Problem 2.

What minimum equilibrium partial pressure of oxygen is required to reduce SiO2 at 1600
°C? Calculate the corresponding CO/CO2 and H2/H2O ratios.
Solution:

Assume the activity of solid and liquid phase is 1.

Partial pressure of oxygen:

For reaction Si(l) + O2(g) = SiO2(s);
ΔG° = -946348 + 197.643·T
T = 1600 + 273 = 1873K
ΔG°= -576162.661 J/mol
∆𝐺° = −𝑅𝑇𝑙𝑛(𝐾),
−∆𝐺° 576162.661𝐽/𝑚𝑜𝑙
𝐾 = exp ( ) = exp ( ) = 1.17 × 1016
𝑅𝑇 8.314×1873𝐾
𝑎𝑆𝑖𝑂2(𝑠)
𝐾= = 1.17 × 1016
𝑎𝑆𝑖(𝑙) ×𝑝𝑂2

𝑃𝑂2 = 8.55 × 10−17

Ratio of CO/CO2:
C(s) + 1/2O2(g) = CO(g) ∆𝐺°1 =-112877 – 86.514·T
C(s) + O2(g) = CO2(g) ∆𝐺°2 = -394762 – 0.836·T
Si(l) + O2(g) = SiO2(s) ∆𝐺°3 =-946348 + 197.643·T
From 2×∆𝐺°2 -(2×∆𝐺°1 )-∆𝐺°3 , we have
SiO2(s) + 2CO(g) = Si(l) + 2CO2(g), ∆𝐺° = 382578 − 26.87 · 𝑇
When 𝑇 = 1873𝐾,
∆𝐺° =332250.49 J/mol
−∆𝐺° −332250.49𝐽/𝑚𝑜𝑙
𝐾 = exp ( ) = exp ( ) = 5.42 × 10−10
𝑅𝑇 8.314×1873𝐾
2
𝑎𝑆𝑖(𝑙) ×𝑝𝐶𝑂
According to the reaction equation, 𝐾 = 2
2
= 5.42 × 10−10
𝑎𝑆𝑖𝑂2(𝑠) ×𝑝𝐶𝑂

2
𝑝𝐶𝑂 𝑃𝐶𝑂2
Then 2
2
= 5.42 × 10−10 , = 2.33 × 10−5
𝑝𝐶𝑂 𝑃𝐶𝑂
𝑃𝐶𝑂
So = 4.30 × 104
𝑃𝐶𝑂2
Ratio of H2/H2O
SiO2(s) + 2H2(g) = Si(l) + 2H2O(g)
H2(g) +1/2O2(g) = H2O(g) ∆𝐺°1 =-247392 +55.849·T
Si(l) + O2(g) = SiO2(s) ∆𝐺°2= -946348 + 197.643·T
From 2×∆𝐺°1 -∆𝐺°2 , we have:
SiO2(s) + 2H2(g) = Si(l) + 2H2O(g) ∆𝐺° = 451564 – 85.945·T
At 1873𝐾 ∆𝐺° = 290589.015 𝐽/𝑚𝑜𝑙
−∆𝐺° −290589.015𝐽/𝑚𝑜𝑙
We have 𝐾 = exp ( ) = exp ( ) = 7.86 × 10−9
𝑅𝑇 8.314×1873𝐾
2
𝑎𝑆𝑖(𝑙) ×𝑝𝐻 2𝑂
Then 𝐾 = 2 = 7.86 × 10−9
𝑎𝑆𝑖𝑂2(𝑠) ×𝑝𝐻 2

2
𝑝𝐻 2𝑂
2 = 7.86 × 10−9
𝑝𝐻 2
𝑝𝐻2
= 1.12 × 104
𝑝𝐻2 𝑂
From Ellingham diagram the value for both H2/H2O and CO/CO2 is obtained