Introduction

An activity coefficient is a factor used in thermodynamics to account for deviations from ideal behaviour
in a mixture of chemical substances.[1] In an ideal mixture, the microscopic interactions between each
pair of chemical species are the same (or macroscopically equivalent, the enthalpy change of solution
and volume variation in mixing is zero).activity coefficient of an electrolyte solution is used to factor in
the concentration-dependent interactions between ions in a solution. Activity coefficient, in chemistry,
the ratio of the chemical activity of any substance to its molar concentration.

activity (symbol a) is a measure of the "effective concentration" of a species in a mixture, in the sense
that the species' chemical potential depends on the activity of a real solution in the same way that it
would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the
American chemist Gilbert N. Lewis in 1907.[1]

Properties of activity coefficient

The activity coefficient of a species is a measure of the effectiveness with which that species influences
an equilibrium in which it is a participant. In very dilute solutions in which the ionic strength is minimal,
this effectiveness becomes constant, and the activity coefficient is unity.

Importance of activity coefficient in ionic solution

An ionic solution is a solution containing ions. Ionic solutions are formed by dissolving ionic compounds
in a solvent (typically water). An example of an ionic solution is common salt (sodium chloride, NaCl)
dissolved in water. Substances that give ions when dissolved in water are called electrolytes. They can
be divided into acids, bases, and salts, because they all give ions when dissolved in water. These
solutions conduct electricity due to the mobility of the positive and negative ions, which are called
cations and anions respectively.

-The activity coefficient is used to both calculate molar solubility from Ksp and to calculate pH for
solutions of ionic compounds in water.In solutions, the activity coefficient is a measure of how much a
solution differs from an ideal solution—i.e., one in which the effectiveness of each molecule is equal to
its theoretical effectiveness and thus the activity coefficient would be 1.

-The activity coefficient gives us a simple empirical expression for the properties of this solution as
compared with a perfect solution of the same composition.

Activity coefficient of an ideal solution

An ideal solution is a mixture in which the molecules of different species are distinguishable, however,
unlike the ideal gas, the molecules in ideal solution exert forces on one another. When those forces are
the same for all molecules independent of species then a solution is said to be ideal.The ideal Solutions
are those which obey Raoult's Law at all concentrations and Temperatures. Some examples of ideal
solution liquid pairs are benzene and toluene, n-heptane and n-hexane, ethyl bromide and ethyl iodide,
chlorobenzene and bromo benzene etc.

*In an ideal solution the activity coefficient = 1, and the activity of the component is equal to its mole
fraction. In general, the greater the amount of dissolved material, the lower the activity coefficients of
each of the species present.

Characteristics of Ideal Solutions

-They follow Raoult's Law.

-The enthalpy of mixing of two components should be zero, that is, Δmix H = 0.

-The volume of the mixing is equal to zero that is, Δmix V = 0.

-The solute-solute interaction and solvent-solvent interaction is almost similar to the solute-solvent
interaction.

Ideal Solutions generally have characteristics as follows: They follow Raoult's Law. This implies that the
partial pressure of components A and B in a solution will be PA = PA0 xA and PB = PB0 xB . PA0 and PB0
are respective vapour pressure in pure form.

Activity coefficient of a neutral molecule

Neutral molecules, such as benzene and acetic acid, have no ionic atmosphere because they have no
charge. To a good approximation, their activity coefficients are unity when the ionic strength is less than
0.1 M (i.e., set γ = 1 for neutral molecules).

How to calculate activity coefficient from ionic strength

Ionic strength is the concentration of ions in a solution. Ionic compounds tend to dissociate and split into
ions upon dissolving in water. Ionic strength is one of the most important properties of an electrolytic
solution. The unit of ionic strength is mol/L of solution (mole per litre) or mol/kg of solvent (mole per
kilogram). The unit depends on whether you used the molarity formula or molality formula to calculate
the ionic concentration.

As the ionic strength of the solution increases, the ionic atmosphere around an ion becomes stronger.
You can see this visually in this figure appearing here.
Figure 2: Stronger ionic strength leads to a stronger ionic atmosphere and less attraction between ions

It is defined as ∑Cizi2/2, where Ci is the molar concentration of the ion species i and zi is the net charge
of the ion i. As the ionic strength of a solution increases, the activity coefficient (γ) of an ion decreases
according to the Debye–Hückel limiting law, log γ = −0.509z2I1/2.

Derivation of Ionic Strength Formula

The ionic strength formula calculates the sum of each ion’s molar concentration multiplied by the
valence squared.

I=12∑ni=1ciz2i

Here, half the term ½ is because we consider both the ions as cation and anion. Furthermore, c refers to
the concentration in molar units’ mol/L. Moreover, z refers to the charge of each ion. For example, ions
contained in sulfate (SO2−4) z = 2. Therefore, the multivalent ion has a bigger contribution.

Ionic strength calculation formula

The ionic strength of a solution is dependant on the ionic concentration and charge on the ions. The
ionic strength calculation formula is written as follows:

I = 1/2 * ∑(ci * zi2)

where:

I - Ionic strength;
∑ - Sum of values;

ci - Concentration of ions; and

zi2 - Charges of ions squared

Example 1 shows how a salt's ionic strength is different than its molar concentration. Tapparent and real
concentrations are not the same.

Calculation of ionic strength of MgCl2

Reference
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Stokes, R. H; Robinson, R. A (1948). "Ionic Hydration and Activity in Electrolyte Solutions". Journal of the
American Chemical Society. 70 (5): 1870–1878. doi:10.1021/ja01185a065. PMID 18861802.

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