CH 48 School of Science and Engineering, ATENEO DE MANILA UNIVERSITY

Experiment 1: The Glass Electrode and Measurement of Activity

Coefficients
1. Introduction

The pH meter is the most commonly used apparatus for measurement of pH and in acid-base
potentiometric titrations. The commercial pH electrode is usually a combination electrode in which the glass
electrode and the reference electrode (usually the Ag/AgCl electrode) are housed in one probe. The probe (cell)
is described as follows:

Glass membrane

Ag(s) | AgCl (s) | Cl- (aq) || H+ (aq, outside) H+ (aq,inside), Cl- (aq) | AgCl(s) | Ag(s)

The pH-sensitive part of the electrode is the thin glass membrane (~ 0.1 mm) that is sensitive to the
activity of H+ ions in solutions---it is a type of an ion-selective electrode. The glass membrane is made of
silicate network in which the negatively charged oxygen atoms are coordinated with monovalent Na+ ions.
These ions have some mobility in the network. The inner and outer surfaces of the glass membrane form
hydrated gels (~ 10 nm thick) which are in ion-exchange equilibria with the H+ ions of the surrounding solution.
A potential develops due to the difference in the activities of the H+ in the internal and external solution, but this
potential is transmitted across the membrane through the Na+ ions; no actual transport of H+ across the glass
membrane occurs.

A Nernstian equation gives the potential between the inner and outer surfaces of the glass electrode:

E = K - (RT/F) ln [aH+ (inside)/ aH+ (outside)] (1)

where K is the asymmetry potential due to differences between the inner and outer surfaces of the glass
membrane, and it includes also such effects as liquid-junction potential and others. The K value is corrected by
calibrating the electrode against standard buffer solutions. Since the inner electrode has a contant concentration
of H+ (and Cl-), then (1) can be written as:

E = Ego + (RT/F) ln aH+ (outside) (2)

or
E = Ego - 2.303 (RT/F) pH (3)
o
where Eg is a lumped constant.

The activity of a univalent electrolyte, such as HCl, is expressed as:

aH+ aCl- = a2 = 2 m2 (4)

where  is the mean ionic activity coefficient and m is the molality of solution. The Debye-Hückel Limiting
Law for dilute aqueous solutions at 25 oC is given by:

log  = - | z+ z-| (0.509) I1/2 (5)

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CH 48 School of Science and Engineering, ATENEO DE MANILA UNIVERSITY

where I is the ionic strength:

I = (1/2)  zi2 mi (6)

Using equations (4) to (6), (2) may also be written as (at 25 oC):

E = Ego + (RT/F) ln ( m)

= Ego + 2.303 (RT/F) log  + 2.303 (RT/F) log m

E = Ego - (0.0301) m1/2 + 0.0592 log m (7)

E - 0.0592 log m = Ego - (0.0301) m1/2 (8)

The Eg can be determined from experimental values of E and m; thus, the values of aH+ and  for every m
o

may then be calculated.

2. Procedure

Prepare 1.0, 0.1, 0.05, 0.025, 0.0125, and 0.00625 M HCl solutions. The exact molar concentrations of
these solutions must be determined by titration against standard NaOH solution using phenolphthalein end point
(freshly boiled, distilled water must be used to prepare the NaOH solution). To convert to molalities, the
densities of various HCl solutions may be looked up in a handbook. The cell electromotive force for each of the
HCl solutions will be determined using a pH meter with mV scale and pH electrode. Follow the instructions in
calibrating the electrode, also taking note of the proper use and care of the instrument. Data should be collected
on duplicate runs.

3. Data Analysis
1/2 o
A plot of the left-hand side of (8) versus m should give the Eg . The values of the activities and
activity coefficients of H+ may then be calculated. The result should be discussed in your report.

A discussion of how the standard potential and activities of other electrolytes may be measured should
also be included in your report. How is knowing the standard cell potential useful? What would be the effect
on your results of the assumption that the working temperature is 25 oC?

4. References

Atkins, P. W. Physical Chemistry, 5/e (ELBS, Oxford, 1994).

Daniels, F. D., R. A. Alberty, J. W. Williams, C. D. Cornwell, P. Bender, and J. E. Harriman, Experimental
Physical Chemistry, 7/e. (McGraw-Hill, New York, 1970)
Ewing, G. W. Instrumental Methods of Chemical Analysis, 4/e (McGraw-Hill, Int’l Student Edition, 1975).
Harris, D. C. Quantitative Chemical Analysis, 2/e (W. H. Freeman Co., New York, 1987).
Shoemaker, D. P. and C. W. Garland, Experiments in Physical Chemistry, 2/e (McGraw-Hill Kogakusha,
Tokyo,
1967).

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