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Solving pH Problems on a Spreadsheet

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298 Chem. Educator 2003, 8, 298ñ302

Solving pH Problems on a Spreadsheet

Robert de Levie,* Guido Frison,Ü and Alberto Calatroniá

Chemistry Department, Bowdoin College, Brunswick, ME, 04011, USA, rdelevie@bowdoin.edu; European
School of Varese, Varese, Italy; and Politecnico of Milan, Milan, Italy
Received May 28, 2003. Accepted July 3, 2003.

Abstract: Starting from the general expression HC = 0 for any mixture of acids, bases, and salts we find the
pH as the root of this expression either by bisection or by using the Newton-Raphson or Levenberg-
Marquardt algorithms. All three are readily implemented on a spreadsheet.

Introduction all proton gainers multiplied by the number of protons they

In the undergraduate chemistry curriculum, especially in a
class such as quantitative chemical analysis, much time and
effort is often devoted to solving mathematical equations
expressing chemical equilibria, such as the calculation of the
pH of a solution, which we will use here as our example.
While the underlying concept of the mass action law and the
accompanying bookkeeping rules of charge and mass balance
are crucial to understanding equilibria, the typical emphasis on
specific, approximate mathematical methods to yield practical
answers to pH problems can be quite distracting to students,
especially when they are not mathematically inclined.
Moreover, the curriculum is under pressure to include newer
aspects of chemical analysis, such as modern developments in
instrumental methods, as well as entirely new subdisciplines,
such as biochemistry, and it may therefore be necessary to
streamline and condense the treatment of more traditional
topics in order to make space for additional material. By using
logarithmic concentration diagrams, students can often gain a
qualitative and semiquantitative insight in chemical equilibria
[1ñ7]. Whenever a more quantitative approach is needed,
ubiquitous modern tools, such as spreadsheets, can be used to
reduce undue emphasis on otherwise tedious and time-
consuming mathematical manipulations.
Usually, the concept of pH and its ramifications have
already been explored in general chemistry, in which case the
students are ready for a more quantitative approach in a
quantitative chemical analysis course. At that point one can
then use the mass action law and the charge and mass balance
equations to derive a simple yet quite general expression for
the pH [8]. But that is only part of the solution; we should also
give the students the specific tools needed to solve such a
general expression. This note therefore illustrates how a
spreadsheet, and more specifically Excel, can be used
conveniently for precise, nonapproximate pH calculations.
As we showed before [8], computing the pH of an arbitrary
mixture of acids and bases can be reduced to solving the single
expression HC = 0, where HC is the proton function, a weighted
sum of concentration terms that reflects the proton gainers and
losers, and can often be written down by inspection.
Specifically, the proton function contains the concentrations of
*
Ü
Bowdoin College; address correspondence to this author.
European School of Varese.
á
Politecnico of Milan.
have gained minus the concentrations of all proton losers times
the corresponding numbers of protons lost, where gaining and
losing are defined with respect to the starting chemicals from
which the solution is prepared. After writing HC explicitly in
terms of the proton concentration [H+], we obtain a
mathematical equation of which we seek the root, which yields
the sought value of [H+]. Finding that root is therefore the crux
of our problem.
Below we will use several specific examples: a C M
aqueous solution of acetic acid; an aqueous C M potassium
hydrogen phthalate buffer; an aqueous buffer mixture
containing C M citric acid plus a C" M strong monoprotic base
such as NaOH; and an aqueous buffer mixture of C M
orthophosphoric acid, C' M citric acid, and C" M NaOH. The
same approach can be used for such ìuniversalî buffer
mixtures as described by Prideaux and Ward [9], Britten and
Robinson [10], and Ellis [11], or for any other mixture of any
number of acids (including amino acids), bases, and their salts.
Specific Results for the Proton Function
For the C M aqueous solution of acetic acid, here denoted by
HAc, the proton function is
Ka C Kw
H
C = [H + ] − [Ac − ] − [OH − ] = [H + ] − +
− (1)
[H ] + Ka [H + ]
where we will assume that the numerical values of the acid
dissociation constant, Ka, and the ion product, Kw, for water
autodissociation are known so that the problem of computing
the pH reduces to finding the root of HC = 0 when HC is given
by eq 1.
For the aqueous solution of the acid salt KHPhth we have
H
C = [H + ] + [H 2 Phth] − [Phth 2 − ] − [OH − ] = [H + ]
([H + ]2 K a1K a 2 )C Kw (2)
+ + 2 +
− +
[H ] + [H ]K a1 + K a1 K a 2 [H ]
where we start from the salt KHPhth so that H2Phth has gained
a proton while Phth2ñ has lost one, just as H+ (or H3O+) has
gained one with respect to H2O, and OHñ lost one.

© 2003 The Chemical Educator, S1430-4171(03)05718-0, Published on Web 8/21/2003, 10.1333/s00897030718a, 850298rd.pdf
Solving pH Problems on a Spreadsheet
For the aqueous solution of the mixture of C M H3Cit plus
C" M NaOH we likewise obtain
H
C = [H + ] − C [H 2 Cit − ] + 2C [HCit 2 − ] − 3C [Cit 3− ] − [OH − ]
[H + ]2 K a1 + 2[H + ]K a1 K a2 + 3K a1K a2 K a3 )} C
= [H + ] − − C "−
[H + ]3 + [H + ]2 K a1 + [H + ]K a1K a2 + K a1K a2 K a3
as can again be found by inspection, simply by considering
how many protons are gained or lost by the acid. The term C″
represents the hydroxyl ions contributed by the fully
dissociated strong base, while the term Kw/[H+] comes from the
autodissociation of water.
For the aqueous buffer mixture of C M citric acid and C' M
orthophosphoric acid (which in a two-to-one concentration
ratio can make a buffer with a near-linear pH as a function of
added NaOH between pH 2 and 7) plus C" M sodium
hydroxide we have
H + −
C = [H ] − [H 2 Cit ] − 2[HCit ] − 3[Cit2− 3−
] − [H 2 PO 4− ]
− 2[HPO 24 − ] − 3[PO34− ] − [OH − ]
([H + ]2 Ka1 + 2[H + ]K a1 Ka2 + 3K a1K a2 Ka3 ) C
= [H + ] −
[H + ]3 + [H + ]2 Ka1 + [H + ]Ka1Ka 2 + Ka1Ka 2 Ka3
([H + ]2 K a1 '+ 2[H + ]K a1 ' K a 2 '+ 3K a1 ' K a 2 ' K a 3 ') C '
− − C "−
[H + ]3 + [H + ]2 K a1 '+ [H + ]K a1 ' K a 2 '+ K a1 ' K a 2 ' K a 3 '
where the Ka values for phosphoric acid are denoted as Ka′.
In the above examples we see that the complexity of the
expressions for HC merely reflects those of the chemistry: for a
simple chemical situation we find a rather simple expression
such as eq 1, whereas a complicated mixture yields a
complicated result for HC, as in eq 4. And while the derivation
of such expressions is relatively straightforward once students
have familiarized themselves with the traditional acid-base
formalism, numerically solving an expression as unwieldy as
eq 4 might frighten most students if we do not also give them
the tools to do so. Fortunately, this is where the computer (as
here demonstrated for the humble spreadsheet) comes to the
rescue.
Using a Spreadsheet
Many students already know how to use Excel, and many
will even have it on their own computer, as part of the
ubiquitous Microsoft Office; therefore, computing and plotting
H
C as a function of pH = ñlog[H+] is not an impossible
assignment when the various K values are given. We will
therefore focus here on finding the zero crossing in a table or
graph, that is, on finding a root of a complicated equation. In
this case such a root must both exist and be real. Moreover,
there can only be one such root within the range of physically
possible [H+] values, and a table or graph of HC versus pH will
roughly indicate where to find that root.
Excel provides two aids in finding a real root: GoalSeek and
Solver. GoalSeek is an implementation of the Newtonñ
Raphson method, and can only handle functions of a single
variable x, but because that is the situation here, with x = [H+],
GoalSeek will do. Solver is based on the Levenbergñ
© 2003 The Chemical Educator, S1430-4171(03)05718-0, Published on Web 8/21/2003, 10.1333/s00897030718a, 850298rd.pdf
Chem. Educator, Vol. 8, No. 5, 2003 299
Marquardt algorithm and can accommodate a number of
variables. Both are very useful general methods that students in
science should know anyway, and their implementation in
Excel is very straightforward and convenient. The only
problem students may encounter is that, for physically
Kw
unrealizable values of [H+], complicated equations such as
[H + ] illustrated above often have additional real (i.e., nonimaginary)
(3) roots. While these are of no concern to chemists, the above
software can nonetheless home in on them, resulting in useless
answers that might confuse the student. Below we will address
how one can usually avoid obtaining such incorrect answers.
Another method is bisection. Bisection is always constrained
to a particular range of values of the independent variable and,
therefore, cannot lead to rogue answers outside that specified
range. Bisection is also conceptually transparent, and we will,
therefore, use it as our point of departure.
The pH of an Aqueous Solution of Acetic Acid
We start with a spreadsheet, in which we reserve the top
rows for a graph, then enter labels and values for the constants
involved: the total analytical concentration C of acetic acid, its
acid dissociation constant Ka, and the water ionization product
Kw. (In Figure 1 we have used 0.05 for C, =10^ñ4.76 for Ka,
and 1Eñ14 for Kw.) Below these we enter column headings for
H
Kw
C, pH, and [H+], and a starting value of, say, 0 for pH. We
then complete the columns as specified in the first three
[H + ]
instructions at the bottom of Figure 1 and plot HC versus pH.
(4) In order to illustrate the principle of bisection, we will here
use decasection. Look at the values computed for HC, which
for the constants shown in Figure 1 change sign between pH 3
and pH 4. We can now use linear interpolation to obtain a first
estimate of the pH of the zero-crossing. We do this in a
separate cell with the instruction =(A20*C21ñ
C20*A21)/(A20ñA21), which yields pH = 3.02. (From hereon
we will use the cell addresses corresponding to Figure 1; you
are of course welcome to arrange the spreadsheet differently,
but then the addresses must be adjusted accordingly.) To find a
more precise answer, we repeat the process in columns D
through F starting with pH = 3 and using smaller increments,
in this example ∆pH = 1. The root is indeed seen to lie
between pH = 3.0 and 3.1 and linear interpolation yields pH =
3.035, see cell F29 in Figure 1.
This approach is somewhat tedious, even though it quickly
leads to an estimate that is sufficiently precise for pH
measurements. The process can readily be automated by a
macro that will do the manipulations in the background. In
fact, it is most efficient for the computer to divide the interval
by two, look whether a sign change has occurred, on that basis
select that half of the data set that contains the sign change
and, therefore, the sought root and repeat the process until
some termination criterion is reached. The custom macro
RootFinder [12] will find the root after the area A17:B37 is
highlighted and the macro is called.
Use of GoalSeek is equally simple, once it has been set
properly. Because Excel is primarily a business tool and
GoalSeek is mainly used for calculations in terms of dollars, its
default resolution is usually set to 0.001, too large for our
purpose; therefore, go to Tools ⇒ Options, and under the
Calculation tab set the Maximum change to 0.000001.
300 Chem. Educator, Vol. 8, No. 5, 2003 de Levie et al.

A B C D E F Here is how to use GoalSeek. Copy the instructions for HC,

1
0.1 pH, and [H+], as illustrated in cells D31:F31 in Figure 1. (You
2
can avoid the copying by using instead, e.g., cells A31:C31,
3 H
4 C but that will affect the graph.) Now enter a plausible value for
5 the pH, such as 3. Then call GoalSeek (which can be found on
6 0 the menu bar under Tools) and complete the input dialog box
7 to make the sequence ìSet cell: D31 To value: 0 by changing
8 cell: F31î (where the information to be entered has been
9 bolded for emphasis), and pressing OK. GoalSeek will yield
10 -0.1
the sought pH.
11
0 2 4 6 8 10 12 pH 14 Solver works much the same way, and in fact it is even
12
13 C= 0.05 Ka= 1.738E-05 Kw= 1E-14 easier because it remembers the previously used settings. (It is
14 assumed here that you have Solver installed on your Excel,
15
H
C pH [H+] H
C pH [H+] otherwise you will first need to do so. Solver is included in the
16 original distribution of Microsoft Office, that is, on its CD, but
17 0.9999991 0 1 0.00015 3.0 0.00100 may have been left out in ìsmallî installation procedures in
18 0.0999913 1 0.1 -0.00028 3.1 0.00079 order to conserve memory.) Call Solver, and use ìSet Target
19 0.0099133 2 0.01 -0.00071 3.2 0.00063 Cell: D31 Equal to Value of: 0 By Changing Cells: F31î. (Do
20 0.0001459 3 0.001 -0.00117 3.3 0.00050 activate the radio button in front of ìValue ofî.) The first time
21 -0.007303 4 0.0001 -0.00169 3.4 0.00040
you use Solver make sure that, in the Solver Parameters dialog
22 -0.031727 5 0.00001 -0.00229 3.5 0.00032
23 -0.047278 6 0.000001 -0.00298 3.6 0.00025 box, under Options, the precision is set to at most 0.000001.
24 -0.049714 7 0.0000001 -0.00381 3.7 0.00020 In short, all three methods, RootFinder, GoalSeek, and
25 -0.049972 8 1E-08 -0.00478 3.8 0.00016 Solver, will get you the same pH of 3.035 to within about
26 -0.050007 9 1E-09 -0.00594 3.9 0.00013 ±0.001 within a few keystrokes. If you change any of the
27 -0.0501 10 1E-10 -0.00730 4.0 0.00010 constants, such as C and/or Ka, the data in A17:C31, D17:F27,
28 -0.051 11 1E-11
and D31:F31 will immediately respond, but you will need to
29 -0.06 12 1E-12 pH= 3.035
30 -0.15 13 1E-13
rerun RootFinder, GoalSeek, or Solver.
31 -1.05 14 1E-14 6.420E-08 3.035 0.00092
The pH of a Phthalate Buffer
cell: copied to:
The approach is the same, only the expression for HC
B18= C17+1 B19:B31 changes from eq 1 to eq 2. The plot of HC versus pH is
C17= 10^-C17 C18:C31 qualitatively similar to that for acetic acid; Figure 2 shows a
A17= C17-$B$13*$D$13/(C17+$D$13)-$F$13/C17 A18:A31 detail of such a plot as you would find for C = 0.02, Ka1 = 10^ñ
E18= E17+0.1 E19:E27
F17= 10^-E17 F18:F27
2.95, and Ka2 = 10^ñ5.41 in the range around the zero-crossing,
D17= F17-$D$13*$B$13/(F17+$D$13)-$F$13/F17 D18:D27 illustrating that, indeed, for sufficiently small intervals of ∆pH,
E29= (D17*E18-D18*E17)/(D17-D18) the plot becomes essentially linear. This is the reason that
F31= 10^-E31 linear interpolation in a data set with ∆pH = 0.1 can often yield
D31= F31-$D$13*$B$13/(F31+$D$13)-$F$13/F31 results to within ±0.001 pH units. All three methods,
RootFinder, GoalSeek, and Solver, yield pH = 4.193.
Figure 1. A spreadsheet showing the computation (in columns A
through C) and plot (in cells A1:F12) of the proton function HC for an
aqueous solution of acetic acid as a function of pH. The open circles
The pH of a Mixture of Citric Acid and a Strong Base
show the calculated data points; the connecting lines are interpolated
by the computer using a cubic spline and are displayed here merely to
Figure 3 illustrates the shape of the plot of the proton
show connectivity. The concentration C and the equilibrium constants function versus pH when we use eq 3 instead. Here we see
Ka and Kw used in the calculation are shown in row 13, and the what can happen at physically unrealizable pH values: pH = 0
specific equations used in the calculations are listed at the bottom. clearly cannot be reached with a 0.2 M diprotic acid nor can
pH 14 be obtained with a 0.3 M base, and their mixture must
have a less extreme pH. Zero-crossings beyond possible pH
0.001
values are therefore of no consequence and should be excluded
H from consideration; we can have only one pH, that is, only one
C
zero-crossing can be meaningful. The extreme points are
0 therefore shown as solid black circles in Figure 3, indicating
that these values should not be included (at least not
simultaneously) in the input data for RootFinder.
Applying RootFinder to block A18:B30 yields pH = 4.760,
-0.001 and the same (correct) answer is found with GoalSeek and
4.0 4.1 4.2 4.3 pH 4.4 Solver as long as we use initial pH values from where HC
changes monotonically to the root, in this case between pH 2
Figure 2. Detail near the zero-crossing of a plot of HC versus pH for and pH 9. With initial pH values of 0 or 1, both GoalSeek and
an aqueous solution of 0.02 M potassium hydrogen phthalate using Solver yield pH = 0.524, a clearly incorrect answer. Applying
Ka1 = 10ñ2.95 and Ka2 = 10ñ5.41.

© 2003 The Chemical Educator, S1430-4171(03)05718-0, Published on Web 8/21/2003, 10.1333/s00897030718a, 850298rd.pdf
Solving pH Problems on a Spreadsheet Chem. Educator, Vol. 8, No. 5, 2003 301

1 Solver yields no answer for an initial pH value of 10, and pH =

13.477 for initial pH-values of 11 and larger.
H While the pH values indicated by gray-filled circles are
C
acceptable for RootFinder, they will give trouble to GoalFinder
0 and Solver, because at these values d(HC)/d(pH) directs the
solution away from the sought root. The open circles are fine
for inclusion in or starting points for any one of these three
methods. We should not be surprised that equations as
-1 complicated as eqs 3 or 4 have multiple roots nor by the fact
0 2 4 6 8 10 12 pH 14 that only one of them has physical meaning. Consequently one
should always start from a reasonably close initial estimate,
Figure 3. Plot of HC versus pH for 0.2 M citric acid (Ka1 = 10ñ3.13, such as can be supplied by a simple table or graph. Otherwise,
Ka2 = 10ñ4.76, and Ka3 = 10ñ6.40) plus 0.3 M NaOH. The Henderson start at pH = 7.
approximation does not yield a satisfactory result when, as in this
case, the Ka values are not several orders of magnitude apart. Black
data points indicate values that should not be included in the range The pH of a Buffer Mixture of Citric Acid, Phosphoric
used for RootFinder; both black and gray data points should not be Acid, and NaOH
used as starting points for GoalSeek or Solver.
Apart from the added complexity of the explicit expression
A B C D E F for the proton function HC, this case is no different from the
1 ones shown before. We use it here to illustrate that there is no
1 limit to the chemical complexity this approach can handle.
2
3
H
Again, the graph (see Figure 4) indicates which points to avoid
4 C for RootFinder (the black ones) and which should not be used
5 as starting points for GoalSeek or Solver (the black and gray
6 0
ones).
7
8
9 Activity Corrections
10 -1
11
0 2 4 6 8 10 12 pH 14
A discussion of pH calculations is not complete without a
12 consideration of activity effects, although it sometimes can be
13 C= 0.2 Ka1= 0.0007413 K'a1= 0.0070795 finessed by making all measurements in a medium of constant,
14 C'= 0.1 Ka2= 1.738E-05 K'a2= 6.31E-08 high ionic strength, such as 1 M LiClO4, in which case one can
15 C"= 0.3 Ka3= 3.981E-07 K'a3= 7.079E-13
assume the activity coefficients to be determined by the
16 Kw= 1E-14
H + H +
essentially constant ionic strength and make the corresponding
17 C pH [H ] C pH [H ]
corrections in the pK values and, if appropriate, in the pH.
18
Activity corrections can easily change the pH by a few tenths
19 0.7008511 0 1 -0.054086 3.5 3.16E-04
20 -0.191916 1 0.1 -0.04142 3.6 2.51E-04
of a pH unit, and they are therefore of a magnitude comparable
21 -0.2347 2 0.01 -0.029302 3.7 2.00E-04 to applying equilibrium potentials determined at 25 °C to
22 -0.123913 3 0.001 -0.017644 3.8 1.58E-04 measurements at some other ìroomî temperature. (The
23 0.0049209 4 0.0001 -0.006297 3.9 1.26E-04 automatic temperature correction of modern pH meters can
24 0.1325785 5 0.00001 0.0049209 4.0 1.00E-04 correct for the temperature dependence of the measurement,
25 0.2526901 6 0.000001 0.016203 4.1 7.94E-05 but not for that in the calculation.)
26 0.3981182 7 0.0000001 0.0277298 4.2 6.31E-05
Activity corrections have problems of two types: conceptual,
27 0.481419 8 1E-08 0.0396447 4.3 5.01E-05
28 0.4979994 9 1E-09 0.0520338 4.4 3.98E-05 and computational. The conceptual problem is that, in contrast
29 0.5003945 10 1E-10 0.0649119 4.5 3.16E-05 to salt activities, ionic activity coefficients are not accessible
30 0.5055906 11 1E-11 by any known experiment and, therefore, depend on model
31 0.5314483 12 1E-12 pH= 3.956 assumptions. To put it in a different context: unlike
32 0.4876228 13 1E-13 expressions for equilibrium cell potentials, formulas for the pH
33 -0.401393 14 1E-14 5.176E-07 3.956 1.11E-04 cannot be written exclusively in terms of salt concentrations
and, therefore, cannot avoid extra-thermodynamic model
Figure 4. Plot of HC versus pH for 0.2 M citric acid (Ka1 = 10ñ3.13, Ka2 assumptions. The DebyeñH¸ckel [13] model is valid only for
= 10ñ4.76, and Ka3 = 10ñ6.40) plus 0.1 M phosphoric acid (Ka1 = 10ñ2.15, rather dilute solutions, and for more practical concentrations no
Ka2 = 10ñ7.20, and Ka3 = 10ñ12.15) plus 0.3 M NaOH. Such a mixture can
generally agreed-upon model is available. Its simplest
be used as a ìuniversalî buffer for acidic solutions with a pH that is
readily adjustable by adding strong base. The calculation of the pH of extension to practical ionic strengths is the Davies equation
such a mixture is well beyond the power of the more traditional [14], which does so without introducing additional parameters
methods taught in undergraduate textbooks. and certainly yields much better agreement with measured salt
activities [15] than the use of, for example, Kiellandís tables
RootFinder to block A17:B31 yields pH = 13.744, a similarly [16]. The method we will describe below does not depend on
erroneous result that shows that even RootFinder can go wrong any special aspect of the Davies equation and can easily be
when the interval is chosen thoughtlessly. GoalSeek finds pH = adapted to alternative models.
13.477 for an initial guess value of pH = 10 and beyond, while There are two main computational problems. (1) The
calculation of pH requires a mixture of proton concentrations
and proton activities. The mass and charge balances are simple

© 2003 The Chemical Educator, S1430-4171(03)05718-0, Published on Web 8/21/2003, 10.1333/s00897030718a, 850298rd.pdf
302 Chem. Educator, Vol. 8, No. 5, 2003
accounting devices and, therefore, deal with number densities,
that is, concentrations. On the other hand, equilibrium
constants reflect energetics, and therefore involve activities,
that is, the products of concentrations and activity coefficients.
(2) A further complication is that what we measure as pH
depends on the type of measurement made. A potentiometric
pH measurement (such as with a glass electrode and a
reference electrode) yields a value closely resembling the
negative logarithm of the proton activity (as long as liquid
junction potential differences are insignificant, as they often
are between pH 3 and 11), whereas a spectrometric pH
measurement (e.g., by using the visible spectrum of a color
indicator) yields the negative logarithm of the proton
concentration. When one includes activity corrections, the
question ìWhat is the pH?î therefore becomes somewhat more
complicated, because it can only be answered properly after
one specifies the model used for the correction as well as the
type of pH measurement made.
The actual mechanics of the activity correction are not that
difficult and have been described explicitly in, for example,
chapter 6 of reference 7; therefore, here we merely indicate the
protocol, which is easily implemented on a spreadsheet.
(a) Given the pH calculated by the method used above (i.e.,
ignoring activity coefficients), compute the ionic strength.
(For the Davies model, this is all that is needed. For other
models, additional parameters may be required.)
(b) Use the Davies equation (or whatever other model one
prefers) to estimate the activity coefficients of the ions
involved.
(c) Correct the equilibrium constants by incorporation of
these activity coefficients.
(d) With the so-corrected equilibrium constants, recalculate
the pH.
In principle, this is an iterative process, that is, steps (a)
through (d) should now be repeated until the pH shows no
further significant change. In practice, such iteration is
seldom if ever necessary in aqueous solutions.
(e) The pH obtained under (d) is still defined as ñlog[H+]. If
the calculated pH is to be compared with an
electrometrically measured value (but not if the
measurement is a spectrometric one), correct the pH to be
equal to ñlog{[H+]f} = ñlog [H+] ñlog f, where f is the
activity coefficient of a monovalent ion.
Discussion
The combination of general expressions, such as HC = 0, and
of general mathematical tools, such as bisection or the methods
of NewtonñRaphson or LevenbergñMarquardt, has several
advantages. First, it reduces the tedium of mathematical
operations and the distraction from chemistry that can result.
Secondly, it avoids the need for approximations that, in many
practical situations, can generate incorrect results. And, last but
not least, it demonstrates that one can use simple chemical
principles for solving rather complicated problems that are well
beyond the range of the traditional, more cumbersome
approach still advocated in most textbooks. The same methods
can of course be implemented in other programs; we have
illustrated them here for Excel because that software is easily
learned and widely used.
© 2003 The Chemical Educator, S1430-4171(03)05718-0, Published on Web 8/21/2003, 10.1333/s00897030718a, 850298rd.pdf
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de Levie et al.
Activity effects are a relatively minor but complicating
factor and are best left out in a first discussion of pH, because
they require a quantitative grasp of ionic interactions, an
understanding of the difference between balance and
equilibrium expressions, and a knowledge of the various ways
in which the pH can be measured. In a second encounter with
the topic, these concepts can all be brought in. Even then,
activity corrections are best introduced after the pH is first
computed without them; to do otherwise might force them,
incorrectly, upon the mass and charge balance expressions and
might thereby lead to incorrect results. After all, the ionic
strength, the main determinant of activity effects in dilute
solutions, is also based on ionic concentrations rather than
activities.
If we are after instilling insight in pH problems, the simple
derivation of HC = 0 plus a few specific examples such as
shown here in eqs 1 through 4 will suffice, preferably in
combination with logarithmic concentration diagrams that can
give the student an overview of the chemical speciation. If we
want to show students how HC = 0 is applied in practice, the
methods discussed here provide a powerful yet painless
illustration. Acidñbase problems present a rare example of a
situation in which the traditional approximations are more
complicated and more limiting than using the exact, general
result. Finally, if we want to introduce the students to the
subtleties of ionic and other interactions, activity corrections
can also be introduced at this point.
References and Notes
1. H‰gg, G. Kemisk reaktionsl‰ra; Geber: Upsala; 1940; Die
theoretischen Grundlagen der analytischen Chemie; Birkh‰user:
Basel, 1950.
2. Seel, F. Grundlagen der analytischen Chemie und der Chemie in
w‰ssrigen Systemen; Verlag Chemie: Weinheim, 1955.
3. SillÈn, L. G. In Treatise on Analytical Chemistry, part 1, vol. 1,
Kolthoff, I. M.; Elving, P. J.; Sandell, E. B, Eds.; Wiley: New York,
1959.
4. Butler, J. N. Ionic Equilibrium, a Mathematical Approach; Addison-
Wesley: Reading, MA, 1964.
5. Fernando, Q.; Ryan, M. D. Calculations in Analytical Chemistry;
Thomson: place of publication , 1982.
6. de Levie, R. Crit. Revs. Anal. Chem. 1997, 27, 51; H‰gg, G. Crit.
Revs. Anal. Chem. 1997, 27, 76.
7. de Levie, R., Aqueous AcidñBase Equilibria and Titrations; Oxford
University Press: Oxford, England, 1999.
8. de Levie, R. Chem. Educator 2001, 6, 272ñ276; DOI
10.1333/s00897010507a.
9. Prideaux, E. B. R.; Ward, A. T. J. Chem. Soc. 1924, 125, 426ñ429.
10. Britten, H. T .S.; Robinson, R. A. J. Chem. Soc. 1931, 1456ñ1462.
11. Ellis, D. A. Nature 1961, 191, 1099ñ1100.
12. Freely available from the author. Please address email requests to
RDELEVIE @ BOWDOIN.EDU.
13. Debye, P.; H¸ckel, E. Phys. Z. 1923, 24, 185ñ206.
14. Davies, C. W. Ion Association; Butterworths: Washington, DC,
1962.
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Butterworths: London, England, 1959.
16. Kielland, J. J. Am. Chem. Soc. 1937, 59, 1675ñ1678.