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Edited by

textbook forum RALPH K. BIRDWHISTELL

University of West Florida
PB~SBCOI~. FL 32504

A Note on the Meaning of the Electroneutrality Condition

for Solutions

M. Sashe and J. A. Santaballa

Colexio Universitario de A Corutia, Universidad de Santiago de Compostela. A Coruiia, Spain

It is common for textbooks of general or even physical

chemistry to state that the activity coefficients and solvation
energies of individual ions cannot be determined. Closely
related to this notionis the practiceof enunciating theprem-
ise that an electrolyte solution as a whole is electrically
neutral, or in mathematical terms
xqz; = x e + z + + ~ C J -= 0 (1)
where the c's and 2's are, respectively, the charges and con-
centrations of the ions in solution.
Weare not the first to point out that theelectricalneutral-
Figure 1. Limiting dlstrlbutlons of equal amounts of charge in a neutral mcrc-
itv condition expressed in ea 1 is far from unambiguou~.'.~
hat a given region of spacemust always contain the same scapic volume. The doned circle represems a Qussian sphere containing
nonzem net charge.
number of charges of either sign, thus ensuring its macro-
scopic neutrality, is something that cannot be deduced from
Maxwell's laws.
In the case of solutions of electrolytes, the distribution of
ions at a given temperature must he compatible with that
which, being more favorable energywise, would be attained
at that temperature by a set of positive and negative charges
in eoual numbers in a dielectric medium. The situation of
nat&ly occurring solutions is therefore more like that of
Figure l a than that of Figure lb, though in both cases
Figure 2. Hypothetical selup for me pmducWan of elechically charged solu-
Z4++X4-=0 tions.

in the volume V considered.

Figure 1serves to emphasize that eq 1is valid only when a where p is the volumetric charge density and 6 is the dielec-
macroscopic volume is considered; otherwise, it is always tric constant.
nossible to find a Gaussian s ~ h e r ein which the net charge Since
differs from zero and eq 1 is'not complied with. The more
carefullv worded textbooks accordinnlv refer to ea 1 as the
~ e r n s t k l a n c kmacroscopic electricai neutrality cindition.3 where 4 is the electric potential, eq 2 becomes Poisson's
The macroscopic electroneutrality condition as presented equation
above does not deny the possibility of situations such as that
shown in Figure l b in which all the charges within a large
volume have been separated, for the solution as a whole in
this figure is electrically neutral.
The reason why such distributions do not in practice occur or in the present context
is based on Gauss's law, whose differential form is
div E = -PIC (2)
where F is the Faraday unit. Rearrangement of eq 5 now

whose left-hand side is the same as in eq 1. If VZ6 z 0,then

' Newman, J. Electrochemical Systems; Prentice-Hall; Englewood evidently xc;z, # 0, or in other words, regions in which
~, ~ ~~ ~.a 72.
New Jersev. 1973: -
there is a nonzero potential gradient will have volumes in
Ibl. N. ~ompr&sive Trea?iseofEIacb~~hemis~;Plenum: New
York, 1983: Vol. 6, p 39, which the charges of opposite sign do not exactly balance
Schultz. S. G. BaSic Principles of Transport Membranes; Cam- eachotber. It should nevertheless be noted that the constant
bridge University: Cambridge. 1980; p 133. factor on the right-hand side of eq 6 is very small. If, for

Volume 66 Number 5 May 1989 403

example, the solvent is water, which has a dielectric constant Conclusion
of ahout 79, the constant factor in eq 6 is of the order of 10-13. As we have stressed above, it is necessary to make it clear
This means that very intense electric fields will be required to students that the Nernst-Planck macroscopic electrical
before xcizi will differ significantly from zero, and vice neutrality condition is not a fundamental law of nature,
versa; the existence of electrically charged regions in a solu- though it is an excellent approximation to reality.
tion will generate enormous potential gradients. So, the ex- At the same time, it should be pointed out that, because of
periment indicated in Figure 2 is, in practice, very difficult the law of electrostatics, eq 1is satisfied in each and every
to perform. For the same reason, it is not easy to produce net macroscopic region of the electrolyte solution and that this is
electric charge in solutions that have been prepared from the reason why it is impossible to prepare electrically solu-
electrically neutral chemicals. tions to measure physicc-chemical quantities.

404 Journal of Chemical Education