Electrolyte Solutions: Activity Coefficients and Debye-Huckel

Theory Chemistry 243

David Ronis McGill University
To understand the thermodynamics of electrolyte solutions, we have to understand how
nature tries to keep systems electrically neutral. (WHY?). In particular, this leads to some additional definitions for the chemical potentials and activities. Consider the electrolyte dissociation
e1":A'r_

v +Az*

* v -8"-,

(l)
-,
where e

where v; is the stochiometric coefficient of the ith ion which has charge Zi, i = + or is the magnitude of the charge on an electron. There is some ambiguity in horv to think about the solution, i.e., as comprised ated ions or of undissociated molecules. Of course, in reality an equilibrium for Eq. established, and thus,
llA,.B,_ = V+llA^

of dissoci-

(l) will

be

* V-Pg"-. pi

(2) + RT h(o,),
(3a)

We've seen that chemical potentials can be written in terms of activities ds ltr = which in our case gives
F A,.8,-

FoA,*o,-

+ RT ln(a 4P,-),

A,. = lt'A,. + RT ln(a

4.),

(3b)

and
ltB,_ = ltoB"_+ RT ln(ag,_).

(3c)
appear. together, e.g., as

It tunrs out that the activities of the positive and negative ions always
the equation for the dissociation equilibrium: oui,-oti,
o

in

Ar.Br_

-K,
(4a)

cf. Eqs. (2) and (3). Because of this it is convenient to define meatr ionic activities as:

p*=v*FL.*v-Pe'- = pl+ RTlna+, V

with

v:

v++v_,

(4b)

Winter Term 2010

vPi= v+Fi"-'lv-P"s,_,
and

(4c)

a!*= au1,.d4.
Hence, the dissociation equilibrium becomes:
auL
_L'

(4d)

%-^
Finally, if we define a mean mole fraction as x! = x?x!- it follows from Eq. (4d) that the mean activity coefficient is given by = fi.f!-. for the activities of dilute electrolyte solutions. Since the undisnext consider model We a sociated molecule is neutral, v+z++v-z-=O.If pi is the concentration of the ith ion, then the fact that we start with a electrically neutral compound implies that

fl

lp;ezi =0.

(s)

Does electro-neutrality hold locally; i.e-, very near to one of the ions? Consider a statistical model for the local charge density. Based on our work on the kinetic theory of gases, we know that
Pro b ab il ity and for electrical problems

n exp(- Energt I k 6T),

(6)

it is reasonable to assume that Energt = ezi$(r)

(7)

p(r) is the electrical potential around one of the ions in the solution, here assumed to be at the origin of our coordinate system, Using these probabilities to moderate the local density, we
where
see that local charge density,

o(r)

is
p,

o(r) = L
i

"r

t exp(-u ig@)l k BT)

(8)

For a positive ion at the origin, we expect that Q@) > 0 and hence, Eq, (8) predicts a net excess negative charge density in the local vicinity of our ion. This is the physical basis of the phenomena of screening. If the elechostatic energies are small compared with thermal energies, i.e., e0@) << kpT,we can use the well known approximation for the exponential,

,2 -. *x*;-*"', e'=l
2

(e)

in Eq. (8) to show that

6(r)=where

2Ie2

W0Q)+"',

(10)

, =)>,p,,?

(l

l)

is called the ionic stength and has units of concentration (indee4 for l-l elecholytes it is simply the concenhation in molecules per unit volume). In obtaining Eq. (10) overall electro-neutrality, Winter Term 2010

Activities & Debye-Huckel Theory

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Chemistry 243

cf. Eq. (5), was used to eliminate the leading order terms.

How much charge will be induced by having an ion (with charge Q) at the origin? Gauss's law strongly suggests that the induced charge, cf. Eqs. (8) or (10), exactly balance the charge at the origin; i.e., local electro-neutrality will hold, and thus,

e=- !dro(r)=4n !* arto{i=2#

li *toe)

(r2)

where the second to last equalrty follows by switching to polar coordinates, and the final one by using Eq. (10). In the absence of screening, the potential is simply Coulomb's law; namely,

0U)=

+Eer

(l 3)

where e is the electric pennittivity of the solvent. How will this change if the charge is screened? To answer this requires some physics that is a bit beyond this course* and instead we'll simply guess the form of the screened potential, i.e.,

0?) = +fiEr {*o,,

(14)

where the exponential accormts for the screening and rp is lnown as the Debye screening wavevector. The screening sets in on a length scale of 22 = llro.

What is the screening length? To answer this last equality in Eq. (12); hence,

we'll impose local electro-neutrality, cf. the

,='# !; *r{*il
Thus, by solving for

2te2Q I ekBT *o

(ls)

rp,we

see that

(16) where the second equality is obtained when fte ionic sfiengtr and electron charge are expressed as mollm3 and the Faraday, I', respectively. For a l:l electrolyte in water at25C, this gives a screening length of

,,=
whaQ.

*=#

(io,i),

where c is the molar salt concentration; hence, the counter-ion cloud around any given ion in a 0.01M salt solution is about SO i.in radius (1o =30.44 but the cloud extends beyond .12 someSpecifically, as you will see in PHYS 242,yort necd to know Poisson's equation for the electric potential due to a charge distribution in a dielectric medium; i.e.,

Y'oe)= -o(r)le.
When Eq. (8) is used for the charge density, we obtain what is known as the nonlinear PoissonBoltmrann equation, which cannot be solved analytically for all but l-dimensional problems. When Eq. (10) is used the linearized Poisson-Bolhnann or Debye-Huckel equation is obtained; this can be solved in closed form and gives the result presented in the text.

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Activities & Debye-Huckel Theory

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Chernistry 243

How much work was done on the system nplacng the ion and the screening ions at the origin? Clearly,

w -- dr g{r)o(r) = o" [

li

&124Q)o(') = -

8rle2

f *]s2b\=-*rA w 8ne ksT to ' Y \"-

'

(17)
a

where we've again switched to polar coordinates and used Eqs. (10), (14), and mole of either of the ions, the work is just done is

(16). Thus, for

Narpdz!
8re
Of course, this is just another contribution to the non-PV work or chemical potential associated with dissolving the ith ionic species. Hence,
(18a)

or
(18b)

This is known as the Debye-Huckel limiting law and is valid at low concentrations (typically, it breals doum in the 0.005 to 0.01 M range). Note that the sign of the ionic charge is irrelwant and that lnyrnlt/2. With Eq. (18) it is easy to work out the mean activity coefficient; specffically,

,
=

---s 61lEst rDe2

rod
E

@*f,+v-*-1
V

(1ea)

67;'*'-,

(leb)

where the second relation follows by noting that the undissociated molecule is neutral.

Winter Term 2010