Você está na página 1de 72

8.

Fundamentals of Charged Surfaces


Moving the reagents
Quickly and with
Little energy
Diffusion
electric fields
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
X=0
N
N
o
G
kT
*
exp =

A
1. Cations distributed thermally
with respect to potential
2. Cations shield surface and
reduce the effective surface
potential
+-
o

+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
X=0
N
N
o
G
kT
*
exp =

A
+-
o

+
+
+
dx
dx
+--
o

* **
dx
+
+
***
+---
o

n
n
e
o
zF
RT
x
+

=

|
\

|
.
| =


cc


o i i
i
z F
RT
d
dx
z FC e
i x
2
2
*
Surface Potentials
Poisson-Boltzman equation
Charge near electrode depends
upon potential and is integrated
over distance from surface - affects
the effective surface potential
Cation distribution has
to account for all species,
i
Dielectric constant of solution
Permitivity of free space
Simeon-Denis Poisson
1781-1840
ze
kT
o

<< 1

o
mV < 50

k
x o
x
e =

|
\

|
.
| =


cc


o i i
i
z F
RT
d
dx
z FC e
i x
2
2
*
Solution to the Poisson-Boltzman equation can be simple if the
initial surface potential is small:
Potential decays from the surface potential exponentially with distance
d
dx
z FC
e
z FC
z F
RT
z F
RT
i i
i
o
z F
RT
i i
i
o
i i i i
i i
2
2
2
1
1
2

cc cc

|
\

|
.
| =

+ +

|
\

|
.
| +

(

* *
......
Largest term
d
dx
F z C
RT
i i
i
o
x
2
2
2

cc

|
\

|
.
| =

*
Let
k
cc
2
2
2
1
=

(
=

x
F z C
RT
a
i i
i
o
*
Then:
d
dx x
x
a
2
2 2

|
\

|
.
| =
General Solution of:
+
x
x
x
x
x
Ae Be
a a
= +

d
dx x
x
a
2
2 2

|
\

|
.
| =
Because + goes to zero as x goes to infinity
B must be zero
+
x
x
x x
Ae Ae
a
= =

k
Because + goes to +
0
as x goes to zero (e
0
=1)
A must be +
0

thus

k
x o
x
e =

Potential decays from the surface potential exponentially with distance

x o o
e = =
1
0367 ( . )
When k=1/x or x=1/k then
The DEBYE LENGTH x=1/k
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+=0.36 +
o

+
+
+
+
+
X=0 X=1/k
+
+
+
+
What is k?
Petrus Josephus
Wilhelmus Debye
1844-1966
k
cc
=
|
\

|
.
|
2
2 2
1
2
n z e
kT
o
*
k = z x C ( . )( )
* /
329 10
7 1 2
Debye Length
Units are 1/cm
( )
( )
k =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|

|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|
|
|
|


2
602 10 1
10
100 160218 10
7849
885419 10
100
138065 10
298
23
3 3
2
2
19
2
25
12 2
2
23
1
2
moles
L
x
mole
L
cm
cm
m
ch e
x C
ch e
unitless
x C
N m
m
cm
Nm
J
x J
K
K
o
C
.
arg
.
arg
.
. .
( )
( )
( )
k =
|
\

|
.
|
|
\

|
.
|
|
|
|
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|

2 160218 10
7849 138065 10 298
6022 10
2
19
2
25
23
1
2
23
#
.
. .
.
cm
x
x
mole
x ions
o
C
k
cc
=
|
\

|
.
|
2
2 2
1
2
C N z e
kT
onc A
o
Does not belong
=1/cm
k
cc
=
|
\

|
.
| zF
n z e
kT
o
2
2 2
1
2
*
k = z x C ( . )( )
* /
329 10
7 1 2
Table 2: Extent of the Debye length as a function of electrolyte
C(M) 1/ ( )
1 3
0.1 9.6
0.01 30.4
0.001 96.2
0.0001 304
Debye Length
Units are 1/cm
In the event we can not use a series approximation to solve the
Poisson-Boltzman equation we get the following:
exp
exp exp
exp exp

|
\

|
.
|
|
+
|
\

|
.
|
|
+
|
\

|
.
|
|

|
\

|
.
|
|
k


x
ze
kT
ze
kT
ze
kT
ze
kT
2 2
2 2
1 1
1 1
0
0
Ludwig Boltzman
1844-1904
Simeon-Denis Poisson
1781-1840
Check as
Compared to tanh
By Bard
Set up excel sheet ot have them calc effect
Of kappa on the decay
Example Problem
A 10 mV perturbation is applied to an electrode surface bathed in
0.01 M NaCl. What potential does the outer edge of a Ru(bpy)
3
3+

molecule feel?
Debye length, x?
k
k
=
= = =
z x C
X
A
x
A
( . )( )
/
( . )( . )
.
* /
/
329 10
1
10
1 329 10 001
304
7 1 2
8
7 1 2
Since the potential applied (10 mV) is less than 50 can use
the simplified equation.
Units are 1/cm

k
x o
x
o
x
x
e e e
z
= = = =



10 7 43
9
30 4 .
.
The potential the Ru(bpy)
3
3+
compound experiences
is less than the 10 mV applied.

This will affect the rate of the electron transfer event
from the electrode to the molecule.
Radius of Ru
Surface Charge Density
The surface charge distance is the integration over all the charge
lined up at the surface of the electrode
o cc

cc

o
a a
a
dx
d
dx
dx
d
dx
= = =


} } 0
2
2
0
The full solution to this equation is:
o cc

o
o o
o
o
o o
kT n
ze
kT
C z
=
=
(8 ) sinh( )
. ( *) sinh( . )
1
2
1
2
2
117 195
C is in mol/L
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+=0.36 +
o

+
+
+
+
+
X=0 X=1/k
+
+
+
+
Can be modeled as a capacitor:
C =
o

d
d
differential
For the full equation
C
z e n
kT
ze
kT
o
o
=
|
\

|
.
|
|
\

|
.
|
2
2
2 2
0
1
2
cc
cosh
( )
( )
C z C z
o
= 228 19 5
1
2
*
cosh .
At 25
o
C, water
d
d
Differential capacitance
Ends with units of uF/cm2
Conc. Is in mol/L
0
2000
4000
6000
8000
10000
12000
-15 -10 -5 0 5 10 15
( )
y x = cosh
o cc k
o o o
=
Can be simplified if
(
o
~ 25 mV),
Specific Capacitance is the differential
space charge per unit area/potential
C
A
dq
Ad
d
d
specific
= =

C
A
o
= cc k
Specific Capacitance
Independent of potential
For small potentials
kcc
o
Flat in this region
Gouy-Chapman Model
C
z e n
kT
ze
kT
o
o
=
|
\

|
.
|
|
\

|
.
|
2
2
2 2
0
1
2
cc
cosh
0
20
40
60
80
100
120
-500 -400 -300 -200 -100 0 100 200 300 400 500
E-Ezeta
C
a
p
a
c
i
t
a
n
c
e
Real differential capacitance plots appear to roll off instead of
Steadily increasing with increased potential
Physical Chemistry Chemical Physics
DOI: 10.1039/b101512p

Paper
Photoinduced electron transfer at liquid/liquid
interfaces. Part V. Organisation of water-soluble
chlorophyll at the water/1,2-dichloroethane interface


Henrik Jensen , David J. Fermn and Hubert H. Girault
*

Laboratoire d'Electrochimie, Dpartement de Chimie, Ecole Polytechnique Fdrale de Lausanne, CH-1015,
Switzerland
Received 16th February 2001 , Accepted 3rd April 2001
Published on the Web 17th May 2001
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
+
X=0
+
+
+
+
Linear drop
in potential
first in the
Helmholtz or
Stern specifically
adsorbed layer

Exponential
in the thermally
equilibrated or
diffuse layer
C
diffuse

C
Helmholtz or Stern

x
2

Hermann Ludwig
Ferdinand von Helmholtz
1821-1894
O. Stern
Noble prize 1943
Capacitors in series
C
z e n
kT
ze
kT
Diffuse
o
o
=
|
\

|
.
|
|
\

|
.
|
2
2
2 2
0
1
2
cc
cosh
C
A
Helmholtz or Stern
o
|
\

|
.
| = cc k
C
C C C
series
N
=
+ +
1
1 1 1
1 2
......
1 1 1 1
1 2
C
C
C C C
series
series
N
= + +......
Wrong should be x distance of stern layer
For large applied potentials and/or for large salt concentrations
1. ions become compressed near the electrode surface to
create a Helmholtz layer.
2. Need to consider the diffuse layer as beginning at the
Helmholtz edge
1 1
2
2
2
0 2 2
0
1
2
C
x
z e n
kT
ze
kT
o
o
= +
|
\

|
.
|
|
\

|
.
|
cc
cc
cosh
Capacitance
Due to Helmholtz
layer
Capacitance due to diffuse
layer
Deviation
Is dependent upon
The salt conc.

The larger the dip
For the lower
The salt conc.
0.63
0.64
0.65
0.66
0.67
0.68
0.69
0.7
0.71
-500 -400 -300 -200 -100 0 100 200 300 400 500
E-Ezeta
C
a
p
a
c
i
t
a
n
c
e
Create an excel problem
And ask students to determine the smallest
Amount of effect of an adsorbed layer
Experimental data does not
Correspond that well to the
Diffuse double layer double capacitor
model
(Bard and Faulkner 2
nd
Ed)
Fig. 5 Capacitancepotential curve for the Au(111)/25 mM KI in DMSO interface with time.
Physical Chemistry Chemical
Physics
DOI: 10.1039/b101279g

Paper
Complex formation between halogens and
sulfoxides on metal surfaces
Siv K. Si and Andrew A. Gewirth
*

Department of Chemistry, and Frederick Seitz Materials Research
Laboratory, Uni ersity of Illinois at Urbana-Champaign, Urbana, IL,
61801, USA
Received 8th February 2001 , Accepted 20th April 2001
Published on the Web 1st J une 2001
Model needs to be altered to account
For the drop with large potentials
This curve is pretty similar to predictions except where specific
Adsorption effects are noted
Graphs of these types were (and are) strong evidence of the
Adsorption of ions at the surface of electrodes.
Get a refernce or two of
deLevie here
Introducing the Zeta Potential
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
+
+
+
+
+
Imagine a flowing solution
along this charged surface.
Some of the charge will be carried
away with the flowing solution.
Introducing the Zeta Potential, given the symbo l,
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
+
+
+
+
+
Shear Plane
Flowing solution
+
zeta

Sometimes
assumed
zeta
corresponds
to Debye
Length, but
Not
necessarily
true
, oo
|
=


C
C
1
2
1
2
exp
The zeta potential is dependent upon how the electrolyte
concentration compresses the double layer. o, | are constants
and sigma is the surface charge density.
Shear Plane can be talked about in
two contexts
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
+
+
+
+
+
Shear Plane
+
+
+
+
+
+
+
+
+
+
+
+
Shear
Plane
Particle in motion
In either case if we push the solution along
a plane we end up with charge separation which
leads to potential
Streaming Potentials
From the picture on preceding slide, if we shove the solution
Away from the charged surface a charge separation develops
= potential
A+
AP
o
=
cc
q
,

,
q
=
=
=

solution resis ce m
zeta potential
vis ity
kg
m s
tan
cos
O
Sample problem here
Reiger- streaming potential
apparatus.
Can also make measurements on blood capillaries
+
o

C
h
a
r
g
e
d

S
u
r
f
a
c
e

+
+
+
+
+
X=0
+
+
+
+
Cathode
Anode
V
app

+
J
o
J
m

J
m

In the same way, we can apply a potential and move ions and
solution
Movement of a charged ion in an electric field
Electrophoretic mobility

tq
=
= =
=
applied electric field
f frictional drag r
v electrophoretic velocity
6
The frictional drag comes
about because the migrating
ions atmosphere is moving
in the opposite direction, dragging
solvent with it, the drag is related to the ion atmosphere
f
v
z e
i
i
i

The force from friction is equal to the electric driving force


Electric Force Drag Force
Direction of Movement
Ion accelerates in electric field until the electric force
is equal and opposite to the drag force = terminal velocity
f z e
electrical i
=
f r
vis ity
r ionic radius
ion velocity
frictional
=
=
=
=
6tq u
q
u
cos
f f
r z e
frictional electric
i
=
= 6tq u
At terminal velocity
u

tq
=
z e
r
i
6
The mobility is the velocity normalized for the electric field:
u
z e
r
i
i
= =
u
tq 6

= = =
v
z e
f
z e
r
u
i
i i
ep

tq 6
Typical values of the electrophoretic mobility are
small ions 5x10
-8
m
2
V
-1
s
-1
proteins 0.1-1x10
-8
m
2
V
-1
s
-1

Frictional drag r = 6tq
(Stokes Law)
r = hydrodynamic
radius
Stokes-Einstein
equation
Reiger p. 97
Sir George Gabriel
Stokes 1819-1903
Insert a sample calculation
u
ep
o
=
2
3
cc ,
q
When particles are smaller than the Debye length you get
The following limit:
Remember: velocity is mobility x electric field
Reiger p. 98
What controls the hydrodynamic radius?
- the shear plane and ions around it
Compare the two equations for electrophoretic mobility
u
f
ep
o o
= =
2
3
cc ,
q
cc ,
q
u
z e
r
ep
i
= =
u
tq 6
f
z e
r
o
i
cc ,
q tq
=
6
r
z e
f
i
o
=
cc , t 6
Where f is a shape term which is 2/3 for spherical
particles
Relation of electrophoretic mobility to diffusion
D
kT
f
kT
r
= =
6t q
Thermal force
Frictional drag r = 6tq
D
kT
f
=
u
z e
r
i
i
= =
u
tq 6
D
kT
f
kT
ze
u
electrophoretic migration
= =
=
Measuring Mobilities (and therefore Diffusion)
from Conductance Cells
-
+
+
+
+
+
+
+
+
-
-
-
-
-
To make measurement need to worry about all the processes
Which lead to current measured
Ac Voltage
-
+
O
R-
+
+
+
+
+
Charging
Electron
Transfer
Solution
Charge
Motion = resistance
-
-
-
-
-
-
+
+
R-
O
Z
f1
Z
f2

R
s

C
t

C
t

Z R
C
f ct
s
C
s
= +

(
(
(
(
+

(
(

(
(
(
(
1
1
2
2
1
2
1
2
1
2
e
e
Electron transfer at electrode surface can be modeled as the
Faradaic impedance, Z
2

diffusion
Related to k
et

An aside
Z
f1
Z
f2

R
s

C
t

C
t

Solving this circuit leads to
R
Z
Z
C
R
Z
Z
C
R
Z C
R
Z C
T
f
f
t
s
f
f
t
T
f t
s
f t
=
+
+ +
+
=
+
+ +
+
1
1
2
2
1 2
1 1
1
1 1
1
1 1
e e
e e
e e ( ) ( )
Applying a high frequency, w, drops out capacitance and Faradaic
Impedance so that R
T
=Rs
What frequency would you have to use
To measure the solution resistance between
Two 0.5 cm
2
in 0.1 M NaCl?
C
A
d
d
d
d
specific
o
o
= = =
o

kcc

kcc
( )
k = = z x C x
m
( . )( ) .
*
329 10 104 10
1
7 1/2 7
C C A A
specific o
= =k cc
Check
Calculation
To show that
It is cm converted to m
C C A A
specific o
= =k cc
C A x
m
x cm x
m
cm
x
C
J m
o
= =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|

|
\

|
.
|
|

k cc 104 10
1
2 05
100
7854 8854 10
7 2
2
12
2
. . . .
C A x
m
x cm x
m
cm
x
C
J m
o
= =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
|

|
\

|
.
|
|

k cc 104 10
1
2 05
100
7854 8854 10
7 2
2
12
2
. . . .
C x
C
J
x
C
CV
x
C
V
x F = = = =

7 2 10 7 2 10 7 2 10 7 2 10
7
2
7
2
7 7
.. .. .. ..
The predicted capacitance of both electrodes in 0.1 M NaCl would
Be 0.72 microfarads
For the capacitive term to drop out of the electrical circuit
We need:
1
1
1 1
7 2 10
14 10
7
6
e
e
C
C
x
x
t
t
<<
>> >> >>

.
.
The frequency will have to be very large.
Solution Resistance Depends upon
Cell configuration
R
A
=

length
A
Resistivity of soln.
Sample calculation in a thin layer cell
Resistance also depends upon the shape
Of an electrode
Disk Electrode
Spherical electrode
Hemispherical
electrode
R
a
=

4
a is the radius
R
a
=

t 4
R
a
=

t 2
From Baranski, U. Saskatchewan
Scan rate 1000 V/s at two different size electrodes for
Thioglycole at Hg electrode
k
RA
= =
1


Conductivity is the inverse of Resistance
Resistivity and conductivity both depend upon
Concentration. To get rid of conc. Term divide
A = = =
k
C
C RCA
1


A plot of the molar conductivity vs Concentration has a slope
Related to the measurement device, and an intercept related to
The molar conductivity at infinite dilution
A=molar conductivity
A
o
s dard molar conductivity = tan
This standard molar conductivity depends upon the solution
Resistance imparted by the motion of both anions and cations
Moving in the measurement cell.
A A
A A

+ +
=
=
t
t
o
o
Where t is a transference number which accounts for the
Proportion of charge moving
Transference
Numbers can be
Measured by capturing
The number of ions
Moving.
Once last number needs
To be introduced:
The number of moles of ion
Per mole of salt
A A A
o
v v = +
+ +
Compute the resistance of a disk electrode
Of 0.2 cm radius in a 0.1 M CaCl
2
solution
A A A
o
v v = +
+ +
( )
( )
( )
( )
A A A
O O O
o
Ca Cl
m
mol
m
mol
m
mol
= + = + =

2 1 2 000763 1 00119 002716
2 2 2
. . .
A
O
=

= =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
002716
1 1
01
10
100
2
3 3
3
.
.
m
mol C
mol
L
L
cm
cm
m

|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
=
1
002716 01
10
100
0368
2
3 3
3
. .
.
m
mol
mol
L
L
cm
cm
m
m
O
O
The resistance is computed from
R
a
m
cmx
m
cm
= =

|
\

|
.
|
=

4
0368
4 02
01
4 6
.
.
.
.
O
O
Remember we were trying to get to mobility
From a conductance measurement!!!!
u
z F
i
o
i
i
=
A
Also remember that mobility and diffusion coefficients are
related
D
kT
ze
u
kT
ze zF
kT
z eF
x
z
J mol
C
i
o
i
o
i
o
= = = =

A A A
2
7
2 2
2 66 10 .
D x
z
J mol
C
i
o
=

2 66 10
7
2 2
.
A
We can use this expression to calculate
Diffusion coefficients
D x
z
J mol
C
i
o
=

2 66 10
7
2 2
.
A
D x
x
m
mol
J mol
C
x
m J
C
3
7
4
2
2 2
10
2
2
2 66 10
302 7 10
3
892 10


= .
.
( )
.
O
O
m J
C
Vs
C
VC
J
m
s
2
2
2
O
O
|
\

|
.
|
|
|
|
\

|
.
|
=
D x
x
m
mol
J mol
C
x
m
s
4
7
4
2
2 2
10
2
2 66 10
442 10
4
7 34 10


= .
( )
.
O
Fe(CN)
6
3-
diffusion coefficient is 9.92x10
-10
m
2
/s

Fe(CN)
6
4-
diffusion coefficient is 7.34x10
-10
m2/s
The more highly charged ion has more solution solutes around
It which slows it down.
How does this effect the rate of electron transfer?
k Z
et el
G
kT
=

-
k exp
A
Probability factor
Collisional factor
Z
kT
m
~
2
1
2
t
|
\

|
.
|
Where m is the reduced mass.
Z is typically, at room temperature,
10
4
cm/s
Activation energy
( )
A
A
G
G
o
-
=
+

2
4
Free energy change
work required to change bonds
And bring molecules together
= +
in out
( )

tc c c
out
o D A DA op s
e
a a r
=

(
(
(
+

(
(
A
2
4
1
2
1
2
1 1 1
a donor radii
a acceptor radii
optical dielectriccons t
regular dielectric cons t
e electron ch e
D
A
op
s
=
=
=
=
=
c
c
tan
tan
arg
A A G e E w w
o o p r
= + ( )
| |
( ) w w U
z z e
e
a
e
a
e
p r
r
a p
a
D
a
A
r
D A
DA
= =

(
(
+
+
+

(
(

2
0
4 1 1 tc k k
k k
k
Formal potential
Work of bringing ions together
When one ion is very large with respect to other (like an electrode)
Then the work term can be simplified to:
( ) w w U ze
p r
r
= = +
The larger kappa the smaller the activation energy, the closer
Ions can approach each other without work