𝑏)0.982 + 4𝑏(0.98)3 = 0.96 𝑎 + 0.8836 𝑏
𝑚𝑜𝑙. 𝐾
Solving for 𝑎 and 𝑏 we get

𝑎 = 4166 and 𝑏 = −1005.3.

e. Using the Margules equation, explain how you will find the composition of the vapor mixture and its
temperature at 1 atm when the (coexisting) liquid phase contains 20 mol% ethanol. You do not have to
solve numerically. [3 points]

𝑣𝑎𝑝
We need to solve for temperature using the relation 𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖 (𝑇)𝛾𝑖 (𝑇).
336.2
With 𝑥2 = 0.8, we find 𝑅𝑇 ln 𝛾1 = (𝑎 + 3𝑏)𝑥22 − 4𝑏𝑥23 = 1150.1𝑥22 + 4021.3𝑥23 = 2795 or 𝛾1 = exp ( 𝑇
).

30.684
Also, 𝑥1 = 0.2, we find 𝑅𝑇 ln 𝛾2 = (𝑎 − 3𝑏)𝑥12 + 4𝑏𝑥13 = 255.1 or 𝛾2 = exp ( 𝑇
)

2
 1598.673
𝑣𝑎𝑝 336.2
Writing 𝑃 = 1.013 𝑏𝑎𝑟 = 𝑥1 𝑃1 (𝑇)𝛾1 (𝑇) + 𝑥2 𝑃2𝑣𝑎𝑝 (𝑇)𝛾2 (𝑇) = 0.2 × 10(5.24677−𝑇−46.424) × exp ( )+
𝑇
1663.125
30.684
0.8 × 10(5.08354−𝑇−45.622) × exp ( 𝑇
) bar.

One needs to solve for 𝑇.

𝑣𝑎𝑝
𝑥𝑖 𝑃𝑖 (𝑇)𝛾𝑖 (𝑇)
Once the temperature is known, we can calculate 𝑦𝑖 = 𝑃
.

f. A liquid mixture contains 0.3 mole water and 0.7 mole ethanol at 1 atm. It is brought to a temperature of
82.3 degree Celsius where liquid and vapor phase can coexist. At this temperature, how many moles in the
mixture exist as liquid phase?
Use data provided in Table 1 to solve. [3 points]

Total number of moles is 1. Therefore 𝑉 + 𝐿 = 1. Furthermore, writing a balance for species 1, 𝑧1 = 𝑉𝑦1 + 𝐿𝑥1 =
𝑧1 −𝑦1 0.3−0.558
(1 − 𝐿)𝑦1 + 𝐿𝑥1 . Finally, 𝐿 = = = 0.8681 𝑚𝑜𝑙.
𝑥1 −𝑦1 0.2608−0.558

2. In ocean waters, dissolved carbon dioxide can be involved in the several reactions, some leading to
carbonate precipitates:
𝐶𝑂2 (𝑎𝑞) + 𝐻2 𝑂 ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞)
𝐻2 𝐶𝑂3 (𝑎𝑞) ⇌ 𝐻 + (𝑎𝑞) + 𝐻𝐶𝑂3− (𝑎𝑞)
𝐻𝐶𝑂3− (𝑎𝑞) ⇌ 𝐻 + (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞)
𝐶𝑎2+ (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞) ⇌ 𝐶𝑎𝐶𝑂3 (𝑠).
a. Show that the ocean pH is related to atmospheric CO2 partial pressure 𝑝𝐶𝑂2 as
1/2
𝑝𝐻 = 𝐴 − log10 𝑝𝐶𝑂 .
2

where 𝐴 is a constant. Find an expression for 𝐴 in terms of the standard chemical potentials and standard activity.

Hints:

(1) Assume equilibrium is achieved.

0
(2) The chemical potential for the dissolved species 𝑖 can be written as 𝐺𝑖 (𝑇, 𝑃, 𝑥) = 𝐺𝑖 (𝑇, 𝑃0 , 𝑥0 ) +
𝑅𝑇 ln 𝑎𝑖 (𝑇, 𝑃, 𝑥) where 𝑃0 = 1 𝑏𝑎𝑟 and 𝑃 is the pressure in the ocean. Assume 𝑃 ≈ 𝑃0 . 𝑇 is the ocean
0
temperature. 𝐺𝑖 (𝑇, 𝑃0 , 𝑥0 ) is the standard chemical potential.
(3) From Henry’s law the activity of CO2 in water follows 𝑝𝐶𝑂2 = 𝐻𝑎𝐶𝑂2 .
(4) Assume activity of water and 𝐶𝑎𝐶𝑂3 (𝑠) is 1.
(5) Assume activity of 𝐶𝑎2+ is constant.
(6) 𝑝𝐻 = − log10(𝑎𝐻+ ), which uses log to the base 10.

[12 points]

Using Henry’s law 𝑥𝐶𝑂2 = 𝐻𝑝𝐶𝑂2 .

For the first reaction 𝐶𝑂2 (𝑎𝑞) + 𝐻2 𝑂 ⇌ 𝐻2 𝐶𝑂3 (𝑎𝑞)

3
 0 0
(𝐺𝐶𝑂2 (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐶𝑂2 (𝑇, 𝑃, 𝑥)) + (𝐺𝐶𝑂2 (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻2 𝑂 (𝑇, 𝑃, 𝑥))
0
= (𝐺𝐻2 𝐶𝑂3 (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥))

0 0 0
𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥) 𝐺𝐶𝑂2 (𝑇, 𝑃0 , 𝑥0 ) + 𝐺𝐶𝑂2 (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐻2 𝐶𝑂3 (𝑇, 𝑃0 , 𝑥0 )
⇒ = 𝐾1 = exp ( ).
𝑎𝐶𝑂2 (𝑇, 𝑃, 𝑥)𝑎𝐻2 𝑂 (𝑇, 𝑃, 𝑥) 𝑅𝑇

For the second reaction 𝐻2 𝐶𝑂3 ⇌ 𝐻 + + 𝐻𝐶𝑂3−

0
(𝐺𝐻2 𝐶𝑂3 (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥))
0 0
= (𝐺𝐻+ (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻+ (𝑇, 𝑃, 𝑥)) + (𝐺𝐻𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥))

0 0 0
𝑎𝐻 + (𝑇, 𝑃, 𝑥)𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥) 𝐺𝐻 𝐶𝑂 (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐻+ (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐻𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 )
⇒ = 𝐾2 = exp ( 2 3 ).
𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥) 𝑅𝑇

For the third reaction 𝐻𝐶𝑂3− ⇌ 𝐻 + + 𝐶𝑂32−

0
(𝐺𝐻𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥))
0 0
= (𝐺𝐻+ (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐻+ (𝑇, 𝑃, 𝑥)) + (𝐺𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥))

0 0 0
𝑎𝐻+ (𝑇, 𝑃, 𝑥)𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥) 𝐺𝐻𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐻+ (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 )
⇒ = 𝐾3 = exp ( ).
𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥) 𝑅𝑇

For the fourth reaction 𝐶𝑎2+ (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞) ⇌ 𝐶𝑎𝐶𝑂3 (𝑠)

0 0 0
(𝐺𝐶𝑎2+ (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐶𝑎2+ (𝑇, 𝑃, 𝑥)) + (𝐺𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 ) + 𝑅𝑇 ln 𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥)) = (𝐺𝐶𝑎𝐶𝑂3 (𝑠) (𝑇, 𝑃0 , 𝑥0 )) +

0 0 0
𝐺𝐶𝑎𝐶𝑂3 (𝑠) (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐶𝑎2+ (𝑇, 𝑃0 , 𝑥0 ) − 𝐺𝐶𝑂3− (𝑇, 𝑃0 , 𝑥0 )
⇒ 𝑎𝐶𝑎2+ (𝑇, 𝑃, 𝑥)𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥) = 𝐾4 = exp ( ).
𝑅𝑇

Multiplying
𝐾1 𝐾2 𝐾3
=𝐾
𝐾4
𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥) 𝑎𝐻 + (𝑇, 𝑃, 𝑥)𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥) 𝑎𝐻 + (𝑇, 𝑃, 𝑥)𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥) 1
= . . .
𝑎𝐶𝑂2 (𝑇, 𝑃, 𝑥)𝑎𝐻2 𝑂 (𝑇, 𝑃, 𝑥) 𝑎𝐻2 𝐶𝑂3 (𝑇, 𝑃, 𝑥) 𝑎𝐻𝐶𝑂3− (𝑇, 𝑃, 𝑥) 𝑎𝐶𝑎2+ (𝑇, 𝑃, 𝑥)𝑎𝐶𝑂3− (𝑇, 𝑃, 𝑥)
[𝑎𝐻 + (𝑇, 𝑃, 𝑥)]2
= .
𝑎𝐶𝑂2 (𝑇, 𝑃, 𝑥)𝑎𝐶𝑎2+ (𝑇, 𝑃, 𝑥)

𝐾′
[𝑎𝐻 + (𝑇, 𝑃, 𝑥)]2 = 𝐾𝑎𝐶𝑂2 (𝑇, 𝑃, 𝑥)𝑎𝐶𝑎2+ (𝑇, 𝑃, 𝑥) = 𝑝 (𝑇, 𝑃, 𝑥)
𝐻 𝐶𝑂2
Finally,
1/2
𝑝𝐻 = − log10 𝑎𝐻+ (𝑇, 𝑃, 𝑥) = 𝐴 − log10 𝑝𝐶𝑂
2

4
3. Effect of temperature on equilibrium constant
At sufficiently high oxygen (gas) pressure, metals can oxidize and form metal oxides.
𝑥
𝑀(𝑠) + 𝑂2 (𝑔) ⇌ 𝑀𝑂𝑥 (𝑠).
2
An example is 𝑀 ≡ 𝐹𝑒 which forms 𝐹𝑒2 𝑂3.
(i) Show that the standard free energy of formation for any species 𝑖 involved in the above reaction obeys
[6 points]

𝑑(Δ𝑓 𝐺𝑖0 /𝑅𝑇) Δ𝑓 𝐻𝑖 0

=− .
𝑑𝑇 𝑅𝑇 2
Here Δ𝑓 𝐺𝑖0 ≡ Δ𝑓 𝐺𝑖0 (𝑇) and Δ𝑓 𝐻𝑖0 ≡ Δ𝑓 𝐻𝑖0 (𝑇) are evaluated at a fixed pressure 𝑃0 . Hint: see table of
equations provided on the next page.

𝑑(Δ𝑓 𝐺𝑖0 /𝑅𝑇) Δ𝑓 𝐺𝑖0 0

1 𝑑(Δ𝑓 𝐺𝑖 ) Δ𝑓 𝐻𝑖0 −𝑇Δ𝑓 𝑆𝑖0 Δ𝑓 𝑆𝑖0 Δ𝑓 𝐻𝑖 0
We can show that 𝑑𝑇
=− 𝑅𝑇 2
+ 𝑅𝑇 𝑑𝑇
== − 𝑅𝑇 2
− 𝑅𝑇
− 𝑅𝑇 2
.

Δ𝑟𝑥𝑛 𝐺 0
(ii) For a chemical reaction, show that the equilibrium constant can be written as ln 𝐾 = and
𝑅𝑇
consequently [3 point]
𝑑 ln 𝐾 Δ𝑟𝑥𝑛 𝐻 0
=− .
𝑑𝑇 𝑅𝑇 2

Δ𝑟𝑥𝑛 𝐺 0 𝜈𝑖 Δ𝑓 𝐺𝑖0
We can write ln 𝐾 = 𝑅𝑇
= ∑𝑖 𝑅𝑇
.

𝑑 ln 𝐾 𝑑 𝜈𝑖 Δ𝑓 𝐺0𝑖 𝜈𝑖 Δ𝑓 𝐻0𝑖 Δ𝑟𝑥𝑛 𝐻 0

Next, = 𝑑𝑇 ∑𝑖 = − ∑𝑖 =−
𝑑𝑇 𝑅𝑇 𝑅𝑇2 𝑅𝑇 2

(iii) Assuming that Δ𝑟𝑥𝑛 𝐻 0 does not vary significantly with temperature obtain a relation for 𝐾(𝑇)/𝐾(𝑇 ′ )
where 𝑇 and 𝑇′ are two different temperatures. [3 point]

𝑑 ln 𝐾 Δ𝑟𝑥𝑛 𝐻 0
Integrating =−
𝑑𝑇 𝑅𝑇 2

Δ𝑟𝑥𝑛 𝐻 0 1 1
′)
ln 𝐾(𝑇) = ln 𝐾(𝑇 − ( − ′ ).
𝑅 𝑇 𝑇