Chem 558 – Kinetics Homework

1] In class we considered the current-potential characteristics of a system where MT effects were

not important. That equation breaks down to the Nernst equation (why?) when equilibrium
conditions prevail. In B+F there is an equation that expressed the i-E characteristics when MT
effects are apparent in the electrochemical cell.

 C (0, t )  nF C red (0, t ) (1   )nF 

i  i0  ox b exp  b
exp  (3.4.10)
 Cox RT C red RT 

Show how this equation breaks down the Nernst equation under equilibrium conditions. What
does the say about the potential of the solution vs. electrode surface when MT effects are
important?

2] The Butler-Volmer equation follows as:

   F   (1   ) F  
itotal  i0  exp    exp    (3.4.11)
  RT   RT 

Using the identity ex  1 + x for small values of x. Show that for small values of , i vs.  is
linear.

3] What is the derived unit of the slope for the relationship discovered in the problem above?
What effect does i0 have on this slope?

4] The Tafel characteristics for a solution of Fe2+/Fe3+ was obtained and the results shown below.
The area of the platinum electrode was 1.5 cm2. Calculate  and i0 for this system.

(V) i (mA)
0.02 3.20
0.05 9.95
0.07 17.03
0.10 35.18
0.012 55.89
0.15 110.78
0.20 343.62

5] If i0 = 2.5e-5 A/m2 and  = 0.5 for the Cu2+ + 2e- = Cu system, calculate the overpotential
required to deposit Cu(s) from a 1 M Cu2+ solution at i = 5e-3 A/m2.
Answers

1] For equilibrium let i = 0;

 C (0, t )  nF ( E  E Nernst ) C red (0, t ) (1   )nF ( E  E Nernst ) 

0  i0  ox b exp  b
exp 
 Cox RT C red RT 

Cox (0, t )  nF ( E  E Nernst ) C red (0, t ) (1   )nF ( E  E Nernst )

b
exp  b
exp
Cox RT C red RT

at equilibrium we should realize that  = ½

1 1
 nF ( E  E Nernst ) nF ( E  E Nernst )
Cox (0, t ) 2 C red (0, t ) 2
b
exp  b
exp
Cox RT C red RT

Cox (0, t ) Cox b

nF ( E  E Nernst )
 b exp
C red (0, t ) C red RT

RT Coxb
Coxb
nF ( E Nernst  E 0 )
note that E Nernst E 
0
ln b or b
 exp sub this into above we
nF C red C red RT
have

Cox (0, t ) nF ( E Nernst  E 0 ) nF ( E  E Nernst )

 exp exp
C red (0, t ) RT RT

Cox (0, t ) nF ( E  E 0 )
 exp or simply
C red (0, t ) RT

RT Cox (0, t )
E  E0  ln
nF C red (0, t )

b
RT Cox
Note that this is the SURFACE potential is different than E Nernst  E  0
ln b which
nF C red
reflects the potential in the BULK of the solution. This indicates that the two potentials are
different when MT effects are in place.

   F   (1   ) F  
2] itotal  i0  exp    exp    using ex  1 + x
  RT   RT 
  F (1   ) F 
itotal  i0 1  1 
 RT RT 

F
itotal  i0
RT

F RT
3] For the plot of i vs.  the slope = i0 . Remember that  volts , and Ohm’s law is
RT F
E = iR. This means that the slope has units of 1/.

RT
The inverse of the slope is , which has units of ohms! This is referred to as the charge
i0F
transfer resistance (RCT). Note as i0 decreases, RCT increases as should expect.

 0.0592 0.0592
4] Tafel eqn.   log i0  log i
 

plot log i vs.  slope = -9.89 = /0.0592  = 0.59

intercept = 0.39 = log i0 i0 = 2.46 mA/cm2

 0.0592 0.0592
5] Using   log i0  log i
 

0.0592 0.0592
 log 2.5  10 5  log 5  10 3 = 0.272 V
0.5 0.5