G. A.

Lonergan
and D. C. Pepper
Trinity College
University of Dublin, Ireland

Transport Numbers and Ionic Mobilities

by the Moving Boundary Method

Few textbooks on physical chemistry

treat the moving boundary method of determining
transport numbers in the same detail that they devote
to Hittorf's method. Texts on practical physical
chemistry usually confine their account to the experiments of MacInnes, Longsworth ( I ) , and others (8, S),
which yield transport numbers only, and are silent
about the obvious pedagogic value of the method in
illustrating the motion of ions during electrolysis and
in yielding absolute mobilities.
The reasons for this silence are plain. To derive ahsolute mobilities we need to know also the value of the
potential gradient, and in the usnal experimental
arrangement this is not usually uniform or measurable,
nor are the changes in the over-all potential gradient
as the boundary moves adequately discussed.
The excellent experiment described by Longsworth
(1) is an electrolysis of a solution of KC1 in a vertical
graduated capillary pipet between an upper cathode
(Ag/AgCI electrode) and a lower anode of cadmium

metal. A sharp, easily visible houndary is formed

between the KC1 and a solution of CdCI2generated by
the electrolysis a t the anode. If the electrolysis
current (i) is kept constant the houndary travels upward a t constant rate, and the transport number of the
potassium ion (T) is simply calculated from
3 dV
T = e,
(1)
z dl
where c = equivdents KCl/ml, 3 = the Farrtday, V = volume
(ml) swept by the boundary in t seconds.

Longsworth's experiment stops a t this point, but the

question arises: can the argument not also be applied
to the Cd++ ions traveling behind the boundary and
yield their transport number? The answer is yes;
but only provided one realizes that the equivalent concentration of cadmium ions behind the boundary is less
than that of the potassium ions in front of it, even
though the cadmium ions are being generated in equivalent numbers a t the anode. The distribution of Cd++
from the anode to the boundary is in fact complex,
consisting of a very concentrated region near the anode
and a fairly uniform region extending from this to the
boundary.
This fact can be demonstrated, and the concentrat,ion
ions and potential gradients in the various regions
measured, by the modified form of experiment described
in this paper. Electrical conductivities are also
measured, so that from a simple experiment, lasting
perhaps one hour, it is possible to derive transport
numbers, absolute mobilities (by two arguments) and
ionic conductances for cations both above and below the
boundary (and also of course for the chloride anion).
Two important relationships can then be verified, viz.,
and

T,/C, = Talc2 dE/dl = potential gradient

p,

dE/dh

= p,

dE/&

p =

mobility

(Subscripts refer to the cations above and below the

houndary.) The second relationship is a necessary condition for stability of the boundary.
Apparatus

The modifications to Longsworth's experiment consist

of:

u
L

Flgure 1 . The apporotur. A, air inlet; B, cathode Ag/AgCl; C, Cathode

compartment; 0, rubber sleeve; E, thermometer; F, 1-ml pipet graduated
in 0.01-mli G, inner gloss envelope sontoining oil; H, glass water jocketi
I , plalnum probe electrodes; I, cadmium cathode; K, piden wox r e d ;
1, brass connector; M, sonnectlonr to conductivity bridge; 0, voltmeter,
0 - 5 0 0 v; N, milliammeter, 0-5 ma; P, varioble 2 0 0 kilohm resistor;
0, power supply 0-500 v, 5 ma, dc.

82 / Journal of Chemical Education

(a) Alteration of the upper catbode compartment so that the po-

tential gradient is virtually confined to the cylindrical part

of the electrolysis vessel, of known diameter and length.
( b ) Insertion of a pair of probe electrodes at a point in the tube
so that the conductivity and hence the concentration of the
solution may be determined before and after the boundary
passes this point.
(c) Connection of a voltmeter between one of the probe electrodes and the electrolysis cathode to permit measurement
of the potential gradient.
(d) Replacement of KC1 by HC1 containing an indicator (2).

A diagram of the apparatus is shown in Figure 1.

The electrolysis tube F consists of a 1-ml pipet graduated in 0.01-ml divisions, whose upper end projects
into a wider tube carrying the Ag-AgCl cathode. Into
the lower end fits a long cadmium rod (made by casting
in a glass capillary of similar bore) adjustable so that its
upper end (point J) may be a t any desired position, and
secured by picien wax a t the bottom. The probe electrodes, a t point I, consist of fairly stout platinum wire
(-0.3 mm diameter) sealed through the capillary waU
and soldered to copper wires led out through the base of
the apparatus. Some care is needed in sealing these
electrodes to avoid excessive distortion of the capillary
bore, and to ensure that they are a t the same level,
otherwise the potential gradient along the tube causes
a potential difference across the probes which upsets
the conductivity measurement. The probe electrodes
should be platinized before any experiments are made.
The tube is mounted in a double-walled jacket, the
inner space filled with paraffin oil to insulate the probe
electrodes and the outer with circulating water for
thennostating. The whole graduated length of the
tube is within the jacket and in the present design the
probe electrodes are fixed at approximately its midpoint,
a t a distance 6 cm (0.36 ml) from the zero graduation
mark and 18 cm from the upper end of the tube (virtual
position of cathode).
The current supply can consist of a simple full-wave
rectifier unit giving about 500 v a t 5 ma. Its output is
connected through a variable resistance (0-200 kilohm)
and an accurate milliammeter (0-10 ma). This resistance must be adjusted a t frequent intervals during the
experiment to keep the current constant as the total
potential drop along the cell increases. Alternatively
a constant current unit may be used (4, 6),which is
more convenient, though more elaborate. A more
accurate measurement of the current may of course be
made by a potentiometer measurement of the voltage
drop across a standard (-100 ohm) resistor connected
in series with the electrolysis cell. However the simpler
arrangement used here gives adequate precision for a
class experiment.
Finally a high impedance voltmeter (e.g., Heathkit
Model V-7A valve voltmeter) is connected between
the cathode and one of the probe electrodes. This
serves to measure the potential gradient first in the HC1
solution and later, when the boundary passes, the increasing potential gradient as high-conductance HCl
solution is replaced by low-conductance CdCI,. A
low-impedance voltmeter is unsuitable since the resistance of the cell containing CdClz solution can reach
100 kilohm.

The conductivity bridge used in this design was a

MuUard Model GM 4140/1 with Magic Eye detector,
giving -2% precision over ranges from 0.1-10' ohm.
An instrument with similar range but greater precision
would be preferable.
The cell is conveniently filled from a 5-ml medical
syringe fitted with a polythene or nylon catheter tube
long and narrow enough to reach to the bottom of the
cell without disturbing the probe electrodes. Washing
water is injected in the same way, and allowed to
overflow into the cathode compartment from which it is
removed by suction or siphoning.
Experimental Procedure

The electrolysis tube is first calibrated, i.e., its volume

to length ratio, dV/dl, and the distance of the probes
from the anode and from the upper end, aremeasured.
The apparatus is assembled, the cell filled to about 1
cm above the upper end of the tube with HC1 solution
of known concentration containing about 0.05 g/l
bromophenol blue indicator. Water is circulated
through the outer jacket to bring the apparatus to constant temperature.
The resistance across the probes is measured on the
conductivity bridge. From literature values (6, 7) of
the conductivity (K) of the HC1 solution the "cell constant" (B) of the probes is evaluated from K = B/R.
The power supply is then connected, the current adjusted to the desired value, and a stopclock started.
The boundary forms sharply within a few seconds and
moves steadily upward. Its time of passing the graduation marks (e.g., every 0.02 ml) is noted. Readings of
the conductivity a t the probes and of the voltage drop
(E) are made at frequent intervals. Periodic adjustments of the variable resistor are made to keep the cnrrent constant.
From these observations, graphs are drawn of V
versus t, E versus t and R versus t, and if desired the
corresponding plots of E and R against (1 - the anodeboundary distance).
Provided the anode is set well below the probes (5-6
cm) a very simple behavior is observed. The volun~e
(and length) traversed by the boundary remains accurately proportional to the time, except for a slight
discontinuity as the boundary moves through the
slightly distorted region of the tube a t the probes. The
probe resistance (R) and the potential drop (E) remain
constant as long as the boundary is below the probes.
As it passes them, the resistance jumps sharply to a
new constant value (R' = 10 R), and E starts a steady
increase, linear with distance traveled beyond the
probes.
The concentration-distribution of the CdCI, solution
behind the boundary can be studied by raising the
anode closer (e.g., 1.5-2 cm) to the probes. The same
initial behavior is observed, but the value of R' remains constant for only a short period after which it
falls, a t first gradually, and then more sharply as the
more concentrated CdC1, solution near the anode diffuses to the probes.
Typical behavior is shown in the diagrams in Figure 2.
Calculations

Figure 2. Variation of V, E ond R with time. (a1 Large di-tonse between

probe electrodes and anode. Ib) Probe electrodes dose to anode.

From the linear V versus t plot the rate of movement

Volume 42, Number 2, February 1965

83

of the boundary with respect to volume dV/dt and length

dl/&

dV/dt
-dV/dl

aor;.,~a
--.
The transport number of the hydrogen ion Tn+ in the
HC1 solution can then be calculated from equation (1)
using dV/dt and the known value of c.
For the cadmium ion T' is calculated in the same way
hut the concentration c' must be derived from the
measured conductivity K' = B/R' by interpolation in
published data (8) relating conductivity to concentra..,+bL:",.
The mobilities may be derived in two independent
ways. They may be obtained from the transport
numbers together with the conductivities, using the
general relationships defining these quantities and the
law of independent migration of ions, i.e.,
aro

m
u
.
.

After the boundary has passed the probes, say by a

length l', the measured potential drop has two components, that in the remaining length of HCl solution
given by (L - 1') (dE/dl),, and a component from the
length 1' of cadmium solution. In principle the
latter may not have a uniform composition, and the
potential gradient may also be nonuniform. However
the constancy of conductivity, K' observed, and the
linear increase of E with 1indicate that it is in fact effectively uniform. The value of the potential gradient
in the Cd solution can then he deduced to be the sum
of the eradient of the E venus 1 d o t d.u s the gradient
in the lHcl
Thus:
E

Equivalent conductance A = Klc

= A+,+

A-

= A+/A

Fur

+ FL

dl

(Lo& inabilities)
= Fp /A

(2)
TAIF = T&FC
They may also be obtained directly from the linear
rate of movement of the ions (boundary) since

i'e.,

p =

- -

T
Podtio. o l
Prober

F ~ ~ U3.W

(")
.d l . r--a

(.E
dl .)H

since Eoconstant and since

1
Potllion el
~oundary

~erivotionof potential gradients.

TOP of
pipet

acd

Journal o f Chemical Educofion

dl/dt
d~
E
(;it

+?)

Results and Conclusions

Table 1 shows some typical results. Better concorby more effective

dance could no doubt he
thermostating and more sensitive instrumentation, hut
there are good reasons for restricting the experiments
to the low concentrations and currents (where the results
agreement with published values (9,10).
in
At the higher concentrations and currents a temporary
disturbance of the boundary is noticed when the
experiment is about half completed-the blue color of
the HC1-bromophenol blue solution becomes bleached
and an anomalous jump is observed in the potential
drop E. This anomaly is probably to be associated
with the diffusion of chlorine produced a t the anode
under conditions of high current density and high accumulation of CdClpa t the anode (see later). Furthermore, a t the higher concentrations the formation of the
various cadmium halide complexes, CdCl+, CdCla-,
CdC14=, will become more important and this would
introduce unnecessary complications into the con?putations.
The value of the experiment lies, however, not so
much in the precision of the results obtainable as in

Table 1

84

L(%)=

dE
l,(&

and

by evaluating the potential gradient in the appropriate

regions of the electrolysis tube. The method is best illustrated by a consideration of the plot of E against 1,
which has the same form as that of E against t in Figure
2a since dl/& remains constant.
The constant value Eo maintained as long as the
boundary is below the probes, measures the potential
drop in the uniform solution of HC1 between the probes
and the outlet (neglecting the very small potential
The potential
in the wide
gradient jn the HCl solution ( d E l d 0 ~is therefore
simply Eo/L.

I-*

dE

p+ =

rate under unit potential gradient = -

.-

(L - 1 0

,., dE
-=

(iorm conductmces)

(& +
+ 1,[(3ca
(?)El]
z , [ ( $ )G)=]
~~

correlating the various "laws" of electrolysis and in

focusing attention on the conditions governing the
migration of ions. For instance, it shows directly
that if a stable boundary is to be formed between a
solution of fast moving cations and one of more sluggish
cations there must be a higher potential gradient in the
latter. It shows, too, that since current must be
"conserved" across the boundary, the concentration of
the slower moving ions must be lower, i.e.,

The realization that, at the boundary, c' < c gives

important insight into the conditions obtained in the
cadmium solution. At the anode the cadmium ions
are generated originally a t a rate equal to that of the
departure of hydrogen ions. The concentration will
then be originally the same (apart from a small effect
of the different partial molar volumes of the cationsneglected here) but will build up to a still higher value
because of the normal Hittorf effect of accumulation in
the "anode compartment." How far does this anode
compartment extend along the electrolysis tube?
The experiment shows that it is confined to a narrow
region (a few mm), and that most of the column of
CdC1, solution in the cell has a uniform composition and

potential gradient.
The experiment could be extended to study the concentration distribution in the anode compartment by
raising the anode to a level close to the probes and
changing the voltmeter connections to register the
potential drop between anode and probe. The conditions in the anode region are however complex depending on the rate of generation and diffusion of
Cd++ and hence on the temperature and the current,
and on the anomalous production of Clz. Such a
study is therefore more suited to a small research
project than to a class experiment.
Literature Cited
(1) LONGSWORTH,
L. G.,3. CHEM.
EDUC.,11, 420 (1934).
(2) DANIELS,F. ET AL., ''Experimental Physical Chemistry," 6th
ed., MeGraw-Hill Book Ca., New York, 1962, pp. 165-9.
(31
S. W.. J. CHEM.EDUC..
38.516 (1961).
~,TOBEY.
.
(4) BENDER,
P. AND LEWIS,D. R., J. CHEM.EDUC.24,454.
(5) TOBEY,
S. W., J. CHEM.EDUC.,38, 517 (1961).
(6) SHEDLOVSICY,
T.
411 (1932).

. .

2811 (1941).
(8)
. . NOYES,A. A. AND FALK,K. G., J. Am. Chem. Soc.,. 34,454
.
(mi).
(9) LUCA~SE,
W. W., J. Am. C h a . Sot., 51, 2605 (1929).
(10) MACINNES,
D. A. AND LONGSWORTH,
L. G., Chem. Reu., 11,
171 (1932).

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85