CHAPTER 2:

FUNDAMENTAL RELATIONSHIPS
1. Physical units
2. Faraday’s law
3. Efficiencies
4. Ionic and electronic conduction
5. Ionic conductance, mobility, Kohlrausch’s laws
6. Grotthuss transport
7. Strong & weak electrolytes (Arrhenius & Ostwald laws)
8. Some additional fundamentals: Field, Potential, Electrical force,
Poisson’s & Laplace’s equations
9. Movement of an ion in an electrical field
10. Walden’s Laws
11. Debye-Huckel-Onsager theory for strong electrolytes
12. Non-aqueous electrolytes.
13. Molten salts
14. Heterogeneous media: Maxwell’s and Bruggemann’s models.
Emulsions, gas evolving electrodes.
15. Conductivity measurements

2-1
CHAPTER 2:
FUNDAMENTAL RELATIONSHIPS

Review of Physical Quantities

MECHANICAL
Force: f = m x a f = [Dyne or Nt] m = [gr or Kg] a= [acceleration, cm/s2 or

m/s2]

Work (or energy): W = F x S W = [erg; Joule; Watt s; KWH; Cal; BTU]

W J 
Power: P  s  Watt ; KW ; HP  746 W = 1 HP
t
ELECTRICAL
Charge: q [cb]
F [1 Faraday = 96,480 cb = 105 cb]

Current: q  Cb 
I   Am p    s 
t

Current densitya I  A   mA   A   A 
i  cm 2  or  cm 2  or  dm 2  or  ft 2 ; ASF 
A  

Power = P = V x I [Watt] = [Ampere] x [Volt]

Work or Energy = W = P t =V I T

THERMAL
Thermal energy: Q [cal]

Heat flux q  C al 
q  s 
t
a
current density units:

 mA   mA A 100 cm 2   A   A 
1 2 
 1 2 2    0.1 2 
~ 1 2 ; ASF 
 cm   cm 1000 m A dm   dm   ft 

2-2
Faraday's Laws:
The quantitative treatment of electrochemical processes was initiated by Faraday.
In 1813, Michael Faraday, a 22 year old bookbinder apprentice joined Davy in his
laboratory at the Royal Institute as an assistant. On the basis of experimental
observations he formulated in 1834 two laws:

The amount of primary product formed at an electrode by electrolysis is directly

proportional to the quantity of electricity passed.
w = [gr]
I = [Amp]
i =[ A/cm2]
w ~ q ( It ) q = [cb] [2-1]
t = [sec]

The amounts of various primary products formed at an electrode by the same quantity of
electricity are proportional to their relative molecular, or relative atomic masses divided by
the change in their charge numbers for the electrode process.

M = At. Wt. = [gr/gr. Atom]

w M n = number of e transferred in
~ [2-2]
q n electrode rxn [Equiv/Mole]

Faraday’s laws can combined as

M It
w [2-3]
Fn
defining the proportionality constant F = Faraday’s number. It’s numerical value is
defined by
F=L.e
L is the Avogadro-Lochschmidt number and e the electron charge, i.e.
1 F = 1 Faraday = L x e = 6.02 x 1023x 4.8 x 10-10(esu) / 3 x 109 (esu/cb)
= 96,500 cb/gr equiv. = 26.8 Ahr/gr equiv.

2-3
 Faraday’s Laws
Faraday’s Laws provides a relationship between the amount of charge passed
to the amount of material reacted in the electrode reaction

w ~ q = It w - weight M – Formula weight

1
q – charge n – number of electrons
w M I – current i – current density
2 
q n t – time h – deposit thickness

Combine:

M Defining 1 M
w It Faraday’s w It
n constant: F n
L – Avogadro No. (6.02 x1023 [atoms/mole])
F = 96, 480 cb =26.8 AHr (=L*e)
e – electron charge (1.6x10-19 [cb/electron])

1 M N
i [M / sec-cm2] or
Deposit
h it Ionic Flux:
F n [gr-ion/sec-cm2]
thickness:
nF

2-4
Example 1: Faraday’s Law:

An electrolytic cell for depositing copper from copper sulfate solution is placed in series
with another for deposition silver from silver nitrate solution. The cathode in this latter
solution is initially 0.1 gr lighter than that in the copper sulfate solution. If electrolysis is
carried out at a constant current of 0.1 ampere, when will the two cathodes be of the same
weight? (Assume 100% efficiency.)

Half Reactions
1 Cu 2  2e   Cu 0
 2  Ag   e   Ag 0
Initial Weight
Cathode 1 : 0.1g
Cathode  2  : 0 g
Equation
0.1g  weight plated 1  weight plated  2 
weight plated 1
 1mol e    1mol Cu 0   63.546 g Cu 0 
w  0.1 A    
   0 t
 96500C   2mol e   1mol Cu 
weight plated  2 
 1mol e    1mol Cu 0   107.868 g Cu 0 
w  0.1 A      
 0 t
 96500C   1mol e   1mol Cu 
t  1268sec  21min

2-5
2-6
2-7
 EFFICIENCIES IN ELECTROCHEMICAL SYSTEMS

Fraction of current or voltage which is useful

Efficiency < 1 or < 100%

Electrolyzer, Battery
Plating Cell
charge:
Faradaic Actual Product Wt Actual Wt
Coulombic Efficiency Theoretical Product Wt Theoretical Wt
Current discharge:
Theoretical Wt reacted
Actual Wt reacted

charge:
E0 E0
Voltaic Efficiency Applied Voltage Actual Voltage

discharge:
Terminal Voltage
E0

Current Efficiency < 1:

Competing reactions (in electrolyte & cell hardware)
Product decomposition
Product recombination

Voltaic Efficiency < 1:

Ohmic overpotential (in cell, electrodes, and external circuitry
Activation overpotential
Mass transport limitation

2-8
Example: Efficiencies in Electrochemical cells:
Assuming that an empty aluminum beer can weighs 20 g, calculate how many hours you
could operate a 100-watt light bulb [at 110V] for the same amount of electricity that is
consumed in producing the aluminum for the beer can. The aluminum reduction proceeds
according to:
2Al2O3 + 3C 4Al + 3CO2
The Faradaic efficiency is 90%. The theoretical Standard Potential (EMF) for the reaction
is 1.8V. However, a voltage of 4.64 is actually applied across the cell. (For simplicity,
you may assume that the light bulb operates on D.C.) Determine:
a) the voltage efficiency of the process
b) the power efficiency of the process
c) where you think the voltage is dissipated and what you could do about it
d) how many hours can you operate the light bulb?
e) how expensive it is to refine the aluminum (assuming a [low] cost of electricity, 5
¢/kW hr).
(The purpose of this problem is to realize the importance of irreversibilities in
electrochemical systems, the physical implication of the magnitude of the Faraday number,
and the cost of electrochemical processes.)

2-9
Solution to Example 1:
Faradaic  0.90
EMF  1.8V
VActual  4.64V
EMF 1.8V
a ) Voltage    38.8%
VActual 4.64V
b) Power  Faradaic  Voltage   0.90  0.388   34.9%
c ) sources of dissipation: ohmic, activation, mass transfer overpotentials 1pt
solutions: bring electrodes closer to minimize IR losses, try different electrodes (geometry, etc)
different electrolyte, mixing, ...
d ) two possible solutions
i ) coulombic based : Al 3  3e   Al 0
1 mol Al 3 mol e  x   96500cb
20 g Al      214603cb
26.98 g Al 1 mol Al  1 mol e 
100W
bulb current   0.909 A
110 A
total charge 214603cb
tbulb    236087 s  65.6hr
current 0.909 A
ii ) power based
214603cb 214603cb W s 1hr
V  P  t   4.64V    307W  hr
Faradaic 0.90 cbV 3600s
100% efficient light bulb
307W  hr
 3hr
100W
e)
i ) coulombic based
$0.05
65.6hr  100W   $0.328
1000W  hr
ii ) power based
$0.05
 307W  hr
1000W  hr

2-10
Example: Faraday’s Law and Faradaic Efficiencies:-
Hydrogen fuel cells have been suggested for automotive application. My current gasoline tank
holds about 18Gal giving me a range of about 250 miles. My car is about 200 HP, but I am willing
to drop to 100 HP for the benefit of going electric. Please calculate the volume of a hydrogen tank
that will give you a similar range. Assume two cases: a. the hydrogen is at 500 atm. b. the hydrogen
is liquefied. (what is the pressure for this case?) Assume that the fuel cell is air breathing (i.e., no
need to carry oxygen). Assume that the fuel cell operates at 0.8 V (instead of the theoretical ’x’
V—what is ‘x’? ) and 10% of the hydrogen crosses over and reacts on the oxygen cathode. You
may need to calculate the energy content of gasoline – assume that it is isopentane. Make any
reasonable assumptions that you need. (The purpose of this problem is to use simple engineering
estimations to critically analyze technical proposals).

2-11
EMF  1.23V
Vactual  0.8V
V  0.65
F  0.9
M  0.585 mechanical / electrical interface
Energy Estimate
18 gal of isopentane  250 miles @150 HP
C5 H12  8O2  5CO2  6 H 2O
H F of C5 H12  179.3 kJ mol
H F of O2  0 kJ mol
H F of CO2  393.5 kJ mol
H F of H 2O  241.83 kJ mol
H F 0  5  393.5 kJ mol   6  241.83 kJ mol    179.3 kJ mol   3239.18 kJ mol
Useful Energy With Gas Efficiency
 3239.18 kJ mol  586.5mol  20%   379956 kJ useful energy goes 250 miles
Fuel Cell Energy needed
T  V FM  0.65  0.9  0.585  0.29
379956 kJ
 1310193kJ needed
0.29
Moles H 2 needed
 4 mol e    96500C   1kJ 
 
1310193kJ    1.23V  X mol H 2   
 2 mol H 2   mol e   1000 J 
X  5326 mol H 2
a ) 500 atm
nRT  5326 mol   0.08296 Latm molK  298K 
V   260.5L  68.8 gal
P 500 atm
b) liquid H 2
  0.0710 g mL
2 g   1mL  
 5326 mol  
L 
     149.9 L  39.6 gal
 mol   0.0710 g   1000mL 

2-12
 Conduction
Metals:

l
R   resistivity [cm]
A
Typical metallic resistivity at 20°C:

Ag 1.6 x 10-6 Ω.cm

Cu 1.7
Al 2.8
Ni 7.8
Fe 10
Hg 96
Carbon (fiber) 4-5000
Graphite 1360

Electrolytes:
= 1/ρ =[ Ω-1cm-1 ] = [S/cm]
 = f(concentration, Z, vi, composition, T, ....)
 ~ 0.1 – 1 S/cm (~ 106 more resistive than metals!) C

 [S cm2 eq.-1]
ZC

Z   j z j    z    z (" valence ")
Implication of limited conductivity:
 Power dissipation (narrow gaps, low current density) C
 Non- uniform current distribution
 Structure of water

2-13
Ionic and Electronic Conduction:
Current passage, whether it takes place in a metallic conductor or in electrolytic solution,
involves the transport of charged species through a medium. The movement of these
species is impeded by collisions with the medium and is therefore associated with a certain
amount of energy dissipation, expressed as a voltage drop.

a) The electrochemical interface:

electronic conducting phase-ionic conducting phase

a. the electrode phase (electronic conducting phase): metal ( ~10-6  cm),

semiconductor
b. the electrolyte phase (ionic conducting phase): ionic solution ( ~10-6  cm),
molten salt (( ~1  cm) , ionic conducting solid ( ~5  cm, 300°C), a plasma

b) Metals:
In metallic conductors the only charge carriers are electrons in the conduction band
and they interact through (a) lattice collisions and (b) collisions with other electrons
not in the conduction band.

The voltage drop is related to the current through Ohm's law:

VI or V=RI
[volts ]=[Ohms ]*[Amperes ]

The resistance, R, of any electrical conductor, is proportional to its length, L, and

L
inversely proportional to its cross sectional area, A : R
A
It-is therefore possible to write;
L
R
A

is an intrinsic property of the conductor and called the specific resistance or

resistivity ( cm).

2-14
Typical metallic resistivities at 20°C:
10-4 – 10-6 ohm cm

Metal Resistivity ( cm)

Ag 1.6
Cu 1.7
Al 2.8
Ni 7.8
Fe 10
Hg 96
Carbon (Filament) 4000 – 5000
Graphite 1360

Temperature coefficient  
1    [0C-1], is positive for metals (~ 0.5 % /0C)
  T 
0
and negative for carbon (~-0.05%/ C), and semiconductors..

c) Electrolytes: conduction is by movement of positive and negative ions in the applied

field. Because of the very much smaller number of charge carriers, as well as the large

resistance offered to the motion of ions (reasonably closely approximated by Stokes

resistance for the motion of spheres), the conductivity of electrolytes dissolved in water is

very much lower than those of metals. Moderately concentrated solutions, in the range of

1-10 moles/liter have resistivities in the order of 1<  <l0cm at room temperature.

The temperature coefficient of resistivity of electrolytes is negative, and

approximately equal and opposite in magnitude of the temperature coefficient of

viscosity: 2-3%/°C.

2-15
Typical values:
1 N KC1 : 10 cm
1 N CuSO4: 40 cm
DI Water: 106-108 cm (‘Megaohm’ water)
In electrochemistry we are more concerned with conductance of a solution rather than its
resistivity. So we define a new term "Conductivity", , such that:
1
 [ 1cm 1 ]   S / cm 

Thus higher the conductivity, lower is the resistivity and hence the material (or solution) is
a better conductor.

It should be noted that typically the conductivity of metals is over 106 (a million) times

larger than the conductivity of electrolytes. That is why we can often (but not always)

neglect the potential drop across metal wires in our calculations involving electrochemical

systems.

Importance of Conductivity:

a. Power dissipation in electrochemical cells P = I2R = I2L/A

Implications: 1. Narrow gap between the electrodes problems:

electrode shorting, mechanical strength, chemicals supply.

2. Low current density (i = I/A), often below 100 mA/cm2 in industrial

processes.

3.. Cooling may be required

Illustration:
Electrochemical machining is a typically high current operation, Assume that the

cathode tool and the part are 1 cm apart and a current density of 100 Amp/cm2 is

applied. The electrolyte is 1 M KC1 (~10 cm). Calculate the electrolyte flow rate

required.

P = 12R = (100)210 = 105 Watt = 2.5x104 cal/sec [1 Watt ~ 1/4 cal/sec]

Rate of heating of electrolyte = 25,000 °C/sec

2-16
High flow rate is required to remove this heat. Assume inlet electrolyte temp. at
30°C and outlet at 90°C:

T = 90°C – 30 °C = 60°C
Q 25, 000
G   400 cc / s  0.4 L / s  24 L / min
 C P T 1x1x60
Current Distribution:
This is very rarely a problem in metals in which the current is assumed to "fill" the entire
conductor. Due to the much higher electrolyte resistance, the current will be distributed in
electrochemical systems in such a manner that the voltage balance is maintained. The
ohmic drop in the electrolyte is just one component of the many voltage drops associated
with electrochemical cells, however often it is very important and most often leads to
extremely non-uniform current distribution (the so-called primary distribution). We will
later spend time in learning how to evaluate this current distribution in a variety of
geometries. Here it will suffice to say that the problem of non-uniform current distribution
is an important one and may lead to inefficient use of electrochemical cells and to serious
damages (burned membrane or deposits).

Determination of Conductivity:

Early D.C. measurements of electrolyte conductivities indicated that Ohm`s law is not
obeyed. This, of course, was an artifact due to non-reversible polarization at the electrodes.
Nowadays, AC Wheatston bridges in the audio range (1-4 K Cycle) with capacitance
compensation are used for simple and accurate conductivity determination.

Conductivity is effected by:

 Concentration C

 Number of charges per ion z

 Ionic velocity v

 Temperature T

 Pressure, Magnetic and electric fields (to a much smaller extent)

2-17
2-18
2-19
2-20
2-21
Law of Independent Ionic Mobilities

Kohlrausch observed that the equivalent conductivity data at infinite dilution, 0, exhibited
some unusual properties. The difference between equivalent conductivities of different
salts with common cation or anion was constant:

salt 0 difference

salt
-.0
difference

KCl 149.86 KC1 149.86

23.41 4 9
NaC1 126.45 XNO3 144..96

KNO3 144.96 NaCl 126.45

23.41 4.9
NaNO3 121.55 NaNO3 121.55

KJ 150.32 LiC1 115.03

23.41 4.9
NaJ 126.91 LiNO3 110.1

 
K  
 Cl   Na  Cl      K  
 Cl   Na  NO  
3

 K   Na  23.41  Cl   NO   4.9
3

This led Kohlrausch to the conclusion that the individual contribution of each ion to the
total conductivity of the solution (at infinite dilution) is specific to the ion, is additive, and
is independent of the other ions in the solution.

Therefore, we can write:

 0  0  0

where 0 , 0 are the equivalent ionic conductivities or limiting ionic conductivities.

Using this technique, tables of limiting ionic conductivities have been prepared, from
which the conductivities of various salts can be obtained by simple addition. It turns out,
and we will see later why, that there is a correlation between the solvated ionic radii and
the limiting ionic conductivities.

2-22
Table 2-1: Equivalent ionic conductivities and solvated ionic radii
ION
 [ohm-1 cm2eq-1] Radius [A] (solvated ionic radius)

Li+ 39 2.36

Na+ 50 1.8

K+ 73 1.21

Rb+ 78

Cs+ 73

Ag+ 62 1.455

Mg++ 53 1.725

SO4-- 79.6 1.15

Cl-- 76 1.2

I- 77 1.16

NO3- 71.4 1.37

H+ 350 0.25 (Grothuss Mechanism)

OH- 200 0.44 (Grothuss Mechanism)

All other ions: ~ 50 ~ 1.5

It should be recognized that these values are valid only for infinitely dilute solutions, and
appropriate corrections should be introduced for concentrated solutions. For C < 1M, the
limiting values provide however a valuable estimate. Close examination of the
conductivity data reveals that with the exception of a H+ and OH- all values fall within
the narrow range of 40-80 ohm-1 cm2 eq-1. For estimating purposes it is very useful and
sufficient to remember one average value of 50. Similarly, a value of 350 should be
remembered for H+ and 200 for OH-. These three numbers permit us to perform simple yet
extremely useful rough calculations without having to resort to handbook values.
2-23
2-24
2-25
2-26
Math Review

2-27
 MATH REVIEW

Tensors (general representation of a parameter)

Rank – ‘dimensionality’ or qualities
Scalars – only magnitude, no direction (rank =0)
Vectors – magnitude + direction (rank = 1,2, or 3)

Gradient
  d   d   d 
 short hand notation for:   i j k
dx dy dz
gradient of a scalar ( ) is a vector

Divergence
Nx Nx+x
 N x N y N z
N j   
x y z
Net flux out of a differential volume element. Divergence is the negative of convergence.
Divergence of a vector is a scalar. Used often to perform mass balance in the electrolyte.

Material Balance (on any volume element)

C j 
    N j  Rj
t
Rate of Rate of
accumulation
of specie j = Net flux in + generation of
of Specie j specie j (e.g., by
in a volume homogenous
element reaction)
Difference

   i   j

2-28
 Electrostatics Review
q2
Force (coulombic)
q1
r1,2
 qi q j ‘short’ range
f  electronic orbital and
4  ri 2,j f
nuclear interactions
(e.g., VanDer Waals

f – force between bodies [dyne or N).

q – charge on a body [cb] r
r - distance
 – permittivity [cb/(V m)]
Long range
0 – permittivity of vacuum [= 8.85x10-14 cb/(V cm)] electrostatic
0 =  Dielectric constant (for water = 78.3) forces
If qi and qj same sign, f >0 (repulsion)
If qi and qj different sign, f <0 (attraction)

Coulomb’s law is sometimes represented as:

 qq
f  kC i 2 j
ri , j

where:

8.988×109 N m2 C-2 (also m F-1) is the electrostatic constant,

or Coulomb force constant, and

8.854×10−12 C2 N-1 m-2 (also F m-1) is the permittivity of free space, also

called electric constant, an important physical constant.

In cgs units, the unit charge, esu of charge or statcoulomb, is defined so that this Coulomb
force constant is 1.

Units:

MKS: [cb]2 [V ][m][cb] [V ][cb] [ J ] [ N ][m]

[N ]   2
    [N ]
cb
[ ][m] 2 [ m ] [ m ] [ m ] [ m ]
Vm

2-29
 [esu ]2
CGS: [ Dyne]  [esu ]  [cm][ Dyne]1/ 2 1 esu  3.3356 10 10 C
[cm]2

ESU or Statcoulomb

The statcoulomb (statC) or franklin (Fr) or electrostatic unit of charge (esu) is the
physical unit for electrical charge used in the centimetre-gram-second (cgs) electrostatic
system of units. The SI system of units uses the coulomb (C) instead. The conversion is

1 statC = 0.1 Am/c ≈ 3.33564×10−10 C

The conversion factor (≈ 3.33564×10−10) is equal to 10 divided by the numerical value
of the speed of light, c, expressed in cm/s.

In the electrostatic cgs system, electrical charge is a fundamental quantity defined via the
electrostatic force (see below); in the SI system, electrical current is fundamental and
defined via the electromagnetic force while electrical charge is a derived quantity. The
electrostatic system derives the electric charge from Coulomb's law and takes the
permittivity as a dimensionless quantity whose value in a vacuum is 1/(4π). Also the use of
the permeability of vacuum, , is avoided, having the consequence that the speed of light
appears explicitly in some of the equations interrelating quantities in this system.

The statcoulomb is defined as follows: if two objects each carry a charge of 1 statC and are
1 cm apart, they will repel each other with a force of 1 dyne. As a result, in the electrostatic
cgs system, Coulomb's law describing the force F between two charges q1 and q2 a
distance r apart takes the simple form:

Note that in order for the Coulomb's law formula to work using the electrostatic cgs
system, the dimension of electrical charge must be [mass]1/2 [length]3/2 [time]-1. This is
different from the dimension of coulombs which accounts for the fact that the factor k
mentioned below is not dimensionless.

In SI units, the electrostatic constant (where is the permittivity of vacuum) has to be

used. Several other laws of electromagnetism also become easier when all quantities are
expressed in electrostatic cgs units; this is the main reason that the cgs system of units is
still in use in physics and electrical engineering. The main drawback of this approach is
that two other sets of cgs units and equations are defined, the electromagnetic and
symmetrical systems (the latter system mixes the first two). The equations in all three
systems are usually written in non-rationalized form, so-called because the factors 2π or 4π
appear often in unexpected places (in situations not involving circular or spherical
symmetry, respectively). It is possible, albeit less often done, to write each set of equations
in rationalized form.

2-30
The coulomb is an extremely large charge rarely encountered in electrostatics, while the
statcoulomb is closer to everyday charges. (Source: WIKIPIDIA)

Field (electrostatic)

Region where forces are present. Forces can be gravitational, magnetic, electrostatic, etc.
We sense the field by putting in the region a test charge (or body) and measure the forces
(if any) acting on it.

 f qj
E 
j 4 rj
qi 2 E – electric field [V/m] or [N/Cb] (or [V/cm])

or [dyne/esu]
Potential

  E

 = electrostatic potential [V] (Similar to elevation lines in a topographical map, or
temperature isoclines in a region.)

[ J ] [W ][ s ] [W ] [V ][ A]
W  qV [V ]    
[cb ] [ A][ s ] [ A] [ A]

Poisson’s Equation
  ( E )   e (Density of free charge)
  (  )  F  z j C j
j

F
 2  

 z jC j however,
F 105
 13  1018
 10
 V cm 
 equiv. 
j  

Laplace’s ’s Equation

 2  0

2-31
Example: Electroneutrality:
Calculate the potential of 10 cc of water in a beaker containing an excess of 10-8 g
ions/liter of positive ions. For simplicity, assume a spherical geometry. (Note that 10-8 g
ions/liter is just below our conventional means of detection. Also, note that
electroneutrality is not a fundamental law of nature.)
(The purpose of this problem is to demonstrate the validity of the electroneutrality
approximation and demonstrate the application of the field and force equations.)

Solution:
10cc water :
3
r 3 V  1.33cm
4
assume positive ions : H  , MW  1 g mol
108 g 1 mol H  1L
 1011 mol cm3
L g 1000cm 3
1011 mol eq
q 96500 C mole eq 10cm 3  9.65  106 C
cm 3
q
 
4 r 2
1  2
  2
r r
 r  
q
4

   r     4
2 q

qr
 r 2 
4
q 9.65  106 C
   5.8  106
4 r 4 (1.33cm)

2-32
 Movement of an Ion in an Electric Field
Electrical force Drag force
d
Fe   qE  ez + FD  6   r v
dx Electric field
d (Volt/cm)
E    
dx
Units:
V  N
MKS: [ N ]  [cb]    [cb]   [ez ]  [cb] = [cb/unit charge][# of unit charges]
m  cb 

CGS: [dyne] = [esu] [dyne/esu]

Steady-state:
d
Fe  FD  ez  6   rv
dx
d
e zj
vj  (~10-3 cm/sec under a field of 1 V/cm)
6   r dx
 m  [cb / ch arg e][# ch arg es ]  V  [cb][V ][ s ] [ J ][ s ] [J ] [ N ][ m]
 s    kg  
m  
[ kg ][ m]

[ kg ][ m]
 
  [ N ][ s ]
m
 m  s  [ m] [ Kg ]  
s

Define “Mobility” (= velocity per unit field or unit force):

vj ez j
R
  (Relative mobility = velocity/unit electric field )
 
U j
d 6r = velocity / volt/cm = [cm2/ V sec]
dx
m
 s   m 2 [cb][#] [cb][ s ] [ J / V ][ s ] [ N * m ][ s ] [ Kg ][ m / s 2 ][ m][ s ]
     
 V  V [ s ]  kg  [ kg ] [ kg ] [V ][ Kg ] [V ][ Kg ]
 m   m  s  [ m]

vj e
Uj   ( Absolute mobility = velocity/( force/mol )
z j F d dx  6   rF = velocity / Nt / M = [cm2 M/ Joule sec]

m
2-33
 s  [ s ][ mol ] [ s ][ mol ] [ s ][ mol ]  m   m [ mol ]  m  [ mol ]
2
[cb]
     
 N / mol   kg  [m][cb / mol ] [kg ]  N   N  s 2  J / m  s   J  s 
 m  s   m / s 2 
Force/mole 
 z jF d
dx  V 
 [eq / mol ][cb / eq ]   
[J ]  N *m 
   [ N / mol ]
 m  [ m][ mol ]  m mol 

Walden “Rules”
1. Any Temp.
   const.
2. Any Solvent
Conductivity:

  F 2  z 2j u j C j   zC j j j  j  F 2 z ju j
j 1, n j 1, n

Example: Estimate the conductivity of water at:

pH = 13 (basic)
pH = 7 (neutral)
pH = 1 (acidic)
Assume only H and OH- are present and contribute to the conductivity. (Is this a good
+

assumption?)

Remember: [H+][OH-] = 10-14 (always). Also, pH = -1g[H+].

(The purpose of this problem is to demonstrate the different mobilities of H+ and OH-
and d the fact that pure water is highly resistive.)

2-34
 cm 2
OH  200
  eq
cm 2
H  350

  eq
    j z jC j
 H   OH    1014 mol L
a)
pH  13   H    1013 mol L OH    101 mol L
 cm 2   1eq   mol   L 
   350    10
13
 
   eq   mol   L   1000cm 3 
 cm 2   1eq   1 mol   L 
  2000    10  3 
 0.02 1 cm
   eq  mol  L  1000cm 
b)
pH  7   H    107 mol L OH    107 mol L
 cm 2   1eq   mol   L 
   350    10
7
 
   eq  mol  L   1000cm 3 
 cm 2   1eq   7 mol   L 
  2000    10  3 
 5.5  108 1 cm
   eq   mol   L   1000cm 
c)
pH  1   H    101 mol L OH    1013 mol L
 cm 2   1eq   1 mol   L 
   350    10  3 
   eq   mol   L   1000cm 
 cm 2   1eq   13 mol   L 
  2000    10  3 
 0.035 1 cm
   eq   mol   L   1000 cm 

2-35
Example Problem
We have seen the steady-state velocity of an ion subject to an electric field. I am now interested in
determining its acceleration period till it reaches this steady state. Assume that an ion (assume Na+)
is suddenly being subject to an electric field of 1 V/cm in dilute aqueous solution (=1cp).
a. Estimate the ion’s steady-state velocity
b. Use Newtonian mechanics to determine the ion acceleration assuming a drag force
that follows Stokes law.
c. How long will it take for the ion to reach its steady-state velocity?
d. What is the time constant the ion acceleration? The time constant is defined as the
time that is required to reach 63.2% of the steady-state velocity.
e. How far will the ion travel before reaching 90% of its terminal velocity?
Data for Na+ ion: r=1.8 A; q=1.6x10-19 C; m=3.82x10-23 g.
Find any other parameters that you may need in textbooks, notes, the web, etc.

Solution:

a) FE = qE; FD = 6πμrν
ΣF = FE - FD = ma
At steady states, ΣF = FE - FD =0

ν= 4.72*10-4 cm/s

b)
dt  qE  6 rv
m dv
mdv
 qE  6 rv   dt
 m ln(qE  6 rv)
t  C1
6 rv
t  0, v  0; C1  ln(qE )
dv
a
dt
c) t is infinity

d)
v  2.98*104 cm / s, t  
m 6 rv
  ln(1  )  1.13*1014 s
6 r qE

2-36
 v  0.9* vss  4.248*104 cm / s
qE 6 r
v (1  exp( t ))
6 r m
t0.9  2.6*1014 s
e) dx
v
dt
qE 6 r
 dx  6 r  (1  exp( m
t ))dt

x  1.28*1017 cm

2-37
The Current Density
i=?

charge/ion = zjF [(eq./mole) (cb/eq) = cb/mole]

Conc. of charge = cjzjF [(mole/cm3) (cb/mole)= cb/cm3]
Current density = i = cjzjFvj [cb/(sec cm2)=A/cm2]
vj
Ionic velocity =vj = ujzjF  uj 
z j F 

i  F 2  z 2j u j C j 
j

Ohm’s Law
   A  A
I     
R L L L

A
I 
i     
A L

  F 2  z 2j u j C j
j

 j  F 2 z ju j D j  RTu j [cm 2 / s ]

    j z jC j
j

2-38
Conduction in Heterogeneous Media
So far we have discussed homogeneous electrolytes, i.e., single phase with a constant
conductivity. However, in certain applications, we may encounter, heterogeneous
electrolytes, consisting of multiple phases with different conductivities. Examples include:
 Bubbles due to gas evolving electrodes, or due to air agitation
 Electrolytes containing particulates, or a dispersed phase, e.g., fluidized electrode
 Blood (contains white and red blood cells)
When a dispersed phase is present, which has a lesser or no conductivity, current lines will
be forced to go, at least partially, around the particles, causing ‘bunching’ of the current
lines leading to increased resistance and lower conductivity. (See Figure below).

From: K.S Cole, “Membranes, ions and impulses”, University of California Press, 1968.

This topic is particularly of interest to biologists who studied extensively such media. A
good reference is K.S Cole, “Membranes, ions and impulses”, University of California
Press, 1968.
Analysis is typically based on representing the heterogeneous system in terms of an
equivalent homogeneous system having a single ‘equivalent’ or ‘effective’ conductivity,
e.

2-39
Zeroth order approximation:

e 1-f
 1 f
C
f
Maxwell derived for a dilute dispersed phase with conductivity d in a continuous phase
with conductivity c:

e d
1 1
C C
 f
e d
2 2
C C
Where

Vdis
f 
Vdis  VCont
And

e  Effective or equivalent conductivity

When the dispersed phase is completely non-conductive, e.g., gas bubbles; d=0 and,

e 1  f

C 1  f
2
Bruggeman extended the treatment to concentrated dispersions. He considered the effect of
compression of additional lines due to the presence of additional particles, considering the
previous case (Maxwell) as a continuum. Bruggeman’s equation is an excellent model for
dispersed phases (“Effective Medium Theory”):
1
e d

C C
1
 1 f 1-f
 e   d 
3
E 1 f
   1   
 C  C 
C 1
f
2

exp 2-40

0
f 1
For d=0, we have,

e 3
 1  f  2
C

1
Emulsions: M&T

E Exp.

Meredith and Tobias, J. Electrochem. Soc. 108 (3) 286 (1961) C

Bruggeman
Gas Evolution: 0 f 1
On vertical electrodes: Charles W. Tobias, J. Electrochem. Soc. 106 (9) 286 (1959)
Here due to accumulating bubbles ‘cloud’ towards the top of the interelectrode gap, the
current distribution is no longer uniform.

2-41
Electrolyte Conductivity Measurements

Measure Resistance:

V  l 1 l
R  
I A  A
Issues:
x
A. What are: l, A?
B. Measure without generating concentration variations

A. What are l, A?
No need to know. Calibrate and determine cell constant, CK.

l
CK 
A
Procedure:
Prepare a known conductivity ref solution e.g., 0.1 M NaCl:
Fill cell with known solution and measure Rref.

V
RRe f 
I
1 l 1
RRe f   CK
 Re f A  Re f Typically, commercial cells
CK  RRe f  Re f have a known (pre-calibrated)
cell constant. The customer
Calculate: can select a cell to fit
application
CK  RRe f  Re f
Replace solution in cell with unknown and measure Rx:
Vx
Rx 
Ix
Calculate:

2-42
 CK
x 
Rx
Implied assumption: The current distribution does not change between standard and
sample. This is a valid assumption because the measurement is conducted under conditions
when there are no concentration variations and no Faradaic electrode reaction takes place.
Under these conditions ‘Primary distribution’ prevails which, as we shall see later, depends
only on the cell geometry. Obviously, the latter does not change.
How do we conduct the measurement such that there are no concentration variations and
no net Faradaic reaction?
Either of two methods:
Very high frequency AC (> MHz)
Zero current measurement (Wheatstone Bridge): Rx R2
At all times:
I x Rx I 3 R3

I 2 R2 I 4 R4
L3 L4
At Balance (Galv=I=0) (R3) (R4)
Rx R3 L3
  Power
R2 R4 L4
Supply

2-43