Chapter 4 – Mass Transport

• Diffusion – movement of a chemical species in the presence

of a concentration or activity gradient – high to low.
Diffusion is inevitable with all electrode reactions!

• Convection - movement of a chemical species due to external

mechanical forces.

• Migration – applicable only for charged analytes. Movement

of chemical species in a potential or electric field.
Electrochemical reactions are generally performed with a high
supporting electrolyte concentration (100x greater than analyte).
This makes the solution electrically conducting and shields a charged
analyte from the potential field thus minimizing migration.
 Chapter 4 – Mass Transport

Nernst-Planck Equation

 C x ( x)  z x F   ( x) 
J x   Dx   DxC x    C x ( x)
 x  RT  x 

J = mol s-1 cm-2 D = cm2 s-1 C = mol cm-3 z = charge of species

F = 96,500 C mole e--1 R = 8.314 J mol-1 K-1 T = Kelvin

Φ = electrostatic potential , V υ = fluid velocity, cm s-1

 Chapter 4 – Mass Transport
Linear diffusion to a flat, planar electrode

D
cm 2
(1x10 5 cm 2 / s)  C 
Rate  Flux   D  
s  x  x o

CO ( x, t )    C ( x, t ) 
 ( )  DO  O 
t x   x 
 Chapter 4 – Mass Transport

inet  C   C 
  Dox    DRe d  
nFA  x  x 0  x  x 0

The flux of R to the electrode surface will decrease with time so the
current will decrease with time, and (ii) the thickness of the diffusion
layer away from the electrode will increase with time.
 Chapter 4 – Mass Transport
Fick’s 2nd Law
t=0 and all x CR(x,0)=CR* nFAD 1/ 2CR
if 
 1/ 2t 1/ 2
t>0 CR(0,t)=0
x=∞ CR(∞,t)=CR*

I. Plot if vs. t-1/2 – linear and through origin, diffusion control (slope related to D)
II. ift1/2 product constant – diffusion control
 Chapter 4 – Mass Transport

1.61nFAD R2 / 3CR1/ 2
if 
 1/ 6

Controlled convection
most often introduced by
rotation the electrode.

Increased rotation rate = increased flux to the surface.

 Chapter 4 – Mass Transport

ν = kinematic viscosity,cm2 s 1.61 1/ 6 D1/ 3

ω = angular velocity = 2π x rotation rate 
s-1  1/ 6

Always a diffusion layer through which analyte molecules have to move to

reach the electrode surface. Diffusion layer becomes thinner with higher
rotation rates. Greater flux!
 Chapter 4 – Mass Transport

 CR  CR  CR ( x  0)
i f  nFAD R    nFAD
 x  x 0 

Constant diffusion layer thickness. Once surface concentration reaches

zero, no further decrease possible so the current plateaus.
Chapter 4 – Mass Transport
Chapter 4 – Mass Transport
Chapter 3 – Electron Transport