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307

Review

Evaluation of Diffusion Coefficients of Metallic Ions in Aqueous


Solutions
Stephen Kariuki and Howard D. DrwalP
Department of Chemistry, Clippinger Laboratories, Ohio University, Athens, OH 45701-2979, USA
Received: June 22, 1995
Final version: August 17, 1995
Abstract
Many techniques are available for the determination of diffusion coefficients of ions in aqueous solutions. A review of classical and modern
techniques is presented. Non-electrochemical methods are discussed briefly. Electrochemical methods reviewed include chronoamperometry, chronopotentiometry, polarography, and h drod namics. Selected values of the diffusion coefficients determined by these
electrochemical methods of the metallic ions Ag', Bi XI , CdY, , Cu", In"', Pb", TI', and Zn" are presented.
Keywords: Diffusion coellicients, Diffusion, Mctallic ions

1. Introduction
Diffusion is the phenomenon whereby solute particles
disperse or intermingle as a result of their potential energy. It
is a spontaneous process which acts to eliminate differences in
concentration and ultimately leads a given mixture to a state of
uniform composition. In a binary system, to which this review is
concerned with, the solute particles have the tendency of moving
from the zone of higher concentration to that of lower. The
solvent tends to move in the opposite direction. This motion is
however random in nature since the solute particles also go from
regions of lower to higher concentrations and solvent particles
in the opposite direction. The overall tendency with time is the
one that reduces the concentration gradient.
Fick [l] described diffusion as given by the expression:
J = -D-

3C
dX

where J is the flux (i.e., the mass of material crossing unit area
perpendicular to the flow in unit time) and dC/dx is the
concentration gradient measured parallel to the flow. D is the
diffusion coefficient. The value of D for a given system is
generally dependent upon both temperature and concentration.
Experimental measurements are exclusively done under isothermal conditions so as to avoid variation of D values. As the
data that follows show, there is practically no one particular D
value determined, even under isothermal conditions, that may
be considered a constant for a given system.
In diffusion based on Equation 1, a steady-state concentration gradient is established between two reservoirs main6 n e d at fixed composition. Most diffusion processes, however,
are based on monitoring the transient processes in which the
concentration changes as a function of both distance and time.
This relationship which has been established from Fick's first
law is given by the expression

So as to get a useful mathematical expression of an unsteadystate diffusion process, Equation 2 must be integrated with
attention to appropriate boundary conditions.
Electrounulysrs 1996, 8, No. 4

Generally, the determination of diffusion coefficients involves


measuring sets of simultaneous values oft, C, and x (or dC/ax).
These measured values are then fitted to a solution of Fick's law
so as to get the diffusion coefficients. Some of these techniques
are discussed below. The purpose of this review is to present and
evaluate some of the most common techniques that have been
used in the determination of D values of electroactive species. D
values of Ag', Bi"', Cd", Cu", InTrT,Pb", TI',and Zn" are
presented. These ions are the most common metallic ions whose
D values are of interest.

2. Ionic Conductivity
Both diffusion and conductance involve movement of ions,
and as such, a connection between them exists. At infinite
dilution, where interionic forces vanish, we may attribute to any
given ion a characteristic drag, proportional to velocity, which
resists motion through the solvent. In conduction, the driving
force is the gradient of electrical potential, whereas in diffusion
it is the concentration gradient. However, in conduction the ions
move in opposite directions and independently of one another,
while in diffusion they move in the same direction and at almost
equal speed, since otherwise a separation of electric charge
would occur. This treatment led to the Nernst-Einstein relation
121:
A=-

ZF~D

(3)
RT
where the symbols are defined in Appendix I . As the above
description indicates, the accuracy of measurements of diffusion
coefficients by conductivity methods depends on the nature of
the solution and better values would only be obtained towards
infinite dilution. A number of issues do arise from this theory [3,
41. The solvent cannot be regarded as stationary since there is an
appreciable counterflow of solvent molecules to accommodate
the transfer of ions. A layer of solvent is electrostatically
attached to each ion as a consequence of dipole induction, and
the resulting species is the one that diffuses. This phenomenon
increases the effective concentration of the solute especially at
higher concentrations.

8 VCH VerlugsgesellschuftmbH. 0-69469 Wernheim, 1996

1040-0397196j0404-307$ 10.00+.25/0

S. Kuriuki, H . D. Drwald

308

3. Porous Diaphragm Methods


Northrop and Anson [S] introduced the diaphragm cell
method which after considerable development by a number of
workers [6-101, particularly by Gordon [I 11 and Stokes [12], has
become a technique of considerable value. Two liquids of
different concentrations are contained in two compartments of
the cell and are separated by a thin porous disk referred to as the
diaphragm. A concentration gradient across the diaphragm
develops and this causes net movement of solute particles from
the compartment of higher concentration to lower concentration. To eliminate the formation of uncertain stationary
layers on the diaphragm surfaces, the liquids must be wellstirred during the diffusion process. The most common
procedure in a diaphragm cell experiment is to allow the
experiment to run for a period (usually a day or more), and then
to analyze the contents of at least one of the compartments. The
initial concentrations and the difference across the diaphragm
can be measured very conveniently if a suitable electrode system
is available. Alternatively, if one component i s labelled with a
low energy emission radiotracer then its concentration in one or
both compartments can be monitored continuously by suitably
placed and shielded detectors. For a diaphragm cell with
compartments of equal volume, McBain and Liu [7]derived the
relation:
KDt

= log C, - log(C,

2Ct)

(4)

K depends upon the effective area and thickness of the


diaphragm which cannot be deduced from the superficial
geometry, because these parameters depend on the internal
pore structure. Therefore, K has to be determined by calibration
of the cell with a solution of known diffusion coefficient. It is
customary to use aqueous potassium chloride solutions, for
which very accurate diffusivity measurements exist.
The diaphragm cell has advantages of simplicity, low cost,
and when used correctly, precision. Its disadvantage is that
accuracy depends largely on the cell calibration and that other
processes such as electrical double layer and adsorption effects
may develop within the porous membrane even after the cell
calibration has been done. Such effects become particularly
serious for dilute solutions. However the method seems to be
reliable in the higher concentration ranges of not less than
0.05 M and even then diffusion coefficients of high accuracy are
not guaranteed [13].

by Gouy [14]. Other optical methods for measuring diffusion


coefficients include: wavefront-shearing interferometry whose
application in diffusion studies was first suggested by Ingelstam
[I51 and Bryngdahl [16] in 1957; and hologram interferometry
[17, 181. The challenges in these optical methods of diffusion
coefficient determinations include: the initial and boundary
conditions assumed in the mathematical model must exist in the
cell; the front and rear walls of the cell must be transparent and
free of optical distortions; good temperature control is
mandatory and should be within &0.01 C since the diffusion
process is strongly temperature dependent, and random thermal
gradients might induce convection. It should be noted that these
refractive index methods are not particularly well-suited for
dilute solutions since a large enough change in the refractive
index may not be attained.

5. Restricted Diffusion Methods


Early diffusion coefficient measurements were exclusively
made by the method of layer analysis, the principle of which
was first described by Graham [19]. Modifications have since
been made [20]. The technique would sometimes have a duration
of several days, and required a strict isolation from vibration,
something very difficult to obtain. The technique is no longer
used.

6. Dispersion Techniques (Flow Injection Methods)


When a pulse of solute is injected into a slow stream of solvent
confined within a narrow bore tube the resulting bolus disperses
in a way dictated by a combination of laminar flow and diffusion
perpendicular to the tube axis. Taylor and others [21-291 have
shown that, provided certain conditions are fulfilled, the
concentration distribution within the solute column as it
passes down the tube can be used to determine the diffusion
coefficient by use of the relation [29],
35.4 L 0.64
A f = p ( z )

4. Optical Methods

7. Chronoamperometric Methods

Optical methods for diffusion coefficient measurements are


exclusively based on concentration gradient determinations in
diffusion cells. The optical methods are particularly useful for
measuring small concentration gradients, provided the concentration change induces a sufficiently large refractive index
change in the diffusion cell. Many optical methods employ free
diffusion from an initially sharp boundary, formed between two
solutions of different concentrations. This may be formed by
injecting a pulse of solution into a flowing stream of different
composition, or at the junction between two stationary phases.
lnterdiffusion occurs across the boundary, and the region over
which concentration changes occur becomes more extensive
with time.
Diffusion coefficient measurements through refractive index
gradients are based on developments of an effect first discovered

The chronoamperometric techniques are based upon the


Cottrell equation [30] or its modification where the potential of
the electrode-electrolyte system is held at a fixed value and the
diffusion limited current versus time is recorded. The diffusion
limited current is given by the following expressions. For a
planar electrode

Electroanalysis 1996, 8, No. 4

~FADJ~C
IL(4 =

(t)1/2

and for a spherical electrode,


I L ( t )= nFADC

[
~

1
(7rDt)/2-t

i]

(7)

Diffusion Coefficients of Metallic Ions

309

Related to Equation 7 is one by Pavlopoulos and Strickland


[3I], given by the expression
IL(t) = 1.4 nFD0.'C1

-+[ir

:]

Koutecky [45]when taking the electrode sphericity into account,


modified the Ilkovic equation to the expression
I L --706 nD'/'Cm2/3t'/6
x [l

in their work on stationary microelectrodes. The diffusion


limited current (id) for a stationary disk electrode (SDE) has
been given by Shoup and Szabo [32] as

(9)
Yap and Doane [33]have also considered the determination of
diffusion coefficients by chronoamperometry at unshielded
planar stationary electrodes. Osteryoung and co-workers
derived expressions for the chronoamperometric response of
the ultramicroelectrode [34, 351. This lead Winlove et al. [36] to
develop an analysis method that allowed for the determination
of both the diffusion coefficient and the concentration of the
electroactive species. Ikeuchi and colleagues [37] have given the
diffusion limited current of normal pulse (NP) voltammetry with
an SDE by the expression

+ 39 D1/2t1/6m-'/3+ 150 t'/3m-2/3 + . . .]

(13)

The third term of this relation is not significant in practical


terms, but the second amounts to about 5 to 10% of the first for
typical diffusion coefficients and capillary characteristics. The
hanging mercury drop electrode (HMDE) expression for the
diffusion limited current, id has been given [46] as

Normal pulse polarography offers another polarographic


technique for diffusion coefficient measurements. The diffusion
limited current expression for the technique has been reported
by Ikeuchi et al. [47].

10. Hydrodynamic Methods


10.1. Rotating Disk Electrode Methods

where A t = t l - t2. The observed current is the integral average


of instantaneous current over a time duration of A t .

8. Chronopotentiometric Methods
In the chronopotentiometric techniques, the current is
controlled and the potential becomes the variable which is
determined as a function of time. One commonly utilized
chronopotentiometric technique in the determination of diffusion coefficients is one in which the current is held constant. In
such a case, the D values may be obtained from Sand equation
[38] given by the expression,

The rotating disk electrode (RDE) consists of a disk which is


spun such that the solution is drawn from below and spread out
uniformly across its surface [48]. Levich has given an expression
[49] from which diffusion coefficients may be calculated. The
expression takes the form:
IL= 0.620 nFAD2/3v-'f6C~'/2

(15)

The Levich equation assumes mass transfer of the species by


convective diffusion. This equation has been modified to include
a kinetic step since the assumption of pure mass transfer is often
not the case. For a totally irreversible reaction the modified
Levich equation [50] is given as

However the number 0.620, an approximation made by Levich


can be improved by doing a better approximation so as to
obtain a more exact value of the limiting current particularly for
low Schmidt ( v / D ) values. Gregory and Riddiford [51] have
improved on Levich's approximation as the expression below
shows.

9. Polarographic
The dropping mercury electrode (DME) has been widely used
for measuring ionic diffusion coefficients in solutions containing
excess supporting electrolytes. Mass transfer at the DME is not
simple since effects of depletion [39] and shielding [40] are
experienced in spite of the fact that methods of reducing the
effects are now known [41]. The polarographic maximum often
interferes and necessitates the addition of surfactants, which
may alter the diffusion current in an unpredictable way [42]. In
addition to these experimental complications, the convective
diffusion [43] to the DME complicates further the mass transfer
processes which increases uncertainties in prediction of the
actual diffusion process.
The polarographic limiting diffusion current predicted from
the Ilkovic equation [44] is given by the expression

The expression agrees with the theoretical value within 1YOfor


Schmidt values > 250. Newman [52] through an analytical
approach has given the expression (below) which gives a

maximum deviation from theoretical values of about 0.1 '/O for


Schmidt numbers > 100.
Compton et al. [53] have combined rotating disk double
potential step chronoamperometry and in situ electrochemical
ESR spectroscopy in the study of kinetics of comproportionation. They demonstrated that there is a very strong correlation
Electroanalysis 1996, 8, No. 4

S . Kuriuki, H. D. Dewuld

310

Table 1. Selected diffusion coefficients of Ag' determined by various techniques. CA1: Chronoamperometry using Cottrell equation; CA2: normal pulse
voltammetry with a stationary disk electrode; CP: chronopotentiometry; D1: diaphragm cell method; FI : flow injection analysis method; PI :
polarography using stationary microelectrodes (Stackelberg modified Ilkovic equation); P 2 hanging mercury drop electrode; P3: dropping mercury
electrode; P4: stationary mercury drop electrode; R I: rotating disk electrode; TI : tracer diffusion method.
Electroactive
species

Conc. of
species ( m M ]

Supporting
electrolyte

Measurement
technique

D x lo5
lcm21sl ial

Ag'

0.185
5
5
0.0936-0.0678
0.0758
0.1000
0.1000
0.25- 0.4
0.25-0.4
0.25-2.0
0.25-2.0
2.5-4.0
2.5-4.0
1.0-2.5
1.0-2.5
1.0-4.0
1.0-4.0

0.5 M KNO?
0.257mol/Kg H2S04
0.257 mol/Kg H2S04
0.2 M KNO,
1 M KNO3
0.1 M HC104
1 M HC104
0.01 M KNO3
0.01 M KNO3
0.05 M KNO3
0.05 M KN03
0.1 M K N 0 3
0.1 M KN03
0.5 M K N 0 3
0.5 M KN03
1.OM KN03
1.OM KNO3

P1
R1
R1 (60C)

1.50
1.38
2.73
1.53
1.55
1.62
1.58
1.562
1.605
1.544
1.566
1.538
1.553
I .546
1.559
1.553
1.571

R1
R1
R1

R1
P3
CA 1
P3
CAI
P3
CAI
P3
CA 1
P3
CA 1

Reference

[a] Measurements done at 25 "C


Table 2. Selected diffusion coefficients of Cd" determined by various techniques.
.-~.~~

species [ m M ]

Cd"

2
2
0.11
3

0.1-0.3
0.1-0.3
0.1-0.3
0.1-0.3
0.1-0.3
2.5
2.5
2.5
2.5
2.5
2.5

Cd"

~~

Conc. of

Electroactive
species

~~~

Supporting
electrolyte

Measurement
technique [ a ]

D x lo5
Icm"~l lbl

Reference

0.1 M KC1
1 M KNO3
1 M KC1
1.O M Na2S04
0.1 M KN03
0.5 M K N 0 3
1.OM KNO,
0.5 M KNO,
1.OM K N 0 3
0.05 M KCI
2.5 M KC1
0.1 M NaN03
0.1 M NaC104
0.1 M (NH4)2S04
1 M KC1
1 M KC1
0. I M KNO,
0.1 M KCI
0.1 M KCI
1 M KN03
0.1 M Al(N03)3
0. I M HNO,
0.1 M Sr(N03)*
0.1 M KNO,
0.1 M KC1

DI
D1
P1
P2
P2
P2
P2
P3
P3
P3
P3
P3
P3
P3
P3
CA 1
P3
P3
CA 1
P3
P3
P3
P3
P3
P3

0 70
0 66
0 80
0 784
0 741
0 710
0 705
0 719
0 721
0 733
0 832
0 738
0 705
0 558
0 789
0 808
0 690
0 716
0 717
0 681
0 6379
0 6866
0 6741
0 7254
0 6793

[661
[661
~311
~671
~461
[681
1681
[681
[681
~ 9 1
~ 9 1
~ 9 1
~ 9 1
~ 9 1
~421
~421
1421
[421
~421
[421
[701
1701
[701
[701
[701

.~

~~

-~

-~

[a] symbols are defined in Table 1; [b] measurements done at 25 "C.

between the ratios of both transient and steady state signals


obtained and that of the diffusion coefficients for the species
involved to an extent that if the D value of the reactant species is
known (or is first computed from one of the signals) then that of
the product may be computed unambiguously without the need
of knowing its concentration.
Bruckenstein, Miller, and co-workers [54,55] have shown that
the D value of an electroactive species depends upon the change
in current that occurs as a result of modulating the speed of
rotation of a disk electrode. Thus the D value of an electroactive
species may be determined from the speed modulation response
without knowledge of the concentration or the number of
Elwtrounulwis 1996, 8 , N o . 4

electrons transferred in the electrode reaction. Hitchman and


Albery [56] reported an accurate method of determining the D
value of an electroactive species by following the first-order
decay of the limiting current as the species is consumed on the
rotating disk electrode. The technique similarly does not require
a knowledge of the concentration of the electroactive species or
the number of electrons.

10.2. Flow Through Methods


The expressions for limiting current with a flow parameter
show a dependence on D2I3 [57].Two of the most popular flow

Diffusion Coefficients of Metallic Ions

31 I

Table 3. Selected diffusion coefficients of Cu" determined by various techniques.


~

Electroactive
species

Cone. of
species [mMJ

Supporting
electrolyte

Cu"
CU"
CU"

0.116
0.219
0.219
10
10
<2

1M NdCI04

cUII

Cu'

-i CUO

D x lo5

Measurement
technique [ a ]

0.1 M N(CzH&C104 in CH3CN


0.1 M N(CzH&C104 in CH?CN
0.01 M H2SO4 & 0.100M Na2S04
0.01 M H2SO4 & 0.100 M Na2S04
0.51 M H2S04
0.1 M AI(N03)3
0.1 M Sr(N03)*
0.1 M KN03

PI
CA 1
CA 1

R1
CP
P4
P3
P3
P3

lcmz/sI

Reference

PI

0.68
1.oo
1.23
0.722
0.694
0.583
0.6707
0.5438
0.7174

.-

~~

[a] symbols are defined in Table 1, [b] measurements done at 25 "C.


Table 4 Selected diffusion coefficients of Pb" determined by various techniques
_______
~-

Electroactive
specter

Cone of
species [ m M ]

Supporting
electiolyte

Measurement
technique ( a ]

D X 105
Icm'lsl [bl

Pb"

2
2
2
0.135
1.047
3
2.5
2.5
2.5

0.1 M KN03
0.1 M KC1
1 M KN03
1 M NaC104
0.100M KC103 in DMSO
1.OM Na2S04
0.1 M KNO3
0.1 M KC1
0.1 M KCI
0.1 M Al(N03)3
0.1 M S T ( N O ~ ) ~
0.1 M K N 0 3
0.1 M HN03
0.1 M KCI
0.10 g/L KCI & 0.0005 M HC1
4.00 g/L KCI & 0.0005 M HC1

D1
D1
D1
PI
P2
P2
P3
P3
CA 1
P3
P3
P3
P3
P3
T1
TI

0.75
0.75
0.67
0.92
0.236
0.774
0.828
0.865
0.869
0.8131
0.8656
0.9849
0.8452
0.8996
0.970
0.794

2
2

~ _ _ _

Reference

[a] symbols are defined in Table I ; [b] measurements done at 25 "C

through electrodes are the wall jet and channel. The current at
the wall jet arises when a stream of solution issued from a
circular nozzle impinges normally on a disk electrode and
spreads out radially over the disk surface [58]. The wall jet
equation is given as

IL= 1.6 .FcoD2/3y-5/12qya-1/2r3/4 (19)


In the channel electrode, the solution flows across the electrode
which is located in a wall of a rectangular duct. This electrode is
most commonly employed in liquid chromatography-electrochemistry (LCEC). Compton et al. [59] have presented a
theoretical treatment which permits the computation of
transient effects at double-channel electrodes. They showed
that the measurement of the transient response between the two
electrodes can be computed readily and used as a sensitive probe
for the D values of electrogenerated species.

11. Evaluation of Diffusion Coefficients


As shown, there are many techniques for the determination of
diffusion coefficients. The determination of the value of the
actual electrochemical active area of an electrode generally
requires an accurate D value of the species under investigation.
The electrochemical active area is considered more important
than the geometric area due to changes on the surface that keep
occurring as the electrode continues to be used. Besides,

accurate D values of various species would enable the


determination of other parameters involved in a reaction and
this would help the diagnosis of a reaction mechanism. The D
values of certain ionic species seem to differ, sometimes
appreciably, from one technique to another even when all
other parameters such as the temperature of the reaction, the
type and concentration of the supporting electrolyte are held
constant. Further even within the same technique, D values of
the same ionic species may vary with the form of equation used.
This leads to vagueness of what the actual D values of some
species would be considered to be. The D values presented in
Tables 1-6 are seen to be dependent upon the concentration of
species, the type and concentration of the supporting electrolyte,
the temperature, the measurement technique and sometimes the
equation used in a given measurement technique. These aspects
complicate the creation of a data base (similar to other
databases at Daresbury in the United Kingdom [60]) for the D
values of electroactive species.
All other factors being held constant, it is observed that the
diffusion coefficient of a species may generally decrease with an
increase in concentration of the supporting electrolyte, as is the
case observed for K N 0 3 supporting electrolyte in Tables 1 and
5. Further, as the concentration of supporting electrolyte
decreases the diffusion coefficient may decrease as observed in
Table 2 with KCI supporting electrolyte. The mentioned factors
indicate that diffusion of a species is affected by its environment
in the sense of how free it moves and how it interacts with the
other ions present. This process may sometimes be difficult to
Electroanalysis 1996, 8, NO.4

S. Kariuki, H. D.Dewald

312
Table 5. Selected diffusion coefficients of TI' determined by various techniques.

n x lo5

Electrouct ive
spwies

Conc. o j
species [ m M ]

Supporting
electrolyte

Measurement
technique [a]

Icm2Isl [ b l

TI'

2
2
0 232
0.519

1 M KNO?
0.1 M KCI
1 M NaC104
1 M KN03, 0.1 M
HOAc & 0.1 M NaOAc
0.1 M KCIO3 in DMSO

DI
DI
PI
P2

1.79
1.67
1.88
1.79

P2
CA2
P2
P2
P2
P3
CA2
FI
P2
P3
P3

0.459
1.92
1.96
1.77
1.74
1.83
1.92
1.49
1.96
1.819
1.744

1.152
400 & 500

0.5 M KNO,
0.1 M KN03
0.5 M KNOq
1 .OM K N 0 3
0.5 M KNO?
0.5M KNO,
1 M KC1
0.1 M KNO?
0.1 M KNO,
0.1 M KCI

1-5
1
1
~

~~~

- .-

~-

~-

~~

Reference

~~

[a] symbols are defined In Table I , [b] meawrements done at 25C


Table 6 Selected diffusion coefficients of BI"', In"' ,and Zn" determined by various techniques
.

__

~~~~~

Electrout rive
spec ies

Conc. of
species [ m M ]

Supporting
electrolyte

Measuremmt
technique [ a ]

BiIll

0.117

1 M HC104
0 072 M Sr(NO&
0 OX M KNOq
0 056M HNO?
0 080 M KCI
0 1 M KNO,
0 1 M HN03
I OM Na2S04
0 1 M KNO?

PI
P3
P3
P3
P3
P3
P3
P2
P3
P3
P3
P2
TI
TI
TI

0.60
0.3 I96
0.3993
0.3145
0.4420
0.6899
0.5176
0.741
0.63X
0.673
0.623
0.226
0.729
0.951
1.02

In"'

Zn"
2.5
2.5
2.5
1.047
5
5
5

OIMKCI
2 OM KNO3
0 1 M KCIO,/DMSO
0 10 g/L KCI & 0 005 M HCI
4 00 g/L KCI & 0 005 M HCI
1 0 F NH40H & 1 0 NH4CI

lo5
Icm21sllhl

Reftwnce

[a] symbols are defined in Table I; [b] measurements done at 25 "C

control as a result of species-electrolyte interactions which are


usually not easy to predict. The type and the concentration of
the electrolyte is important since it dictates increased or reduced
migration of the species under investigation. The effects of
temperature may be seen from Table 1. As the temperature
increases, the kinetic energy of the species increases and also the
viscosity of supporting electrolyte decreases thus enhancing the
rate of diffusion of a given species. The tables represent a cross
section of D values determined by various techniques and
varying conditions. These D values present a challenge to
scientists to come up with procedures for accurate D value
determinations. It is observed that some degree of variation of D
values exists even when determined with the same technique.
Although a thorough verification of each technique is
needed, hydrodynamic, chronoamperometric and polarographic methods appear a good choice for the D values
determination. Earlier reports by von Stackelberg et al. [42]
and Adams [61] may be consulted for discussion on the
evaluation of D values for organic substances and other
inorganic species. The C R C Handbook of Chemistry and
Physics [62] is also a source of D values of ions based on the ion
molar conductivity. The D values of metallic ions not available
in the literature may be estimated by using Equation 3 provided
Elec.tr.ctunulysu 1996, 8, No. 4

the ions' molar conductivity values are known. Those of


nonelectrolytes in dilute aqueous solutions may be estimated
by using expressions such as the revised forms of the Othmer
and Thakar or Wilke and Chang equations [63].

Appendix I - Symbols for Expressions


Symbol
A
a
C
Co

C,

ri

D
F

Definition
Surface area of the electrode
Diameter of wall jet nozzle
Concentration of a species in
the bulk
Initial concentration of a
species in bulk
Concentration of a species in
bulk after time t
Density of mercury
Diffusion coefficient of a species
Faraday constant; charge on
one mole of electrons
Current

Usual units
cm2
cm

M, mol ~ m - m
~M
,
M , mol cm-3, mM
M, mol cmP3, m M
gcmP3
cm2 s-'

C
A, PA

Diffusion Coefficients of Metallic Ions


Limiting current
Kinetically limited current
Diffusion limited current at
time t
Cell constant
Distance between injection port
and the detector
cm
Flow rate of mercury at DME
mg C'
Electrons per molecule oxidized
or reduced
Flow rate of liquid stream
Radius of electrode
Gas constant
Time the reaction has taken
S
place
Transference number
K
Absolute temperature
Time duration of a reaction
S
between two timings, tl and tz
Peak width
S
Distance from electrode
cm
Charge of ion
cm2
Molar conductivity of an ion
cm
Diffusion layer thickness
Kinematic viscosity of a
solution
CP
Transition time
S
Angular frequency of rotation
S-'

313

rnol-'

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Electrounulysi,~
1996, 8, No 4