Stephen W.

Tobey1 Simplified Moving-Boundary

West Virginia Wesleyon College
Buckhonnon
Transference Cell

The transference cell shown in the

figure is considerably easier to construct and operate
than similar simple cells described earlier2? for deter-
Cu -
The predominate anode reaction during operation is
Cut+ + 2e,
although the deposition of a small amount of a white
mining cation transference numbers by the moving
boundary method, and the necessary materials for its precipitate on the tip of the anode during opewtiot~
construction will usually he readily available in any suggests that the reaction sequence
chemistry laboratory. Cu- Cu+ + le
To prepare the cell for use, the upper (cathode)
chamber is filled with the solution to be used in the
cu+ + C1-- CuCl +
experiment, a beaker is placed under the anode, and may also be occurring simultaneously. The mobilities
the anode stopper is momentarily loosened. The of Cu++ and Cd++ are almost the same, so that no
downward sweep of electrolyte effectively frees the difficulty is created by substituting Cu for Cd in the
capillary of any impurities or air bubbles present. anode. The cathode reaction is simply
2H+ + % - H I ?
Since this reaction takes place far removed from the
KNURLED W M B COPPER COUPLlND
SCREW
9)UXRDD JOINT 2 HOLE RUBBER
capillary in which the moving boundary is generated,
STMPER
GLASS TUBlNG VENT
no complications due either to depletion of the catholyte
RUBBER STOPPER in C1- or mixing of the solution-byevolving H2arise.
13" 100nm PYREX
Table 1 gives the results of a typical experiment
PI4COPPER
WlRE SPIRIL TEST TUBE WlTH
HOLE BLOWN IN
performed using the apparatus described. The value
TEST TUBE SIDE of t,. calculated from this data is 0.806, to be com-
pared with the literature value, 0.823.6 Although
circulation of constant temperature water around the
capillary is not absolutely essential, the results obtained
MIIOENSER
JACKET
with thermostating were significantly better than those
obtained on a prototype model which had only a large
D-,.Om1 PVREX
PlPETTE WITH volume of water surrounding the capillary to act as a
a 0 Z m l DlYlSlDNS
heat sink.
A convenient power supply for providing the neces-
sary regulated current for this apparatus is described
X 14 COPPE
WlRE
elsewhere in THIS JOURNAL.^
RUBBER STCPPER Table 1. Sample Experimental Results with 0.1022 M
RUBBER STOPPER
SOLDERED JOINT
HCl at 2 5 0 ° C

CCPPERCDWNG KNURLED THUMB

SCREW

The cell has been used to determine the transference

number of H + ion in dilute HCI solutions. Malachite
Green Oxalate4 indicator is more satisfactory than the
usually specified Methyl Violet in these experiments
because it does not decolorize. If a strip of white
paper is taped to the back of the condenser jacket the
ascending column of colored solution is much easier to
see.

' Present address: University of Wisconsin, Madison.

a DANIELS,FARRINGTON, MATREWS,JOSEPHH., ET AL., "EX-
perimental Physical Chemistry," 5th ed., McGraw-Hill Book
Co., Inc., New York, 1956, p. 150. SMITE,E. R., AND MACINNES,D. A,, J . Am. Chem. Sac., 47,
a LONGSWORTH, L. G., J. CHEM.EDUC.,11, 420 (1934). 1012 (1925).
* Eastman Kodak No. 1264. TOBEY,S. W., J. CHEM.Eoac., 38,517 (1961).

516 / Journal of Chemical Education