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0 views2 pagesSome considerations regarding the concept of electroneutrality in an electrolytical solution

Sep 11, 2019

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Some considerations regarding the concept of electroneutrality in an electrolytical solution

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Some considerations regarding the concept of electroneutrality in an electrolytical solution

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University of West Florida

PB~SBCOI~. FL 32504

for Solutions

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

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.

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

yields

' Newman, J. Electrochemical Systems; Prentice-Hall; Englewood evidently xc;z, # 0, or in other words, regions in which

Cliffs.

~, ~ ~~ ~.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

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.

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