CHEM 355

Experiment 5
Determination of Activity Coefficients
of Hydrochloric Acid Solutions

The deviation of a solution from ideal behavior can be represented by means of activity coefficient ().
The activity coefficient, based upon molality (m) is defined as:

where a is the activity. An ideal solution is defined as one for which  is unity, but for a non-ideal
solution it differs from unity. However, even for non-ideal solutions, in the limit of zero ionic strength,
the activities of ions are equal to their concentrations. The activity coefficients, thus, become unity in
the limit of zero ionic strength. The ionic strength I is defined by the expression;

where ci is the concentration and is the charge of the ions of type i. The Debye-Hückel "limiting law"
predicts the mean ion activity coefficient (+) by the equation:

where , are the charges of anion and cation respectively. The constant A has the value 0.509 at
25 °C for aqueous solutions. For 1:1 (uni-univalent) electrolytes and I = m

 (4)

But this simple Debye-Hückel limiting law is valid for only very dilute solutions. In practice deviations
from the limiting law become appreciable in the concentration range from 0.005 to 0.01 molar.
Guggenheim has shown that the mean activity coefficient, obeys the following relation up to 0.2 molal
concentrations for 1:1 electrolytes.

where is a function of ‘interaction coefficients’ for each possible cation-anion combination, and
“ = 0.5084” at 25 °C.
There are several methods for the determination of activity coefficients. The measurement of
electromotive force of a cell is one of the most convenient methods.

Consider the following cell:

Pt, QH2| HCl(xM)| KCl(1M)| Hg2Cl2| Hg

(xM means that different molarities of HCl solution are used.)

The half reaction for the right electrode is; Hg2Cl2(s) + 2e 2Hg (l) + 2Cl and the half-cell potential is;
- -

At 25 C

The left side is quinhydrone electrode. The electrode reaction is;

1/2 Q + H+ 1/2 QH2

The Nerst Equation is;

In a saturated solution of quinhydrone the concentrations of quinone (Q) and hydroquinone are equal
and the activities are equal. Hence = ; so that

The overall cell potential E is;

Where

Furthermore since and 

For HCl, =m
Substituting  in Eqn 10:

Substituting the value of   into Eq 12 and rearranging to obtain final

equation given below:

At infinite dilution, the solution behaves ideally and then “a” and “ ” are identical, thus ‘ ’ is unity.
Hence when the left hand side of Eq 10.13 is plotted vs , extrapolation to intercept results the value
of . is then obtained from the slope. Values of  can be determined from equation ( 
) for various molalities.

Purpose: The purpose of this experiment is to calculate “mean ionic activity coefficient of HCl”.

Apparatus and Chemicals

Electrodes:

a. Saturated Calomel Electrode Hg/Hg2Cl2: It will be used as reference electrode. Wash this
electrode thoroughly with water and 0.1M HCl.

b. Quinhydrone Electrode: This consists of a quinone-hydroquinone redox system, with electrical

contact made by a platinum wire.

Solutions:

Reagent grade hydrochloric acid is used in all experiments. The concentration of 0.1 M HCl is
calculated after a determination of its density, more dilute solutions are made by dilution of this
standard.
Procedure:

1. Prepare 40 mL of 0.02 M, 0.04 M, 0.06 M, 0.08 M and 0.1 M HCl solutions.

2. Saturate the HCl solution with quinhydrone, stir vigorously, and wait 15 minutes to reach equilibrium.

3. Wash the electrodes thoroughly with water and 0.1 M HCl.

4. Measure the electromotive force (E.M.F) for each solution (as in figure 1).

Figure 1. The experimental set-up for the determination of the electromotive force for each solution

Treatment of Data:

1. Plot the left hand side of the Eq 13 vs. m using the E.M.F values (E) of the solutions

2. E° from the intercept of the straight line.

3. Find B values from the slope.

4. Calculate the values of ± of the solutions from Eq 5.

5. Calculate your errors. (Compare your experimental value of ± with literature values given for HCl
solutions of different concentrations.)

6. Calculate what the error would be if Eq 3 were used instead of Eq 5.

Discussion

1. Why do we use a reference electrode to find E.M.F.?

2. Why do we use saturated solution of quinhydrone?

3. Compare your results with theoretical ones.

DATA SHEET Experiment 5. Determination of Activity Coefficients of
Hydrochloric Acid Solutions

Group Number:…………………………………Group members:……………………………………………

Date……………………………………………. Assistant name and signature:………………………………

1. Fill the following Table.

HCl (M) E.M.F.(V) Left side of Eq 13

0.02

0.04

0.06

0.08

0.1

2. Plot left side of Eq 13 versus molality of HCl solution.

Find B from the slope of the line.

3. Calculate ± for each molalities of HCl solution using Eq 5 and also Eq 3. Fill in the following
table.

HCl (M) ± (from Eq 5) ± (from Eq 3)

0.02

0.04

0.06

0.08

0.1