Transport in electrolyte

solutions
Sähkökemian peruseet
KE-31.4100

Tanja Kallio
tanja.kallio@aalto.fi
C213

CH 3.1 – 3.2
Ion distribution in the bulk and near the
surface

Spatial distribution of ions obeys Boltzmann

distribution
ci (r )  cib e  zi ( r )

J. Israelachivili,
Intermolecular and surface
forces
Transport and reactions
electrolyte
electrode

i) mass transfer
ii) adsorption Cu2+ + e  Cu+
i
r   J Cu 2  J Cu 
F x 0 x 0

r  kred cCus 2  kox cCus 

e- r = reaction rate
Ji = flux of i
iii) (electo)chemical reaction

iv) desorption v) mass transfer

Transport and mobility
charged particle in an electric field (Fc) Einstein
Fc  Ff kT
v
f 
Ff Fc qE  zeE   f v D
q
kT zeD zFD
zeE  v  v E E
D kT RT

mobility
zFD
v  uE  u 
RT
Ff = friction force
q = charge of the particle
E = electric field
v = velocity
D = diffusion coefficient
u = mobility
Mobility, molar conductivity and
diffusion coefficient
Ohm’s law adapted Faraday’s law
    k ck
i  E i  F  zk J k  F  zk vk ck k
k k

from previous slide

F2 F 2 z k2 Dk
i
RT
k z Dk ck  E  k  RT & k  zk uk F
2
k

Stokes’ law can be applied to determine friction coefficeint for ions

kT  = viscosity
f  6a  D 
6a a = ion radius
 
for
m

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
am
idi
DM
D

SO
Walden rule

HC
OO
H
kT

n-p
6a

rop
ano
li
NM
F
et a
nol
i
ves
i
DM
F
me
tan
 D  constant

oli
TH
F
DM
OE
K+(●)

AC
N
Cs+ (■)

ase
t on
i
Measuring conductivity

F2 kT

RT
 zk2 Dk ck
k
& D
6a

    k ck
k

johto-
kyky- 1 l
mittari
Rs 
 A

• Exchange current
• Pt-electrodes
• calibration
Electronic vs. ionic conductivity
Material Cond / S cm-1
Electronic conductivity: current is
Ag 1.59×105
transported by electrons
i) conductors Cu 1.68×105
ii) semi conductors Au 2.44×105
iii) insulators
Pt 1.06×104
Ionic conductivity: current is transported C (amorphous) 5-8×101
by ions
C (graphite)* 2.5-5.0×103 / 3.0×101
i) strong electrolytes
ii) weak electrolytes Ge 4.6×10−2
iii) non electrolytes Si 10-1 - 10-5

Water 10-9

Glass 10-16 - 10-12

PTFE (Teflon®) 10-16 -10-12

http://wiki.answers.com/Q/Wh
ich_metals_are_the_most_co
nductive#ixzz25OZd6XAR
Structure, mobility

Proton transport via

Grothus or hopping ii
mechanism

iii
Strong electrolytes - Kohlrausch’s law (1/2)

Dependency of diffusion coefficient on concentration

  ln  i 
Di  Di,  1  
  ln ci

Debye-Hückel limiting law for 1:1 electrolytes

I
1
 zi2 ci c
log    z  z  A I  A c 2 i

Using above diffusion coefficient can be written as

 ln  i  ln  i 1  2.303 
c  B c Di  Di , 1  A c B = 2.303 A
 ln c c 2  2 
Strong electrolytes - Kohlrausch’s law
(2/2)
      

F 2 z k2 Dk     K c Kohlrausch’s law
k 
RT
 2,303 
Di  Di , 1  A c
 2 
Weak electrolytes – Ostwald dilution law
(1/2)

(1 -  )c
  c   c
A B    A   B
 

Kd 
 A cA    B cB  

   
  
      c      1 
c AB 1 

 is small  ± ~ 1. So for 1:1 electrolytes

 2c
Kd 
1 
Weak electrolytes – Ostwald dilution law
(2/2)

c+ and c- are low  + ~ +, and - ~ -,


  c  c ,  ,   c  


Combining this with rearranged equation for equilibrium constant for 1:1
electrolytes

1 c 1 1 c
 1    Ostwald dilution law
 Kd    K d 2
Comparison of a weak and a strong
electrolyte

KCl

http://chem-
guide.blogspot.fi/2010/04/vari
ation-of-conductivity-
with.html
Electrolyte dissociation in an organic
solvent
Dissociation is incomplete → Ostwald dilution law
Because of interactions ± must be included tetrabutyyliammoniumtetrakis
For 1:1 electrolytes (4-klorofenyyli)borate in 1,2-
diklooriethane

Kd 
 A cA   BcB 
 


 2 2 c
cAB 1

K d  1  4 2 c / K d  1
  
2 2 c

It has been noted experimentally that


      K c 