CHE 545 HW1: MODEL ANSWERS

Question 1
0
𝑆𝑛2+ + 2𝑒 − → 𝑆𝑛 Φ𝑆𝑛 2+ /𝑆𝑛 = −0.138 𝑉 𝑣𝑠 𝑆𝐻𝐸

0
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 Φ𝐶𝑢 2+ /𝐶𝑢 = 0.337 𝑉 𝑣𝑠 𝑆𝐻𝐸

Tin will corrode when coupled with the copper.

0 0
𝐸𝑐𝑒𝑙𝑙 = Φ𝐶𝑢 2+ /𝐶𝑢 − Φ𝑆𝑛2+ /𝑆𝑛 = 0.337+0.138

= 0.475 𝑉 𝑣𝑠 𝑆𝐻𝐸
The Gibbs free-energy change when one mole of tin is consumed is:

ΔG = −𝑛𝐹𝐸 0 = −2 ∗ 96485 ∗ 0.475

ΔG = −91.7 𝑘𝐽

Question 2
The half-cell reactions are:
0
𝐹𝑒 3+ + 𝑒 − → 𝐹𝑒 2+ Φ𝐹𝑒 3+ /𝐹𝑒 2+ = 0.771 𝑉 𝑣𝑠 𝑆𝐻𝐸

0
𝑍𝑛2+ + 2𝑒 − → 𝑍𝑛 Φ𝑍𝑛 2+ /𝑍𝑛 = −0.762 𝑉 𝑣𝑠 𝑆𝐻𝐸

Because
0
Δ𝐺 0 = −2.303𝑅𝑇𝑙𝑛𝐾 = −𝑛𝐹E𝑐𝑒𝑙𝑙
0
𝑛E𝑐𝑒𝑙𝑙
𝑙𝑜𝑔𝐾 =
0.059
The electrode potentials for the individual half-cell reactions are:

0 𝑎𝐹𝑒 2+
Φ𝐹𝑒 3+ /𝐹𝑒 2+ = 0.771 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
𝑎𝐹𝑒 3+
0 𝑎𝑍𝑛
Φ𝑍𝑛 2+ /𝑍𝑛 = −0.762 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
𝑎𝑍𝑛2+
Because the equilibrium constant is a ratio between the activities of the products and reactants, it follows
that
𝑎𝐹𝑒 2+ 𝑎𝑍𝑛
0.771 − 2.303𝑅𝑇𝑙𝑜𝑔 ( ) = −0.762 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
𝑎𝐹𝑒 3+ 𝑎𝑍𝑛2+
𝑎𝐹𝑒 2+ ∗ 𝑎𝑍𝑛2+ (0.771 + 0.762)
𝑙𝑜𝑔 ( )= = 52 = log(𝐾)
𝑎𝐹𝑒 3+ ∗ 𝑎𝑍𝑛 0.059

𝐾 = 1052
Question 3
Cell notation: 𝑃𝑏/𝑃𝑏 2+ , 𝑆𝑂42− , 𝐻 + /𝐻2
Cell reactions (assumption):
𝑃𝑏 → 𝑃𝑏 2+ + 2𝑒 − (Anode)
2𝐻 + + 2𝑒 − → 𝐻2 (Cathode)
𝑃𝑏 + 2𝐻 + → 𝑃𝑏 2+ + 𝐻2 (Overall)

0 𝑃𝐻2
Φ𝐻 + /𝐻 = 0 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
2 (𝑎𝐻+ )2

0 𝑎𝑃𝑏2+
Φ𝑃𝑏/𝑃𝑏 2+ = 0.126 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
𝑎𝑃𝑏
𝑎𝑃𝑏2+
𝐸𝑐𝑒𝑙𝑙 = 0.126 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
(𝑎𝐻+ )2
0.01
𝐸𝑐𝑒𝑙𝑙 = 0.126 − 2.303𝑅𝑇𝑙𝑜𝑔 ( )
(0.1)2
𝐸𝑐𝑒𝑙𝑙 = 0.126 𝑉 𝑣𝑠 𝑆𝐻𝐸
The cell potential is positive, indicating that the reaction proceeds spontaneously. The lead will corrode,
while the hydrogen electrode will serve as the cathode.

Question 4
𝐶𝑢 → 𝐶𝑢2+ + 2𝑒 −

𝐹𝑒 2+ + 2𝑒 − → 𝐹𝑒
0 0 0
E𝑐𝑒𝑙𝑙 = Φ𝐹𝑒 2+ /𝐹𝑒 + Φ𝐶𝑢/𝐶𝑢2+ = −0.440 − 0.337

0
E𝑐𝑒𝑙𝑙 = −0.777𝑉 𝑣𝑠 𝑆𝐻𝐸

0
150𝑘𝐽
Δ𝐺 0 = −𝑛𝐹E𝑐𝑒𝑙𝑙 = −2 ∗ 96500 ∗ (−0.777) = >0
𝑚𝑜𝑙
The reaction will not proceed spontaneously as written
The spontaneously reaction is:

𝐶𝑢2+ + 𝐹𝑒 → 𝐹𝑒 2+ + 𝐶𝑢
Question 5
The hydrogen over potential 𝜂 is the difference between the potential of the iron electrode (𝐸 =
−0.716 𝑉 𝑣𝑠 𝑆𝐶𝐸) and the potential of the hydrogen reaction
0
𝜂 = 𝐸 − 𝐸𝑒𝑞

For the hydrogen reaction;

0
2𝐻 + + 2𝑒 − → 𝐻2 Φ𝐻 + /𝐻 = 0.00 𝑉 𝑣𝑠 𝑆𝐻𝐸
2

Or,
0
Φ𝐻 + /𝐻 = −0.241 𝑉 𝑣𝑠 𝑆𝐶𝐸
2

0
Φ𝐻+ /𝐻2 = Φ𝐻 + /𝐻 − 0.059(𝑝𝐻) = −0.241 − (0.059 ∗ 2)
2

Φ𝐻+ /𝐻2 = −0.359 𝑉 𝑣𝑠 𝑆𝐶𝐸

The hydrogen over potential 𝜂 is the difference between the potential of the iron electrode (𝐸 =
−0.716 𝑉 𝑣𝑠 𝑆𝐶𝐸) and the potential of the hydrogen reaction

𝜂 = −0.716 − (−0.359) = −0.357 𝑉