Lecture 17.

HydrodynamicMethods

Rotated Disk Electrode Voltammetry RDEV

insul

ator

r1

2f
t or
duc
n
o
C
e
trod
elec

in s-1, so f in rps

revolutions
per second

dead or
diffusion layer

Laminar flow occurs up to a point, at too high , we find

that turbulent flow occurs. This is when the value
~

05
1
x
2
Re =

r1 2

exceeds the Reynolds

number for that particular fluid with a given kinematic
viscosity, , in cm2 s-1.
n g cm 1s 1 (Poise)
v
d g cm 3
v

vH 2O is ~ 0.01 cm 2 s 1 at 20 C
(*what is vCH 3CN at 20 C ?? *) Look in Table 9.2.1
So, should be ~ 2 105 /r2, but other limitations actually
mean < 1000 s-1 or f 10,000 rpm.
On the low side, must rotate fast enough to establish constant,
homogeneous supply of material to electrode surface. > 10 s-1

Lecture 17.2

HydrodynamicMethods

If one applies a potential which is that needed to obtain

mass-transport limited conditions, then what is i?

ne
+
O nly O
o

consider:
- hydrodynamics
- diffusion

R t
sen
e
r
p

Why?
,
wly
o
l
E s-1
n
ca
s
st s 0 m V
u
M 10
<

Co
C

Real
profile

Recall that is F(1/).

So,

C( o ,t )

i nFAD o

Do

How solve? As we did before except incorporate hydrodynamics.

i nFA mo Co ; mo

Also:

Co ( x,0) Co
Co (, t ) Co
Co (0, t ) F ( E )

Two Cases:
1. Reversible
use
expression (Nernst)
2. Before reach MT limit
and
- irrev.
- quasi-rev. ET rxns.

no iDL effects.

HydrodynamicMethods

Case 1:

Lecture 17.3

Levich Equation

ilim 0.62nFAD o2 / 3 1/ 6 1/ 2Co

Know:

1.6 D1/ 3 1/ 6

;
1/ 2

Know:

Levich Layer

Levich plot

If reaction is DC, then ilim vs. 1/2 is linear with zero intercept.
Also if ET reversible:
e
No
denc pe
n
e
p
de
sha
ave
w
f
o
!
on

0.059 DR
o

EE
log
n
Do

Then plot of Eapp vs.

Case 2A:

2/3

il ,c i
0.059

log
n
i

E1/2
i i
0.059
log l will be straight with slope
V
i
n

Totally irreversible; O only

i nFA kf Co k bCR

Zero

But, kf is F(E) , so we denote this kf(E).

We call this current iK and it is:

iK nFAk f E Co

na F E E o
kf k exp

RT

This is the Kinetic current.

So, at high enough -, we should get k ??

NO.

Lecture 17.4

HydrodynamicMethods

We have no ET effects at -,
Irrev.
Rev. for i, so we merely get ilim
B-V / No MT

ic

MT effects

E vs Ref
ET effects

So, if we could vary E and measure iK, we

could get k ??

i
Yes!a How?

1 1 1
; iK nFAk f E Co
i iK ilim

Turns out we have:

i F 1/ 2

Kouteck Levich or
Inverse Levich plot

1
1 / 2
vs.
at a given Eapp.
i

So make plot of
E1

1
i

1
i

Slope is

turbulence

1
0.62nFAD o2 / 3v 1/ 6Co

intercept is

1
iK

iK

Same slopes
In each.

vary

E1
E2
E3
E4(on i lim)

Eapp

-1/2

-1/2

Levich line
(for E>E4)

1/2

E1>E2>E3>E4
More
-

Lecture 17.5

HydrodynamicMethods

1
at Eapp . We know

nFAk ( E )C
f
o

n, F , A, Co . Get k f at Ei .

So, we get intercept

Plot ln k f vs. or ( E E o ) and get intercept of ln k o .

na F
RT
Why? k f ( E ) k o exp na F / RT

Also, slope is

Case 2B:

Quasi Reversible

for O and R
MT?

n
his o
Do t
.
own

your

1 b 1 b b1

i 1 b i o il ,c
il , a
Fnc(E)

ET

b k exp nF E E

/ RT

Now we have both kf and kb a function of n. Thus, the

Kouteck Levich plots do not have same slope for various
Potentials ().
Problems! Minimize errors by using small potential range
near the foot of the wave where i is not changing so drastically.

Lecture 17.6

HydrodynamicMethods

RRDE

r1
(R) Ring

r3
(D) Disk

D
r2

R = D

r1 disk radius
r2 r1 gap
r3 r2 width of ring
The collection Efficiency, N, is defined as

iR
N
iD
It is a Function of electrode geometry but is independent

of , C o , Do , DR , etc. if R is stable.
kchem

If R

Z occurs, then Nexptl < Ntheo and N = F().

Lecture 17.7

HydrodynamicMethods

For RRDE Collection Experiments:

1. ERing is held positive enough so as to oxidize any R.

2. No bulk R , C R 0
3. EDisk is scanned.
4. iDisk is measured.
5. iRing is measured.
O + ne

iD,c

ERing
iD,lim

- EDisk vs. Ref

iR,lim
R
iR,a
iR

iD

O + ne

F ( ) if R is stable and reaction is D C.

For D C , iD 1/ 2 and iR 1/ 2
Review:

i
stable R : DPSCA r 0.293; CV
iF
RRDE

i p ,a
i p ,c

N F ( )