HOMEWORK 16

PROBLEM 1:
a) Briefly explain the difference between oxidation and reduction electrochemical reactions.
Oxidation occurs when a reactant loses electrons during the reaction while reduction occurs
when a reactant gains electrons during the reaction.
b) Which reaction occurs at the anode and which at the cathode?
Reduction occurs at the cathode. Therefore, oxidation occurs at the anode.

PROBLEM 2: A Zn/Zn2+ concentration cell is constructed in which both electrodes are pure zinc.
The Zn2+ concentration for one cell half is 1.1 M, for other, 11-2 M. Is a voltage generated between
the two cell halves? If so, what is its magnitude and which electrode will be oxidized? If no voltage
is produced, explain this result.

We must determine whether or not a voltage is generated in a Zn/Zn 2+ concentration cell, and,
if so, its magnitude. Let us label the Zn cell having a 1.0 M, Zn2+ solution as cell 1, and the other
as cell 2. Furthermore, assume that oxidation occurs within cell 2, wherein, [𝑍𝑛2+2] = 10- 2 M.
Hence,

𝑍𝑛20 + 𝑍𝑛+2 → 𝑍𝑛2+2 + 𝑍𝑛

0.0592 [𝑍𝑛2+2 ]
∆𝑉 = − log
2 [𝑍𝑛+2 ]
−2
[10 𝑀]
0.0592
∆𝑉 = − log = +0.0592 𝑉
2 [1.0 𝑀]
Therefore, a voltage of 0.0592 V is generated when oxidation occurs in the cell having the
𝑍𝑛2+ concentration of 10−2 𝑀.

PROBLEM 3: An electrochemical cell is composed of pure copper and pure lead electrodes
immersed in solutions of their respective divalent ions. For a 0.6 M concentration of Cu2+, the lead
electrode is oxidized yielding a cell potential of 0.507 V. Calculate the concentration of Pb2+ ions
if the temperature is 25°C.

We are asked to calculate the concentration of 𝑃𝑏 +2 ions in a copper-lead electrochemical cell.

The electrochemical reaction that occurs within this cell is just,

𝑃𝑏 0 + 𝐶𝑢+2 → 𝑃𝑏 +2 + 𝐶𝑢0
While ∆𝑉 = 0.507 𝑉 𝑎𝑛𝑑 [𝐶𝑢+2 ] = 0.6 𝑀. Thus this equation is written in the form.
0 0
0.0592 [𝑃𝑏 +2 ]
∆𝑉 = (𝑉𝐶𝑢 − 𝑉𝑃𝑏 )− log
2 [𝐶𝑢+2 ]
This equation may be rewritten as,
0 0
[𝑃𝑏 +2 ] ∆𝑉(𝑉𝐶𝑢 − 𝑉𝑃𝑏 )
log = −
[𝐶𝑢+2 ] 0.0296
+2
Solving this expression for [𝑃𝑏 ] gives
 0 0
∆𝑉 − (𝑉𝐶𝑢 − 𝑉𝑃𝑏 )
[𝑃𝑏 +2 ]= [𝐶𝑢+2 ] exp − [2.303 ]
0.0296
0 0
The standard potentials from table 17.1 are 𝑉𝐶𝑢 = +0.340 𝑉, and 𝑉𝑃𝑏 = −0.126 𝑉. Therefore

0.507 − (0.340 + 0.126)

[𝑃𝑏 +2 ] = [0.6 𝑀] exp − [2.303 ] = 2.5 × 10−2 𝑀
0.0296

PROBLEM 4: A 1.5 -m-square steel plate is coated on both sides with a 0.008-cm-thick layer of
zinc. A current density of 0.03 A/cm2 is applied to the plate in an aqueous solution. Assuming that
the zinc corrodes uniformly, determine the length of time required before the steel is exposed.
𝐴 = (1.5 𝑚)2 = 2.25 𝑚2 = 22500 𝑐𝑚2
𝜌𝑐𝑜𝑟𝑟𝑖𝑒𝑛𝑡𝑒 = 0.03 𝐴/𝑐𝑚2
𝜌𝑍𝑛 = 7.13 𝑔/𝑐𝑚3
𝑀𝑍𝑛 = 65.38 𝑔/𝑚𝑜𝑙
𝐶𝑎𝑟𝑔𝑎 = 2(𝑛)
𝐹𝑎𝑟𝑎𝑑𝑎𝑦 = 95.500 𝐶
𝑔
𝑊 = (7.13 ) ( 22500 𝑐𝑚2 )(0.008 𝑐𝑚) = 1283.4 𝑔
𝑐𝑚3
From the Faraday equation time is cleared.
𝐼𝑡𝑀 𝑖𝐴𝑡𝑀
𝑊= =
𝑛𝐹 𝑛𝐹
𝑊𝑛𝐹
𝑡=
𝑖𝐴𝑀
(1283.4 𝑔)(2)(96.500 𝐴 × 𝑠/ 𝑚𝑜𝑙)
𝑡= = 5612.68 𝑠
(0.03
𝐴
) (22500 𝑐𝑚 2 ) (65.38 𝑔 )
𝑐𝑚2 𝑚𝑜𝑙

PROBLEM 5: A piece of corroded steel plate was found in a submerged ocean vessel. It was
estimated that the original area of the plate was 14 in.2 and the approximately 2.9 kg had corroded
away during the submersion. Assuming a corrosion penetration rate of 215 mpy for this alloy in
seawater, estimate the time of submersion in years. The density of steel is 7.9 g/cm3.

𝑨 = 14 𝑖𝑛2
Mass corroded away = 2.9 Kg
𝐶𝑃𝑅 = 215 𝑚𝑝𝑦
𝜌𝑠𝑡𝑒𝑒𝑙 = 7.9 𝑔/𝑐𝑚3
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 534
𝐾×𝑊 (534)(2.9 × 106 𝑚𝑔)
𝑡= = = 65124.7 ℎ
𝐴 × 𝐶𝑃𝑅 × 𝜌𝑠𝑡𝑒𝑒𝑙 (14 𝑖𝑛2 )(215 𝑚𝑝𝑦) (7.9 𝑔 )
𝑐𝑚3
1 𝑑í𝑎 1 𝑎ñ𝑜
65124.7 ℎ × × = 7.43 𝑎ñ𝑜𝑠
24 ℎ 365 𝑑í𝑎𝑠