Electrochemistry Ionic activity, mean activity coefficient

Activity Activity of a molecule or ion in a solution is referred to as effective concentration. Recalling the definition of activity from equilibrium thermodinamics a= mi m0

m0 is the standard concentration, (1 mol kg-1), mi the molality of ith component of a solution, is the concentration dependent activity coefficient. Both a and have no unit. On diluting the solution, i.e. c0 1 then a c

activity becomes equal to the concentration. In very dilute solution interactions are insignificant and concentration and effective concentration are the same. Though, activity and activity coefficient have no unit their values depend on the concentration units used. E.g., concentration of the same solution can be given in units molkg-1, moldm-3, molar fraction and so on. Ion activity Activities of ionic solutions serve us for calculating accurate chemical potentials accurate equilibrium constants Taking into account the activity has a greater importance in ionic solution than that of non-electrolytes. Intermolecular forces are greater among ions. Ions in aqueous solution. Strong electrolytes are the ionic compounds that completely dissociate into ions when they are dissolved. NaCl(aq) Na+(aq) + Cl(aq). The chemical potentials for the formation of ions,
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 NaCl, aq =

Na + , aq

Cl , aq

which also implies that standard chemical potentials

0 NaCl, aq = 0 Na + , aq

+ 0

Cl , aq

We also know that we can (must?) write

0 NaCl, aq = NaCl, aq + RT ln aNaCl, aq

When working with ionic solutions we would like to be a little more specific about the activities of the species in solution. It is customary to use units of molality, m, for ions and compounds in water solution. If the solutions were ideal we could write ai = mi m0

and the chemical potential would be written

i = i0 + RT ln

mi mi0

Two things must be said about this equation. First, it must be understood that there is an implied mio dividing the mi inside the logarithm, and second, the standard state is the solution at concentration mi = mio. Usually we set mio = 1 mol kg-1. However, ionic solutions are far from ideal so we must correct this expression for chemical potential for the nonidealities. As usual, we will use an activity coefficient, , and write the activity as

ai =

mi i mi0

and consistent with what we have been doing, we will set mio to 1 molal and not write it in the equation. The form of equation indicates that activity and activity coefficient are dimensionless, i.e. they have no unit.Thus the chemical potential will be written

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 i = i0 + RT ln mi i
The standard state for this equation is a hypothetical standard state. The standard state is not actually realizable. We are using the so-called Henry's law standard state in which the solution obey's Henry's law in the limit of infinite dilution. That is, i 1 in the limit when mi 0. We will simplify matters by writing m+ , + and m , for the molalities and activity coefficients of the positive and negative ionic species, respectively. We will also refer to the ionic compound simply as the "salt." With this notation we can rewrite former Equations as,

salt = + +
or
0 0 0 salt + RT ln asalt = + + RT ln m+ + + + RT ln m .

In a simplified form
0 0 0 salt + RT ln asalt = + + + RT ln m+ + m

The sum of standard chemical potentials is equal to that of the salt

0 0 0 salt = + +

The logarithmic term on the left is identical to the logarithmic term on the right,

RT ln asalt = RT ln m+ + m
from which we conclude that

asalt = m+ + m

The activity coefficients, + and can't be measured independently because solutions must be electrically neutral. In other words, you can't make a solution which has just positive or just negative ions. You can't calculate the individual activity coefficients from theory, either. However, you can measure a "geometric mean" activity coefficient and, within limits, you can calculate it from theory.
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Geometric mean. Geometric mean. Numbers like x1, x2,xn form a geometric mean which can be given as, m = n x1 x2 ...xn The actual form of the geometric mean depends on the number of ions produced by the salt. Right now we will define it for NaCl and then give more examples later. For NaCl we define,
2 + =

or

( + )

1 2

+ = which says that It turns from the form of eqution above that equal amount of activity coefficient property is divided to positive and negativ ions.
So,
2 asalt = m+ m

But for a NaCl solution of molality, m, we have m+ = m and m = m so that

2 asalt = m 2

Keep in mind that this is for NaCl, but it is correct for any one-to-one ionic compound. Try MgCl2, MgCl2 Mg2+ + 2 Cl
0 salt + RT ln asalt = 0 2 + + RT ln mMg 2 + + + 20 + 2 RT ln mCl Mg Cl 0 2 salt + RT ln asalt = 0 2 + + 2 0 + RT ln m+ + m 2 Mg Cl

so
2 asalt = m+ m 2 +

But for MgCl2 at molality, m, we know that m+ = m and m = 2m. Further, we define the geometric mean activity coefficient by,
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1 2 + 3

Then
asalt = m ( 2m ) 2 3 = 4m 3 3

Other ionic compounds are done in a similar manner. After some practice you can probably figure out the expression for asalt just by looking at the compound. Until then, or when in doubt, go back to the expressions for chemical potentials as we have done here. (For practice you might want to try Al2(SO4)3.). General formula Absolute activities of cations and anions can not be determined experimentally. The definition of the mean activity coefficient depends on the number of ions into which a molecule dissociates when it is dissolved. In the laboratory it is impossible to study solutions which only contain one kind of ion. Instead, solutions will have at least one positive and one negative type of ion. For the generic electrolytic compound dissolving in water: A x By xA z + + yBz
x x we will find terms such as aA aB in eqilibrium constant, Ka and in reaction quotient, Q values. Expressing such products in terms of molalities and activity coefficients, we first note that for a solution containing A x By component of concentration m, the ion concentrations are [A] = xm and [B] = ym. The activity product then becomes:
x y y aA aB = ( A mA ) x ( BmB ) y = ( A xm ) x ( B ym ) y = x x y y m ( x + y ) x B A

We can define a mean activity coefficient as: = x y A B

)1/( x+ y )

x y and this allows us to rewrite equation as: aA aB = x x y y m ( x + y ) (x + y )

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Relationship between Ka and Km The equilibrium constant given in terms of activities is the thermodynamic equilibrium constant. Use an example of dissociation equilibrium of a weak acid to show this relationship; HA H+ + Athe equilibrium constant of the reaction, (introducing the standard concentration, mo again)

Ka =

a+ a m+ + m 1 = aHA mHA HA mo

Knowing
2 + =

and m+ = m- = m
2 a+ a m2 Ka = = aHA mo mHA HA

K a = K c K
where

m2 Kc = o m mHA

2 K = HA

The equilibrium constants given in terms of molality and activity coefficient. Ka = f(T,p) but independent of molalities.

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Debye-Hckel Limiting Law. Theoretical calculation of . The Debye Hckel limiting law gives the in terms of the ionic strength, I, defined as,.

I=

1 mi zi2 2 i

where zi is the charge on ion i, and mi is the molality of ion i and The ionic strength, I emphasizes the charges of ions because the charge numbers occur as their squares. Examples a. What is the value of ionic strength of HCl solution with molality 0.010: mH+ = mCl- = 0.01 mol/kg, zH + = zCl = 1
2 2

I=

1 0.01 ( + 1) 2 + 0.01 ( 1) 2 = 0.01 mol kg -1 2

b. the ionic strength of 0.10 molal Na2SO4

We must include all ions in the solution. The ionic strength is a measure of the total concentration of charge in the solution. Notice that it includes contributions from both the number of ions in the solution and the charges on the individual ions. Mean activity coefficient determination via calculation: Debye-Hckel theory The chemical potential or activity of ions cannot be determined on a purely thermodynamic basis.

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This is due to the fact that the effects of an ion cannot be separated from the effects of the accompanying counter-ion, or in other terms, the electrochemical potential of the ion cannot be separated into the chemical and the electrical component. Such a separation must necessarily be based on a nonthermodynamic convention. The mean activity coefficient can be calculated at very low concentrations by the Debye-Hckel Limiting Law

lg = A z+ z I 1 / 2
where A = 0.509 / (mol kg-1)1/2 for an aqueous solution at 25 oC, in general, A depends on the relative permittivity of solvent and the temperature. The log10 of mean activity coefficient also depends on the product of

z+ z

the absolute value of cation and anion charge number. When the ionic strength of the solution is too high for the limiting law to be valid, it is found that the activity coefficient may be estimated from the extended Debye-Hckel law.

lg =

0.511 z+ z I 1 / 2 1 + b I1/ 2

Where b is a measure of distance between ions. In the limit of small concentration I1/2<< 1, and in the denominator of Eq. I1/2 can be neglected, therefore we receive Debye-Hckel Limiting Law again. Lets try to make sense of our equation for the mean activity coefficient by taking it apart

= 10

0.511 AB

I 1/ 2 , where A = z + z ; B = 1 + I 1/ 2

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A Greater charges produce more negative the argument for the exponential, is farther away from 1, its ideal value. B The term B varies between 0 and 1. When I is small B ~ 0, and ~ 1. Example: for A = 1, B = 0.001, the argument for the exponential is -0.000511, and

= 10 0.000511 = 0.9988
Calculating ionic strength Calculate I for a solution that is 0.3 molal in KCl and 0.5 molal in K2Cr2O7.

1 mK + 12 + mCl ( 1) 2 + mCr2 O 7 ( 2 ) 2 2 mK + = mKCl + 2 mK 2Cr2 O 7 I= I = 0.5 (1.3 + 0.3 + 2 ) = 1.8

(KCl)

)
mol/kg

0.511 1 1.81 / 2 lg = = 0.2928 1 + 1.81 / 2

= 0.5096 ,
(K2Cr2O7)

lg =

0.511 2 1.81 / 2 1 + 1.81 / 2

= 0.5855

= 0.26

Therefore ionic activities are clearly dependent on the overall composition of the solution.

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