Acids and Bases, Part 2: Use of Log C-PH Diagrams and The Toth Equation

6
ACIDS AND BASES, PART 2:
USE OF Log C-pH DIAGRAMS

AND THE TOTH EQUATION
291
Contents
6.1 GRAPHICAL SOLUTIONS FOR SETS OF SIMULTANEOUS

EQUATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
6.2 USING LOG C-pH DIAGRAMS TO SOLVE WEAK ACID/BASE
PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
6.3 THE MASS BALANCE ON H (THE TOTH EQUATION AND
PROTON CONDITION) . . . . . . . . . . . . . . . . . . . . . . . 308
6.4 DEFINING THE COMPOSITION OF THE SYSTEM:
COMPONENTS, SPECIES, AND THE SYSTEM TABLEAU . . . 310
6.5 EXPRESSING INPUT AND EQUILIBRIUM CONCENTRATIONS
IN TERMS OF COMPONENTS; COMPONENT MASS
BALANCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
6.6 IDENTIFYING DOMINANT SPECIES . . . . . . . . . . . . . . . 327
6.7 COMPARISON OF APPROACHES FOR SOLVING ACID/BASE
PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
6.8 SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
6.9 APPENDIX 6A: ARITHMETIC OPERATIONS AND LOG-LOG
DIAGRAMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
6.10 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
6.1 GRAPHICAL SOLUTIONS FOR SETS OF

SIMULTANEOUS EQUATIONS
In Chapter 5, the key equations that characterize acid/base equilibria were presented
and solved analytically, in some cases after applying various simplifying assump-
tions. Then, a spreadsheet was developed that allowed us to identify the approximate
equilibrium condition simply by scanning a column that characterizes how closely
the charge balance is satisfied at various pH values. Log C-pH diagrams were also
introduced as a convenient vehicle for visualizing acid/base speciation over a wide
292
range of conditions, and the point was made that these diagrams convey essentially
the same information as is in the spreadsheet. In this chapter, we combine those ideas
to demonstrate how the equilibrium pH (and indeed, the speciation of the whole so-
lution) can be determined using log C-pH diagrams in conjunction with either the
charge balance or a new equation (the ‘T OT H equation’ or ‘proton condition’) that
can be viewed as a mass balance on H+ . We also introduce a concise format for
conveying all the equilibrium and mass balance data associated with such problems.
Before computers were widely available, this approach was used almost universally
to solve complex acid/base problems, using hand-drawn log C-pH diagrams.
For many types of problems, the graphical approach can be carried out very
rapidly and can yield very good approximations for the equilibrium speciation, even
using rough back-of-the-envelope sketches. However, in systems where both
acid/base and other types of reactions are important, this approach becomes imprac-
tical, and software packages written specifically for solving chemical equilibrium
problems offer the only reasonable means of solving the problems. This type of soft-
ware is introduced in Chapter 7 and is used to analyze problems later in the text.
Of course, simple problems as well as complex ones can be solved using the soft-
ware that is introduced in Chapter 7. However, solving the problems manually in
conjunction with log C-pH diagrams can help us develop an intuitive feel for the key
relationships that control solution behavior in acid/base systems, and that approach is
therefore demonstrated here before introducing the computerized approach in Chap-
ter 7.
6.2 USING LOG C-pH DIAGRAMS TO SOLVE WEAK

ACID/BASE PROBLEMS
In Chapter 5, we used both algebraic and spreadsheet analyses to determine the equi-
librium pH of a solution of 10 3 M HPr (pKa = 4.87). Consider now how we might
solve the same problem with the help of a log C-pH graph. The graphical solution
must, of course, satisfy the same set of equations as a numerical solution. In the
current case, these equations are the relevant equilibrium constant and mass balance
expressions, and the charge balance.1
We start by showing the speciation of HPr and Pr– on a log C-pH diagram, using
the techniques developed in Chapter 5. The dependence of log(H+ ) and log(OH )
on pH is trivial, and we plot those values on the same log C-pH graph. The result is
a single plot, shown in Figure 6.1, that tells us what the equilibrium values of (H+ ),
(OH– ), (HPr), and (Pr– ) would be at any pH in a system with the given T OT Pr.
1 As has been noted in previous chapters, equilibrium constants relate activities, while mass and
charge balances relate concentrations. Here, and in the remainder of the text, we assume all solutes
behave ideally unless otherwise indicated, and we continue to use parentheses to represent both the
activity and the molar concentration when the assumption applies. Parentheses are also used to represent
the activity of water, but the concentration of water is represented by square brackets.
293
Figure 6.1 A log C-pH diagram for a solution containing 10 3M T OT Pr.
To expand on a point that was made in Chapter 5, this log C-pH diagram displays
exactly the same information, no more and no less, as is contained in the Ka and Kw
expressions and in the mass balance on Pr. That is, just as a straight line on a graph
is completely equivalent in information to an equation of the form y = mx + b, the
group of lines representing (H+ ), (OH– ), (HPr), and (Pr– ) on the log C-pH diagram
has equivalent information content to the set of Ka , Kw , and mass balance equations
that characterize the system. (The same can be said for the columns in a spreadsheet
showing the concentrations of these species as a function of pH.)
Although the values of (H+ ), (OH– ), (HPr), and (Pr– ) shown in Figure 6.1 at any
pH satisfy the Ka , Kw , and T OT Pr equations, at most pH’s those values do not satisfy
the charge balance. In fact, the charge balance is satisfied at only one pH, so only at
that pH are all the equations characterizing the system satisfied simultaneously. We
can find that pH by plotting curves representing the two sides of the charge balance
on the log C-pH diagram.
The charge balance equation is
(H+ ) = (Pr ) + (OH ) (6.1)
If we draw curves on the diagram representing the left-hand side [LHS = (H+ )]
and right-hand side [RHS = (OH ) + (Pr )] of this equation, the point where those
curves intersect will be the pH where the charge balance is satisfied; that is, they will
intersect at an x value corresponding to the equilibrium pH.
The curve for the LHS is trivial to draw: it simply overlays the (H+ ) line. The
curve for the RHS is a bit trickier, since we want to represent a linear summation on
a logarithmic scale; i.e., we want to plot a curve representing log[(OH ) + (Pr )].
To plot this curve exactly, we would need to carry out some simple, but neverthe-
less tedious, calculations. (Recall from basic math that log[(OH ) + (Pr )] does not
294
equal log(OH ) + log(Pr )!) It turns out, however, that a very close approxima-
tion of log(RHS) can be plotted without any such calculations. To understand this
approximation, consider the data in Table 6.1, showing the results of the relevant
calculations at a few pH values.
Table 6.1 Values of log[(OH ) + (Pr )] at various pH values for a system containing
10 3.0 M T OT Pr
pH log(OH– ) log(Pr– ) log[(OH– )+(Pr– )]

4.0 10.00 3.92 3.92
6.0 8.00 3.03 3.03
8.0 6.00 3.00 3.00
10.0 4.00 3.00 2.96
11.0 3.00 3.00 2.70
12.0 2.00 3.00 1.96
14.0 0.00 3.00 0.00
The values in the final column of the table correspond to log(RHS); i.e., they are
the values we want to plot. Comparison of these values with log(OH ) and log(Pr )
shows that, over most of the pH scale, log(RHS) is almost exactly equal to either
log(OH ) or log(Pr ), whichever is larger (the values shown in boldface type in the
table). As a result, over most of the graph, a curve representing log(RHS) simply
overlays the higher of the log(OH ) and log(Pr ) curves.
The only region where this approximation does not hold is where OH ⇡
Pr , in this example near pH 11. When OH = Pr , log[(OH ) + (Pr )]
equals log[2(OH )], which is the same as 0.3 + log(OH ). Thus, at the pH where
that equality applies (i.e., at the intersection of the OH and Pr curves), log(RHS)
is exactly 0.3 log unit larger than log(OH ) and log(Pr ). Considering all of the
preceding information, we can plot RHS in regions where OH and Pr are sig-
nificantly different from one another, and also at the point where they exactly equal
each other; we can then sketch the curve near the intersection point to obtain a good
approximation of RHS across the whole pH range. Both LHS and RHS are shown
in bold in Figure 6.2a, and Figure 6.2b shows an expanded view of the region where
the RHS curve shifts from being dominated by Pr to being dominated by OH .
The intersection of the RHS and LHS lines is circled in Figure 6.2a and is ap-
proximately at pH = 3.95. At this pH, the concentrations of all the species in solution
can be read from the graph as
(H+ ) = 10 3.95 (HPr) ⇠

= 10 3.03
(OH ) = 10 10.05 ⇠ 10
(Pr ) = 3.95
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Figure 6.2 (a) A reproduction of Figure 6.1, with additional lines (in bold) indicating the
values of the left-hand side (LHS) and right-hand side (RHS) of the charge balance
equation for a solution of 10 3 M HPr. (b) An expanded view of the pH region
from pH 9.5 to 12.5, where OH is close to Pr .
The accuracy of the result can be checked by evaluating the charge balance (CB)
and the Ka expression using these estimates. As shown below, both equations are
indeed satisfied to a close approximation.
?
3.95 = 3.95 + 10 10.05
Check CB: 10 10
(10 3.95 )(10 3.95 )
?
4.87 = 4.87
Check Ka : 10 3.03
= 10
10
If we needed a more accurate answer than the approximate one determined using
the log C-pH diagram (which is unlikely), we could at least use the graph to note that
296
at the equilibrium condition (OH ) ⌧ (H+ ) and then solve the problem numerically
as shown in Chapter 5. In such a case, the graph would provide a quick way to
determine which assumptions are reasonable; more often, however, an answer within
±0.05 of the exact pH is obtainable and entirely satisfactory, so the graphical method
can be used to solve the problem without carrying out any calculations at all.
The preceding discussion demonstrates (not surprisingly) that the spreadsheet,
graphical, and analytical solutions all yield essentially the same information. How-
ever, the graphical approach makes it much easier to visualize the behavior of the
various species as a function of pH than does either of the other two approaches, be-
cause in the analytical and numerical solutions, all the information about the system
is embedded in equations or lists of numbers. This advantage of the graphical ap-
proach is marginal in the very simple example system analyzed above, but it becomes
dramatic when one is analyzing more complex systems, as shown in the remainder
of the chapter.
The simplicity and benefits of the graphical analysis derive primarily from the
fundamental similarity of the equations characterizing acid/base speciation in all sys-
tems. That is, the equations for a0 and a1 are essentially identical for any monoprotic
acid/base system, differing only in the value of Ka , and the equations describing (H+ )
and (OH ) as a function of pH are the same in all systems. As a consequence, the
graphs “look” very similar for any monoprotic acid or base system: the lines for
(H+ ) and (OH ) always have slope 1 and +1, respectively, and always intersect at
(7.0, 7.0), and the curves for (HA) and (A ) have consistent, characteristic shapes,
regardless of which acid/base pair is under consideration. Increasing the total con-
centration of the acid/base group (i.e., T OT A) moves both the HA and the A curves
“up” the graph, and increasing pKa moves both to the right (higher pH). Regardless
of the total concentration and pKa value, however, the shapes of these curves and
their relationship to one another never change – they always intersect at pH = pKa
and at a value on the ordinate that is 0.3 log unit below T OT A.
Furthermore, it is very common for each side of the charge balance equation to
be dominated by a single term at any given pH, as was the case in the preceding ex-
ample. In such cases, the LHS or RHS curve is just a linked series of sections, each
overlaying the species that makes the largest contribution to the LHS or RHS sum-
mation in that pH region. Occasionally, two or more terms contribute significantly
to one side of the charge balance over a fairly wide pH range. A simple algorithm
for drawing the LHS and RHS lines in such situations is described in Appendix 6A.
An additional advantage of the graphical approach is demonstrated in the following
example.
Example 6.1
Use a graphical analysis to determine the equilibrium concentrations of all species
in a solution of 10 3 M NaPr.
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Solution
As in the analysis of the 10 3 M HPr solution, we start by drawing the log C-
pH diagram that characterizes the system. When we identify the equations that are
needed to draw the (H+ ), (OH– ), (HPr), and (Pr– ) curves on the graph, however,
we reach an extremely useful conclusion: Ka , Kw , and the mass balance on Pr are
identical to those in the previous problem, and those are the only equations that are
used to draw the four curves. As a result, all the lines in Figure 6.1 are applicable to
this problem as well, and we can use the same graph to solve the problem! Since we
want to represent the concentrations of all dissolved species on the graph, we need
to add a line for (Na+ ), but this is trivial, because (Na+ ) = 10 3 , independent of pH.
We also need to include Na+ in the charge balance, which becomes
(Na+ ) + (H+ ) = (Pr ) + (OH )
As before, we can draw lines on the graph to represent the LHS and RHS of the
charge balance, and again, in each case, the LHS or RHS curve simply overlays the
higher of the two curves in the corresponding summation. Unfortunately, though,
these curves do not readily identify a single pH where the charge balance is satisfied.
Rather, they indicate that the equation is approximately satisfied over the entire range
6  pH  10 (Figure 6.3a). Thus, the graph is not sufficiently precise to allow us to
solve the problem using the charge balance directly. Note that the graph is still a
perfectly valid representation of the system, and the RHS and LHS lines actually
do intersect at a single point which characterizes the equilibrium condition. The
problem we are encountering is strictly a practical one, related to the fact that we
cannot draw lines thin enough to pick out the exact point of intersection.
The difficulty in identifying the pH at which RHS = LHS in this problem can
be circumvented in at least two ways. One approach would be to return to using a
spreadsheet to solve the problem, taking advantage of the fact that the numerical pro-
cessing in the spreadsheet is much more precise than can be displayed graphically.
Although that approach is effective, it would still be nice to take advantage of the
features in the graphical approach for solving the problem, and this can be accom-
plished by combining the charge balance with two of the mass balances. Specifically,
if we equate the mass balances for Na and Pr (since T OT Na = T OT Pr = 10 3 ) and
then substitute the resulting expression for (Na+ ) in the charge balance, we obtain
CB: (Na+ ) + (H+ ) = (Pr ) + (OH )

Equating the two MBs: (Na+ ) = (Pr ) + (HPr)
Substituting into the CB: (Pr ) + (HPr) + (H+ ) = (Pr ) + (OH )
Modified CB: (HPr) + (H+ ) = (OH )
298
Figure 6.3 (a) A log C-pH diagram for a solution of 10 3 M NaPr, with the RHS and LHS
of the charge balance shown in bold. (b) The same diagram as in part (a), but
with the RHS and LHS based on an equation developed by combining the charge
balance with the mass balance on Pr.
By plotting the LHS and RHS of this modified charge balance equation on the
graph (Figure 6.3b), it is easy to identify their point of intersection. This intersection
point indicates that the equilibrium pH is 7.95, consistent with the numerical solution
in Chapter 5 (where we found the exact pH to be 7.94). Reading values from the graph
at pH 7.95, the concentrations of the various species at equilibrium are
(Pr ) = 10 3.00 (H+ ) = 10 7.95 (Na+ ) = 10 3.00
(HPr) = 10 6.05 (OH ) = 10 6.05
299
Checking the value of Ka as a way of confirming the result, we see that the com-
puted concentrations do indeed meet the criterion for equilibrium:
(10 7.95 )(10 3.00 )

4.90 ? 4.90
Ka = 10 = 6.05
= 10
10
The preceding example points out that although the graphical analysis might pro-
vide the best big-picture view of the relationships of interest, it suffers from the draw-
back that, at least in some cases, we need to combine the charge balance with one or
more mass balances to solve the problem. Two obvious questions arise from this
outcome: (1) How can we know which equation(s) to combine with the charge bal-
ance to obtain the best equation to use with the graph? and (2) Can we write the
desired equation directly, without going through the algebra of combining multiple
equations?
The answer to the first question is fairly straightforward. For the NaPr system,
each side of the charge balance consists of the sum of two numbers:
(Na+ ) + (H+ ) = (Pr ) + (OH )
The problem we encounter when trying to solve this equation directly is that, over
a fairly wide region near where it is satisfied, one of the numbers on each side [(Na+ )
on the left, (Pr– ) on the right] is much larger than the other. As a result, even though
the equation is satisfied exactly at only one pH, it is satisfied approximately over a
wide range where (Na+ ) ⇡ (Pr ). To “home in” on the pH where the equation is
satisfied exactly, we need to eliminate the large number from each side of the equa-
tion; this need was the basis for using the mass balances on Na and Pr to convert the
charge balance into a more useful equation for the graphical analysis. Generalizing
this result, whenever a charge balance appears to be satisfied over a wide pH range,
we need to combine the charge balance with mass balances that allow us to elimi-
nate the largest number on each side of the equation. Additional examples employing
this approach and extending the analysis to systems containing mixtures of acids and
bases or multiprotic acids are provided next; we defer answering the second question
until after those examples.
Example 6.2
Find the equilibrium concentrations of H+ , HOCl, OH– , and OCl– when the fol-
lowing chemicals are added to pure water. Recall that pKa,HOCl = 7.53.
(a) 10 3M KOCl
(b) 10 4M KOCl + 9 ⇥ 10 4M HOCl
300
Solution
(a) The charge balance for a solution of 10 3M KOCl is
CB: (K+ ) + (H+ ) = (OCl ) + (OH )
Plotting the two sides of the charge balance directly on a log C-pH diagram
for a system with 10 3 M T OT K and 10 3 M T OT OCl (Figure 6.4a), we run
into the same problem as in the NaPr system: the unique intersection point of
the RHS and LHS cannot be discerned from the graph. Noting that (K+ ) and
(OCl– ) are the largest terms on the left and right sides of the charge balance,
respectively, we can equate the mass balances on K and OCl and subtract the
resulting equation from the charge balance to obtain the desired equation:
CB: (K+ ) + (H+ ) = (OCl ) + (OH )

MB: (K+ ) = (OCl ) + (HOCl)
(H+ ) + (HOCl) = (OH )
Plotting LHS and RHS of the combined CB/MB equation (Figure 6.4b), we
find their intersection at
pH = 9.26 pOH = 4.74 log(HOCl) = 4.74 log(OCl ) = 3.01
(10 9.26 )(10 3.01 )

? 7.53
Ka = 4.74
= 10
10
(b) The charge balance for a solution of 10 4 MKOCl+9⇥10 4 M HOCl is shown

below, and the two sides of the equation are plotted in Figure 6.5.
CB: (K+ ) + (H+ ) = (OCl ) + (OH )
Although this charge balance has the same form as the one in part (a), it differs
in that the K+ concentration is only 10 4 M. As a result, the intersection point
of the LHS and RHS is easily identified on the graph without any modification
of the equation. The equilibrium condition is such that (K+ ) ⇡ (OCl ), at
which point the composition of the solution is
pH = 6.58 log(OCl ) = 4.00 log(K+ ) = 4.00

log(OH ) = 7.42 log(HOCl) = 3.05
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Figure 6.4 LogC-pH diagram for a solution containing 10 3 M T OT OCl. The LHS and RHS
of (a) the CB, and (b) a combined CB/MB are shown for a solution made by
adding all the OCl as KOCl.
Example 6.3
Prepare log C-pH graphs for the following solutions, and determine the specia-
tion in each system. pKa for HAc is 4.76, and that for NH+4 is 9.24.
(a) 10 3M HAc + 5 ⇥ 10 4M NH4 Cl
(b) 10 3M NaAc + 2.5 ⇥ 10 4M NH3 + 2.5 ⇥ 10 4M NH4 Cl
Solution
Because both solutions contain 10 3 M T OT Ac and 5 ⇥ 10 4 M T OT NH3 , a
single graph can be used to determine the equilibrium composition of both of them
302
Figure 6.5 LogC-pH diagram for a system containing 10 3 M T OT OCl. The RHS and LHS
of the charge balance are shown in bold for a system comprised of 10 4 M KOCl
plus 9 ⇥ 10 4 M HOCl.
(Figure 6.6). However, in both cases, the charge balance must be combined with
a mass balance to determine the equilibrium pH. The various manipulations of the
equations and the final results are summarized below.
Figure 6.6 LogC-pH diagram for a system containing 10 3M T OT Ac and 5 ⇥ 10 4M
T OT NH4
303
(a) (H+ ) + (NH+
4 ) = (OH ) + (Ac ) + (Cl )
+ (Cl ) = (NH+
4 ) + (NH3 )
(H+ ) = (OH ) + (Ac ) + (NH3 )
pH ⇡ 3.91, where (H+ ) ⇡ (Ac )
(b) (NH+ + +
4 ) + (Na ) + (H ) = (Ac ) + (OH ) + (Cl )
+ (Ac ) + (HAc) = (Na+ )

(NH+ +
4 ) + (H ) + (HAc) = (OH ) + (Cl )
(NH+ 4
4 ) + (H ) + (HAc) = (OH ) + 2.5 ⇥ 10
+
pH ⇡ 9.19 (⇡ pKa,NH+ ), where (NH3 ) = (NH+ 4

4 4 ) = 2.5 ⇥ 10
Note that, in Example 6.3b, the (HAc) term contributes negligibly to the LHS of
the combined CB/MB at the point where the equation is satisfied, and (Ac– ) does not
appear in the equation at all. As a result, the acetate species have essentially no effect
on the result; i.e., the pH is the same in this solution as it would be if we had added
the ammonia species but no Ac at all. The log C-pH diagram makes it clear why this
is so. At the equilibrium pH, almost all the Ac in the system is present as acetate
ion, Ac– . Since that is also the form in which all the Ac was added to the solution,
we conclude that acetate enters this solution as Ac– and then undergoes no further
reaction. In particular, virtually none of the Ac– ions combine with H+ to form HAc.
In essence, then, in this system, NaAc acts not like a base but rather like an inert salt.
This result applies because the NH3 increases the pH to a value where the Ac– has
no significant tendency to become protonated.
Example 6.4
(a) What are the concentrations of all species in solutions of (i) 10 2M Na2 CO3 ;
(ii) 10 2 M NaHCO3 ; (iii) 10 2 M H2 CO3 ?
(b) A solution has three times as much H2 CO3 as CO2–

3 . What is its pH?
Solution
(a) As in the previous examples, the chemical relationships in this system can be
expressed by a combination of mass balances, equilibrium constants, and a
charge balance. The mass balance on T OT CO3 and the equilibrium equations
304
are the same for all three solutions, so they can be characterized by a single
log C-pH graph, which is shown in Figure 6.7.
Figure 6.7 log C-pH diagram for a system containing 10 2M T OT CO3
(i) CB : (Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )
This charge balance differs from the ones analyzed in the previous exam-
ples because, under conditions where the last term on the right dominates
that side of the equation, RHS ⇡ 2(CO23 ). Thus, under these conditions,
the curve representing RHS will not overlap the (CO2–3 ) curve, but rather
2–
will coincide with a curve representing 2(CO3 ). To determine where
such a curve lies on the graph, we can rewrite the approximation as fol-
lows:
⇥ ⇤
log(RHS) ⇡ log 2(CO23 ) = log 2 + log(CO23 ) = 0.3 + log(CO23 )
This result indicates that, when RHS is dominated by the term 2(CO23 ),
the curve for log(RHS) is 0.3 log unit above the log(CO23 ) curve, as
shown in Figure 6.7.
The two sides of the charge balance are shown in Figure 6.8, labeled as
RHS-(i) and LHS-(i), respectively. It is not too difficult to estimate the
equilibrium pH by using the charge balance in this case, but that pH can
be identified more accurately if the largest terms in the charge balance
are eliminated. Based on the intersection of the RHS-(i) and LHS-(i)
curves, the largest terms in the equation at the equilibrium pH are (Na+ )
and 2(CO2–3 ) respectively. Eliminating these terms from the equation is
305
easily done, since T OT Na = 2 T OT CO3 . Subtracting that equality from
the CB equation, we obtain
(Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )

(Na+ ) = 2(H2 CO3 ) + 2(HCO3 ) + 2(CO23 )
2(H2 CO3 ) + (HCO3 ) + (H+ ) = (OH )
Figure 6.8 LogC-pH diagram for Example 6.4. The bold lines show the two sides of the
unmodified charge balance equation for part (i). The solutions for part (i) using
the modified charge balance and for parts (ii) and (iii) are also shown.
(H+ ) = 10 11.13 (OH ) = 10 2.87
(H2 CO3 ) = 10 7.64 (HCO3 ) = 10 2.86 (CO23 ) = 10 2.06
(ii) CB : (Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )
Once again, identifying the pH where the RHS and LHS are equal is
difficult, and we can overcome the problem by substituting to eliminate
the largest terms. In this case, the mass balances are related by T OT Na =
T OT CO3 . Combining this expression with the CB yields
(Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )
(Na+ ) = (H2 CO3 ) + (HCO3 ) + (CO23 )
(H2 CO3 ) + (H+ ) = (OH ) + (CO23 )
306
The resulting equation is satisfied at (H2 CO3 ) ⇡ (CO23 ), pH 8.34. This
point is circled and labeled (ii) in Figure 6.8. The composition of the
solution is
(H+ ) = 10 8.34 (OH ) = 10 5.66
(H2 CO3 ) = 10 4.00 (HCO3 ) = 10 2.01 (CO23 ) = 10 4.00
(iii) CB : (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )
The point where this CB is satisfied can be identified directly on the

graph. The result is that the equilibrium pH is 4.18, where (H+ ) ⇡
(HCO3 ).
(H+ ) = 10 4.18 (OH ) = 10 9.82
(H2 CO3 ) = 10 2.00 (HCO3 ) = 10 4.17 (CO23 ) = 10 10.32
(b) In this problem, we know the relative concentrations of two species and want
to determine the solution pH. One approach for doing this is to generate a
reaction relating the two species of interest and H+ by adding the reactions for
dissociation of H2 CO3 and HCO–3 . Recalling that when we add reactions, we
must multiply equilibrium constants, we find
H2 CO3 )* HCO–3 + H+ Ka1
HCO–3 )* CO2–
3 +H
+
Ka2
H2 CO3 )* CO2–
3 +2H
+
Ka02 = Ka1 Ka2 = 10 16.68
(CO23 )(H+ )2 16.68

= 10
(H2 CO3 )
Substituting the given information that (H2 CO3 )/(CO23 ) = 3, we can com-
pute the solution pH:
(H+ )2 = 3 ⇥ 10 16.68 = 10 16.20
(H+ ) = 10 8.10 pH = 8.10
To summarize, the preceding discussion and examples demonstrate how a log C-

pH diagram can be used to determine the pH of a system with known inputs. The
307
graph contains information about the relevant acidity constants (indicated by the in-
tersection points of conjugate acid/base pairs), the dissociation of water (indicated by
the positions of the H+ and OH– lines), and the total amount of each weak acid/base
group in the system (indicated by the largest value that log C approaches for the indi-
vidual acid and base species). Once the graph is drawn, all we need to do to solve for
the equilibrium speciation of the system is to write the charge balance equation and
find the unique pH where that equation is satisfied.
In some cases, we can determine the equilibrium pH directly from the graph and
charge balance; however, in other cases, it is necessary to derive a new equation by
combining the charge balance with a mass balance before the graphical analysis can
be used. While knowing how to convert the charge balance into a more useful form
is helpful, it would be even better if we could write the final form of the equation
directly, without going through the charge balance at all. An approach for accom-
plishing that goal is presented next.
6.3 THE MASS BALANCE ON H (THE TOTH EQUATION

AND PROTON CONDITION)
Recall that, when writing the mass balances that characterize acid/base systems, we
chose not to evaluate the mass balance on H. The reason for this decision is most
easily understood by contrasting the mass balance on H with that for other substances
in the system.
Consider a hypothetical system containing 10 6 M total arsenate (75 µg AsO4 /L).
The arsenate acid/base group is triprotic, forming arsenic acid (H3 AsO4 ) when it is
fully protonated; the general chemistry of this group is very similar to that of the
phosphate group. However, whereas phosphate is a major component of nucleic acids
and adenosine triphosphate (ATP, the key chemical used to store energy in most cells),
arsenate is a poison at relatively low levels. It has been used as an herbicide in the
past, but its use in such applications and in industrial processing is now severely
limited.2
The acidity constants of arsenic acid are close to those of phosphoric acid, so
the forms most likely to be found in natural waters are the mono- and divalent ions
H2 AsO–4 and HAsO2– 3–
4 , with arsenic acid and arsenate ion (AsO4 ) present at much
lower concentrations. Nevertheless, in the mass balance, we consider the contribu-
2 Most current environmental concerns about arsenic in the developed world are related to its pres-
ence in drinking water and to the cleanup of a few severely contaminated but localized sites of soil
pollution. As of 2013, the maximum contaminant level (MCL) for arsenic in the United States was
10 µg/L, and the maximum contaminant level goal (MCLG) was zero. In a few locations in the world,
water that has been used as a potable source has arsenic concentrations that far exceed safe levels, lead-
ing to disastrous epidemiological consequences. In those cases, the source of the contamination has
usually been natural, arsenic-bearing rocks in the aquifer.
308
Increased awareness of the risks associated with arsenic ingestion have caused several governments
to lower the allowable level of arsenic in drinking water. In Bangladesh, natural concentrations
of arsenic in groundwater have had a devastating e↵ect on some communities. The photograph
on the left shows some of the symptoms of arsenic poisoning, and that on the right shows
sheep being dipped in an arsenic-based solution to kill external parasites. (Left: http://bd-
halchall.blogspot.com/2010/03/arsenic-pollution-in-bangladesh.html; Right: G.R. Roberts/G.R.
“Dick” Roberts Photo Library.)
tions of all four species to T OT AsO4 . Thus, in the example solution, the mass balance
on arsenic is
6.0
T OT AsO4 = 10 = (H3 AsO4 ) + (H2 AsO4 ) + (HAsO24 ) + (AsO34 )
The baseline arsenic concentration that we use when we do this accounting is

zero. That is, the total amount of arsenic present is quantified by comparison with a
solution containing zero arsenic. This choice is so logical and obvious that it is nor-
mally taken for granted. However, there are times when it is more useful to quantify
the amount of some substance in solution by comparison with a baseline other than
zero. One easy way to understand this concept is to consider a nonchemical example,
such as banking.
Banks provide monthly statements that tell people how much money they have in
their accounts, and these statements are based on a balance of zero as the baseline.
However, let’s say you have an account that provides free checking if you maintain
a balance of at least $500. If you want to make sure that you always maintain the
minimum balance in your checkbook, you might keep track of your available funds,
meaning the balance above $500. In this case, you might record a balance of $650
on the bank’s statement as a balance of only $150 in your checkbook. Furthermore,
if your real balance did dip below the minimum (say, to $350), your records would
show that your balance had become negative ( $150). This scenario is perfectly
rational (at least I think so; I used to use it!), and it is as accurate and reliable as
a more conventional accounting practice. The only critical requirement is that you
know what the accounting rules are in order to interpret the numerical data correctly.
In the absence of a good reason to define a nonzero baseline for a chemical mass
balance, we generally do not do so, and as noted above, we generally do not even
309
take note of the fact that we are choosing “zero substance” as the baseline condi-
tion. When writing a mass balance on H, however, we do have a good reason for
using a nonzero baseline. Specifically, the concentration of H atoms associated with
H2 O molecules is enormous (2 ⇥ 55.6 M) compared to the concentration present in
all other species in solution. This fact makes it very inconvenient to try to keep
track of all the H in the system. Rather, it is much easier to do the accounting by
defining a large absolute concentration of H (approximately equal to the H concen-
tration present as part of H2 O molecules, but also including a few other terms) as the
baseline, and to keep track of H concentrations relative to that baseline.
The mass balance on H using a nonzero baseline has traditionally been written in
two forms. One form is exactly analogous to the mass balances on other components
of solution, except for the nonzero baseline. In this equation, the total concentration
of H relative to the baseline is designated as T OT H, and the equation is called the
TOTH equation. Because of its similarity to the other mass balances that character-
ize the system, the T OT H equation is particularly well-suited for inputting the data
into computer software for solving chemical equilibrium problems. In the other, only
slightly different form of the equation, terms are shifted so that the LHS and RHS of
the mass balance each involves only additions and no subtractions. This version of
the equation is called the proton condition (PC); the proton condition is better suited
than the T OT H equation for solving problems graphically using log C-pH diagrams.
In the next section, an algorithm is presented for simultaneously developing all
the mass balance equations applicable to a system, including the T OT H equation.
The conversion of the T OT H equation to the PC is then demonstrated, and the PC
is used to solve several problems graphically; the T OT H equation is used to solve
similar problems in Chapter 7, where chemical equilibrium software is introduced,
and in subsequent chapters.
6.4 DEFINING THE COMPOSITION OF THE SYSTEM:

COMPONENTS, SPECIES, AND THE SYSTEM
TABLEAU
We begin by assigning special meanings to two terms that have been used in a more
general way to this point. Specifically, we define a system’s species as the group of
chemicals expected to be present in the system at equilibrium, and the components
for the system as any group of chemicals that satisfies the following two criteria: (1)
combinations of the components can be used to generate all the system’s species,
and (2) none of the components can be generated by a reaction involving only other
components. Note that, based on these criteria, components only have meaning when
defined as an entire group. Those familiar with the terminology of linear algebra
will recognize these restrictions as establishing that the components ‘span the space’
310
of species. Formation of a group of four species from three components is shown
schematically in Figure 6.9.
Figure 6.9 Schematic showing the formation of four species from various combinations of
three components. The numbers next to the arrows indicate the stoichiometric
coefficients for forming each species.
As indicated in the figure, it is allowable to either add or subtract components

from one another to form species. For instance, Spec 3 is formed by subtracting
(i.e., removing) one unit of Comp C from one unit of Comp B. An example of such a
reaction would be the formation of the species OH– by removing one H+ ion from a
water molecule. The figure also indicates that Spec 1 consists of one unit of Comp A
and nothing else. Thus, Spec 1 and Comp A are chemically identical. However, the
operations that we will carry out on components are different from those on species,
so we will distinguish between them, even if in some cases a component is the same
chemical entity as a species.
To make the process of defining species and components more explicit, consider
a system made by adding 2 ⇥ 10 3 M HAc to water. The chemicals expected to be
present at equilibrium (i.e., the system’s species) include H2 O, H+ , Ac– , OH– , and
HAc. Say we chose H2 O, H+ , and Ac– as components. Three of the species (H2 O, H+ ,
and Ac– ) are chemically identical to components, so obviously those species could be
formed from the components directly. The remaining two species can be generated
by appropriate combinations of components: OH– can be made by “subtracting” an
H+ from an H2 O molecule, and HAc can be made by adding an H+ to an Ac– . When
written as chemical reactions, these ways of generating OH– and HAc bear a close
and obvious relationship to reactions for the dissociation of water (the Kw reaction)
and the acetic acid dissociation reaction, respectively:
311
Reaction forming species as a Reaction written
combination of components conventionally
H2 O H+ )* OH– H2 O )* H+ + OH– (6.2)
H+ + Ac– )* HAc HAc )* H+ + Ac– (6.3)
The (conceptual) ability to form all the species by various combinations of the
components satisfies the first criterion for using H2 O, H+ , and Ac– as a set of com-
ponents for the system. Since it is not possible to generate any of the components by
a reaction involving only other components (for instance, it would not be possible to
form H+ by any combination of H2 O and Ac– without simultaneously generating or
removing other chemical species), the second criterion is satisfied as well, and the
proposed set of components is acceptable.
Next, the stoichiometry for forming each species from the components is formal-
ized. The simplest way to do this is to fill in the stoichiometric coefficients for the
components in reactions like the following for forming each species:
nA, j Comp A + nB, j Comp B + ... + nN, j Comp N )* 1Spec j (6.4)
where ni, j is the stoichiometric coefficient for component i in the reaction forming
species j. The same set of components is used to form all the species in the system.
Thus, for example, for a solution of HAc in water, the reactions would be:
1 H2 O + 0 H+ + 0 Ac– )* 1 H2 O (6.5)
0 H2 O + 1 H+ + 0 Ac– )* 1 H+ (6.6)
0 H2 O + 0 H+ + 1 Ac– )* 1 Ac– (6.7)
1 H2 O + 1 H+ + 0 Ac– )* 1 OH– (6.8)
0 H2 O + 1 H+ + 1 Ac– )* 1 HAc (6.9)
Although the choice of H2 O, H+ , and Ac– as components is acceptable for this

system, this set is not unique; several other choices are equally acceptable. For in-
stance, the group H2 O, H+ , and HAc meets the criteria for an acceptable component
set, as does the group H2 O, HAc, and Ac– . On the other hand, it would not be allow-
able to choose H+ , HAc, and Ac– as a component set, both because it is possible to
generate Ac– by a reaction involving only the other components (by HAc dissocia-
tion) and because it is impossible to generate H2 O or OH– solely by a combination of
these three components. These examples reinforce the idea that no individual chem-
ical entity is inherently acceptable or unacceptable as a component; components can
only be acceptable or unacceptable as complete sets, and any system can be repre-
sented by many different sets.
312
It is even possible to choose chemicals that are not present in the system or that
are not realistic molecules as components. For instance, if we thought it would be
useful for some reason, we could specify ways to make all the species in the example
system using H2 O, Ac– and H4 Ac3+ as components, even though H4 Ac3+ has never
been detected in solution. The stoichiometry for forming the five species from this
set of components would be
1 H2 O + 0 Ac– + 0 H4 Ac3+ )* 1 H2 O
0 H2 O + 1 Ac– + 0 H4 Ac3+ )* 1 Ac–
1 H2 O + 0.25 Ac– + 0.25 H4 Ac3+ )* 1 OH–
0 H2 O + 0.25 Ac– + 0.25 H4 Ac3+ )* 1 H+
0 H2 O + 0.75 Ac– + 0.25 H4 Ac3+ )* 1 HAc
Thus, if we include the possibility of using unrealistic components, an infinite

number of acceptable component sets can be used to describe any system. However,
once a component set is chosen, there is only one way to write the reaction forming
each species from those components; i.e., the stoichiometric coefficients for forming
each species are uniquely defined once the components have been chosen.
Each reaction forming a species from the components can be assigned a unique
equilibrium constant. In the baseline system, the equilibrium constants for forming
H2 O, H+ , and Ac– , i.e., for Reactions (6.5) through (6.7), are trivial: they must be
1.0, as is obvious if the reactions are rewritten leaving out the components that have
coefficients of zero. These reactions are repeated below, with the components shown
in bold to distinguish them from the corresponding species.
1 H2 O )* 1 H2 O KH2 O = 1.0 (6.10)

1 H+ )* 1 H+ KH+ = 1.0 (6.11)
1 Ac– )* 1 Ac KAc = 1.0 (6.12)
Keep in mind that, in terms of our formal algorithm, these reactions are not just
saying that one water molecule forms one water molecule [Reaction (6.10)] or that
one acetate ion forms one acetate ion [Reaction (6.12)]. Rather, Reaction (6.7) [or
its abbreviated version, Reaction (6.12)] indicates that the species Ac– is formed by
combining one unit of the component Ac– plus zero units of the component H2 O plus
zero units of the component H+ , and then applying an equilibrium constant of 1.0 to
that reaction.
The equilibrium constant for Reaction (6.8) can be derived formally as follows:
313
H2 O )* H+ +OH– Kw
(H+ )* H+ ) K = 1.0
1 H2 O 1 H+ )* OH K(6.8) = Kw K = 10 14.00
Similarly, the equilibrium constant for Reaction (6.9) is
1 Ac– + 1 H+ )* HAc K(6.9) = Ka 1 = 10+4.76 (6.13)
The five equilibrium constant equations relating the species to the components
are summarized in both algebraic and logarithmic form in Table 6.2. The same infor-
mation is also presented in a more concise matrix format in Table 6.3, with each row
in the matrix containing the stoichiometric coefficients and log K value for forming a
particular species from the components. This type of matrix is widely referred to as
a tableau.
Table 6.2a Formal algebraic expressions for relating species activities to component activities
for an aqueous solution of HAc
Reaction Algebraic equations to compute species activity at equilibrium

(6.5) (H2 O) = K(6.5) (H2 O) = K(6.5) (H2 O)1 (H+ )0 (Ac– )0
(6.6) (H+ ) = K(6.6) (H+ ) = K(6.6) (H2 O)0 (H+ )1 (Ac– )0
(6.7) (Ac ) =K(6.7) (Ac– ) = K(6.7) (H2 O)0 (H+ )0 (Ac– )1
(H O)
(6.8) (OH ) = K(6.8) 2+ = K(6.8) (H2 O)1 (H+ ) 1 (Ac– )0
(H )
(6.9) (HAc) = K(6.9) (H+ )(Ac– ) = K(6.9) (H2 O)0 (H+ )1 (Ac– )1
Table 6.2b Logarithmic forms of the equations in Table 6.2a
Reaction Logarithmic equation

(6.5) log(H2 O) = log K(6.5) + 1 log(H2 O) + 0 log(H+ ) + 0 log(Ac– )
(6.6) log(H+ ) = log K(6.6) + 0 log(H2 O) + 1 log(H+ ) + 0 log(Ac– )
(6.7) log(Ac ) = log K(6.7) + 0 log(H2 O) + 0 log(H+ ) + 1 log(Ac– )
(6.8) log(OH ) = log K(6.8) + 1 log(H2 O) 1 log(H+ ) + 0 log(Ac– )
(6.9) log(HAc) = log K(6.9) + 0 log(H2 O) + 1 log(H+ ) + 1 log(Ac– )
314
Table 6.3 Tableau showing the key features of the equilibrium expressions in Table 6.2
Stoichiometric Coefficient⇤
Component: H2 O H+ Ac– log K
Species
H2 O 1 0 0 0.00
H+ 0 1 0 0.00
Ac– 0 0 1 0.00
OH– 1 1 0 14.00
HAc 0 1 1 4.76
⇤ For forming the species in a given row from the components.
Example 6.5
Prepare a tableau like that shown in Table 6.3 for the same system (addition of
HAc to water), but using H2 O, OH– , and HAc as components.
Solution
The reactions and equilibrium constants for forming the five species from the
new set of components are shown below, and the information is summarized in the
following matrix. Convince yourself that the equilibrium constants are correct for
the reactions shown.
1 H2 O + 0 OH– + 0 HAc )* 1 H2 O K = 1.00

0 H2 O + 1 OH– + 0 HAc )* 1 OH –
K = 1.00
–
0 H2 O + 0 OH + 1 HAc )* 1 HAc K = 1.00
1 H2 O + 1 OH– + 1 HAc )* 1 Ac –
K = 109.24
1 H2 O + 1 OH– + 0 HAc )* 1 H+ K = 10 14.00
Stoichiometric Coefficient
Component: H2 O OH– HAc log K
Species
H2 O 1 0 0 0.00
–
OH 0 1 0 0.00
HAc 0 0 1 0.00
–
Ac 1 1 1 9.24
H+ 1 1 0 14.00
315
Example 6.6 Prepare the tableau for a solution of 10 3 M NaAc, using H2 O, Na+ ,
H+ , and Ac– as components. Note that, in this case, some sodium-containing chem-
ical must be added as a component, in order to be able to “make” the species Na+ .
Sodium ion is the simplest choice for such a component.
Solution
The matrix is shown below. Confirmation of the values shown for the equilibrium
constants is left as an exercise.
Component: H2 O H+ Na+ Ac– log K
Species
H2 O 1 0 0 0 0.00
+
Na 0 0 1 0 0.00
H+ 0 1 0 0 0.00
–
Ac 0 0 0 1 0.00
–
OH 1 1 0 0 14.00
HAc 0 1 0 1 4.76
6.5 EXPRESSING INPUT AND EQUILIBRIUM

CONCENTRATIONS IN TERMS OF COMPONENTS;
COMPONENT MASS BALANCES
Because all the species in a system can be represented as combinations of the com-
ponents, we can imagine a process in which the species in the equilibrium solution
are all decomposed into a mixture of components and nothing else. Using the same
terminology as in Equation (6.4), if the system contains Meq species, the total con-
centration of component i in the mixture of decomposed species will be
Meq
T OTieq = ni,1 c1 + ni,2 c2 + ... + ni,M j cMeq = Â ni, j c j (6.14)
j=1
where ni, j is the stoichiometric coefficient for component i in the reaction forming
species j, and c j is the concentration of species j in the solution at equilibrium. In
words, each term in the summation on the right side of Equation (6.14) can be viewed
as the concentration of component i “embedded” in species j in the equilibrium solu-
tion, so the summation is the concentration of i embedded in all species in the whole
316
solution. The coefficients ni, j are listed in the column for component i in the tableau
so, for example, the three applications of Equation (6.14) to the data in Table 6.3 are:
T OT H2 Oeq = 1[H2 O]eq + 1(OH )eq (6.15)

T OT Heq = 1(H+ )eq 1(OH )eq + 1(HAc)eq (6.16)
T OT Aceq = 1(HAc)eq + 1(Ac )eq (6.17)
where the subscript emphasizes that the concentrations are those in the equilibrium
solution. Note that we can represent the concentrations of the solutes as being equal
to their activities, but for H2 O, we need to distinguish between those two terms and
use the concentration when calculating T OT H2 Oeq .
Equation (6.14) is based on the (conceptual) decomposition of the equilibrium
species into a mixture of the components. Since these species were all either input
into the system directly or generated via reactions among the input chemicals, it must
be the case that the input chemicals can also be decomposed into the components. We
can therefore write a T OTi expression based on the inputs by an equation analogous
to (6.14), as follows:
Min
T OTiin = ni,1 c1 + ni,2 c2 + ... + ni,Min cMin = Â ni,k ck (6.18)
k=1
where ni,k is the stoichiometric coefficient for component i in the reaction forming
the input chemical k, ck is the dose of k added (moles of k input per liter of solution),
and Min is the number of input chemicals used to prepare the system.3 Applying this
equation to the example system, which was prepared using two inputs (Min = 2: H2 O
and HAc), we find:
T OT H2 Oin = 1[H2 O]in + 0[HAc]in = 55.6 (6.19)

3
T OT Hin = 0[H2 O]in + 1[HAc]in = 2 ⇥ 10 (6.20)
3
T OT Acin = 0[H2 O]in + 1[HAc]in = 2 ⇥ 10 (6.21)
We can incorporate this information into the tableau by adding a row to the bottom
for each input chemical. When we do that, and also add a column for the input and
equilibrium concentrations, the tableau is expanded as shown in Table 6.4.
3 As used here, ‘inputs’ include all chemicals that have entered the solution prior to the time when
it reaches equilibrium. In some cases, our interest is in a solution where all the inputs are known; in
others, we might know the composition of the solution at some initial point without knowing exactly
what chemicals were added to prepare that solution, and also know the inputs that entered subsequently.
In such cases, we can consider the ultimate solution to be a combination of the initial solution and the
later inputs, and we can calculate T OTiin based on that conceptualization. Example 6.8 demonstrates
this idea.
317
Table 6.4 Expanded tableau showing inputs and equilibrium species for the example system
Component: H2 O H+ Ac– log K Conc’n
Species
H2 O 1 0 0 0.00 [H2 O]eq
H+ 0 1 0 0.00 [H+ ]eq
Ac– 0 0 1 0.00 [Ac ]eq
OH– 1 1 0 14.00 [OH ]eq
HAc 0 1 1 4.76 [HAc]eq
Inputs
H2 O 1 0 0 55.6
HAc 0 1 1 2 ⇥ 10 3
Finally, we can equate the total concentration of each component in all the equi-
librium species [Equations (6.15)-(6.17)] with that in all the inputs [Equations (6.19-
6.21)] to obtain
T OTieq = T OTiin (6.22)

i =H2 O: [H2 O]eq + (OH )eq = 55.6 (6.23)
i =H: (H+ )eq (OH )eq + (HAc)eq = 2 ⇥ 10 3 (6.24)
i =Ac: (HAc)eq + (Ac )eq = 2 ⇥ 10 3 (6.25)
Equations (6.23) through (6.25) can be considered mass balances on the three
components. However, of the three equations, only Equation (6.25) looks like a
conventional mass balance. For example, the mass balance on H+ [Equation (6.24)]
does not include any of the H+ associated with water molecules, and it counts the
concentration of OH– as a negative contribution to T OT H, even though OH– ions
do contain H+ . Similarly, the mass balance on H2 O [Equation (6.23)] includes OH– ,
even though OH– molecules do not contain a full molecule of H2 O.
These initially counterintuitive results arise because the mass balances shown
are written not in terms of conventional chemical groups, but rather in terms of the
molecules we have chosen as components. Thus, the species HAc is included in the
mass balance on Ac– because, according to our algorithm, one unit of the component
Ac– is required to ‘make’ the species HAc. Similarly, H3 O+ and OH– are included
in the mass balance on H+ with coefficients of 1 and 1, respectively, because 1 and
1 ‘units’ of H+ are used when these species are made from the components.
318
In terms of the discussion that introduced this section, the component choices we
have made can be viewed as shifting the baseline for the mass balances on those com-
ponents. For example, the baseline for H+ is defined to include all the components
other than H+ , meaning that those components are treated as though they contain
zero H+ , regardless of their actual molecular composition. The baselines for the other
components (H2 O and Ac– ) are defined in analogous ways. Like in the banking ex-
ample given earlier, this way of accounting is perfectly valid and, as shown next, it
can have significant advantages over more traditional methods.
Because of the centrality of H2 O to all systems we will explore, we will always
choose it as a component, and so a mass balance on H2 O will always be one of the
equations that must be solved to determine the equilibrium speciation. However, this
mass balance is invariably like Equation (6.23), in that it includes a summation of
[H2 O] plus one or more other species that are present at orders of magnitude lower
concentrations. Thus, the mass balance can always be approximated as [H2 O] = 55.6,
so there is no need to “solve” for the equilibrium concentration of H2 O. Similarly,
unless otherwise indicated, we will always assume that the activity of H2 O is 1.0.
Therefore, in the subsequent discussion, we will include H2 O in the list of compo-
nents, but will not explicitly list it as an input chemical or write the accompanying
mass balance.
Example 6.7
(a) Prepare two tableaus for a solution made by adding 10 2 M each of HAc and
Na2 CO3 to water, using the two different sets of components listed below.
Component set #1: H2 O, H+ , HAc, Na+ , CO2–

3
Component set #2: H2 O, H+ , Ac– , Na+ , HCO–3
(b) Convert the resulting T OT H equations to proton conditions (PCs), and use
the PCs in conjunction with a log C-pH diagram to solve for the equilibrium
pH. What are the dominant species of each acid/base group in the equilibrated
solution?
Solution
(a) The two tableaus are shown below. (The final column in the top portion of the
tableau is unnecessary and has therefore been left blank.) The species that are
present at equilibrium are, of course, identical in the two tableaus, but the way
in which they are generated is not; as a result, the equilibrium constants for
generating some of the species differ in the two tableaus. Study the tableaus
carefully to make sure you understand how the stoichiometric coefficients and
equilibrium constant for each species and each input chemical were derived.
319
Tableau using component set #1
Component: H2 O H+ HAc Na+ CO2–
3 log K Conc’n
Species
H2 O 1 0 0 0 0 0.00
+
H 0 1 0 0 0 0.00
HAc 0 0 1 0 0 0.00
+
Na 0 0 0 1 0 0.00
CO2–
3 0 0 0 0 1 0.00
–
OH 1 1 0 0 0 14.00
Ac– 0 1 1 0 0 4.76
HCO–3 0 1 0 0 1 10.33
H2 CO3 0 2 0 0 1 16.68
Inputs
HAc 0 0 1 0 0 1.0 ⇥ 10 2
Na2 CO3 0 0 0 2 1 1.0 ⇥ 10 2
Tableau using component set #2

Component: H2 O H+ Ac– Na+ HCO–3 log K Conc’n
Species
H2 O 1 0 0 0 0 0.00
+
H 0 1 0 0 0 0.00
HAc 0 1 1 0 0 4.76
+
Na 0 0 0 1 0 0.00
CO2–
3 0 1 0 0 1 10.33
–
OH 1 1 0 0 0 14.00
–
Ac 0 0 1 0 0 0.00
HCO–3 0 0 0 0 1 0.00
H2 CO3 0 1 0 0 1 6.35
Inputs
HAc 0 1 1 0 0 1.0 ⇥ 10 2
Na2 CO3 0 1 0 2 1 1.0 ⇥ 10 2
320
(b) The T OT H equations for the two component sets are written by equating
T OT Heq [from Equation (6.14)] with T OT Hin [from Equation (6.18)]. The
results are as follows:
T OT H equation for component set #1:
H+ OH Ac + HCO3 + 2 H2 CO3
2 2
= 0 1.0 ⇥ 10 + 0 1.0 ⇥ 10 =0
T OT H equation for component set #2:
H+ OH + (HAc) CO23 + H2 CO3

2 2
= 1 1.0 ⇥ 10 1 1.0 ⇥ 10 =0
The T OT H equations can be converted to PCs by moving terms around so that

both sides of the equation contain only summations, i.e.,
Proton condition for component set #1:
H+ + HCO3 + 2 H2 CO3 = OH + Ac
Proton condition for component set #2:
H+ + (HAc) + H2 CO3 = OH + CO23
A log C-pH diagram for the system is shown in Figure 6.10, with the LHS
and RHS of each PC highlighted. The equilibrium pH is not easily identified
using the PC from the first component set. If we had investigated only that
set of components, we would have had to combine the T OT H equation and/or
PC with some other equation (another mass balance or the charge balance) to
obtain an equation that was easily evaluated in conjunction with the graph. On
the other hand, the PC derived from the second component set can be used
directly with the graph to identify the equilibrium pH, which is 8.34. At this
pH, almost all the acetate in the system is present at Ac– , and almost all the
carbonate is present as HCO–3 .
Note that, in the solution of this problem, the log K values listed in the tableau
were not used explicitly. The reason for this is that the same information was
already embedded in the log C-pH diagram. This situation will apply to all
the problems we analyze in the remainder of the chapter. Nevertheless, we
will continue to populate the log K columns of the tableaus, because that in-
formation becomes useful (and necessary) when we explore computer-based
approaches for solving these problems in Chapter 7.
321
Figure 6.10 LogC-pH diagram for the example system. The solid bold lines are the LHS and
RHS of the PC based on component set #1, and the broken bold lines are for the
PC based on component set #2. The oval and circle indicate the regions where
LHS⇡RHS for the two equations.
The preceding example demonstrates that, even though there are many acceptable
choices for the component set for a given system, not all choices are equally useful
when applied in conjunction with a log C-pH diagram to find the equilibrium solution
composition – some choices lead to a PC whose LHS and RHS nearly overlap in the
region where the equation is satisfied, making it difficult to identify the equilibrium
pH. This is, of course, the same problem we encountered earlier when we tried using
the charge balance in conjunction with a log C-pH diagram. In all these cases, the
problematic situation arises when the largest term on each side of the equation is
insensitive to pH in the region where the equation is satisfied. Correspondingly, the
problem can be overcome by subtracting from both sides a value equal to the largest
term on one side. The question then becomes: How can we choose components
wisely, so that we derive equations that can be used directly to find the equilibrium
pH, without going through the step of modifying the PC?
To answer this question, we take advantage of two observations. First, the line
representing a species on a log C-pH diagram is nearly horizontal (i.e., insensitive
to pH) only in the pH region where that species is the dominant one in its acid/base
group. For example, for the carbonate group, the dominant species is H2 CO3 at
pH < 6.35, HCO–3 between pH 6.35 and 10.33, and CO2– 3 at pH > 10.33. In each of
these regions, the line for the dominant species has a slope near zero, while the lines
for the other (nondominant) species have slopes close to ±1 or ±2. Thus, if we can
choose components in a way that assures that the T OT H equation (and therefore the
PC) does not include the dominant species of any group in the pH region where the
322
equation is satisfied, then we will have assured that the lines representing the RHS
and LHS of the PC will not be nearly horizontal in that region, and hence will not
(nearly) overlap.
Second, according to our algorithm, the baseline for the mass balance on H+
includes all the components other than H+ . Therefore, if a species has the same
chemical formula as a component, the coefficient for that species in the H+ column of
the tableau will be 0, and the T OT H equation will not include the concentration of the
species. For example, reviewing the two T OT H equations and PCs in Example 6.7,
we see that when HAc and CO2– 3 were chosen as components (set #1), neither (HAc)
2–
nor (CO3 ) appeared in the resulting T OT H equation or PC. The same applies to set
#2, where Ac– and HCO–3 do not appear in the T OT H equation or the PC because
they were chosen as components.
Combining these observations, we conclude that the way to develop a PC that can
be used directly to find the equilibrium pH is to choose the species that are dominant
in the equilibrium solution as components. The following example shows how we
can take advantage of this conclusion.
Example 6.8
A wastewater at pH 7.0 contains 250 mg/L total organic carbon (TOC) and 1.5 ⇥
10 3 M total inorganic carbon (TIC, which is typically taken to be T OT CO3 ). The
TOC is distributed among a variety of molecular forms. However, since the waste is
thought to be mostly carbohydrates and is highly biodegradable, you have decided to
treat all the TOC as if it were the simple sugar glucose (C6 H12 O6 ). Write the T OT H
equation and determine the equilibrium pH of the solution after microorganisms con-
sume essentially all the TOC, respiring one-half of it to carbonic acid by the reaction
C6 H12 O6 +6 O2 )* 6 H2 CO3 and converting the other half to new biomass. Assume
that neither glucose nor the biomass participates in any acid/base reactions. Use H2 O,
H+ , and HCO–3 as components, at least in the initial analysis.
Solution
At pH 7.0, the alpha values for the carbonate system [computed using Equa-
tions (5.38) through (5.40)] are a0 = 0.18, a1 = 0.82, and a2 = 10 3.33 . The con-
centrations of H2 CO3 , HCO–3 , and CO2– 3 in the initial solution can be computed as
ai T OT CO3 and are 2.70 ⇥ 10 4 M, 1.23 ⇥ 10 3 M, and 7.0 ⇥ 10 7 M, respectively.
The statement that the solution contains 250 mg/L TOC means that 250 mg C/L is
present as part of organic molecules. If one-half of this TOC is respired, 125 mg C/L
becomes part of H2 CO3 molecules. From a chemical perspective, the appearance of
H2 CO3 in solution as the result of a reaction is no different from addition of the same
chemical from outside, so we can treat this conversion as an input. On a molar basis,
this input is
✓ ◆✓ ◆✓ ◆
mg TOC 1 mol C 1 mol H2 CO3 2 mol H2 CO3
125 = 1.04 ⇥ 10
L 12,000 mg C mol TOC L
323
Therefore, after the biological conversion, the solution can be thought of as a combi-
nation of the initial solution containing the carbonate concentrations in that solution
and a subsequent addition of 1.04 ⇥ 10 2 M H2 CO3 .
The tableau for the system, using the specified components, is shown below.
Note that the carbonate species in the initial solution are included in the lower part
of the tableau along with the H2 CO3 that was added by respiration, since all of those
species are considered ‘inputs’ that were added to pure water to generate the solution.
The T OT H equation and PC are shown below the tableau.
Component: H2 O H+ HCO–3 log K Conc’n
Species
H2 O 1 0 0 0.00
+
H 0 1 0 0.00
HCO–3 0 0 1 0.00
–
OH 1 1 0 14.00
H2 CO3 0 1 1 6.35
CO2–
3 0 1 1 10.33
Inputs
H2 CO3 † 0 1 1 2.7 ⇥ 10 4
HCO–3 † 0 0 1 1.23 ⇥ 10 3
CO2–
3
† 0 1 1 7.0 ⇥ 10 7
H2 CO3 ‡ 0 1 1 1.04 ⇥ 10 2
H2 O 1 0 0 55.56
† From TIC present initially.

‡ From respiration of TOC.
4 3 7
T OT Hin = 2.7 ⇥ 10 (1) + 1.23 ⇥ 10 (0) + 7.0 ⇥ 10 ( 1)
2 2
+ 1.04 ⇥ 10 (1) = 1.07 ⇥ 10
T OT H equation: (H+ ) + H2 CO3 OH CO23 = 1.07 ⇥ 10 2
PC: (H+ ) + H2 CO3 = OH + CO23 + 1.07 ⇥ 10 2
The LHS and RHS of the PC are shown by the solid bold lines in the log C-pH
diagram in Figure 6.11. The intersection is in the range between pH 4.5 and 5.5, but
is difficult to specify more precisely. As in previous examples, we could try to deter-
mine expressions that we could subtract from each side of the PC to obtain a more
324
useful form of that equation. However, the preceding discussion in the text suggests
that we can resolve the problem immediately by rewriting the T OT H equation using
the dominant species at equilibrium as components. Even though we cannot deter-
mine the equilibrium pH from the graph, we can see that, at equilibrium, the dominant
carbonate species will be H2 CO3 . We therefore revise the tableau, choosing H2 CO3
as a component. This change alters the stoichiometric coefficients for formation of
all the carbonate species in both the inputs and the equilibrium solution.4 The new
tableau, T OT H equation, and PC are shown below. Plotting the LHS and RHS of this
PC in Figure 6.11 (broken bold lines) allows us to easily identify the equilibrium pH
of 5.4.
Component: H2 O H+ H2 CO3 log K Conc’n
Species
H2 O 1 0 0 0.00
H+ 0 1 0 0.00
HCO–3 0 1 1 6.35
–
OH 1 1 0 14.00
H2 CO3 0 0 1 0.00
CO2–
3 0 2 1 16.68
Inputs
H2 CO3 0 0 1 2.7 ⇥ 10 4
HCO–3 0 1 1 1.23 ⇥ 10 3
CO2–
3 0 2 1 7.0 ⇥ 10 7
H2 CO3 0 0 1 1.04 ⇥ 10 2
4 3 7
T OT Hin = 2.7 ⇥ 10 (0) + 1.23 ⇥ 10 ( 1) + 7.0 ⇥ 10 ( 2)
2 3
+ 1.04 ⇥ 10 (0) = 1.23 ⇥ 10
T OT H equation: (H+ ) OH HCO3 2 CO23 = 1.23 ⇥ 10 3
PC: (H+ ) + 1.23 ⇥ 10 3 = OH + HCO3 + 2 CO23
4 The change in components also alters the log K values for forming the carbonate species. However,
because the correct equilibrium relationships are already embedded in the diagram, the only information
we need from the tableau is the set of stoichiometric coefficients for the mass balance on H+ , i.e., the
coefficients that appear in the T OT H equation. Therefore, although the log K values in the tableau
change when we choose new components, we need not compute the new values. Nevertheless, the
correct values are shown in the tableau here for completeness.
325
Figure 6.11 LogC-pH diagram for the example system.
In addition to illustrating how choosing the dominant species as a component can

facilitate the identification of the equilibrium pH, the preceding example illustrates
two useful points about the relationship between the T OT H equation and the charge
balance. First, note that the problem statement specified the pH and TIC of the origi-
nal solution, but it did not provide any information about other solutes. We know that
at least one additional cation must have been present to balance the negative charge of
the carbonate species, and the solution might have contained many additional cations
and anions, but the problem statement provides no way to assess which ones or in
what proportions. In such a situation, we can write a generic charge balance that ac-
knowledges our limited information about the ionic composition of the solution. For
this example, that charge balance would be
H+ init
+ Â ci |zi | = OH init
+ HCO3 init
+ 2 CO23 init
+ Â cj zj
all other all other
cations i anions j
(6.26)
where ci and c j are the concentrations of the cations and anions, respectively, that are
in the solution but are not represented explicitly in the rest of the equation, and |zi |
and |z j | are the absolute values of the charges on those ions.5
The charge associated with the known inputs can be computed based on the infor-
mation in the bottom portion of the tableau. For instance, the net charge associated
with the inputs in both tableaus in Example 6.8 is 1.23 ⇥ 10 3 M, indicating that
5 The summations Â ci |zi | and Â c j z j are commonly represented as CB and CA , respec-
all other all other
cations i cations j
tively, based loosely on the assumption that all unspecified cations and anions are monovalent salt ions
that entered the solution as part of a strong base (B) like NaOH or a strong acid (A) like HCl. Equation
(6.26) is more general and also clarifies that the summation is on charge, not mass.
326
the unknown constituents of the initial solution must carry a net positive charge of
+1.23 ⇥ 10 3 M. The net charge associated with the unknown inputs is preserved as
the solution equilibrates, so, at equilibrium, the unknown constituents will still carry
a charge of +1.23 ⇥ 10 3 M. The known constituents in the equilibrated solution
must therefore carry a charge of 1.23 ⇥ 10 3 M; that is, the charge on the known
constituents is the same before and after the equilibration process.
Although we have been referring to the charge-related equation that is used in the
solution algorithm as a charge balance, it is more correctly described as a statement
of charge conservation, establishing that the charge on the known input chemicals
equals that on the known equilibrium species. The preceding discussion establishes
that this equation is valid regardless of whether the total computed charge is balanced
(yielding zero net charge) or not. Furthermore, we have seen that if we satisfy the
charge conservation equation, we guarantee that the full charge balance equation will
be satisfied as well, even though we do not know all the terms that would be included
in that equation. Thus, we can use the charge conservation equation considering
only known species and be assured of obtaining a correct result for the equilibrium
speciation of the solution.
A related observation is that, because all charges associated with the inputs are
preserved when the inputs are expressed as an equivalent mixture of components, the
net charge is reflected entirely in the T OT H equation if all the components other than
H+ are neutral species. For instance, when component set #2 was used to analyze the
solution in Example 6.8, the components other than H+ were the neutral compounds
H2 O and H2 CO3 . As a result, all the charge associated with the inputs ( 1.23 ⇥
10 3 M) appeared as the numerical constant in the T OT H equation.
6.6 IDENTIFYING DOMINANT SPECIES

We have now established that, to solve problems using log C-pH diagrams, (1) it is
useful to develop a T OT H or PC equation that does not contain the concentrations
of species that are dominant in the equilibrium solution, and (2) we can accomplish
that by choosing components that are identical to the dominant species. We have
also seen that, by choosing an arbitrary set of components, we can quickly identify
the dominant species. The final issue we address is how we can identify the domi-
nant species initially, without going through the process of developing a preliminary
tableau and then revising it. In this section, a procedure is described for making
good guesses about which species will be dominant at equilibrium, so that we can
choose components that will allow us to solve acid/base problems graphically using
the T OT H equation or PC directly. In addition to assisting in the choice of a good set
of components for use with the graphical analysis, the procedure provides insight into
the behavior of acid/base systems when those systems are titrated with other acids or
bases. Such titrations, which are central to many water treatment processes and are
frequently used in chemical analysis protocols, are discussed in detail in Chapter 8.
327
The basis for the procedure is the idea that equilibrium solutions have no “mem-
ory”. That is, once a solution has reached equilibrium, it is impossible to tell which
chemicals were added, or the order in which they were added, to prepare the solu-
tion; all that one can say for sure is that all the species in the equilibrium system
were added in some form. To be more explicit, if a solution contains 3 ⇥ 10 3 M
HOCl, 1 ⇥ 10 3 M OCl– , and 1 ⇥ 10 3 M Na+ at equilibrium, we can be certain that
4 ⇥ 10 3 M T OT OCl was added to the solution, but not whether that T OT OCl was
added entirely as HOCl (perhaps followed by some NaOH), as a mixture of HOCl
and NaOCl (followed by a smaller amount of NaOH), or as a mixture of only HOCl
and NaOCl.
A corollary of the idea that equilibrium solutions have no memory is that we are
free to imagine that the solution was concocted in any way we like and, as long as
we account for all the species that are present in the actual solution, our imaginary
concoction will behave identically to the real system. In fact, in the procedure about
to be described, we will imagine that solutions can be prepared in a totally unreal-
istic way: by adding everything but the H+ ions first, then adding the H+ later. In
reality, it is impossible to add individual ions to solutions; anytime we add an anion,
we must add an equal and opposite amount of cationic charge. Nevertheless, this
imaginary procedure proves useful for predicting the dominant species in the system,
and because solutions have no memory, we can analyze systems as though they were
prepared in this way without any risk of drawing incorrect conclusions.
For the purposes of this procedure, the key attribute of acid/base systems that we
will rely on is that, except at pH values quite near pKa , each conjugate acid/base pair
is present almost entirely as the acid or almost entirely as the base. For instance, in
a solution at pH 6 containing some OCl species (pKa = 7.53) and some Ac species
(pKa = 4.76), almost all the OCl is protonated [i.e., T OT OCl ⇡ (HOCl)], whereas
almost all the Ac is deprotonated [T OT Ac ⇡ (Ac )]. Recall that bases are sometimes
called proton acceptors; the greater the tendency to accept a proton, the greater the
strength of the base. Thus, the higher degree of protonation of the OCl species reflects
the fact that OCl– is a stronger base than Ac– .
Generalizing the behavior in the example system to other combinations of acid/
base groups, we make the approximation that the H+ ions added to a system combine
sequentially with the various bases in the system, starting with the strongest base and
working toward the weakest, and that weaker bases do not begin to protonate until
stronger ones have become fully protonated. That is, although in reality all bases in a
solution are at least slightly protonated at any pH, and no bases are 100% protonated,
we treat them as though each base does go from 0% to 100% protonated before the
next weaker base becomes protonated at all.
Now consider what happens in the hypothetical procedure in which we add all
328
other chemicals to the solution before adding the H+ . In such a case, a concentration
T OTi of each acid/base group is present initially, all as the most deprotonated species
of the group. We then imagine adding the H+ in small increments. The first such
increment will combine (in our idealized scenario) exclusively with the strongest
base in the system. After we have added enough H+ to convert all of that base to its
conjugate acid, protonation of the next strongest base begins, and the process repeats
itself. Successively weaker bases become protonated until we have added all the H+
available. At that point, we can review the speciation of each acid/base conjugate pair
and determine which species in each group is dominant.
Consider, for example, a system made by adding 10 3 M HAc, 2 ⇥ 10 3 M NaAc,
3 ⇥ 10 4 M NaOCl, and 5 ⇥ 10 4 M NaOH to water. We could imagine that all the
salt ions and bases were added first, before any H+ . At that point, the solution would
contain 2.8 ⇥ 10 3 M Na+ , 3.0 ⇥ 10 3 M Ac– , 3.0 ⇥ 10 4 M OCl– , and 5 ⇥ 10 4 M
OH– , and we would have 10 3 M H+ still “waiting” to be added. Listing the bases in
the system from strongest to weakest (highest to lowest pKa ), we can fill in the first
three columns in Table 6.5.
Table 6.5 Hypothetical sequential protonation of bases in the example system.
Base/Acid pKa TOTi Fraction H+ Remaining

Protonated
1.0 ⇥ 10 3
0%
OH– /H2 O 14.00 5 ⇥ 10 4
5.0 ⇥ 10 4
100%
5.0 ⇥ 10 4
0%
OCl– /HOCl 7.60 3 ⇥ 10 4
2.0 ⇥ 10 4
100%
2.0 ⇥ 10 4
0%
Ac– /HAc 4.76 3 ⇥ 10 3
6.7% 0
The 10 3 mol/L of available H+ is expected to combine first with the OH– , con-
verting it to its conjugate acid, H2 O. This conversion requires 5 ⇥ 10 4 mol/L H+ ,
so once it is complete, we still have 5 ⇥ 10 4 mol/L H+ to add. Conversion of the
OCl– to HOCl consumes 3 ⇥ 10 4 mol/L of these H+ ions, leaving 2 ⇥ 10 4 mol/L.
These remaining protons combine with Ac– , but since T OT Ac is 3 ⇥ 10 3 M, the
available H+ can convert only 6.7% of the Ac– to HAc. These steps are all sum-
marized in the final two columns of the table. We therefore conclude that, at equi-
librium, the dominant species of the weak acid/base groups will be HOCl and Ac– .
329
Example 6.9
Predict the acid/base species that will be dominant at equilibrium in a system
prepared by combining 10 3 M HCl, 10 2 M NH3 , 10 2 M NaHCO3 , and 10 3 M
butyric acid (HBut). Butyric acid is a four-carbon carboxylic acid, in the same chem-
ical family as but larger than formic acid (one carbon), acetic acid (two carbons), and
propionic acid (three carbons). It is the highly distinctive, foul-smelling constituent
of stomach acid that can induce (or be an unpleasant consequence of) nausea. It also
sometimes accumulates in anaerobic waste treatment systems that are not operating
properly, to the dismay of all around. The pKa for HBut is 4.82, very close to that of
its smaller analogs.
Solution
A table listing the acid/base conjugate pairs in the system in order of decreas-
ing basicity along with the corresponding T OTi values is shown below. The two
acid/base pairs of the carbonate system are listed independently, and water is in-
cluded as a base that could be protonated to form H3 O+ .
Fraction
Base/Acid pKa TOTi H+ Remaining
Protonated
1.2 ⇥ 10 2
0%
CO2– –
3 /HCO3 10.33 10 2
0.2 ⇥ 10 2
100%
0.2 ⇥ 10 2
0%
NH3 /NH+4 9.24 10 2
20% 0
HCO3 /H2 CO3 6.35 10 2 0

0%
But /HBut 4.82 10 3 0

0%
H2 O/H3 O+ 0.00 55.6 0% 0
As before, we imagine that the solution initially contains only inert salt ions
(10 3 M Cl– and 10 2 M Na+ ) and the bases that were added to the solution (10 2 M
NH3 , 10 2 M CO2– 2 – +
3 , and 10 M But ). The concentration of H available to add to
2
this hypothetical solution is 1.2 ⇥ 10 M, consisting of the protons added with the
NaHCO3 , HBut, and HCl. The strongest base in the solution is CO2– 3 , with a total
concentration of 10 2 M. We assume that 10 2 M protons combine with the CO2– 3
to convert it all to HCO–3 , while all the other bases remain completely deprotonated.
330
This leaves 0.2 ⇥ 10 2 M H+ to combine with the other bases. The next strongest
base is NH3 . It would take 10 2 M H+ to convert all the NH3 , to NH+4 , but only
0.2 ⇥ 10 2 M H+ is available. We therefore expect the available protons to convert
approximately 20% of the NH3 to NH+4 . Correspondingly, approximately 80% of the
NH3 and 100% of the HCO–3 and But– remain in the basic form, so the dominant
species in the equilibrium solution are expected to be HCO–3 , NH3 , and But– . The
whole process is summarized in the preceding table.
Example 6.10
Which species would you expect to be dominant in solutions prepared by adding
the following chemicals to water?
(a) 5 ⇥ 10 3M KH2 PO4 + 10 2M NaOH + 10 2M Na2 HPO4
(b) 10 4M H2 CO3 + 10 4M NH3 + 10 2M HCl
Solution
(a) The deprotonated forms of the acid/base groups in the solution are PO3–
4 and
–
OH , and the available proton concentration is
[H+ ]avail = 2(5 ⇥ 10 3 ) + (1 ⇥ 10 2 ) = 2 ⇥ 10 2
The expected sequence of protonation reactions is summarized in the follow-

ing table. The protons will bind first to the OH– (1 ⇥ 10 2 M) and will then
convert two-thirds of the PO3– 2– 2–
4 to HPO4 , so we predict that HPO4 will be the
dominant form of phosphate at equilibrium.
Fraction
Protonated
2.0 ⇥ 10 2
0%
OH– /H2 O 14 10 2
1.0 ⇥ 10 2
100%
1.0 ⇥ 10 2
0%
PO34 /HPO24 12.38 1.5 ⇥ 10 2
67% 0
HPO24 /H2 PO4 7.20 1.5 ⇥ 10 2

0% 0
H2 PO4 /H3 PO4 2.15 1.5 ⇥ 10 2 0

0%
331
(b) The available proton concentration in this solution is
[H+ ]avail = 2(1 ⇥ 10 4 ) + 10 2

⇥ 10 2
The protons will bind to the bases in the system in the following sequence and
quantities:
1 ⇥ 10 4M H+ to convert CO2– –
3 to HCO3
1 ⇥ 10 4M H+ to convert NH3 to NH+4

1 ⇥ 10 4M H+ to convert HCO–3 to H2 CO3
As shown in the following table, after all these weak bases are converted to
their fully protonated forms, the dominant species will be NH+4 and H2 CO3 ,
and 0.99 ⇥ 10 2 M H+ will still be available. These protons will combine with
the next-weakest base in the system, H2 O, forming H3 O+ . The concentration
of H2 O is 55.6 M, so clearly its capacity to acquire H+ will never be exhausted.
We therefore conclude that the dominant species in this solution will be NH+4 ,
H2 CO3 , and (as always) H2 O. In addition, we can estimate that the final solu-
tion will contain 0.99 ⇥ 10 2 M H3 O+ , so the pH will be approximately 2.0.
Fraction
Protonated
1.02 ⇥ 10 2
0%
CO2– –
3 /HCO3 10.33 10 4
1.01 ⇥ 10 2
100%
1.01 ⇥ 10 2
4 0%
NH3 /NH+
4 9.24 10
1.00 ⇥ 10 2
100%
1.00 ⇥ 10 2
4 0%
HCO3 /H2 CO3 6.35 10
0.99 ⇥ 10 2
100%
0.99 ⇥ 10 2
0%
H2 O/H3 O+ 0.00 55.6
0.02% 0
A little thought leads to the conclusion that [H+ ]avail (i.e., the concentration of H+
available to protonate the bases in our hypothetical procedure) is identical to T OT Hin
332
for an analysis in which we choose water and the fully deprotonated bases as com-
ponents. (As an exercise, confirm this statement for the initial solutions in Example
6.10.) Recognition of this fact is helpful in the analysis of acid/base titrations in
Chapter 8.
The method described above will almost always correctly identify the dominant
species in a system. The only time it may fail is when there are several acid/base pairs
in the system with nearly identical Ka values. In that case, when we try to evaluate
the PC graphically, it will be evident which species are dominant, and we can revise
the tableau and solve the problem.
Having developed the basic procedures for drawing log C-pH diagrams, identi-
fying the species expected to be dominant at equilibrium, and writing the T OT H
equation or PC, we are in a position to determine the equilibrium composition of vir-
tually any mixture of acids and bases. A couple examples of this process are provided
next. In reading through the examples, it is worthwhile to mentally compare this ap-
proach with the numerical approaches presented in Chapter 5. To review, the steps
involved in the graphical approach include:
• Drawing the log C-pH diagram to understand how speciation varies with pH;
• Assessing the strength of the bases in the system and comparing their concen-
trations with the concentration of available H+ to predict which species will be
dominant at equilibrium;
• Preparing the system tableau, using the species that are predicted to be domi-
nant at equilibrium as components;
• Writing the T OT H equation, and converting it to a PC; and
• Adding curves to the graph for the LHS and RHS of the PC, and determining
the equilibrium solution composition based on their intersection.
Example 6.11
A model anaerobic waste solution is prepared as a mixture of 10 2 M NaHCO3 ,
10 4 M Na2 S, and 4 ⇥ 10 3 M HAc. Upon dissolution, sodium sulfide (Na2 S) re-
leases sulfide ion (S2– ), a strong base that can protonate to form bisulfide ion (HS– )
or hydrogen sulfide (H2 S). Hydrogen sulfide can enter the gas phase to generate a
rotten egg smell that can be detected even at extremely low concentrations. Organic
sulfides (R SH) also tend to have strong, unpleasant odors and are also generated
in anaerobic environments, as well as being found in some industrial wastes (e.g.,
from pulping). The values of pKa1 and pKa2 for H2 S are 7.02 and 17.04, respectively.
Determine the composition of the model waste solution at equilibrium.
333
Solution
The species expected to be dominant at equilibrium can be determined by imag-
ining the solution to be prepared by adding the salts and deprotonated bases (Na+ ,
CO2– 2– – +
3 , S and Ac ) and then adding the available H , in this case equal to 10 M
2
3
from the NaHCO3 plus 4 ⇥ 10 M from HAc. Based on that value and the following
summary table, the dominant species are likely to be H2 S, HCO–3 , and Ac– .
Fraction
Protonated
1.40 ⇥ 10 2
2– – 4 0%
S /HS 17.04 10
1.39 ⇥ 10 2
100%
1.39 ⇥ 10 2
0%
CO23 /HCO3 10.33 10 2
0.39 ⇥ 10 2
100%
0.39 ⇥ 10 2
4 0%
HS /H2 S 7.02 10
0.38 ⇥ 10 2
100%
0.38 ⇥ 10 2
2 0%
HCO3 /H2 CO3 6.35 10
38% 0
Ac /HAc 4.76 4 ⇥ 10 3 0
0%
The system tableau using the expected dominant species as components is shown
on the following page. The corresponding T OT H equation and PC are
T OT H : H+ (1) + OH ( 1) + HS ( 1) + S2 ( 2) + H2 CO3 (1)

+ CO23 ( 1) + (HAc) (1) = (1 ⇥ 10 )( 2) + (4 ⇥ 10 3 )(1)
4
3
= 3.8 ⇥ 10
PC: H+ + H2 CO3 + (HAc) =
OH + HS + 2 S2 + CO23 + 3.8 ⇥ 10 3
334
Component: H2 O H+ H2 S Na+ HCO–3 Ac– log K Conc’n
Species
H2 O 1 0 0 0 0 0 0.00
+
H 0 1 0 0 0 0 0.00
H2 S 0 0 1 0 0 0 0.00
+
Na 0 0 0 1 0 0 0.00
HCO–3 0 0 0 0 1 0 0.00
–
Ac 0 0 0 0 0 1 0.00
–
OH 1 1 0 0 0 0 14.00
–
HS 0 1 1 0 0 0 7.02
335
2–
S 0 2 1 0 0 0 24.06
H2 CO3 0 1 0 0 1 0 6.35
CO2–
3 0 1 0 0 1 0 10.33
HAc 0 1 0 0 0 1 4.76
Inputs
NaHCO3 0 0 0 1 1 0 1.0 ⇥ 10 2
Na2 S 0 2 1 2 0 0 1.0 ⇥ 10 4
HAc 0 1 0 0 0 1 4.0 ⇥ 10 3
The log C-pH diagram is shown in Figure 6.12, indicating that the equilibrium
pH is 6.57, at which the dominant acid/base species are HCO–3 , Ac– , and H2 S, as we
anticipated. The composition of the equilibrium solution is
(H+ ) = 10 6.57 (OH ) = 10 7.43
(H2 CO3 ) = 10 2.42 (HCO3 ) = 10 2.20 (CO23 ) = 10 5.96
(HAc) = 10 4.21 (Ac ) = 10 2.41
(H2 S) = 10 4.13 (HS ) = 10 4.58 (S2 ) = 10 15.10
Figure 6.12 LogC-pH diagram for a system consisting of 10 2M NaHCO3 , 4⇥10 3M HAc,
and 10 4 M Na2 S.
Example 6.12
Prepare system tableaus using the dominant species as components for each of
the following solutions, and write the corresponding PCs. Then, construct a log C-
pH diagram for a system containing 0.10 M T OT PO4 and determine the equilibrium
pH and the concentration of all species in the solutions.
(a) 0.10 M NaH2 PO4
(b) 0.10 M Na2 HPO4
(c) 0.10 M Na3 PO4
336
Solution
Because all three solutions have the same T OT PO4 , they can all be characterized
by a single log C-pH diagram (Figure 6.13). However, we anticipate that the T OT H
equations and PC’s will be different for each system, causing them to have different
compositions at equilibrium.
Figure 6.13 LogC-pH diagram for a solution containing 10 2M T OT PO4 .
Using the approach outlined in the preceding section, we surmise that H2 PO–4 ,
HPO2– 3–
4 , and PO4 are likely to be the dominant PO4 -containing species in parts (a),
(b), and (c), respectively. (Carry out the calculation to convince yourself of this
result.) System tableaus using the anticipated dominant species as components, the
corresponding T OT H equation and PC, and the log C-pH diagram with curves added
showing the right and left sides of the PC are provided on the following pages.
Note that, in parts (b) and (c), the LHS of the PC contains terms that are 2
or 3 times the concentrations of particular species; i.e., the PC contains terms like
3(H3 PO4 ) and 2(H2 PO–4 ). As before, we incorporate these coefficients in the graphi-
cal analysis based on the following relationships:
⇥ ⇤
log 3 H3 PO4 = log 3 + log H3 PO4 = 0.48 + log H3 PO4
⇥ ⇤
log 2 H2 PO4 = log 2 + log H2 PO4 = 0.30 + log H2 PO4
Thus, curves representing 3(H3 PO4 ) and 2(H2 PO4 ) are, respectively, 0.48 and 0.30
log unit above the (H3 PO4 ) and (H2 PO4 ) curves.
337
(a) 0.10 M NaH2 PO4
Component: H2 O H+ Na+ H2 PO–4 log K Conc’n
Species
H2 O 1 0 0 0 0.00
+
H 0 1 0 0 0.00
Na+ 0 0 1 0 0.00
H2 PO–4 0 0 0 1 0.00
–
OH 1 1 0 0 14.00
H3 PO4 0 1 0 1 2.15
HPO2–
4 0 1 0 1 7.20
3–
PO4 0 2 0 1 19.57
Inputs
NaH2 PO4 0 0 1 1 0.10
T OT H : H+ (1) + OH ( 1) + H3 PO4 (1)

+ HPO24 ( 1) + PO34 ( 2) = 0
PC: (H+ ) + H3 PO4 = OH + HPO24 + 2 PO34
338
(b) 0.10 M Na2 HPO4
Component: H2 O H+ Na+ HPO2–
4 log K Conc’n
Species
H2 O 1 0 0 0 0.00
+
H 0 1 0 0 0.00
Na+ 0 0 1 0 0.00
H2 PO–4 0 1 0 1 7.20
–
OH 1 1 0 0 14.00
H3 PO4 0 2 0 1 9.35
HPO2–
4 0 0 0 1 0.00
3–
PO4 0 1 0 1 12.38
Inputs
Na2 HPO4 0 0 2 1 0.10
T OT H : H+ (1) + OH ( 1) + H3 PO4 (2)

+ H2 PO4 (1) + PO34 ( 1) = 0
PC: (H+ ) + 2 H3 PO4 + H2 PO4 = OH + PO34
339
(c) 0.10 M Na3 PO4
Component: H2 O H+ Na+ PO3–
4 log K Conc’n
Species
H2 O 1 0 0 0 0.00
+
H 0 1 0 0 0.00
+
Na 0 0 1 0 0.00
H2 PO–4 0 2 0 1 19.57
–
OH 1 1 0 0 14.00
H3 PO4 0 3 0 1 21.72
HPO2–
4 0 1 0 1 12.38
3–
PO4 0 0 0 1 0.00
Inputs
Na3 PO4 0 0 3 1 0.10
T OT H : H+ (1) + OH ( 1) + H3 PO4 (3)

+ H2 PO4 (2) + HPO24 (1) = 0
PC: (H+ ) + 3 H3 PO4 + 2 H2 PO4 + HPO24 = OH
340
The equilibrium pH and concentration of all species are summarized in the fol-
lowing table.
pH log(H3 PO4 ) log(H2 PO–4 ) log(HPO2–

4 ) log(PO3–
4 )
(a) 4.69 3.54 1.00 3.51 11.20

(b) 9.74 11.14 3.54 1.00 3.64
(c) 12.58 17.23 6.80 1.42 1.21
6.7 COMPARISON OF APPROACHES FOR SOLVING

ACID/BASE PROBLEMS
To conclude the chapter, we compare the various approaches that have been pre-
sented thus far for solving acid/base speciation problems. We saw in Chapter 5 that
the problem of determining the equilibrium solution composition for a system with
known inputs, or of determining the required input of a particular chemical to attain
the desired composition (e.g., to reach a specified pH), could be formulated as one of
evaluating a number of unknowns by solving an equal number of independent simul-
taneous equations. We also identified the unknowns as the concentrations of all the
dissolved species at equilibrium, and showed that the mass balances on different ‘ion
types’, equilibrium constants for formation of various species, and the charge balance
(or, more generally, a statement of charge conservation) provided the required num-
ber of equations. We then solved those equations, either analytically or numerically,
for several example problems. We also saw that, if the solutions were not ideal, the
same approach could be used, but ‘effective’ equilibrium constants that accounted
for the nonideality had to be used instead of conventional equilibrium constants.
LogC-pH diagrams were also developed in Chapter 5, and we saw that those
diagrams provide a concise visual representation of speciation over a wide pH range
in systems where the total concentrations of acid/base groups and salt ions are known.
It was emphasized that the diagrams contain all the same information as is used in
the analytical or numerical solution of the problems, except for the charge balance.
Therefore, the equilibrium speciation could be determined by identifying the unique
pH where the charge balance was satisfied.
The tableau format introduced in this chapter is, in one sense, just another way
of organizing and presenting the input information for these types of problems. One
could even argue that it adds complexity to the problem by requiring us to choose
a group of components whose concentrations need to be determined; i.e., the equi-
librium concentrations of the components are additional unknowns. Thus, formally,
341
the tableau formulates a problem with N components and Meq equilibrium species as
having N + Meq unknowns. However, this complexity is more than balanced by the
simple, consistent, and concise way in which the required equations are organized.
In essence, each of the Meq rows in the upper portion of the tableau provides the
information for an equation relating the concentration of one of the species to the
concentrations of the components, and each of the N columns provides the informa-
tion for a mass balance on a component. Thus, the tableau implicitly summarizes all
N + Meq equations needed to solve the problem.
The log C-pH diagram contains all the information that is in the tableau, except
for the mass balance on H+ . Thus, we can determine the equilibrium condition by
scanning the diagram to find the unique pH where the T OT H equation is satisfied.
When we carry out this scanning exercise manually, it is convenient to convert the
T OT H equation to a PC. Looking back, it should be evident that the modified CBs
developed early in the chapter were, in fact, the PCs that are obtained when the
dominant species are chosen as components.
The most important difference between the equations included implicitly in the
tableau and those used previously to solve these kinds of problems is that, in the
tableau format, the charge conservation equation is replaced with a mass balance on
H+ (i.e., the T OT H equation). The advantages of using the T OT H equation are that
(1) by choosing the components wisely, we can be assured that the PC will allow us
to identify the equilibrium pH directly, without additional steps, and (2) because the
formulation of the T OT H equation is essentially identical to the formulation of the
mass balances on the other components, it is more easily incorporated into an input
algorithm for computer solutions to these kinds of problems; such solutions are intro-
duced in Chapter 7. Thus, the T OT H equation has certain practical advantages over
the charge balance (or charge conservation) equation for this particular application.
However, we also saw that the charge balance is implicitly satisfied when the T OT H
equation is solved, so we ultimately reach the same conclusion about the equilibrium
speciation regardless of which equation is used.
6.8 SUMMARY
This chapter demonstrates the development and use of graphical approaches for ana-
lyzing acid/base systems. The graphs that are used in these analyses highlight certain
universal features of such systems. In particular, they emphasize the fact that the acid
form of an acid/base conjugate pair is present at a larger activity than the basic form
at any solution pH less than pKa , and the reverse is true at pH’s greater than pKa .
At a pH equal to the pKa , the acid and base are present at equal activities. If the
assumption of ideal behavior of the solutes applies, then these same statements apply
to the species’ concentrations.
The species concentrations shown at any pH on a log C-pH graph satisfy the
342
mass balances on the acid/base groups that are present, the Ka expressions, and the
Kw expression. Under the circumstances, only one additional, independent equation
need be satisfied to establish the equilibrium composition of the system. The most
common choices for this equation are the charge balance, the T OT H equation, and
the proton condition, any of which can be used, and all of which can be derived from
one another and the mass balances.
The pH at which the additional equation is satisfied is sometimes difficult to iden-
tify directly on the log C-pH graph, but the difficulty can be overcome by writing a
new equation that eliminates the largest value from each side of the equation. The
resulting equation is, in effect, a mass balance on protons using a nonzero baseline
concentration. This equation can be written directly by developing the T OT H equa-
tion using dominant species as components, and then converting that equation into a
PC by moving terms so that each side contains only summations and not differences.
A simple algorithm can be used to predict which acid/base species will be domi-
nant once equilibrium is attained. This algorithm treats the system as though it could
be prepared by first adding all the bases in their fully deprotonated forms, while with-
holding the H+ ions (i.e., the available protons). The protons are then added, and an
approximation is made that they bind first to the strongest base in the system and
then to progressively weaker ones, until all the protons that were present in the real
system have been taken into account. The basis of this algorithm is that solutions
have no memory, so that any approach that generates the same total inputs of species
yields the same predicted equilibrium composition, regardless of how or in what or-
der the chemicals were added. Once the dominant species have been identified, they
can be chosen as components when developing the system tableau. In such a case,
the T OT H and PC equations will not contain terms for the dominant species and will
therefore be easy to use in conjunction with the log C-pH diagram to determine the
equilibrium solution composition.
6.9 APPENDIX 6A: ARITHMETIC OPERATIONS AND

LOG-LOG DIAGRAMS
One of the keys to using either a charge balance, TOTH equation, or proton condition
in conjunction with a log C-pH diagram is recognizing that each side of the equation
is often dominated by a single term, so that the summation can be approximated as
that term alone. Although that situation is common, there are times when two or more
terms must be considered over a fairly wide pH range. Most often, this complication
arises when two or more lines on the diagram are parallel and fairly close to one
another. In such a case, it might not be an acceptable approximation to ignore the
contribution of the species represented by lower line to the summation.
The complication that arises when we try to draw a line representing the sum of
343
the other two is that the values on the graph are logarithmic, while the summation is
arithmetic. To compute the sum correctly, we need to take the anti logarithm of the
log C values for the two lines, add these values, and then take the logarithm of this
sum and plot it. The equation of the line representing the summation can be derived
as follows.
Let CU be the concentration represented by the upper line, and CL be the con-
centration represented by the lower line. Define x as the vertical distance between
the two lines on a logarithmic scale, as shown in Figure 6.14.
log CU = log CL + x (6.27)
Figure 6.14 A logarithmic plot of the values of two individual terms (CL and CU) and the
value of their sum.
Taking the antilogarithm of each side of the Equation (6.27), we obtain
10log CU = 10log CL+x (6.28)

log CL log CU x
10 = 10 (6.29)
x
CL = CU 10 (6.30)
x
CU + CL = CU 1 + 10 (6.31)
x
log (CU + CL) = log(CU) + log 1 + 10 (6.32)
Thus, a line representing the logarithm of the sum of the two concentrations is
displaced vertically from the upper line by an amount log (1 + 10x ). If x = 0, then
the two lines are on top of each other, and the vertical displacement is log (1 + 1), or
0.3 units. This is the maximum displacement possible. If the lower line is one log
344
unit below the upper one, the shift is log (1.1), or 0.04 log units. This is about the
smallest displacement we would logically be concerned about. Thus, if two lines are
separated by less than one log unit, we would probably want to consider that the sum
of the corresponding concentrations is somewhat larger than the value represented
by the upper line alone. On the other hand, if the lower line is more than one log unit
below the upper one, we can probably ignore it without affecting our conclusions
substantially.
6.10 PROBLEMS
In solving these problems, use K a data from Table 5.1 and assume ideal solution
behavior unless the question states otherwise or the ionic strength is given. If
you prepare a log C-pH diagram, label the axes and the individual curves, and
include a caption. The range of values on the axes will depend on the details of
the problem, but they should typically be 8 to 14 pH units on the abscissa and 6
to 10 log units on the ordinate.
1. Using a graphical approach, solve for the pH of the following solutions.
(a) 10 3M HAc (e) 10 3M HCN

(b) 10 3M HOCl (f) 10 3M Na2 CO3
(c) 10 3M NaCN (g) 10 3M NaHCO3
(d) 10 3M Na2 Oxalate (h) 10 3M (NH4 )2 CO3
2. Prepare a log C-pH diagram for a solution containing 10 4 M chromic acid

(H2 CrO4 ). Indicate the values of the slopes of the lines on the diagram. What
is the predominant species of chromium in this solution, and what is its con-
centration, at pH 6? at pH 8?
3. What are the concentrations of all species in a solution of 10 2M Na2 CO3 ?

10 2 M NaHCO3 ? 10 2 M H2 CO3 ?
4. Identify the dominant species and prepare a tableau using those species as
components for the solutions described below. Prepare a log C-pH diagram
and determine the equilibrium pH and the concentrations of all species in each
system.
(a) 10 3M NaHCO3 +10 2M HCl +10 2M NaOH

(b) 10 3M NaHCO3 +10 3M HCl +10 2M NaOH
(c) 10 3M NaHCO3 +10 2M HCl +10 3M NaOH
345
5. Write the T OT H equation for each of the following systems, using the domi-
nant species as components.
(a) 0.02 M HCl

(b) 10 3M NaCN
(c) 10 3M HOCl
(d) 10 4M NaHCO3 +10 4M NH4 Cl
(e) 10 3M NaCN +10 3M HOCl
6. Write the T OT H equation for the following systems.
(a) 10 3 M Na3 PO4 +10 4M Na2 HPO4 + H2 O, using PO3–

4 as a compo-
nent.
(b) Same system as (a), using HPO2–
4 as a component.
(c) 10 3 M NH4 Cl +5 ⇥ 10 3 M HNO3 +2 ⇥ 10 3M NaOH +H2 O, using
dominant species as components.
7. The effluent from an anaerobic digester is simulated as a mixture of 5⇥10 4 M

each of NaH2 PO4 and Na2 HPO4 , and 6 ⇥ 10 4 M each of NH3 , H2 CO3 , and
NaHCO3 .
(a) Identify the species that you think will be dominant in each acid/base
group in the equilibrated solution.
(b) Write the T OT H equation for the system, using H2 O, H+ , H2 PO–4 , NH3 ,
HCO–3 , and Na+ as components.
(c) Estimate the equilibrium pH, assuming ideal solute behavior. (You can
sketch a log C-pH diagram if you’d like, but you need not do so to answer
the question.)
8. The organic chemical ethylene diamine tetra-acetate (EDTA4– ) is used exten-

sively in industrial processes to prevent metals from precipitating as solids.
The pKai values for H4 EDTA are 2.11, 3.12, 6.27, and 10.95 for i equal to 1
through 4, respectively.
(a) At what pH or over what pH range is the activity of HEDTA3– greater

than that of H4 EDTA?
(b) Write the expression and compute the value of Kb for the reaction in
which H3 EDTA– serves as the conjugate acid.
(c) Prepare a log C-pH diagram for a solution of 3 ⇥ 10 3 M T OT EDTA.
What is the slope of the curve for H4 EDTA at pH = pKa3 ?
346
(d) A solution of 1 ⇥ 10 3 M Na2 H2 EDTA and 2 ⇥ 10 3 M Na3 HEDTA is
prepared. Develop the tableau for the solution using the EDTA species
that you expect to be dominant as a component. Write the T OT H equa-
tion, and determine the speciation of EDTA at equilibrium.
9. A solution is made by adding 2 ⇥ 10 4 moles of oxalic acid (which we will

represent as H2 Ox), 5 ⇥ 10 4 moles Na2 HPO4 , and 5 ⇥ 10 4 moles CuCl2 to
1.0 L of pure water.
(a) Prepare a log C-pH diagram showing the speciation of T OT Ox, T OT PO4 ,
and T OT Cu in the system.
(b) H3 PO4 is added to the original solution until the pH is 5.5. Designating
the dose of H3 PO4 added (in mol/L) as x, write out the T OT H equation
for the solution, using the species that are expected to be dominant in the
new solution as the components.
10. A wastewater from an electroplating process is at pH 2.5, due primarily to

the presence of nitric acid, HNO3 , with pKa = 1.5. The solution contains
6 ⇥ 10 4 M T OT Cu, almost all of which is present as Cu2+ . The wastewater is
to be neutralized using a solution that was originally prepared as 0.2 M NaOH.
However, the NaOH solution has been exposed to the atmosphere for some
time, and CO2 has dissolved into it, so that T OT CO3 is now 0.02 M.
(a) Prepare a log C-pH diagram for a solution containing 0.02 M T OT CO3
and use it to determine the pH of the NaOH solution after the CO2 dis-
solves.
(b) Add curves to the log C-pH diagram for Cu2+ and Cu(OH)2x x species
for x  4. Write a T OT H equation for the waste solution after 30 mL of
the alkaline, neutralizing solution has been added per liter of wastewater.
Because the volume of titrant added is only 3% of the volume of wastew-
ater solution, dilution of the wastewater can be ignored. What is the pH
of the mixture?
11. A log C-pH diagram for a solution containing 10 3M hydrogen sulfide (H2 S)
is provided below.
(a) Label the lines with the species they represent and assign correct values
to the axes.
(b) Draw lines for H+ and OH– on the diagram.
(c) What is the pH of a solution of 10 4M NaHS plus 9 ⇥ 10 4M H2 S?
(d) Would a solution of 0.5 ⇥ 10 4 M Na2 S plus 9.5 ⇥ 10 4 M H2 S be more
acidic, more alkaline, or the same as the solution in part (c)? Explain
your answer in one or two sentences or equations.
347
12. Consider an acid H2 A with pKa1 = 5.5 and pKa2 = 9.5, in a solution with
10 2 M T OT A.
(a) At what pH or in what pH range (if any) will the following conditions be
met?
(i) The concentration of A2– increases by approximately a factor of 100
for every increase of one pH unit?
(ii) The concentration of HA– decreases by approximately a factor of 10
(iii) The concentration of H2 A increases by approximately a factor of 10
(iv) The ratio (H2 A)/(A2 ) decreases by approximately a factor of 100
(v) The value of p(HA– ) is approximately 2.3?
(vi) The value of p(H2 A) is approximately 4.0?
(b) What is the pH of a solution of 0.005 M H2 A + 0.005 M NaHA?
(c) Write the T OT H equation and determine the pH of a solution of 5 ⇥
10 3 M Na2 A +5 ⇥ 10 3 M H2 A.
(d) Will a solution of 10 2M NaHA be acidic, neutral, or alkaline?
(e) Write the equilibrium equation and the form and the value of Kb for HA– ,
i.e., HA– acting as a base.
13. The following figure is a log C-pH diagram for oxalic acid.
(a) What is T OT Ox? What are pKa1 and pKa2 ?

(b) Over what range of pH values is HOx– the predominant oxalate species?
(c) Is H2 Ox a relatively strong or weak acid?
348
(d) If 10 2M NaHOx were added to water, what would the solution pH be?
14. A log C-pH diagram for an acid/base system containing 10 2.7 M T OT A is

shown below. The fully protonated form of the acid is H4 A. However, the
curves are shown for only three species, because one of the potential Hn A4–n
species is so unstable that its concentration in this system is always less than
10 10 M. The ‘s’ values indicate the approximate slopes of the curves in the
given region, and the pH values indicate the intersection points of the various
curves.
(a) What is the equilibrium constant for the reaction H3 A )* HA + 2 H+ ?
(b) What is the value of Kb for a reaction in which HA is the acid?
15. Nickel can combine sequentially with three OH– ions to form ‘nickel hydroxo
complexes’ via the following reactions.
349
Ni2+ + OH– )* NiOH– log K = 4.60
Ni2+ + 2 OH– )* Ni(OH)2 log K = 8.96
Ni2+ + 3 OH– )* Ni(OH)–3 log K = 11.98
(a) Combine these reactions with Kw so that they have the form of Ka ’s.
Determine which species is dominant at any given pH in the range from
0 to 14.
(b) Prepare a log C-pH diagram for a solution containing 10 2 M T OT Ni in
the pH range 6 to 13 and for log C values from 2 to 8. (Hint: the
diagram might be difficult to draw at first, because the acidity of vari-
ous nickel species is unusual in a way that will be apparent from the Ka
values. Despite the unusual features, the diagram must reflect the basic
equations that characterize any acid/base system: the mass balances and
equilibrium constants. On the other hand, there is nothing fundamental
about the “look” of graphs that you have become accustomed to. If you
are having difficulty drawing the graph, use a spreadsheet to compute the
a values of the different species over a range of pH values, and plot the
results. Once you have drawn the graph, you will be able to see how and,
hopefully, why the appearance of this graph is slightly different from that
of most log C-pH diagrams you have seen previously.)
(c) What is the pH of a solution of 10 2M Ni(NO3 )2 ?
16. Chromic acid (H2 CrO4 ) is a diprotic acid which has important uses in indus-
trial processes and in preparation and analysis of environmental samples. Un-
der certain conditions it can “dimerize” according to the following reaction:
2 HCrO )* Cr2 O27 + H2 O log K = 1.54
The product shown is called dichromate ion and is the deprotonated form of a
strong diprotic acid. The acidity constants for chromate are pKa1 = 0.20 and
pKa2 = 6.51, and those for dichromate are pKa1 < 0; pKa2 = 0.07. Find the
pH and composition of the following two solutions:
(a) 0.2 M Na2 CrO4 + H2 O

(b) 0.2 M NaHCrO4 + H2 O
(Hint: Because of the dimerization reaction, the total molar concentration of

dichromate species in a system where most of the Cr is dimerized is different
from the total molar concentration of chromate in the system when most of
the Cr is present as the monomer. Write out the mass balance and equilibrium
350
equations as the first step in your analysis. Then either solve those equations or
develop a log C-pH diagram by substituting into the mass balance on Cr until
it contains H+ and one Cr containing species as the only variables. You can
then solve that equation at various pH values and use the results to determine
the concentrations of the other Cr containing species, so that the complete
diagram can be drawn. Note that only one Cr-containing species can be chosen
arbitrarily as a component for the T OT H equation.)
17. Citric acid is triprotic (H3 Cit), with acidity constants pKa1 = 3.13, pKa2 =
4.76, and pKa3 = 6.40.
(a) Write out the expressions for a0 , a1 , a2 , and a3 as a function of the Ka

values and (H+ ).
(b) Identify the region where each citrate species is dominant.
(c) Determine which terms in the denominators for the a values are signifi-
cant at pH 7.5 (terms contributing less than 5% to the summation can be
considered negligible). For a solution with 10 1 M total citrate, write out
an approximate equation of the form: [log C = constant + n pH] for each
citrate species at pH 7.5, approximating the dominant species’ concen-
tration as T OT Cit.
(d) Draw a log C-pH diagram for a solution with 10 1M T OT Cit over the
pH range 1.0 < pH < 8.0.
(e) Find the pH of the following solutions:
(i) 10 1 M H3 Cit + water
(ii) 10 1 M Na2 HCit + water
(iii) 0.05 M Na3 Cit + 0.05 MNaH2 Cit + water
18. A wastewater is simulated as an ideal solution containing 10 2.7 M NaHCO3

and 10 3 M NH4 Cl.
(a) Prepare a log C-pH diagram for the system.

(b) Predict the dominant species in the equilibrium solution, and prepare a
system tableau using those species as components.
(c) Write the T OT H equation and use it to determine the pH of the solution.
(d) The utility hopes to remove nitrogen from the solution by driving out
NH3 gas. To prepare for that step, 148 mg/L Ca(OH)2 (hydrated lime)
will be added to raise the pH and convert NH+4 to NH3 (aq). Calculate the
pH after lime addition, but before any NH3 exits the solution.
351
19. Acid drainage from coal mines can make the receiving waters uninhabitable
by fish. To remediate one such situation, a consultant has recommended dis-
solving limestone, CaCO3 , in the drainage water to neutralize the acid. The
pH of the untreated water is 2.40 due to the following overall reaction:
FeS(s) + 2.25 O2 (aq) + 2.5 H2 O ! Fe(OH)3 (s) + SO24 + 2 H+
(Note: This reaction is shown only to illustrate how the SO2– +

4 and H enter the
water. The following questions focus just on the concentrations of these ions
in solution; you need not consider the other chemicals in the reaction when
answering the questions.)
(a) Determine the concentration of T OT SO4 in the drainage water using

manual calculations. Use the Davies equation to model activity coef-
ficients. Is HSO–4 a strong acid in this solution? (Hint: write out the
mathematical expressions that relate the concentrations of H+ , HSO–4 ,
and SO2– 4 to known values and/or each other. Some of these relation-
ships will include activity coefficients. Then, make a guess for the ionic
strength of the solution, compute the activity coefficients, and solve for
the species concentrations. Finally, test whether the ionic strength based
on those concentrations is consistent with your guess. If not, iterate on
the guess until it converges with the computed value.)
(b) Prepare the system tableau for the solution after it has been neutralized
to pH 7.0 by addition of CaCO3 , and write the corresponding T OT H
equation. Use the expected dominant species as components.
(c) What is T OT Ca in the stream after the pH has been raised to 7.0? As in
part (a), use the Davies equation to estimate activity coefficients.
352

Acids and Bases, Part 2: Use of Log C-PH Diagrams and The Toth Equation

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6

ACIDS AND BASES, PART 2:

USE OF Log C-pH DIAGRAMS

6.1 GRAPHICAL SOLUTIONS FOR SETS OF SIMULTANEOUS

6.1 GRAPHICAL SOLUTIONS FOR SETS OF

6.2 USING LOG C-pH DIAGRAMS TO SOLVE WEAK

(H+ ) = (Pr ) + (OH ) (6.1)

pH log(OH– ) log(Pr– ) log[(OH– )+(Pr– )]

(H+ ) = 10 3.95 (HPr) ⇠

(Na+ ) + (H+ ) = (Pr ) + (OH )

CB: (Na+ ) + (H+ ) = (Pr ) + (OH )

(Pr ) = 10 3.00 (H+ ) = 10 7.95 (Na+ ) = 10 3.00

(HPr) = 10 6.05 (OH ) = 10 6.05

(10 7.95 )(10 3.00 )

(Na+ ) + (H+ ) = (Pr ) + (OH )

(b) 10 4M KOCl + 9 ⇥ 10 4M HOCl

(a) The charge balance for a solution of 10 3M KOCl is

CB: (K+ ) + (H+ ) = (OCl ) + (OH )

CB: (K+ ) + (H+ ) = (OCl ) + (OH )

pH = 9.26 pOH = 4.74 log(HOCl) = 4.74 log(OCl ) = 3.01

(10 9.26 )(10 3.01 )

(b) The charge balance for a solution of 10 4 MKOCl+9⇥10 4 M HOCl is shown

CB: (K+ ) + (H+ ) = (OCl ) + (OH )

pH = 6.58 log(OCl ) = 4.00 log(K+ ) = 4.00

(a) 10 3M HAc + 5 ⇥ 10 4M NH4 Cl

(b) 10 3M NaAc + 2.5 ⇥ 10 4M NH3 + 2.5 ⇥ 10 4M NH4 Cl

Figure 6.6 LogC-pH diagram for a system containing 10 3M T OT Ac and 5 ⇥ 10 4M

(H+ ) = (OH ) + (Ac ) + (NH3 )

pH ⇡ 3.91, where (H+ ) ⇡ (Ac )

+ (Ac ) + (HAc) = (Na+ )

pH ⇡ 9.19 (⇡ pKa,NH+ ), where (NH3 ) = (NH+ 4

(b) A solution has three times as much H2 CO3 as CO2–

Figure 6.7 log C-pH diagram for a system containing 10 2M T OT CO3

(i) CB : (Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )

(Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )

(H+ ) = 10 11.13 (OH ) = 10 2.87

(H2 CO3 ) = 10 7.64 (HCO3 ) = 10 2.86 (CO23 ) = 10 2.06

(ii) CB : (Na+ ) + (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )

(H+ ) = 10 8.34 (OH ) = 10 5.66

(H2 CO3 ) = 10 4.00 (HCO3 ) = 10 2.01 (CO23 ) = 10 4.00

(iii) CB : (H+ ) = (OH ) + (HCO3 ) + 2(CO23 )

The point where this CB is satisfied can be identified directly on the

(H+ ) = 10 4.18 (OH ) = 10 9.82

(H2 CO3 ) = 10 2.00 (HCO3 ) = 10 4.17 (CO23 ) = 10 10.32

H2 CO3 )* HCO–3 + H+ Ka1

(CO23 )(H+ )2 16.68

(H+ )2 = 3 ⇥ 10 16.68 = 10 16.20

(H+ ) = 10 8.10 pH = 8.10

To summarize, the preceding discussion and examples demonstrate how a log C-

6.3 THE MASS BALANCE ON H (THE TOTH EQUATION

The baseline arsenic concentration that we use when we do this accounting is

6.4 DEFINING THE COMPOSITION OF THE SYSTEM:

As indicated in the figure, it is allowable to either add or subtract components

nA, j Comp A + nB, j Comp B + ... + nN, j Comp N )* 1Spec j (6.4)

Although the choice of H2 O, H+ , and Ac– as components is acceptable for this

Thus, if we include the possibility of using unrealistic components, an infinite

1 H2 O )* 1 H2 O KH2 O = 1.0 (6.10)

Similarly, the equilibrium constant for Reaction (6.9) is