Article

Cite This: J. Chem. Educ. 2019, 96, 936−943 pubs.acs.org/jchemeduc

Buffer Squares: A Graphical Approach for the Determination of

Buffer pH Using Logarithmic Concentration Diagrams
Spiros A. Pergantis,*,†,‡ Iakovos Saridakis,† Alexandros Lyratzakis,† Leonidas Mavroudakis,†,‡
and Tamsyn Montagnon†
†
Department of Chemistry, University of Crete, Voutes Campus, Heraklion 70013, Greece
‡
Environmental Chemical Processes Laboratory, University of Crete, Voutes Campus, Heraklion 70013, Greece
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Teaching the concept of pH buffers is considered to be important

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both in the final high-school years and at the early undergraduate level. Here, we
propose the use of pH−log C diagrams to investigate the properties of pH buffers.
This graphical approach is extremely simple to employ because it only requires
drawing a simple square that can then be used to determine relevant pH-buffer
parameters. This square is based on the Henderson−Hasselbalch equation with the
length of each of its sides equal to abs(pH − pKa) and abs(log Cb − log Ca). In
addition, the “buffer square”, as we propose naming it, can be used by instructors
as a pedagogical tool to introduce the concept of buffer capacity, to help determine
pH change upon the addition of an acid or base, and to easily calculate the
required concentrations for preparing a pH buffer with specific properties. Finally,
we consider this approach to be especially powerful for helping students visualize
the location of a buffer system on a full pH−log C diagram and, thus, help them
evaluate if the Henderson−Hasselbalch equation is valid for accurate pH
determination as an alternative to the more complex cubic or quadratic equations that are needed to describe acid−base
equilibria more precisely in some cases.
KEYWORDS: First-Year Undergraduate/General, Analytical Chemistry, Biochemistry, Environmental Chemistry,
Analogies/Transfer, Mnemonics/Rote Learning, Acids/Bases, Aqueous Solution Chemistry, pH

■ INTRODUCTION
Diagrams of pH−logarithmic concentration (log C) have been
used extensively to enhance conceptual understanding of acid−
base equilibria and to help solve equilibrium problems of
varying difficulty without the need to resort to complicated
mathematical calculations. The pH−log C coordination system
was first introduced by Niels Bjerrum, a Danish chemist, in
1915.1 Since then, numerous scientists have contributed
towards making these diagrams more useful, popular,2,3 and
universally applicable.4−6 Currently, only a limited number of
chemistry textbooks introduce this approach to help students
understand acid−base equilibria. Among these examples, a
recent undergraduate analytical chemistry textbook has
demonstrated the use of pH−log C diagrams in solving
numerous acid−base-equilibrium problems.7 Prior to this
publication, a tutorial book by Robert de Levie gave an
extensive account on the use of pH−log C diagrams.8 The
most comprehensive mathematical coverage of the pH−log C
diagram topic was published recently as a book authored by
Kahlert and Scholz.9 Educational papers on this topic
published in scientific journals, including the J. Chem. Ed.,
have also appeared over the years, with the objective of
promoting the use of pH−log C diagrams in undergraduate
teaching.10−12
© 2019 American Chemical Society and
Division of Chemical Education, Inc.
The main advantages of constructing and using pH−log C
diagrams is that they provide detailed information about the
concentrations of acid−base-equilibrium species over several
orders of magnitude. This helps chemists to visualize the
distribution of chemical species and, thus, allows them to
decide which species are important and which can be ignored
in order to conveniently calculate relevant chemical parame-
ters. Another attractive feature is the fact that most associated
problems (e.g., what the pH of a weak acid solution is) can be
solved using the diagram without any requirement for time-
consuming and complicated mathematical calculations. In
addition, these diagrams can be used to assist in the drawing of
titration curves, a tedious task when done by using calculations
alone.12 Constructing and using pH−log C diagrams, as
described by several authors,7−11 is a relatively trivial task once
a few basic rules have been understood and followed.
Even though the approach has many benefits it also has
some limitations. As described by Kovac,11 these limitations
include their use in the treatment of buffer solutions. Because
buffer systems are very close to the system point and, therefore,
Received: July 22, 2018
Revised: March 17, 2019
Published: April 3, 2019
936 DOI: 10.1021/acs.jchemed.8b00588
J. Chem. Educ. 2019, 96, 936−943
Journal of Chemical Education
fall within the curved region of the pH−log C diagram, it is
difficult to study them using hand-drawn diagrams. As a result,
most of the existing approaches are not sufficiently accurate in
this region. With this in mind Kovac concludes, “A carefully
drawn diagram can be used to solve buffer problems, but it is
probably better to use the Henderson−Hasselbalch equation
and solve the problem algebraically.”11 In the present tutorial
paper, we wish to demonstrate that indeed buffer systems can
be conveniently studied using pH−log C diagrams. In this way
relevant information regarding buffer pH can be extracted
conveniently, along with the acid and conjugate-base
concentrations needed to make a buffer with a specific pH,
the pH changes observed when adding known amounts of
strong acid or base to a buffer, the buffer’s capacity, and the
parameters that affect it. Most importantly, the procedure
proposed here does not include any “difficult to draw” figures
but uses only the simple drawing of four intersecting straight
lines to form a square. In fact, the student does not need to
have any prior knowledge of drawing and manipulating
conventional pH−log C diagrams to study the full range of
an acid−base equilibrium. However, some basic knowledge of
the topic may help the reader better understand and appreciate
the benefits of using pH−log C diagrams to study buffer
systems.
We must stress that the proposed buffer-square approach is
not intended to replace the way in which pH buffers are
currently being introduced in general-chemistry courses. It is
rather intended as a complementary approach to help students
better understand pH-buffer concepts and how to graphically
solve pH-buffer problems. Finally, it also provides a convenient
and difficult-to-forget mnemonic for remembering the
Henderson−Hasselbalch equation.
■
THEORETICAL BACKGROUND OF THE
GRAPHICAL APPROACH FOR BUFFER-pH
DETERMINATION
The graphical approach proposed in this tutorial for the
determination of buffer pH is based on the Henderson−
Hasselbalch equation following the rearrangements shown
below:
Cb
pH = pK a + log ⇒ or instructor (blank paper, graph paper, or software) and what
Ca
pH = pK a + (log C b − log Ca) ⇒
(pH − pK a) = (log C b − log Ca) ⇒
abs(pH − pK a) = abs(log C b − log Ca) (1)
Equation 1 can be represented graphically on a pH−log C
diagram (the x-axis is the pH axis, whereas the y-axis is the log
C axis) by drawing a geometric figure having a vertical side
with a length equal to log C b − log Ca and a perpendicular
horizontal side with a length equal to pH − pKa. From eq 1, it
is apparent that the two sides have equal length. These two
sides form the basis for drawing a square in the pH−log C
diagram (Figure 1). In the remainder of this manuscript, we
will refer to this Henderson−Hasselbalch-derived square as the
“buffer square” (b-SQ). Throughout this tutorial, the b-SQ will
be used to determine several pH-buffer parameters. However,
it can only be used within the range of 0.1 ≤ Cb/Ca ≤ 10,
where an acceptable buffer capacity can be achieved (i.e.,
−1 ≤ log C b − log Ca ≤ +1 and, thus, −1 ≤ pH − pKa ≤ +1).
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Figure 1. pH−log C diagram showing a square (ABCD) that
represents the Henderson−Hasselbalch equation describing a pH
buffer. We have named this square the buffer square (b-SQ), whose
sides cannot be greater than 1 log unit, and thus it cannot have an area
greater than 1, or else the system is not considered a pH buffer,
because its buffering capacity drops off significantly outside these
limits.
Therefore, the b-SQ can have a maximum side length of 1 log
unit. As a result, if the b-SQ has an area greater than 1, then the
system under investigation is not an efficient pH buffer. In this
case, the b-SQ graphical approach is not suitable, and the full
pH−log C diagram approach becomes more relevant for
determining the system’s pH.
■
HOW TO CONSTRUCT A pH−LOG C DIAGRAM TO
DETERMINE BUFFER pH
In order to examine pH-buffer properties in a graphical
fashion, we can apply any one of the following three graphical
approaches. These approaches include (a) using a blank piece
of paper to hand-draw the b-SQ and obtain relevant parameter
values, (b) using graph paper to construct the b-SQ and extract
relevant pH-buffer parameters, and (c) using a spreadsheet to
construct the b-SQ and extract relevant parameters. All three
approaches are simple to implement, and so the approach
chosen ultimately depends on what is available to the student
best matches the learning objectives set by the instructor.
Using a Blank Piece of Paper to Construct a pH−log C
Diagram for Determining Buffer pH
Let us consider a pH buffer containing CH3COOH (Ca =
0.020 M and pKa = 4.77) and CH3COONa (Cb = 0.050 M).
How do we determine its pH using a graphical approach on a
blank piece of paper? First of all, the log Ca and log Cb values
need to be calculated, as is always necessary when constructing
pH−log C diagrams. Thus, log Ca = log(0.020) = −1.7 and log
Cb = log(0.050) = −1.3. The initial step in this graphical
procedure is to draw an ABCD square anywhere on an
imaginary xy-coordinate system (x = pH, y = log C), with point
A being the top left corner and all subsequent points following
in a counter-clockwise fashion (Figure 2). The size of the
square does not matter as long as it is a square. Subsequently,
the sides of the b-SQ can be labeled according to the
parameters of eq 1; the opposite vertical sides, AB and CD,
correspond to the pKa and pH lines, whereas the opposite
horizontal sides, BC and AD, correspond to the log Ca and log
Cb lines. The left vertical line, AB, corresponds to the pKa or
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Figure 2. Hand-drawn or back-of-the-envelope b-SQ suitable for
determining the buffer-solution pH.
pH, whichever has the lowest value, and the right vertical line,
CD, corresponds to whichever has the highest value. However,
in the present example, this does not help in assigning each of
the vertical sides, because the pH is unknown. However,
because log Cb > log Ca (more base in the buffer than acid),
the buffer pH must be greater than the acid pKa, and thus the
pH will correspond to the right vertical CD line, whereas the
pKa will correspond to the left vertical AB line. The opposite
holds true when log Cb < log Ca. We can define the horizontal
sides, AD and BC, as corresponding to the log Cb and log Ca
lines, respectively. This is because the AD line (i.e., the top
line) corresponds to the highest log C value, which is the log
Cb value, whereas the bottom BC line corresponds to the
component with the lowest concentration (i.e., log Ca). The
constructed b-SQ has now been labeled with all the important
Figure 3. Buffer square (b-SQ) drawn within a pH−log C diagram and its use for determining buffer pH.
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buffer parameters (Figure 2). Because the distance between the
AD and BC lines equals the absolute difference between log Cb
and log Ca (=0.4), and we are dealing with a square, the
difference between the pKa and pH must also be 0.4. Thus, the
pH is 0.4 greater than the pKa value (4.77); that is, pH = 4.77
+ 0.4 = 5.17. Note that the plus sign (+) used here would be
minus (−) if the pH line was to the left of the pKa line (i.e., log
Cb < log Ca).
A logical mnemonic for conveniently constructing the buffer
square is that when Ca > Cb, its sides should be in the following
order when starting from side AB and going clockwise around
the square: pH line (side AB) → log Ca line (side AD) → pKa
line (side CD) → log Cb line (side BC). In contrast, if we
know that Cb > Ca, then the order of the square sides, starting
from side AB and going clockwise, should be pKa line (side
AB) → log Cb line (side AD) → pH line (side CD) → log Ca
line (side BC).
Using Graph Paper to Construct a pH−log C Diagram for
Determining Buffer pH
To demonstrate the application of the slightly more detailed
graph-paper approach for determining buffer pH, an NH3/
NH4Cl buffer system with the following properties is
considered: NH4+ with Ca = 0.040 M and pKa = 9.26 and
NH3 with Cb = 0.060 M. On the graph paper, the pH scale is
represented on the x-axis, spanning a range from pKa − 1.0 =
8.26 to pKa + 1.0 = 10.26 (Figure 3). It is recommended that
the midpoint on the pH axis should be a value close to the acid
pKa. The range, however, may be selected in order to maximize
resolution and, thus, achieve better accuracy for pH
determination. The diagram’s y-axis, which corresponds to
log C, can be drawn to have a range that depends on the log Ca
and log Cb values and the difference between them. In the
example discussed here, it has a range of 1 log unit. In our
example, we have Ca = [NH4+] = 0.040 M and Cb = [NH3] =
0.060 M and, thus, log Ca = −1.40 and log Cb = −1.22,
respectively. (Note that the log C calculations need to be
made, which is also the case for all pH−log C diagrams.)
Once the pH−log C diagram axes have been prepared, the
following three lines need to be added to the diagram. First,
the acid pKa is noted on the x = pH axis, and a vertical line is
drawn (yellow line in Figure 3); subsequently, the log Ca and
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Figure 4. Snapshot of a pH−log C diagram drawn from a spreadsheet for buffer-pH determination. The red line (pH line) cuts the x-axis at pH =
7.37. Notice that the b-SQ is formed from the four lines corresponding to system’s pKa, log Ca, log Cb, and pH values.
log Cb points are located on the y = log C axis, and horizontal
lines are drawn parallel to the pH axis (green log Ca line and
blue log Cb line in Figure 3). These lines intersect the pKa line
(yellow) at points B and A, respectively. The distance between
points A and B can be easily determined visually on the graph
paper by counting the squares between the two points. The
distance AB is then added or subtracted horizontally to the pKa
line at point B, resulting in a new point, C. Choosing to add or
subtract depends on whether the buffer’s component base or
acid has the highest concentration, respectively. For the buffer
system given here, we can conveniently draw the pH line by
starting from the pKa line (point B) and adding distance AB
horizontally to its right. In the current example, the conjugate
base has a higher concentration than the acid; therefore, the
distance is added to point B, resulting in a new point, C,
located to the right of B. From point C, a vertical line is drawn
that intersects the pH axis to give the buffer pH. Using this
approach, the buffer pH has been determined graphically to be
9.44 (Figure 3). It should be noted, that the pH line also cuts
the log Cb line at point D, thus completing the b-SQ. Provided
that the recommended graph ranges have been used, the
precision of this approach is to the second decimal point of the
pH value. In this way, no precision has been lost compared
with the experimental precision and relative to the pH value
derived from mathematical calculations.
Overall, this is an extremely simple approach to utilize in
order to determine the pH of a buffer, because it only requires
a piece of graph paper and the ability to draw a square along
with knowledge of the weak-acid pKa, the acid log Ca, and the
conjugate-base log Cb values.
Using a Spreadsheet Program to Construct a pH−log C
Diagram for Determining Buffer pH
To further increase the versatility of this approach, we have
configured a macro-containing spreadsheet in order to
automatically construct these lines in the way we have just
described and, thus, provide immediate graphical determi-
nation of the buffer pH upon entering the values of the pKa, log
Ca, and log Cb. A snapshot of the spreadsheet graph is shown in
Figure 4. The actual spreadsheet file is provided as part of the
paper’s Supporting Information.
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Ultimately, any of the b-SQ approaches described here can
be used to graphically determine any of the four parameters
shown in eq 1, provided that the distance between any two
opposite sides is known, and the absolute value of a third side
is also known.
Using the b-SQ Approach to Better Understand Buffer
Capacity
The b-SQ approach may also be used to provide students with
better insight into a system’s pH-buffer capacity. If the b-SQ’s
area is less than 1, because the square sides must be ≤1 log
unit each, then we are dealing with a pH buffer; whereas, if the
square’s area is greater than 1, its buffering capacity may be
significantly reduced. Furthermore, because the b-SQ approach
is based on the Henderson−Hasselbalch equation it may not
be as accurate in this case, and therefore, a full pH−log C
diagram should be used to determine pH and species
concentrations. The reason the b-SQ area should be less
than 1 is because it is generally accepted that in order for a
buffer to have adequate buffering capacity, the acid−conjugate-
base concentrations must be within the range 0.1 ≤ Cb/Ca ≤
10 ⇒ −1 ≤ log Cb − log Ca ≤ +1; thus, −1 ≤ pH − pKa ≤ +1.
Therefore, the b-SQ system becomes a simple tool for
evaluating buffer capacity because high buffer capacity is
associated with small squares having an area ≪1, low buffer
capacity is associated with the b-SQ having an area close to 1,
and maximum capacity is provided when the square has
collapsed into a single point (the area is 0).
Let us now further examine what the b-SQ can reveal about
buffer capacity by assuming we have a 1.0 L buffer solution
consisting of CH3COOH (Ca = 0.0016 M ⇒ log Ca = −2.80,
pKa = 4.77) and CH3COONa (Cb = 0.0024 M ⇒ log Cb =
−2.62). To apply the b-SQ approach, we draw a vertical pKa
line at x = 4.77 and two horizontal lines at −2.80 and −2.62
(Figure 5a). The two horizontal lines cut the vertical pKa line
at points A and B. The distance AB is then added to the
vertical pKa line at point B to produce a new point C in the
horizontal direction. Subsequently, a vertical line drawn from
point C will give us the system’s pH, which is 4.95. Now, let us
examine what will happen to the buffer pH if 0.30 mmol of H+
(monoprotic strong acid) are added (assuming no change in
volume). The outcome of course has to do with the buffer’s
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Figure 5. Demonstrating buffer-pH capacity using the b-SQ approach before (a), during (b), and after (c) the addition of a monoprotic acid.
capacity to mitigate pH change upon the addition of acid or
base. In the present example, the 0.30 mmol of H+ added will
react with the conjugate base, and, thus, decrease its amount
by 0.30 mmol/L, concomitantly affording an additional 0.30
mmol/L acid. Therefore, the new log Cb′ = log(0.0024 −
0.00030) = −2.68, and a new horizontal log Cb′ line should be
drawn, as shown in Figure 5b. The acid concentration also
changes, as log Ca′ = log(0.0016 + 0.00030) = −2.72. This is
represented by another horizontal line, also shown in Figure
5b. These two new log C lines dissect the pKa line at points A′
and B′, respectively. Once again, the distance A′B′ is added to
point B′ to produce C′ in the horizontal direction (Figure 5c).
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The vertical line we draw through point C′ cuts the x-axis at
4.81, which is the buffer’s new pH. This process clearly shows
the high buffer capacity of the system under examination,
because only a relatively small pH change occurred (pH 4.95
to 4.81), following the addition of a significant amount of acid
to the system.
If a similar experiment were to be conducted for the same
acid−conjugate-base system but with the component concen-
trations outside the buffering area (i.e., the system having been
adjusted to have a pH of 7), then a conventional full-scale
pH−log C diagram must be used to determine the new pH
(Figure 6). In this case, however, when the acid is added at
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Figure 6. Full-range pH−log C diagram for a solution prepared to
contain CH3COOH/CH3COONa, adjusted to have pH = 7. Addition
of 0.3 mmol/L acid results in the solution pH being reduced to 5.9.
The blue box is the area where the buffering capacity of the system is
at its maximum. Outside this box it drops significantly. The dotted red
line shows the solution pH before the acid addition, whereas the solid
red line shows the pH following acid addition. The solid blue line
represents the CH3COOH species, whereas the dashed pink line
represents the CH3COO− species. The diagonal solid black line
represents the H+ concentration, which has a slope of −1, whereas the
black dotted line represents the OH− concentration, which has a slope
of +1.
However, this may not always be the case. For example, let
us examine an acid−conjugate-base system with pKa = 2.26, Ca
= 0.4 M, and Cb = 0.04 M. In this case, [H3O+] is about the
same as Cb, and thus the former term cannot be ignored in eq
3. As a result, use of the Henderson−Hasselbalch equation is
not very accurate, as it will give a pH of 1.26 instead of the
more accurate pH 1.52 calculated using a version of eq 3 in
which the term Kw/[H3O+] is omitted as negligible. This is a
confusing point for students as they will sometimes fail to take
this parameter into account and proceed with the use of the
simplified Henderson−Hasselbalch equation. However, when
using the b-SQ approach this limitation is more easily
identified, especially when using the graph-paper approach to
draw the b-SQ. All the student has to do is look for the [H3O+]
or [OH−] lines close to or within the b-SQ that they have
drawn (Figure 7a). This is simple because the [H3O+] line,
which has a slope of −1 (the equation is y = −x, where y is log

0.30 mmol/L, the pH changes from 7.0 to 5.9. This dramatic

pH change is due to the lack of buffering capacity when the
acid−conjugate-base pair CH3 COOH/CH3 COONa are
present in a solution with pH = 7.

■ USING THE b-SQ APPROACH TO READILY

IDENTIFY SITUATIONS FOR WHICH THE
HENDERSON−HASSELBALCH EQUATION IS NOT
VALID
The exact cubic equation that describes ionic equilibria for a
mixture containing a weak acid (HA) and its salt (NaA) is
[H3O+]3 + (C b + K a)[H3O+]2 − (K w + K aCa)[H3O+]
− K wK a = 0 (2)
This equation was derived by rearranging the following acid-
dissociation-equilibrium equation:
[H3O+]{C b + ([H3O+] − K w /[H3O+])}
= Ka
Ca − ([H3O+] − K w /[H3O+]) (3)
To solve buffer problems, we assume that the amounts of
[H3O+] and Kw/[H3O+] are usually significantly lower than Ca
and Cb, and therefore, eq 3 can be simplified to give eq 4,
which is readily converted into the Henderson−Hasselbalch
equation (eq 1):
[H3O+]C b Figure 7. Buffer square for an acid−base system with the following
≈ Ka parameters: pKa = 2.26, Ca = 0.4 M, and Cb = 0.04 M. (a) Close-up of
Ca (4) the b-SQ (blue area). Note the [H3O+] line passing through the b-
SQ. (b) Full pH−log C diagram showing the b-SQ (blue area), with
This assumption is usually valid because for the preparation the solid blue line representing the nondissociated acid species (HA),
of buffered solutions, Ca and Cb are usually maintained at high and the dashed pink line representing the dissociated species (A−).
concentrations, generally between 1 and 0.02 M, in order to The diagonal solid black line represents the concentration of H+ and
provide adequate buffer capacity. Thus, the Henderson− has a slope of −1, whereas the black dotted line represents the
Hasselbalch equation can be used without a problem. concentration of OH− and has a slope of +1.

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C, and x is pH), has the following (x, y) coordinate pattern: (0,

0), (1, −1), ..., (2, −2), ..., (7, −7), ..., (14, −14). So, if the
student locates any such points on the b-SQ graph, there is
cause for concern, because it means that a relatively significant
H3O+ concentration from water self-dissociation is present,
and thus more complex equations must be employed. This is
also the case when the [OH−]-water-self-dissociation line
passes close to or through the b-SQ. This can easily be checked
because the [OH−] line has a slope of +1 (the equation here is
y = x − 14 or log C = pH − 14) and thus the (x, y) coordinates
of (0, −14), ..., (1, 1 − 14), ..., (2, 2 − 14), (3, 3 − 14), ..., (7, 7
− 14), ..., (14, 14 − 14). Once again, if any such points exist
near or within the b-SQ, then using the Henderson−
Hasselbalch equation may be problematic because water self-
dissociation, which is now significant, has not been taken into
account. All this analysis, of course, can also be visualized on
the full pH−log C diagram (Figure 7b).

■ HOW TO USE THE b-SQ APPROACH TO PLAN THE

PREPARATION OF A BUFFER SOLUTION
Let us assume that we want to prepare a buffer system
consisting of CH3COOH (pKa = 4.77) and CH3COONa with
a pH of 3.95. How can the b-SQ approach be used to help us
prepare it? To examine this question, we need to draw a b-SQ
as already demonstrated. To do this, we make the two vertical
pH and pKa lines at 3.95 and 4.77, respectively (i.e., 0.82 log
units apart; Figure 8). This means that log Cb − log Ca must
also be equal to 0.82 log units. Thus, the resulting b-SQ is 0.82
log units by 0.82 log units. To find the acid−base
concentrations that are required to achieve a pH of 3.95, we
can move this b-SQ up and down the pH and pKa lines (i.e.,
we can treat these lines as “railway tracks”). Once we stop
moving the b-SQ, we can extend its two horizontal lines to cut
the y-axis at their corresponding log C a and log C b
concentrations. The higher the b-SQ is on the “railway
track” the higher the buffer capacity will be (i.e., higher
concentrations of acid and base). Once these two concen-
trations have been decided upon, it is easy to calculate Ca =
antilog Ca and Cb = antilog Cb. Their sum, Ca + Cb, can be the Figure 8. Using the b-SQ approach to determine acid−base
starting concentration of the acid CH3COOH used to prepare concentrations required to prepare a pH buffer with a specific pH.
the buffer. Subsequently, an appropriate amount of strong base
(NaOH) is added in order to partially convert the acid to its
conjugate-base form (CH3COO−) and, thus, achieve a buffer Even though there is extensive educational literature
with a pH of 3.95 as described by the b-SQ approach. The describing pH buffers, it is based almost exclusively on the
lower the b-SQ is located on the “railway tracks” (i.e., the more Henderson−Hasselbalch equation and its mathematical
dilute it is), the lower its buffer capacity becomes. Finally, solution, with very few exceptions, such as the recently
when it gets close to the diagonal [H+] and [OH−] lines, the reported 3-D Surface Visualization of pH Titration “Topos”
Henderson−Hasselbalch equation becomes less accurate for approach, which describes buffer plateaus.13 This means that
determining the system’s pH, and thus the b-SQ approach is students either remember the Henderson−Hasselbalch equa-
also less accurate. tion by heart and use it, hopefully correctly, or do not

■
CONCLUSIONS
In this tutorial, we have described a unique graphical approach
that we hope will allow students to improve their under-
standing of pH buffers and their parameters. The buffer square
is easy to construct as it is based on a square drawn in a pH−
log C coordinate system. This square can be conveniently used
to determine buffer pH if Ca and Cb are known, to determine
the pKa of a buffer acid−conjugate-base pair when their
concentrations and the solution pH are known, and also to
determine the Ca and Cb required to make a buffer with a
specific pH.
942
remember it and either have to derive it from the equilibrium-
constant expression by ignoring species that are of negligible
concentration or are simply unable to solve pH-buffer-related
problems. Offering a unique graphical approach involving a
simple “square”, a geometric figure the characteristics of which
all students are well acquainted with from their earliest
mathematical forays in primary school, provides students with
an extremely user-friendly alternative way of solving pH-buffer
problems. Instead of having to remember an abstract equation,
they now only need to remember that a square consisting of a
vertical abs(log Cb − log Ca) side and a horizontal abs(pH −
pKa) side can be used to describe pH-buffer properties.
Knowing the length of one side allows them to draw the other
DOI: 10.1021/acs.jchemed.8b00588
J. Chem. Educ. 2019, 96, 936−943
Journal of Chemical Education
side as well. It also becomes easy for students to associate
component properties with buffer capacity by remembering
that smaller squares have greater buffer capacity than larger
ones. Finally, squares with an area greater than 1 unit start to
lose their buffer capacity significantly. At the very least, the pH-
buffer-square approach can provide students with a way to
check the validity of their Henderson−Hasselbalch-equation
calculations. This new way to examine pH buffers and their
properties may significantly help visually inclined students and
should thus be taught to undergraduate students as it will
probably be nigh on impossible for them to forget it. In some
cases, it can even serve as the starting point to derive the
Henderson−Hasselbalch equation if one has forgotten it.
In this tutorial paper, we certainly do not claim that the
buffer square approach is simpler or faster to use than the
Henderson−Hasselbalch equation for calculating buffer pH.
For the ammonia/ammonium ion buffer solution example
described previously, all a student needs to do is drop three
numbers into the Henderson−Hasselbalch equation and
immediately calculate the resulting pH value. This is extremely
simple; however, if he or she does not remember the exact
form of the equation, things get a little more complicated. The
student would have to spend time deriving the equation from
acid−base-equilibrium theory, which they must know very
well. In contrast, the buffer-square approach (in its simplest
form using a blank piece of paper) only requires that the
student draw a square and assign its sides in a logical fashion to
buffer parameters (i.e., the vertical pKa line is parallel to the pH
line, and the horizontal log Ca line is parallel to the log Cb line).
The line order follows a logical sequence; if log Cb > log Ca
then the pH line is right to the pKa line and vice versa. The
labeled square that results contains information about all buffer
parameters, so the b-SQ approach may in some cases be the
faster and simpler approach.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available on the ACS
Publications website at DOI: 10.1021/acs.jchemed.8b00588.
Calculations for pH change upon the addition of a
monoprotic acid for Figure 6 (PDF)
Macro-containing spreadsheet for automatically con-
structing buffer-square lines that provide immediate
graphical determination of the buffer pH upon entering
the pKa, log Ca, and log Cb (ZIP)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: spergantis@uoc.gr.
ORCID
Spiros A. Pergantis: 0000-0002-9077-7870
Notes
The authors declare no competing financial interest.
■ DEDICATION
S.A.P. would like to dedicate this educational paper to
Nikolaos P. Evmirides, Emeritus Professor at the University
of Ioannina (UoI), Greece, who first introduced the topic of
log C diagrams to him when he was an undergraduate student
at UoI in the mid-1980’s.
943
■
Article
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DOI: 10.1021/acs.jchemed.8b00588
J. Chem. Educ. 2019, 96, 936−943