CH 117 PS2 Solutions

Jim Maiolo February 16, 2009

Problem 1 - Bard Problems

3.1
a) The equation wed like to use to tackle this is (Bard 3.4.6): i0 = F Ak 0 CO And therefore: j0 =
(1) CR

(1)

i0 (1) = F k 0 CO CR A

(2)

Plugging in CO = CR = 106 mol/cm3 , = 0.3, n = 1, and k 0 = 107 cm/s, we nd: j0 = 9.65 109 A/cm2 = 9.65 103 A/cm2

b) Neglecting mass transfer, and dividing both sides by A, we nd (Bard 3.4.11): j = j0 ef e(1)f (3) Plugging in the values above, we nd the plot shown below. 1

CH 117 - PS2

Solutions

c) Taking the log, we obtain the following plot:

CH 117 - PS2

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3.3
a) We rst calculate i0 , il,c , and il,a as shown below (see Bard 1.4.9 and 1.4.17 for the limiting currents). i0 = F Ak 0 CO
(1) CR = 9.65 104 A

il,c = nF AmO CO = 9.65 101 A il,a = nF AmR CR = 9.65 103 A

We then apply the equation listed in problem 3.2, as directed: i= ef e(1)f

1 i0

ef il,c

e(1)f il,a

The values obtained and the resulting plots are shown below. Note that the data are plotted with respect to NHE. As a result, we need to use overpotential values calculated based on = E Eeq , where Eeq is obtained from the Nernst equation: Eeq = E 0 +
RT CO ln = 0.5V + 0.118V = 0.382V nF CR

Thus, all of the plots go through zero current at E = 0.382V .

CH 117 - PS2

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CH 117 - PS2

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CH 117 - PS2

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b) Plugging in a range of k 0 values, we see that anything higher than k 0 = 1 is indistinguishable from the Nernstian situation.

c) Plugging in dierent values of we obtain:

CH 117 - PS2

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3.6
a) Rearranging equation (2) to solve for k 0 , and plugging in j0 = 2 103 A/cm2 , and CO = CR = 2 106 mol/cm3 , we nd: k0 = F j0 0.5 (CO CR ) = 1.0 102 cm/s

b) Using the value of k 0 from above, we nd that changing the concentrations of each species to 1 M gives an exchanged current density of j0 = 1.0 A/cm2 . c) We calculate i0 = 1.0 105 A for a 0.1 cm2 electrode using equation (1). Then, we again use the equation for the charge transfer resistance, with n = 1. RT = 2.57 k RCT = nF i0

4.3
We use the following equation to calculate the thickness of a diusion layer (Bard 4.4.3): = 2Dt = 0.044 cm Thus, to have at least ve diusion layer thicknesses, the working electrode must be at least 2.2 mm away from the cell wall.

Problem 2
Given the RC time constant for the cell, we rst calculate the length of time that we must wait before there is negligible contribution from the doublelayer charging. Typically we can use about 5 times the RC constant as a rule of thumb. Thus, t = 5 ms. At this time, the smallest current that we can detect using our potentiostat is 0.1 A/cm2 . We can rearrange the Cottrell

CH 117 - PS2

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equation to obtain the desired concentration:

= CO

id (t) A

1/2 t1/2
1/2 nF DO

= 4.11 1011

mol mol = 41.1 nM = 4.11 108 3 cm L

If 3RC is used instead 5RC, 31.8 nM is obtained as the smallest detectable concentration.