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Buffer problems can be quite challenging for many students.

It is the purpose of this

handout to help guide you through simple buffer problems you might encounter in this
course. The best way to solve these problems, and many other problems for that matter,
is to follow a step-by-step pattern. I will show you the pattern needed for buffer problems
in this document.

When making a buffer, one must consider two major concepts: First, what chemical
species are going to actually release or absorb added hydrogen ions; and second, at what
concentrations do these species need to be in order to be an effective buffer. Buffers are
not generally effective more than 2 pH units away from the pKa of the weak acid/base
pair of the buffer, and normally buffers are made using ingredients whose pKa’s are as
close as possible to the desired pH of the buffer. Additionally, the more concentrated the
buffer, the better able it is to resist a change in pH. However, considerations of ionic
strength often preclude the use of concentrated buffering systems. A compromise
involving pH, pK, and concentration is often necessary.

Consider the following question:

Starting with 1.0M acetic acid and 0.50M NaOH, how would you prepare 100.mL of
0.10M acetate buffer, pH = 4.50? pKa of acetic acid is 4.74

(Abbreviations: acetic acid = HAc, Acetate = Ac–)

The first step to solving any buffer problem is to recognize what is the weak acid/base
pair that will exist in the buffer solution. To do this, write out the equilibrium equation
for the buffering species.

HAc + H2O H3O+ + Ac–

acid (H+ – attached) base (H+ – not attached)

Then identify the weak acid (HA) and base (A) in the reaction.

HA = HAc A = Ac–

Write down the pK associated with this pair. You will be given this information as an
actual pK or as a Ka. If you are given the Ka you must take the –log(Ka) to get the pKa.

pKa for acetic acid / acetate is 4.74

Write out the Henderson-Hasselbach equation using the information given.

pH = pKa + log(A/HA)
4.50 = 4.74 + log(acetate/acetic acid)

Calculate the ratio of A to HA that will exist in your buffer (Solve for A/HA).
A/HA = 10(4.50-4.74) = 10–.24 = 0.575 = 0.58
Next, calculate the total number of millimoles of buffer needed (total acetic acid + acetate
or HA + A) by multiplying the volume of the buffer in mL times the molar concentration
of the buffer.

100.mL x 0.10 mmols/mL = 10. mmols total buffer.

Determine how to divide the total millimoles into the A and HA forms such that the final
ratio will be equal to that calculated (0.58 for this problem). To easily do this, divide the
total number of millimoles by 1 + the ratio calculated.

10.millimols / 1.58 = 6.3 mmols

This will be the number of millimoles of HA needed to get the buffer to the proper pH
assuming the remainder is in the A form.

HA = 6.3 millimoles = millimoles of acetic acid in 100 mL of buffer

A = 10. millimoles – 6.3 millimoles = 3.7 millimoles of acetate in the 100mL

Check your calculations:

pH = Pka + log(A/HA) = 4.74 + log(3.7 mmols / 6.3 mmols) = 4.51

The small (0.1) error is roundoff error and is acceptable in terms of two significant
figures in this calculation.

We must now determine how you will get 6.3 mmols of acetic acid and 3.7 mmols of
acetate. Begin by looking at the starting materials given in the problem. In this problem
you are starting with 1.0M acetic acid and 0.50M NaOH. Since you are not given a direct
source of the base acetate, you will have to use NaOH to convert some acetic acid into
sodium acetate. Remember, one mmol of a strong base like NaOH or KOH will convert
an equivalent amount of a weak acid into its conjugate base. In this case, every mmol of
NaOH added will convert an equal number of mmols of HAc into Ac–.

Start by adding 10.mL of 1.0M HAc (10.mmols) to a flask. This will provide all the
acetic acid/acetate necessary to give the correct concentration in 100mL of buffer. We
then must convert 3.7 mmols of the HAc into Ac–. To do this we must add 7.4mL of
0.50M NaOH (7.4mL x 0.50mmols/mL = 3.7mmols) to the flask.

The flask will now contain a solution whose pH is equal to 4.5. However, the
concentration will not be 0.10M. We must add water to the flask to give a final volume of
100.mL. Mix and our buffer is complete!

The question above is about simple as a buffer problem can be. However, even more
complex problems require one to answer the same basic questions. Problems usually
vary in the following ways:
You are given a base such as an amine and a pKb instead of a pKa. Often the base is in a
protonated form, such as ammonium ion or methyl ammonium chloride. The easiest
solution is to write out an acid dissociation reaction and convert the pKb to a pKa by
subtracting the pKb from 14. These problems are usually difficult for the student.

You are given a polyprotic acid such as phosphoric acid. Assumming you start with
phosphoric acid the typical phosphate problem will require you to convert all of the
phosphoric acid to dihydrogen phosphate (H2PO4–1)and then some of the dihydrogen
phosphate into monohydrogen phosphate (HPO4–2) ( most phosphate buffers are around
pH=7). Problems using polyprotic acids can also start with intermediates such as
H2PO4–1and HPO4–2 . It is important you write out the equilibrium and determine
where you are (starting materials) and where you need to be (A and HA).

You are given a substance like an amino acid that has both acidic and basic functional
groups. Again, writing the equilibrium is crucial to understanding where you are at any
given time while solving the problem. In such compounds, pKa’s are normally given and
not pKb’s, even when the functional group is a base, like an amine. Remember, the term
HA in the H-H equation refers to the protonated form of the group and A refers to the
group as it exists without a proton attached. For a carboxylic acid group, HA = R-COOH
and A = R-COO–. For an amino group, HA = R-NH3+ and A = R-NH2 .