Paradox of the Activity Coefficient 7,
Ei-lchiro Ochiai
Junlata College, Huntingdon, PA 16652
The Paradox
Most modem physical chemistry textbooks deal with the
activities and activity coefficients of an ionic salt
(M,+Z+X,-2-) solution in the following way:
+
where n = n+ n-. It appears, therefore, that y+ represents
a kind of geometric mean of y+ and y-. Let us use the
simplest Debye-Huckel equation, which is derived in accord
with the notations given ahove, to calculate y values:
where A = - d l . "P'in this eauation is the ionic strength
. of
the solution.
Now let us do some calculations. Case 1:Let us add 0.1 mol
of CuSO4 to a 0.2 m NaCl(0.2 mol in 1000 g water). We are
interested in estimating y for Cu2+in the solution, but the
textbooks suggest that we should calculate a+ or y* instead;
so we do the following:
Since y+2= yc,yso,, it may be assumed that:
YC* = Y* = YSO, (4)
Then:
(Here NaCl is assumed, as usual, to he providing an ionic
environment).
Case 2: Next let us suppose that we add 0.1 mol of CuClz to
a 0.1 m NanS04 solution. A simple calculation will tell you
that the ionic strength of this solution is the same as that of
the first solution above. As a matter of fact, these two solu-
tions are chemically the same. But let us move on. We calcu-
late y+' (for CuC12) as follows:
Now, because y+'3 = ~ C , , ~ itCmay
I ~ , appear (to an uninitiat-
ed) that:
y,, = y,' = yc, (becausethis Leads to ycuyc? = Y*'~) (7)
Then:
In y,? = A(2+)(1-) = 2A or yc, = 7,' = exp @A) (8)
Here lies the paradox. We have come up with two different
y+ values, which are supposed to represent yc, in the two
chemically identical solutions.
lhs Solutlon and Suggestions
Fortunately or unfortunately, the kinds of examples and
exercises usually found in the textbooks do not encounter
this difficulty. Obviously, some assumptions or suppositions
are not valid in the argument above. But I suspect that an
average student would have a hard time solving this mystery
because no clue is given in the description above nor is any
good clue given in the textbooks.
The resolution of this paradox can be uncovered as fol-
lows: the supposition represented by eq 7, which may be
derived from the general implicit assumption made in the
first paragraph of this article, is invalid. Admittedly, no
textbook states that such a supposition is valid; in fact none
of them makes any comment on the relationship between y+
and the individual y+ or y- values (other than relevant to
that of eq 1,that is.). I t can be shown that yc, = yso, = y+ in
case 1is correct (within the Debye-Huckel approximation),
whereas in case 2 yc, = y+I2and y a = .\/y&'. Therefore, yc,
= y,(= exp (4A)) = yhf2(=exp (4A));thus, they are recon-
ciled.
The clue lies in the derivation of the DehytHuckel equa-
tion. Equation 2 is derived from the more fundamental
equation:
where Z; is the electric charge of an ionic species i. The
derivation (from eq 9) of the final limiting law for y+ (eq 2) is
rather circuitous, though legitimate. Equation 9, therefore,
occurs only in passing, and no significance seems to be at-
tached to it in most textbooks.
The problem, it seems, stems from the statements (made
in the textbooks) that (1)activities or activity coefficients
for individual ions cannot be measured because an individ-
ual ion cannot exist independently in a solution, and (2)
.- is the onlv meanineful measure of activitv
therefore.. r+
coefficient.
The activitv and. hence, the activitv coefficient of an indi-
vidual ion can, however, he measured-at least approximately
by, for example, an ion-selective electrode. The classical
glass electrode is an example. Therefore, statement 1does
not seem to be warranted, and the corollary 2 may need to be
abandoned, though it is still true that no solution containing
only one kind of ion is possible.
A logical solution to these problems would be to assume
that we should he able to calculate (at least conceptually)the
activity coefficient for an individual ion using eq 9 (or the
modifications thereof). A treatment of ionic activity based
on this equation would he, pedagogically, less confusing and
more crisp and straightforward. If one chooses, one can still
use the notation of y+ in comparing the experimental and
theoretical y values in appropriate cases; but now this can be
explicitly related to those of the individual ions.
Volume 67 Number 6 June 1990 489