Buffers: what they are and why

we can't live without them

by John Gipps
John Gipps is a professional officer in the Faculty of Education at Monash University and is involved in
the training of primary teachers and secondary science teachers.

Buffers are mixtures that resist changes in pH when acids or alkalis are added. They play a crucial role in
regulating chemical conditions in animals and plants and also in global environmental systems such as the
oceans. In this article I use computer-interfaced titrations to demonstrate the behaviours of some important
buffer systems.

Introduction consider to be relevant to the concept efficiency of maintaining a constant

buffer is a solution of a of buffers. internal environment. It also looks

A substance or mixture that The Victorian VCE Chemistry Unit

resists pH changes when acids 3 topic 'Equilibrium' covers the pH
or bases are added to it. The typical of solutions of weak acids and the
at the changing composition of blood
and the necessity for removal of
carbon dioxide (pages 40 and 41 of
study guide).
buffer is a mixture of a weak acid HA applications of chemical equilibrium
and its conjugate base A. in living systems (page 23 of study Buffers are important to both
(1) HA + H.O ^ A- + up- guide), the VCE Biology Unit 2 topic biological and environmental
'Functioning Organisms' covers systems. Most biological systems
(2} A + H,O <-• HA + OH biological gas exchanges and the operate within narrow pH ranges,
When hydroxide ions are added, they functions of blood in circulatory and the more complex the system
are neutralised by hydrogen ions, the systems (page 17 of study guide) and the narrower that range tends to be.
equilibrium of equation (1) n:\oves to the VCE Environmental Science Unit While some individual enzymes may
the right, HA is used up and the pH 2 topic 'Monitoring the Environment' operate over a reasonably broad pH
increases slightly. When hydrogen looks at environmental indicators range, the optimum performance
ions are added, they are neutralised such as pH in water bodies (page of an entire 'orchestra' of enzymes
by hydroxide ions, the equilibrium of 16 of study guide). The Western requires more controlled conditions.
equation (2) moves to the right. A" is Australian Year 12 Chemistry We require buffers inside our cells,
used up and the pH slightly decreases. topic 'Acids and Bases in Aqueous in our blood and in other bodily
A major change in pH will not occur Solution' describes weak acids and fluids. If these buffers are deficient
until sufficient acid is added to use up bases and requires students to be able or if we overload them with excessive
almost all of the A or sufficient alkali to use the concept of hydrolysis to amounts of acid or base we will
to use up almost all of the HA. describe what happens when strong become very sick. Most plants grow
A buffer is at its most effective when acids are reacted with weak bases and best in rich soils that have effective
the concentrations of HA and A" are strong bases with weak acids (page buffers, both organic and inorganic.
the same, and at this point the pH of 95 of study guide). The New South Oceans absorb vast amounts of acid
the buffer has the same value as the Wales HSC Stage 6 Chemistry topic gases such as carbon dioxide, while
pKa of the acid HA. 'The Acidic Environment' covers buffers maintain the steady pH
the solubility of carbon dioxide in required by their ecosystems. But
The Ka of the acid is given by: water as an equilibrium process, despite the immensity of the oceans,
Ka = lHp-l[A]/[HA] mentions conjugate acid/base pairs they too could become sick if we try
If [A] - [HA] then Ka = [H^O^ and requires students to be able to to push carbon dioxide into them at
describe 'the effect of buffers with too great a rate.
Taking the negative log of both sides, reference to a specific example in a
pKa - pH. natural system' (pages 54 and 55 of In this article I present the results
The theory of buffers is discussed study guide). The Stage 6 Biology of some acid-base titrations that
briefly in the Year 12 Chemistry topic 'Maintaining a Balance' covers demonstrate the properties of buffers
textbooks Commons et al (1999), homeostasis, both physical and of biological and environmental
Sharwood ct al (2000) and James et al chemical, refers to the effect of pH on importance.
(2000), and in more detail in Perrin enzyme activity and asks students to
and Dempsey (1974). Here are some explain the importance to metabolic
Methods
examples of curriculum topics that I In all but one of the experiments

30 TEACHING SCIENCE I VOLUME 51 NO 1 1 AUTUMN 2005

 features

below, the method I chose to illustrate
the pH range of action of the buffer
was to take an aliquot of a 0.1 M
solution of the weak base and titrate
it with 0.1 M hydrochloric acid, using
data logging to display the pH as the
acid was added. The buffers I looked
at in this way were the ammonium,
ethanoate, phosphate, citrate and
carbonate systems. In the remaining
experiment 1 used titration with 0.01
M sodium hydroxide to follow the
buffering action of a system set up to
model seawater.
Merck buffer tablets at pH 4.0, 7.0 and
9.2 to calibrate the probe, but despite
this it did not appear to be accurate
at pH values over 12. 1 used Excel
spreadsheets to generate the graphs
that appear as Figures 2 to 5.
Results and discussion
Simple buffers
Figure 2 shows the results of titrations
of 0.1 M HCI with 0.1 M solutions of
role in enabling the kidneys to remove
acidity (generated by metabolic
products such as lactic acid) without
the pH falling to uncomfortable levels
(Strasinger & Di Lorenzo, 2001). The
system may also contribute to the
regulation of soil pH.
Complex buffers
Some systems have more than one range
in which they are effective as buffers.
Figure 3 shows the results of titrations

Titration and data logging

The titration used a Mariotte bottle to
deliver titrant to the titration vessel at
a constant rate. The Mariotte bottle is
described in detail in an earlier article
(Gipps 1994) but for convenience I

pipette

Separating
funnel

25 50 75
0.1 MHCImL
acid Figure 2 Simple Buffers
of 0.1 M HCI with sodium phosphate
sodium hydroxide, sodium ethanoate (0.1 M) and sodium citrate (0.1 M).
and ammonia solution.
Phosphoric acid has three ionisation
burette tip Sodium hydroxide is a strong base, so stages.
this titration is effectively a control to
H3PO, + H P - + H3O-
demonstrate the result of having no pKa = 2.1
buffer system at all. Near the end-
point the addition of only a few drops H^PO; + H,O --
pKa = 7.2
Figure 1 The Mariotte bottle of acid causes the pH to plummet
from 10 to 4. PO Hp-
- 12.7
have included a diagram as Figure 1. Sodium ethanoate is the conjugate The titration curve shows good
base of ethanoic acid, which has a pKa
When the tap is open and atmospheric buffering in the range 11 to 12,
of 4.8, and the titration demonstrates
air is bubbling into the bottle at point corresponding to the third ionisation,
that the ethanoic acid / ethanoate and 6 to 7.5, corresponding to the
A, there will be a constant hydrostatic
system is a good buffer in the range second ionisation. There should also
head between point A and the tip
3.5 to 6. be buffering in the area around pH 2,
of the burette. Provided the tip is
not obstructed, the rate of delivery CH3COOH + OH ^ CH^COO + up but it is not obvious from this curve as
of liquid is a constant that can be CH3COO + H3O — CH,COOH + H P the range is not much different from
calibrated in terms of mL.s\ The Ammonia is the conjugate base of the pH values generated by excess HCI
titration vessel was a 250 mL beaker the ammonium ion, NH^ , which has after the final end-point. Phosphate
fitted with a magnetic stirring bar to a pKa of 9.1, and the titration curve buffers are widely used in chemical
ensure rapid mixing of the liquids. shows that the ammonium / ammonia and biological experiments where a pH
Unless otherwise specified, the burette close to neutrality is required. Together
system is a good buffer in the range with proteins they play a major role in
contained 0.1 M HCI and 50 mL of
8.5 to 10.5. regulating the internal pH levels of
base or basic salt solution was added
to the titration vessel. 1 clamped a pH NH.* + OH- ^ NH3 + up both plant and animal cells, contribute
probe in place so that the pH values NH3 + up- NH/ + up to the buffering of urine and can also
be significant in controlling soil pH.
could be sampled at one-second Ammonia is excreted in small
intervals by a Tain TecMaster interface quantities in urine, and together with Citric acid also has three ionisation
connected to a computer. I used citrate and phosphate plays a major stages.

TEACHING SCIENCE I VOLtJME 51 N O ! I AUTUMN 2005 31

features

or smoking, where carbon dioxide

cannot be removed fast enough, the
pH will become too low. This system
is so important that there is an enzyme,
carbonic anhydrase, that catalyses
the decomposition of carbonic acid to
optimise the rate of exchange of carbon
dioxide between blood and air.
Blood acidosis is when the pH falls
below 7.35, and alkalosis is when the
pH is above 7.45. Either condition
can lead to the functioning of various
body organs, notably the brain being
impaired. Alkalosisbyhyperventilation
25 50
is effectively self-correcting in that the
75 100 125 150 175
brain loses consciousness, the person
0.1 M HCt mL faints and stops hyperventilating.
Figure 3 Phosphate and Citrate Acute acidosis can result in brain
, + Hp < > Hp* = 3.1 The carbonate system shows two seizures, while long-term acidosis will
buffering ranges, one of 5.5 to 7.5 promote the leaching of calcium from
^ pKa = 4.8 bones, causing osteoporosis.
and the other 9 to IL The HCO^/
C H 0.=- + H,0 -- C Hp_^ + p ^ pKa = 6.4 Seawater has an average pH of 8.2,
H^CO,/ CO, mixture plays the major
But here the pKa values are so close role in buffering the pH of blood to although it can vary from 7.9 to 8.4
to each other that the buffering ranges a narrow region around 7.4 (Staub, depending on temperature and exact
merge with no clear end-points 1991), although hemoglobin is also a chemical conditions, and it is the
between them. The citric acid/citrate significant contributor. A pH of 7.4 is carbonate system that is primarily
system serves, therefore, as an effective
buffer across the whole range of 2.5 to
7. Some antacids such as ENO 'fruit
salts' contain a mixture of sodium
hydrogen carbonate and citric acid that
react in water to form a citrate buffer.
This buffer is effective in reducing the
acidity of the stomach while leaving
it with a pH low enough to enable it
to perform its functions. Citrate is
excreted as an essential component
of urine, where it helps to control the
pH and at the same time reduce the
formation of kidney stones.
And the most important buffer of all.
I consider the carbonate system to
be the most important buffer of all.
On a physiological level it is mainly
responsible for the maintenance of
blood pH and on a global scale it plays 25 50 75 100 125
the chief role in stabilising the pH of 0.1 MHCImL
oceans. Figure 4 Carbonate Buffer
Figure 4 shows the curve generated by
the acid titration of sodium carbonate very close to the alkaline end of the responsible for keeping it in this range
(0.1 M). buffering range and the system works (Home 1969). A quick glance at the
only because the substances most likely titration curve in Figure 4 would
Carbonic acid has two ionisation suggest that the carbonate system ought
to enter the blood stream and affect the
stages. to be almost useless as a buffer at pH
pH are adds such as carbon dioxide
HpO, + H p <-> HCO; + H30*pKa = 6,4 and lactic acid. Regulation of breathing 8.2, but seawater also contains calcium
HCO, + H p ^- CO3' + H3O^ pKa - 10.3 is closely connected to the maintenance ions, which complicate the picture.
For the final experiment I put 0.01 M
Carbonic acid itself usually forms only of this pH of 7.4. If we hyperventilate
NaOH in the burette and 50 mL of 0.01
a small part of such mixtures as much so that carbon dioxide is removed from
the blood stream faster than metaboUc M NaHCO3 mixed with 50 mL of 0.05
of it decomposes to carbon dioxide.
processes can replace it, the pH will M CaClj in the beaker. Figure 5 shows
HpO, ^ CO,(aq) + H p the titration curve for this mixture.
become too high. If, on the other hand,
CO>q) - CO^(g) we have a condition such as asthma The pH initially increased from 7.9 to
32 TEACHING SCIENCE I VOLUME 51 NO 1 I AUTUMN 2005

8.3, then actually decreased to 8.0 even
though hydroxide was still being added.
At about the same time as this decrease
the clear solution became cloudy as
calcium carbonate precipitated.
HCO,- + OH- -^ CO/- + H,O
Ca=^ + CO^^ -- CaCO,(s)
The calcium carbonate did not
precipitate instantaneously, and in the
small delay the levels of carbonate
built up. When the precipitation
occurred much of the carbonate was
removed from solution, leaving a
0.1 M NaOH mL
Figure 5 Calcium Carbonate
buffer with a high preponderance of
hydrogencarbonate and a pH slowly
increasing from 8,0. I used hydroxide
to demonstrate the operation of this
buffer system because the alternate
method using acid was impracticable.
While calcium carbonate is slow to
precipitate at these pH levels, it is even
slower to redissolve, so a titration of the
solid carbonate with acid would have
to be stretched out over a 'realistic'
period of time (hours or days) to get a
realistic result.
Seawater contains a mixture of calcium,
carbonate and hydrogencarbonate
ions, carbonic acid and carbon dioxide,
all in contact with calcium carbonate
as limestone, sediment, coral and
seashells (Chester 2000). If an excessive
amount of carbon dioxide enters the
oceans some calcium carbonate must
eventually redissolve to balance it.
Seawater therefore acts as a 'sink' for
carbon dioxide, although the system
may take thousands of years to return
to equilibrium. There are limits to how
much and how fast calcium carbonate
can redissolve and how low the pH can
TEACHING SCIENCE I VOLUME 51 NO 1 1 AUTUMN 2005
features
drop before there is significant damage References
to marine ecosystems. Chester, R. (2000). Marine geochemistry.
Maiden, United States: Blackwell
Appendix Publishing.
Solutions Commons, C, Jarrett, S., McKenzie,
Hydrochloric acid 0.1 M was prepared C, Mosely, W., Porter, M. and
by diluting 10 mL of concentrated HCl Williamson, M. (1999). Chemistry Two
to 1000 mL and standardising against (3"^ Ed.). Melbourne: Heinemann.
dried potassium carbonate.
Cipps, J. (1994). Acids, bases and
Sodium hydroxide 0.1 M was prepared computers. Australian Science Teachers
by dissolving 1.00 g of NaOH in 250 journal, 40(2), 48-52.
mL of water and standardising against
the 0.1 M HCl. Home, R.A. (1969). Marine chemistry.
New York: Wiley Interscience.
James, M., Stokes, R., Ng, W. and
Moloney, J. (2000). Chemical connections
2 (2'"^ Ed.). Brisbane: Jacaranda.
Perrin, D. and Dempsey, B. (1974).
Buffers for pH and metal ion eontrol.
London: Chapman & Hall.
Sharwood, J., Willis, J., O'Shea, P,
Briggs, D., Hartshorn, R., Sweeney,
T. and Lyon, K. (2000). Chemistry
VCE units 3 & 4. Melbourne: Nelson
Thomson.
Staub, N.C. (1991) Basie respiratory
physiology. New York: Churchill
Livingstone.
Strasinger, S.K. and Di Lorenzo, M.S.
(2001). Urinalysis and bodily fluids.
Philadelphia: F.A. Davis Co.
Sodium hydroxide 0.01 M was prepared WARNING
by diluting 50 mL of 0.1 M NaOH to
These solutions include
500 mL.
strong acids and alkalis that
Ammonia solution 0.1 M was prepared
by diluting 6.5 mL of concentrated NH^
can burn skin and damage
to 1000 mL and standardising against eyes. You should wear eye
the 0.1 M HCl. protection, gloves and a
laboratory coat You should
Sodium hydrogen carbonate 0.01 M
was prepared by dissolving 0.84 g of use a fume cupboard while
in 1000 mL of water. diluting concentrated
Calcium chloride 0.05 M was prepared solutions of hydrochloric
by dissolving 1.84 g of CaCl.2Hp in acid and ammonia.
water and making up to 250 mL.
0.1 M solutions of the following basic For a list of web addresses
salts were made by dissolving the relevant to this article you can
specified amounts of solid and making contact the author at John.
up to 250 mL. Sodium citrate (7.35 g of aipps(S)education.monash.edu
Na3C^Hp^.2H,O), sodium ethanoate
(2.05 g'of arihydrous NaCH3COO),
sodium phosphate (9.50 g of
Na3PO^.12H,O) and sodium carbonate
(2.65 g of anhydrous Na^CO,). As none
of these salts are standard substances, I
have assumed that the concentrations
should not be specified to better than
0.1 M.
33