258 STANLEYBUKATA

A N D JACOBA. MARINSKY

12.66 and 3.35 cal./(mole OK.), respectively, for penta- lated by Westrum and Payne and, as such, is further
erythrityl fluoride. A sum of the two transitions in evidence for the proper choice of mechanism for the
each of these substances gives the disorder present observed transitions.
above their common lattice energy. Subtracting this Acknowledgment. This work was performed under
sum for the fluoride from that of the alcohol gives 26.0 the auspices of the United States Atomic Energy Com-
- 16.0 = 10.0 cal./(mole OK.). This is well within mission. The authors are indebted to Dr. Elfreda
experimental error of the 10.1 cal./(mole O K . ) calcu- Chang for assistance in the evaluation of the data.

Jobs Method of Continuous Variations with Ion Exchange

for the Study of Complexes in Solution

and Jacob A. Marinsky3

by Stanley Bukata1f2

Department o j Chemistry, State University o j Aew York at Buffalo, Buffalo, New York (Received J u n e 18, 1963)

The use of ion-exchange properties for determining the nature of complex species in solution
by Jobs continuous variations method has been developed. The CU+~-EDTA,Caf2-
EDTA, and Ca+2-citrate systems were studied to demonstrate the method. The results
obtained were in agreement with the results of earlier investigations of these systems.

Introduction resin. Assume that A and B react to form a single com-

Jobs method of continuous variations4 of isomolar plex according t o
solutions has been used frequently for the study of com-
plexes in solution. Solution properties, which are
A + nB AB, (1)
linear functions of the concentrations of the species in- Further, assume A undergoes cation exchange according
volved, are analyzed in applying the method. Some to the equation
properties which have been employed are refractive
index15heat of mixing6 densityI7dielectric constantI8
and light a b s o r p t i ~ n . ~A
~ solution
~ property adaptable (1) Union Carbide Predoctoral Fellow, 1961-1962.
to ,Jobs method and not previously discussed in the (2) This paper is based on a portion of a dissertation submitted by
S. Bukata in partial fulfillment of the requirements for the de-
literature is ion exchange. The discussion below is gree of Doctor of Philosophy.
given for cation exchange but would be similar for (3) Correspondence t,o be addressed to this author.
anion exchange. (4) P. Job, Ann. Chem., 9 , 113 (1928).
1st mixtures be made by the addition of z ml. of B to (5) G. Spacu and E. Popper. Bul. soc. stiints Cluj.. 7,400 (1934)
(VT - t) ml. of A when both solutions are a t a concen- (6) M. M. Chauvenet, P. Job, and G . Urbain, Compt. rend., 171,855
(1920).
tration of 114 moles/l. The symbol VT corresponds to
(7) Y. Wormser, Bull. aoc. chim. France, 15, 395 (1948).
the total volume of the mixtures which is presumed to N. Q. Trinh, Compt. rend.. 226, 403 (1948).
(8)
be essentially constant in the absence of appreciable (9) W .C. Vosburgh and G . R. Cooper. J . Am. Chem. SOC..63, 437
volume change on mixing. Allow these isomolar (1941).
solutions to undergo cation exchange with a suitable (10) R. K. Gould and W. C . Vosburgh, ibid., 64, 1630 (1942).

The Journal of Physical Chemistry

CONTINUOUS WITH IONEXCHANGE
VARIATIONS 259

where the subscripts S and R refer to the solution and

resin pha,se, respectively. The cation Pi must not form
a complex with B and B and AB, are expected to be ex-
cluded from the resin, being anionic or neutral entities. Thus, where C3 is a maximum or a minimum, n can be
In the presence of excess N, the ion exchange may often determined by use of eq. 17.
be represented by a linear equation In general, C3is not measured directly; instead use is
made of the ion-exchange property of the solution to
AR = k~As (3)
evaluate C3.
where An is the concentration of A in the resin phase at Letting Y equal the difference between the observed
equilibrium and A S is the concentration of A in the removal from solution of A by exchange with N and by
solution phase. At equilibrium, eq. 1, 2, and 3 must complexing with B (M(VT- x) - kDC1 - C,) and the
be satisfied simultaneously. Let calculated removal of A without complex formation
{ r n ( ~ T- x) - kDCl] then
Ci = (As) (4)
C2 = (B) (5)
C3 = (AB,) (6)
in a concentration region in which eq. 3 holds. Dif-
where the parentheses signify millimolar concentration. ferentiating eq. 18 with respect to x
Then for any mixture
dY - 1 dC3
c1 := M(VT - x) - c3 -- kDCl (7) dx 1 +
k~ dx
(19)
C2 = Mx - nC3 (8) where dCsdx = 0, dY/dx = 0, a plot of Y us. x will have
C1C2" = KC3 (9) a maximum or a minimum with Ca and eq. 17 continues
to be valid.
where K is the equilibrium constant for reaction 1.
The condition for a maximum or a minimum in the Experimental
curve of C3 plaltted against x is Several aqueous systems in which the complex species
dC3 were already well defined were studied to test the above
-=o treatment. Dowex-50-4x in the sodium form was used
dx
throughout. The concentration regions studied werle
Differentiating eq. 7, 8, and 9 with respect to x where the ion exchange was governed by a linear rela-

At dCs/dx = 0, the position of the maximum or mini-

0.8

0.7
i
mum z 0.6
-'

a 0.5
0.4

and 0.3

_- M
dCz 0.2
dx
0.1
substituting these values into (13)
0

and using eq. 7, 8, and 9 Figure 1. Cu +2-EDTA system, Job's plot.

Volume 68, Number 2 February, 1964

260 STANLEY AND JACOB A. MARINSKY
BUKATA

4.0
1 4.0

*0
.
3 3.0
X
h

2.0

1.0

10 20 30 40 60
X , ml. of EDTA.
Figure 2. Ca+LEDTA system,Jobs plot. 0
10 20 30 40 50
X , ml. of citrate.

tion. Constant ionic strength was maintained in the Figure 3. Ca+2-citrate system, Jobs plot.
solutions. The total volume of solutions used was 50
ml. sharply as would be expected for the existence of just
Results one complex species. We attribute this behavior to
the presence of more than one complex. The existence
Jobs plot for the CU+~-EDTAsystem is given in
of two calcium-citrate complexes has been noted in the
Fig. 1. Cupric nitrate (0.01 M) and the disodium salt
literature. l 1
of ethylenediaminetetraacetic acid (Na2H2EDTA)
The results obtained are in agreement with the litera-
(0.01 M) were used. An ionic strength of 0.52 was
ture. The treatment given is limited to systems where
maintained by means of sodium nitrate. The maxi-

only one predominant complex is formed. The method
mum occurs a t x = 25 corresponding to n = 1 in agree-
should be useful for those systems where other functions
ment with the literature.
of the concentration are not linear or involve large ex-
Figure 2 is Jobs plot for the Ca+2-EDTA system a t
perimental difficulties or costly equipment.
an ionic strength of 0.62; n = 1 in agreement with the
literature. Acknowledgment. Financial support through Con-
Jobs plot for the Ca+z-citrate system a t a pH of 6.6 tract No. AT(30-1)-2269 with the U. s.Atomic Energy
to 7.2 is given in Fig. 3. Sodium citrate solutions were Commission is gratefully acknowledged.
used as the source of ligand. A maximum occws where
(11) J. Schubert and J. W. Richter, J . Phga. Colloid Chem., 5 2 , 350
n = 1 but as x increases, the curve does not drop as (1948).

The Journal of Physical Chemistry