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

mi
a
m0

m0 is the standard concentration, (1 mol kg-1),

mi the molality of ith component of a solution,
γ is the concentration dependent activity coefficient. Both a and γ have no unit.
On diluting the solution, i.e.

c→0 γ→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 mol·kg-1, mol·dm-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.

When ionic compounds dissolve they are completely dissociated into ions. A
strong electrolyte will form.

NaCl(aq) → Na+(aq) + Cl−(aq).

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This way of stating it includes compounds like AgCl, which are not regarded as
soluble ionic compounds, but do give very small concentrations of ions in water
solution.

The chemical potentials for the formation of ions,

μNaCl,aq  μ μ
Na  , aq Cl  , aq

which also implies that standard chemical potentials

0 0 0
μ NaCl, aq  μ Na  ,aq  μCl  ,aq

We also know that we can (must?) write

0
μ NaCl,aq  μ NaCl, aq  RT ln a NaCl,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

mi
ai 
m0

and the chemical potential would be written

mi
i  i0  RT ln
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, γ , and write the activity as

mi  i
ai 
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

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coefficient are dimensionless, i.e. they have no unit.Thus the chemical potential
will be written

 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,

γ i → 1 in the limit when mi → 0.

We will simplify matters by writing m+ , γ + and m− ,γ − 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      

0
or  salt  RT ln asalt   0  RT ln m    0  RT ln m  .

In a simplified form
0
salt  RT ln asalt   0   0  RT ln m    m 

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

0
 salt   0   0

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, γ + and γ − 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

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from theory. 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,
1
       2 or       2   
It turns from the form of eqution above that      which says that
equal amount of “activity coefficient property” is divided to positive and negativ
ions.

So,

asalt  m  m 2

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

asalt  m 2 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   0Mg2   RT ln mMg2     2 0Cl  2 RT ln mCl  

0
salt  RT ln asalt   0Mg2   2 0Cl   RT ln m    m2  2

so

asalt  m m2   2  

But for MgCl2 at molality, m, we know that m+ = m and m− = 2m. Further, we

define the geometric mean activity coefficient by,

 
1
2
   3

Then

asalt  m   2m  2   3  4m 3 3

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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 

we will find terms such as aAx a Bx 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:

  
aAx a By    A mA  x   BmB  y    A xm  x   B ym  y  x x y y m  x  y   xA  By 
We can define a mean activity coefficient as: 
    xA  yB 1/  x y 
and this allows us to rewrite equation as: aAx aBy   x x y y m  x  y   x  y 

For MgCl2
2
a Mg  aCl 1

-  1 2
2

m 3 3  4m 3 3

Relationship between Ka and Km

The equilibrium constant given in terms of activities is the thermodynamic
equilibrium constant.

Use an example to show this relationship;

AgCl(s) → Ag+(aq) + Cl−(aq).

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 a a
Ka  m  m   m m 2
1

The activity of AgCl is one as it is a one component heterogeneous phase.

Then,

Ka
m m   Kc
 2

If we are just dealing with AgCl in water the concentrations of the ions are
pretty small so γ ± is approximately unity. If, however, we are dealing with the
common ion effect, for example, the solubility of AgCl in 0.10 m HCl, then the
γ ± for the ions in this stronger solution is not equal to one, not even
approximately so.

Which takes us to the Debye-Hückel Limiting Law.

Theoretical calculation of γ ± .

The Debye Hückel limiting law gives the γ ± in terms of the ionic strength, I,
defined as,.

1
I 
2 i
mi zi2

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,
2 2
0.010 m HCl: mH+ = mCl- = 0.01 mol/kg, zH   z  1
Cl

I
1
2
 
0.01    1 2  0.01    1 2  0.01 mol  kg -1

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0.10 m 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-Hückel theory

The chemical potential or activity of ions cannot be determined on a purely
thermodynamic basis.
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 non-
thermodynamic convention.

In Debye-Hückel theory ionic atmosphere has a central role.

The mean activity coefficient can be calculated at very low concentrations by

the Debye-Hückel 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 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-Hückel law.

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  0.511  z  z I 1 / 2
lg   
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-Hückel Limiting Law again.

Let’s try to make sense of our equation for the mean activity coefficient by
taking it apart

I 1/ 2
   10 0.511 AB , where A  z   z ; B 
1 I
1/ 2

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.

I
1
2

 mK   12  mCl     1 2  mCr2O 7    2 2 
mK   mKCl  2  mK 2Cr2O 7 mol/kg
I  0.5  1.3  0.3  2   1.8

  (KCl)

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  0.511  1 1.81 / 2
lg     0.2928
1  1.81 / 2

   0.5096 ,

  (K2Cr2O7)

 0.511  2 1.81 / 2
lg     0.5855
1  1.81 / 2
   0.26

Therefore ionic activities are clearly dependent on the overall composition

of the solution.

Mechanism of conductivity: relaxation effect

When electric field is on. The potential directs central ion to move toward the
electrode with opposite charge. The rearrangement of asymmetric ion
atmosphere takes time. During this time the central ion is dragged by this
asymmetric field. This reduction of ions’ mobility is called the relaxation effect.

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 Figure 3. a. A distribution of chloride ions around a sodium ion in crystalline
NaCl; b. distribution of chloride ions around a sodium ion in solution. This
distribution is very similar, but less organized and the interionic distances are
larger. There are still more chlorides around the sodium ion than sodium ions.

Figure 4. Relaxation. a. a stationary central positive charge with a spherical,

symmetrical positioning of negative and positive charges; b. a positive charge
moving to the right. The ion atmosphere behind is relaxing while that in front is
building up. The effect is an asymmetric distribution of negative charges.
 
Mechanism of conductivity: electrophoretic effect.
The ionic atmosphere and central ion have opposite charge both of them
surrounded by solvent molecules. They migrate opposite direction, positive ions
upstream of negative ions, therefore they impede each other in motion parallel to
the electric field.

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