Teaching the Truth about pH
Stephen J. Hawkes
Oregon State University, Corvallis, OR 97331
What do you tell a student who measures the pH of 0.1
M HCl a n d finds t h a t ( 1 ) i t i s 1.1when s o u have just
taught him a method of calculation t h a t saysit is l.OO?kny
explanation reduces to a n admission t h a t s o u deceived
him about the definition of pH.
When the student calculates from t h e published densi-
ties t h a t -log [HI] varies by only 0.01 between 0 and 90°C,
why does t h e pH vary (2)from 1.08 to 1.13?
If he should ever find out t h a t the pH of 0.01 M HCI i n
5 m LiCl is 0.8 (3)instead of t h e 2.00 t h a t you taught him
to calculate, what will he think of your professional compe-
tence?
When we teach methods of calculation t h a t give answers
t h a t a r e substautially different from experimental reality,
we accept a grave responsibility. When we teach a defini-
tion of pH that h a s been obsolete for half a century, we are
guilty of professional malpractice.
Yet no introductory text t h a t I have seen suggests that
-log [H+lis only a n approximation to pH. Conversely, when
they discuss the measurement of pH they do not say t h a t
the reading on a pH meter is only a n approximation to t h e
-log [Ht' t h a t they have given incorrectly as the definition
of pH.
Students who have been taught t h a t p H i s -log [H+lwill
--
obviouslv exoect t h a t their o H meter will read -log 1Htl.
Even p r ~ f e s ~ owho
-
r s have t c e usual background i n physi-
cal chemistry have t h e same expectation. Arecent puhlish-
ed experiment (4) contained this expectation i n the second
decimal! Students who make lab measurements carefullv
and compare their result with the expectation can he ex-
~ e c t e dto cheat.
The consequences are worse when they apply their un-
--
derstanding of DH to real-world Droblems after thevrrmdu-
ate. Our teaching has lead them into error.
Such teaching i s unnecessary.
How to Tell the Truth
Any approach to p H must be simple enough for introduc-
tory students to understand, must not be misleading, and
must lead correctly into whatever calculations we think i t
necessary to teach. But let u s understand what i s impor-
tant. MacInnes, one of t h e leading workers on p H theory in
his time, made this clear (5)when h e said:
In possibly all but one case in a thousand, it is not necessary
to consider the meaning of pH in terns of solution theory at all,
but only to accept the numbers as a practical scale of acidity
and alkalinity.
So how much should we teach about pH? Are our calcn-
lations necessary? Whatever our answer to this, i t is clear
t h a t we need to emphasize the practicality of t h e pH scale
a s far more important than any calculations for which i t
may be used. Moreover, our decision to teach calculations
should not compromise the essential simplicity of the con-
cept of pH.
The following sequence puts the concepts i n a n order in
which they can be taught logically, with t h e most impor-
t a n t concepts first, and without resorting to untruths. It
can he halted a t whatever level a teacher thinks appropri-
ate to the students.
pH is a measure of the acidity of a solution.
pH decreases as acidity increases.
acidity is the tendency of a solution to supply Hi to a
reaction.
the tendency of a solution to supply H+is represented in cal-
culations by a quantity called the "activity" of Hi in the solu-
tion.
the "activity" is directly proportional to the concentration of
Hi in the solution and is also a function of any other sub-
stances in the solution whose molecules are close enough to
H+ ions to have any effect on them and is also a function of
the solvent itself, which is usually water. It varies slightly
with temperature even when the hydrogen ion concentration
does not change.
other ions in the solution affect the activity of Ht more than
neutral molecular species because of the interaction of their
electric field with that of the Hf.
DHdecreases bv one unit for each tenfold increase in activitv.
pH may, therefore. be measured hy rhc rxrrnr ro which o so-
lution interact* \nth a n electrode th;lt is scnairi\,r t o H'. ur
how it affect3 the tquhbnum h e t w e n n rolorrd arid and its
conjugate base.
the potential at the electrode is the conventional measure of
pH. The electrode is calibrated against standard solutions of
which the H+ activity has been determined as accurately as
possible by methods that are outside the scope ofthe course.
Standard solutions have been recommended hy national and
international authorities with recommended pH values for
calibration of the electrodes.
.because the ~otentialat an electrode varies emonentiallv
poses as 10-P".
in solutions so dilute and so pure that Hi ions are not influ-
enced bv anvthinn- exceDt
. the solvent.. DH
. = -log 1Htl.
u~ ~
in mos&al;tians, pH differs from -log IHt1 in the first deei-
mal, but this may sometimes be near enough for very ap-
proximate calculations.
in most calculations the activity must be used.
the activity often is represented as lgammaiIH+l where
(gamma1 represents the effects of the solvent and the other
substances in the solution: in aqueous solutions it is between
0.05 and 13 in every case that I have found but is usually
between 0.5 and 1.0. It is 0.7 in seawater
The Definition of pH
The International Union of Pure and Applied Chemistry
(6)h a s defmed pH essentially a s the reading on a pH me-
t e r t h a t has been standardized against standard buffers.
That i s
Volume 71 Number 9 September 1994 747
 This is the same definition as that used in the standards needed is to reverse the calculation. The most useful
of all national bodies that have ruled on the question. The source of critically evaluated constants is the six-volume
actual standard buffers varv from one authoritv to an- work by Smith and Martell (111, but they give concentra-
other. Most use NRS ~NationhBureau of ~tandarhs) buff- tion ratios. They explain that they do this so as to make the
ers as standards. while IUPAC and some others use 0.05 m definition fall into line with the definitions of the stability
potassium hydrdgen phthalate, but all give the same val- constants of metal complexes that are the main part of
ues of pH within 0.005 unit. They are chosen so that their their compilation and these are most usefully defined as
recommended pH equals -log aH+as closely as theory per- concentration ratios. They give the method of reversing
mits the activity to be calculated. their calculation to obtain the above "practical" definition,
The symbol pH has its origin in a paper by Sorensen (7) by adding a constant, which is tabulated in their introduc-
in 1909 about the effect ofH+on the action of enzymes. The tion, to the log of the concentration ratio. Of course, both
concept of activity was not available to Sorensen in 1909, the concentration ratio that is usually given in introduc-
so he believed that the output from his electrodes bore a tory texts and the more useful practical constant have the
Nemstian relation to [HI] and when inventing the useful complication that they vary with the ionic strength of the
term pH for this paper he naturally defined it as -log [H'I. solution especially if the acids are ions as in NH4+or
It is ironic that the natural and inevitable misconception of HP04". Usually this is ignored in introductory texts, al-
this pioneer haunts our introductory texts nearly a century though the concentration ratios used in them to define K.
later, even though their authors have the benefit of a mod- are even more dependent on ionic strength than the prac-
e m education. Sorensen himself came to realize his mis- tical constants. This deceives students into believing that
conception within a decade and invented (8)a new term they can be used in situations where they are useless, and
paH, where aH is the activity of Ht, but this became short- this deception stays with them even after they have be-
ened (9) in common usaee to DH. In time. it was realized come full professors. This problem will be elaborated in
that even the activity was too'dificult to measure and in- later papers.
volved uncertain methods of interoretine exoerimental I have calculated pK.(practical) for the acids most com-
data. So one national body after anbther,&d'eventually monly quoted by teachers of introductory chemistry, using
IWAC, agreed on the unambiguous and simple definition the data and the correction in (11)and they are compiled
that depends only on an experimental datum. Theoretical in the table.
electrochemists need alternative definitions that are usu-
ally given special subscripts and refer to various methods
of defining activity. There is a useful discussion of such ap- Rationalization
proaches in the recent text (10) by Galster, but it is not The error is ingrained so deeply from our own training
necessary to include such refinements in introductory in high school and college that we seek a rationalization
courses. The simple definition as the output from a pH me- that releases us from it. The one I have heard most often is
ter is the most useful for the practical purposes that will be that there are two definitions of pH, one involving concen-
valuable to graduates of an introductory chemistry course. tration and the other involving activity. Atenn can be de-
Eauilibrlum Calculations p& (Practical) for Acids Commonly Quoted in Texts
Equilibrium calculations involving H' must necessarily
involve the activity rather than the concentration, both be-
cause it is the activity that affects the equilibrium and be-
cause in any real equilibrium it is the activity, not the con- Ionic strengthC
centration, that is experimentally measurable through the
pH. The activities of the other substances in the solution 0.0
usually are not known, but their concentrations are known -
H3P04 2.15
from the stoichiometry. The useful definition of the equilib-
rium constant, therefore, involves the activity of H+ and HzP04i 7.20
the concentrations of everything else. The acid dissociation ~ ~ 0 4 ' - 12.38
constant K, for example would be HzC03 6.35
aH+[A-l HCO3- 10.33
&=- CsH5(COzH)z 2.95
[HA]
CsH5(COzH)COz- 5.41
This is variously known as the "mixed" or "Brmsted" or
"practical" constant. In dilute solutions with negligible (COZH)~ 1.25
ionic strength it is identical with the concentration ratio HOzCC02- 4.27
and also with the activity ratio which is the thermody- NH4' 9.24
namic definition. But few real-world problems involve CH3NH3* 10.64
such solutions. Indeed, most of the problems that appear
in textbooks have ionic strengths greater than 0.1, so that HF 3.17
the thermodynamic constant is useless, and the mixed con- CBHSCOZH 4.20
stant is essential and may be only 213 of the concentration CHjCOzH 4.76
ratio, as is the case in seawater. HCN 9.21
The name "practical constant" should convince readers
that it is unethical to use any other variation of K, in an HCOzH 3.75
introductory course. Introductory students will have no HN02 3.15
use for the esoterica of the electmchemist, but will need a H20a 14.00 13.89 13.89 13.93
practical method of getting correct answers to practical 'for H20. Ib(Mactica1I is the Dractical Kw, that is awJOH1. Where I O H l
problems if they need such calculations at all. occurs in a n y &i'culation;it may, therefore, be replacsd bj. ~,ipractical)iam.~
Where are such values tabulated? They are the original b ~ ~ decimaln d not available or varies too greatly with the nature of the
data from which other forms of K,, such as concentration interfering ions to be generally significant.
ratios or the ratio of activities are calculated, so all that is Tonic strength = 0.5oi[(molaritiesofion$+(chargeof ions)?]

748 Journal of Chemical Education

fined in any way we choose, but this dual definition has no
foundation in either convention or lopic.
I t is logical to define pH in a way that is useful in prac-
tice. Because the concentration of Hi cannot be obtained
from the experimental pH, a definition in terms of concen-
tration makes subsequent calculations impossible, while
definition in terms of activity lends itself to calculation of
other quantities.
I can find no evidence of a convention allowing both defi-
nitions. I n the nine reference works (6,12-19) that I have
consulted, not one quotes both definitions a s valid. Three
of them quote -log [H*] as a n approximation, and two give
it as the only definition. The remainder give the definition
correctly.
How Close is Activity to
The solution being tested and the standard solution usu-
ally differ from each other in ionic strength and in other
ways. This makes even the determination of activity a n
approximation because of junction potentials in the cell,
althoueh
" it is much closer than DH is to -loe IHil.
good enough approximation? T L ~IUPAC document (6)
--
- Is it a
puts the difference between pH and -log a H + a s no more
than 0.02 for aqueous solutions more dilute than 0.1 M. I n
more concentrated solutions the difference may be greater
but may be offset by compensating errors. In standard
seawater. for examole. the difference (20) is about 0.05.
oceanographers either specify standard buffers that are
specifically designed to eliminate this error when measur-
ing the pH of seawater, or they use sophisticated methods
of correction that are outside the scope of a n introductory
course, or determine the activity d ~ c ~ t r o ~ h o t o m e t r i r a ~ ~ y . ,003."" SO" J. Condensed Chpm&l
The official procedure (211 for determining the pII of blood
involves
~-~ ~ ~secondam standards referred to the NBS stand-
~
ard buffers, with solutions that simulate those properties
of blood that affect pH measurement.
Conclusion
I t has been nearly half a century since MacInnes (5)
wrote
The relation pH = -lag [Htl is an approximation anly, and
using it as a definition may lead to serious errors. It is the
author's rather forlorn hope that compilers of handbwks and
authors of textbooks someday will indicate that the expression
pH =-log [HI1is not a definition and that it may be anly a very
rough approximation.
His "forlorn hope" has been realized in most handbooks,
but is not yet fulfilled in any introductory text that I have
seen. Perhaps he was too nice. Let us lay it on the line.
Authors that define pH a s -log [H+I are deceiving their
readers and leading them into serious error. Those of us
who have taught this error for decades, a s I have, are
guilty of professional malpractice and need to correct our
teaching in the future.
The error can be avoided easily, a s has been shown
above, by a trivial change in pedagogy that will not cause
difficulty to teachers or students.
Literature Cited
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15, No.6.
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~ , nictionory of physicoi cheminry; bentice
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13. Lewis, R.
Dictionary: Van Nostrand Reinhold: New York,
A""",
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15. K q t . D.Dcctionary of Chem~callkchnology; Elsevier. 1980. p 284.
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1993. pp G34.35.
18. Dean, J. A. Langds Hondbwk ofChrm&try. 14th ed.; MeGraw-Hill, 1992: pp 8-103
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MGraw-Hill: New York, 1989: p 1404.
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New York. 1981: p 200.
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Volume 71 Number 9 September 1994 749