GUEST AUTHOR
I Textbook Errors, 74
Richard A. Durstl
Boston College Mechanism of the Glass
Chestnut Hill, Massachusetts
Electrode Response
Although glass membrane electrodes
have been studied since the early twentieth century,
the mechanism by which the electrode potential de-
velops in response to hydrogen ion activity has only
recently been clarified by critical experiments. Nu-
merous theories of the glass electrode potential forma-
tion have been proposed. Among them, the most
widely accepted were the adsorption-potential, the
membrane-potential, and the phase-boundary-potential
theories, all of which give satisfactory explanations
of the glass electrode behavior.
The adsorption-potential theory postulates an ad-
sorbed layer of hydrogen ions on the glass surface
causing a potential drop at the glass-solution interface,
corresponding to the difference in chemical potential
between the free and adsorbed ions. However, this
theory predicts a change of less than 59 mv per pH unit
change and cannot explain the glass electrode behavior
in strongly acidic or basic solutions.
In the membranepotential theory, the glass membrane
is considered to be permeable to hydrogen ions, and the
potential developed is due to the difference in diffusion
rates of ions through the glass. This theory correctly
predicts the behavior of the glass electrode in acidic
and basic as well as neutral media. Although this
mechanism is cited in a number of recently published
textbooks as the explanation of the pH response of the
glass electrode, the concept of an actual penetration
through the glass membrane by substantial amounts
of hydrogen ion has been definitely disproved by the
work of HaugaardZ and the coulometric tracer experi-
ments of Schwabe and D a h m ~ . It ~ was shown that
hydrogen ions become bonded in the silicon-oxygen net-
work of the gel layer and contribute little to the con-
Guest columns and suggestions of material suitable for them
should he sent with as many details as possible, particularly with
references to modern textbooks, to W. H. Eberhardt, School of
Chemistry, Georgia Institute of Technology, Atlanta, Ga.
30332. Since the purpose of this column is to prevent the spread
and continuation of errors and not to evaluate individual texts,
the sources of error will not be cited. In order ta be presented, an
error must occur in at leest two independent recent standard
books.
Present address: Chemistry Building, Room B326, National
Bureau of Standards, Washington, D.C. 20234.
a HAUGAARD, G., J. Phys. Chem., 45, 148 (1941).
SCHWABE, K., AND DAHMS,H., Z . Elektrochem., 65, 518
11461 \
S C B ~ ~K.,E AND
, SUSCHHE,H. D., Sngew. Chem., 76, 39
(1964).
SCAWABE, K., AND DAHMS,H., Z . Elektrochem., loe. eit.
BATES,R. G., "Determination of pH, Theory and Practice,"
John Wiley & Sons, New York, 1964, Chap. 10.
duction of the slight current through the glass, while
most of the current appears to be carried by the more
labile sodium ions.
At the present time, the most generally accepted
theory of the glass electrode mechanism is based on an
ion exchange equilibrium occurring a t the solution-glass
boundary. The phase-boundary-potential (or Donnan-
potential) theory assigns the development of the glass
electrode potential to a thermodynamic equilibrium be-
tween the electrolyte solution and the glass. However,
since the potential is established much faster than could
be expected from a true phase equilibrium, it must be
assumed that only the gel layer of the glass directly
participates in the eq~ilibrium.~Indeed, it has been
shown5 that the cationic exchange only occurs in the
external part of the gel layer, which does in fact act as a
semipermeable membrane to hydrogen ions, and the in-
ner regions of the glass have little effect on the potential
formation. Using the mechanism in which alkali
metal ions in the silicon-oxygen network of the glass
exchange with ions in the test solution, the pH response
and the acid and base errors of glass electrodes can be
explained!
Qualitatively, the negative acid error is due to the
migration of the acid anions into the gel layer and/or
a change in the activity of the water in the gel layer
thereby affecting the hydrogen ion activity. The grad-
ual dissolution of the outermost layer of glass may also
account for the error in strongly acid solution by pre-
venting the formation of a steady-state Donnan po-
tential. The positive alkaline error is due to the partial
exchange of cations, other than hydrogen ion, between
the pH sensitive surface layer of the glass and the
basic solution. In general, the alkaline error will be
large when the test solution contains a cation in com-
mon with the glass, or a cation of the same group but
of smaller atomic number.
In summary, the glass electrode can be considered to
exhibit an overall potential which is the sum of several
independent potentials: (a) the potential of the inner
reference electrode, (b) the potential developed a t the
inner surface of the glass membrane, (c) the asymmetry
potential, and (d) the pH responsive potential a t the ex-
ternal glass membrane surface. The potentials (a)
and (b) are constant and only dependent on the par-
ticular solution contained in the glass electrode envelope.
The asymmetry potential is somewhat variable and
attributed to differences in thc inner and outer sur-
faces of the glass membrane, e.g., uneven stwin in the
glass or differences in the chemical composition of
the glass. In using the glass electrode, the potentials
Volume 44, Number 3, March 1967 / 175
( a ) , (b), and (c) are normally canceled by standardiza-
tion of the glass electrode in a buffer solution. The
remaining pot,ential difference developed in response
to the pH of the test solution is given by the equation:
RT 2.3RT
A& = - ( A h am+) = - (APE)
5 5
i.e., 0.05915 v / p H unit at 25'C, except in very acid or
alkaline solutions as noted above. Thus, according to
the presently accepted theory of the glass electrode,
it is an ion emhange process in the gel layer of the glass
176 / Journal of Chemical Education
membrane producing a phase boundary potential that de-
termines the pH response of the electrode and not a diffusion
of hydrogen ions through the entire glass membrane.
For a more detailed discussion of the glass electrode
and the development of the above theories, the reader
is referred to a recent review by Schwabe and Suschke?
An earlier review by Eisenman8on cation selective glass
electrodes may also be of interest.
7 K., AND SUSCRKE,
SCRWABE, H. D., Angew. C h a . , loc. eit.
G., Bwphya. J., 2, 259 (1062).
EISENMAN,