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+

-
water with
cations, Na
+
, Ca
2+

anions, Cl
-
, SO
4
2-
...
+
+
+
+
+
+
+
-
-
-
-
-
-
-
-
-
-
+
+
+
+
+
+
+
+
+
+
~ 3 nm
electrical double layer; where the
electrochemistry happens
d
dz
|
~ 10
7
V
m
An electrolyte:
Electrolyte and Double Layer
mixture composition:
54 mol H
2
O
1 mol CaCl
2
1 mol Ca
2+
2 mol Cl
-
n n n n = + + =
+ H2O Ca2 Cl
57
n n n
H2O Ca2 Cl
= = =
+
54 1 2
mole fractions:
x
n
n
H2O
H2O
= =
54
57
x
n
n
Ca2
Ca2
+
+
= =
1
57
x
n
n
Cl
Cl


= =
2
57
x
c
c
i
i
w
~
c
w
= 55 mol l
-1
dilute solutions in water
Mole Fractions
The Film and Electroneutrality
diffusion film , thick
Az ~10000 nm
d
dz
|
~ 10
2
V
m
almost no charge separation
electroneutrality:
z
i i
i
x =

0
Az
+
+
+
+
+
+
-
F Faraday constant 96 5 . kC mol
1
|
electrical potential, V
z
i charge number (Na
+
: +1; SO
4
2-
: -2 ...)
F
i |
F
d
dz
i i |
|
= Fz Fz
i
z
A|
A
Electrical Forces
differential
equation
difference
equation
MS-Equations

= |
.
|

\
|
| A +
A

i j
j i
j i i j
i
i
i
i
c k
N x N x
RT a
a
x
,
) (
Fz

=
=
|
.
|

\
|
|
+
i j
j i i j
j i
i
i
i
N x N x

RT
dz
d
dz
a d
RT cx ) (
ln
,
Fz
10
4
10
3
10
2
1.0
0.8
0.6

i
i x
i i
i
=

1
2
2
z
2 =
i
z
1 =
i
z
Debye-
Hckel
in dilute solutions, the non-ideality
variation is not large
A A

<<
x
x
Non-ideality
in dilute solutions of stagnant water
Nernst-Planck equation
u
w
= 0
=
A A| x
x RT
u
k
i
i
i i
i
Fz
,W
N c
dx
dz
x
RT
d
dz
i i w
i i i
= +

(
,
Fz |
difference equation
= RT
d x
dz
d
dz
RT

u
i
i
i w
i
ln
,
Fz
|
Dilute Solutions
(

| A + A =
RT
x
x c k N
i i
i j i i
Fz
,
( )
H
+
1
( )
Cl

2
o |
|
+
-
why do they move at the same rate?
electrical gradient retards H
+
,
accelerates Cl
-

13
9 2 1
9 3 10
,
. =

m s

2 3
9 2 1
2 0 10
,
. =

m s
HCl in Water
electroneutrality:
no current:
x x x
1 2
= =
+
-
transport equations:
diffusion potential
velocity
diffusivity
=
A A| x
x RT
u
k
F
13 ,
u u u
1 2
= =
A| =
|
\

|
.
|
RT
k k
u
F
1 1
2 3 13 , ,
u
k k
x
x
= +
|
\

|
.
|

2
1 1
13 2 3
1
, ,
A


HCl
= +
|
\

|
.
|

2
1 1
13 2 3
1
, ,
+ =
A A| x
x RT
u
k
F
2 3 ,
Potential, Velocity and Diffusivity
18
3
2
1
HCl
NaCl
you might think that NaCl would
diffuse to the right with a diffusivity:
this is wrong!
|
Na
+
the electrical gradient (due to HCl)
forces Na
+
against its composition
gradient

Na, W
2 1
m s =

13 10
9
.

Cl, W
2 1
m s =

20 10
9
.

NaCl
2 1
m s =

16 10
9
.
Mixed Electrolyte
Diffusivity of Lysozyme
12+
-
-
-
-
-
-
-
-
-
-
-
Ly
12+ 13 Cl
-
-
+
-
-
H
+
c
KCl
mol m
3
D
eff
10 m s
-10 2 1
c
KCl
= 0
excess electrolyte
1
10
0 100 200
lysozyme is pulled
by its counter ions
not for high ionic
strength
Lysozyme Calculations
transport equations
=
A
A|
A
x
x RT
u
z
i
i
i i
i W
Fz
,
no current
x u
i i i
i
z =

0
i = 1 4
u
1
D u z
eff 1 1 ,
= A
these yield and
Cl
-
(4)
K
+
(3) H
+
(2)
lysozyme (1)
mole fractions
o
|
top layer
bottom layer
+
-
-
+
A| ~ 1V
current
Az =

10
2
m
u
2
u
3
(1) water
(2) cation
(3) anion
( ) ( )
3 2 3
3 , 2
1 2 1
2 , 1
2
2
ln
u u x

RT
u u x

RT
dz
d
dz
a d
RT + =
|
Fz
( ) ( )
2 3 2
3 , 2
1 3 1
3 , 1
3
3
ln
u u x

RT
u u x

RT
dz
d
dz
a d
RT + =
|
Fz
no concentration
gradients
small water
velocity
N N
2 3
,
Conductivity Cell
current density ( )
I F z z = + N N
2 2 3 3
Am Cm s

2 2 1
conductivity
k
|
=

I
d
dz
( )
k = +
+
+
F
z z
2
2 2
2
12 3 3
2
13
1
2 13 3 12
2 3
1 c
RT
x x
x
x x

, ,
, ,
,

using electroneutrality
effect of friction between ions
x x
2 2 3 3
0 z z + =
Conductivity
t
t
z
z
z
z
2
3
2 2
3 3
2 12
3 13
= =
N
N

,
,
t t
2 3
1 + =
Transport Numbers
Which fraction of the current is carried by which ion?
10
8
10
9
10
10
10
11
10
2
10
1
10
0
10
1

Na,Cl
c
NaCl
1
mol l

i j ,
m s
2 1

W,Cl

W,Na

+,w
and
-,w

almost constant
c
+ ,
.
~
0 5
NaCl in water,
20
o
C
Diffusivities
of NaCl
Ion - Water
Diffusivities
10
10
10
9
10
8
10
7
10
2
10
1
10
0
10
1
c
salt
1
mol L

Na
+
H
+
Ca
2+
La
3+
Cl
-

i j ,
m s
2 1
OH
-

`
)
much higher
than the others
increasing
charge and
size
20
o
C
10
9
10
11
10
13
10
4
10
2
10
0
CuSO
4
LaCl
3
K
2
SO
4
NaCl
HCl
c
salt
1
mol l


i
+
+
+
=
+
,
, ,
.
.
W W
2
0 55
2 3
z z
i x
i i
i
=

0 5
2
. z
approximate, empirical

,
m s
2 1
Anion - Cation
Diffusivities


10
8


10
10


10
12
10
4
10
2
10
0
negative!
1-1
1-2
1-3
c
salt
1
mol l


+ +

, ,
or
m s
2 1
Plus-Plus &
Minus-Minus

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