Buffer solution

For an individual weak acid or weak base com-

ponent, see Buffering agent. For uses not related
to acid-base chemistry, see Buffer (disambigua-
tion).

A buffer solution (more precisely, pH buffer or hydrogen

ion buffer) is an aqueous solution consisting of a mixture
of a weak acid and its conjugate base, or vice versa. Its pH
changes very little when a small amount of strong acid or
base is added to it. Buffer solutions are used as a means of
keeping pH at a nearly constant value in a wide variety of
chemical applications. In nature there are many systems Addition of hydroxide to an equilibrium mixture of a weak acid.
−
that use buffering for pH regulation. For example, the HA, and its conjugate base, A
bicarbonate buffering system is used to regulate the pH
of blood. quantity of strong acid added. Similarly, if strong alkali is
added to the mixture the hydrogen ion concentration de-
creases by less than the amount expected for the quantity
1 Principles of buffering of alkali added. The effect is illustrated by the simulated
titration of a weak acid with pKₐ = 4.7. The relative con-
centration of undissociated acid is shown in blue and of its
conjugate base in red. The pH changes relatively slowly
100
% formation relative to A

in the buffer region, pH = pKₐ ± 1, centered at pH = 4.7

AH 10 where [HA] = [A− ]. The hydrogen ion concentration de-
80 creases by less than the amount expected because most of
A- the added hydroxide ion is consumed in the reaction
60 8
pH pH OH− + HA → H2 O + A−
40
6
and only a little is consumed in the neutralization reaction
20 which results in an increase in pH.
4
0 OH− + H+ → H2 O
0 0.4 0.8
titre volume / ml Once the acid is more than 95% deprotonated the pH rises
rapidly because most of the added alkali is consumed in
the neutralization reaction.
Simulated titration of an acidified solution of a weak acid (pKa
= 4.7) with alkali.
1.1 Buffer capacity
Buffer solutions achieve their resistance to pH change be-
cause of the presence of an equilibrium between the acid Buffer capacity, β, is a quantitative measure of the resis-
HA and its conjugate base A− . tance of a buffer solution to pH change on addition of
hydroxide ions. It can be defined as follows.
HA ⇌ H+ + A−

When some strong acid is added to an equilibrium mix- dn

ture of the weak acid and its conjugate base, the equilib- β = d(p[H+ ])
rium is shifted to the left, in accordance with Le Châte-
lier’s principle. Because of this, the hydrogen ion concen- where dn is an infinitesimal amount of added base and
tration increases by less than the amount expected for the d(p[H+ ]) is the resulting infinitesimal change in the

1
2 2 APPLICATIONS

cologarithm of the hydrogen ion concentration. With this work only under very precise conditions; if the pH moves
definition the buffer capacity of a weak acid, with a dis- outside of a narrow range, the enzymes slow or stop work-
sociation constant Kₐ, can be expressed as ing and can denature. In many cases denaturation can
permanently disable their catalytic activity.[3] A buffer of
( ) carbonic acid (H
dn CA Ka [H ]+ 2 CO
= 2.303 2 3) and bicarbonate (HCO−
d(pH) (Ka + [H+ ])
3) is present in blood plasma, to maintain a pH between
7.35 and 7.45.
where CA is the analytical concentration of the acid.[1][2]
Industrially, buffer solutions are used in fermentation pro-
cesses and in setting the correct conditions for dyes used
in colouring fabrics. They are also used in chemical
analysis[2] and calibration of pH meters.
The majority of biological samples that are used in re-
search are made in buffers, especially phosphate buffered
saline (PBS) at pH 7.4.

2.1 Simple buffering agents

For buffers in acid regions, the pH may be adjusted to a

desired value by adding a strong acid such as hydrochloric
acid to the buffering agent. For alkaline buffers, a strong
Buffer capacity for a 0.1 M solution of an acid with pKa of 7 base such as sodium hydroxide may be added. Alterna-
tively, a buffer mixture can be made from a mixture of
pH is defined as −log10 [H ]. This equation shows that an acid and its conjugate base. For example, an acetate
+

there are three regions of raised buffer capacity. buffer can be made from a mixture of acetic acid and
sodium acetate. Similarly an alkaline buffer can be made
from a mixture of the base and its conjugate acid.
1. At very low p[H+ ] the [H+ ] term in the denominator
predominates and buffer capacity rises exponentially
with decreasing pH. 2.2 “Universal” buffer mixtures
2. The buffer capacity of a buffering agent is at a local
By combining substances with pKₐ values differing by
maximum when p[H+ ] = pKₐ. It falls to 33% of the
only two or less and adjusting the pH, a wide range of
maximum value at p[H+ ] = pKₐ ± 1 and to 10% at
buffers can be obtained. Citric acid is a useful component
p[H+ ] = pKₐ ± 1.5. For this reason the useful range
of a buffer mixture because it has three pKₐ values, sepa-
is approximately pKₐ ± 1. Buffer capacity is pro-
rated by less than two. The buffer range can be extended
portional to the concentration of the buffering agent,
by adding other buffering agents. The following mixtures
CA, so dilute solutions have little buffer capacity.
(McIlvaine’s buffer solutions) have a buffer range of pH
[4]
3. At very high p[H ] the second term in the denomi- 3 to 8.
+

nator is effectively constant and buffer capacity rises

exponentially with increasing pH because of the
[H+ ] term in the numerator; [H+ ]=10-pH .
A mixture containing citric acid, monopotassium phos-
Properties 1 and 3 are independent of the presence or ab- phate, boric acid, and diethyl barbituric acid can be made
sence of added buffering agents. They are concentration to cover the pH range 2.6 to 12.[5]
effects and reflect the fact that pH is related to the loga-
Other universal buffers are the Carmody buffer[6] and the
rithm of the hydrogen ion concentration.
Britton–Robinson buffer, developed in 1931.

2 Applications 2.3 Common buffer compounds used in bi-

ology
Buffer solutions are necessary to keep the correct pH for
enzymes in many organisms to work. Many enzymes For effective range see Buffer capacity, above.
 3

3 Calculating buffer pH

3.1 Monoprotic acids

First write down the equilibrium expression.

HA ⇌ A− + H+

This shows that when the acid dissociates equal amounts

of hydrogen ion and anion are produced. The equilibrium
concentrations of these three components can be calcu-
lated in an ICE table.

The first row, labelled I, lists the initial conditions: the

concentration of acid is C 0 , initially undissociated, so the
concentrations of A− and H+ would be zero; y is the initial
concentration of added strong acid, such as hydrochloric
% species formation calculated for a 10 millimolar solution of
acid. If strong alkali, such as sodium hydroxide, is added
citric acid.
y will have a negative sign because alkali removes hy-
drogen ions from the solution. The second row, labelled
C for change, specifies the changes that occur when the
acid dissociates. The acid concentration decreases by an
amount −x and the concentrations of A− and H+ both in- When the difference between successive pKₐ values is less
crease by an amount +x. This follows from the equilib- than about three there is overlap between the pH range
rium expression. The third row, labelled E for equilib- of existence of the species in equilibrium. The smaller
rium concentrations, adds together the first two rows and the difference, the more the overlap. In the case of citric
shows the concentrations at equilibrium. acid, the overlap is extensive and solutions of citric acid
To find x, use the formula for the equilibrium constant in are buffered over the whole range of pH 2.5 to 7.5.
terms of concentrations: Calculation of the pH with a polyprotic acid requires a
speciation calculation to be performed. In the case of cit-
+ − ric acid, this entails the solution of the two equations of
[H ][A ]
Ka = mass balance
[HA]
Substitute the concentrations with the values found in the
last row of the ICE table: CA = [A3− ]+β1 [A3− ][H+ ]+β2 [A3− ][H+ ]2 +β3 [A3− ][H+ ]3

CH = [H+ ]+β1 [A3− ][H+ ]+2β2 [A3− ][H+ ]2 +3β3 [A3− ][H+ ]3 −Kw [H+ ]−1
x(x + y)
Ka =
C0 − x CA is the analytical concentration of the acid, CH is the
analytical concentration of added hydrogen ions, βq are
Simplify to:
the cumulative association constants

x2 + (Ka + y)x − Ka C0 = 0
log β1 = pKa3 , log β2 = pKa2 +pKa3 , log β3 = pKa1 +pKa2 +pKa3
With specific values for C 0 , Kₐ and y this equation can be
solved for x. Assuming that pH = −log10 [H+ ] the pH can K is the constant for self-ionization of water. There are
be calculated as pH = −log10 (x + y). two non-linear simultaneous equations in two unknown
quantities [A3− ] and [H+ ]. Many computer programs are
available to do this calculation. The speciation diagram
3.2 Polyprotic acids for citric acid was produced with the program HySS.[8]
Polyprotic acids are acids that can lose more than one pro-
ton. The constant for dissociation of the first proton may
be denoted as Kₐ₁ and the constants for dissociation of 4 See also
successive protons as Kₐ₂, etc. Citric acid, H3 A, is an
example of a polyprotic acid as it can lose three protons. • Henderson–Hasselbalch equation
4 6 EXTERNAL LINKS

• Buffering agent

• Good’s buffers
• Common-ion effect

• Metal ion buffer

• Mineral redox buffer

5 References
[1] Butler, J. N. (1964). Ionic Equilibrium: A Mathematical
Approach. Addison-Wesley. p. 151.

[2] Hulanicki, A. (1987). Reactions of acids and bases in an-

alytical chemistry. Translated by Masson, Mary R. Hor-
wood. ISBN 0-85312-330-6.

[3] Scorpio, R. (2000). Fundamentals of Acids, Bases, Buffers

& Their Application to Biochemical Systems. ISBN 0-
7872-7374-0.

[4] McIlvaine, T. C. (1921). “A buffer solution for colorimet-

ric comparaison” (PDF). J. Biol. Chem. 49 (1): 183–186.

[5] Mendham, J.; Denny, R. C.; Barnes, J. D.; Thomas, M.

(2000). “Appendix 5”. Vogel’s textbook of quantitative
chemical analysis (5th ed.). Harlow: Pearson Education.
ISBN 0-582-22628-7.

[6] Carmody, Walter R. (1961). “Easily prepared

wide range buffer series”. J. Chem. Educ. 38
(11): 559–560. Bibcode:1961JChEd..38..559C.
doi:10.1021/ed038p559.

[7] “Buffer Reference Center”. Sigma-Aldrich. Retrieved

2009-04-17.

[8] Alderighi, L.; Gans, P.; Ienco, A.; Peters, D.; Saba-
tini, A.; Vacca, A. (1999). “Hyperquad simulation and
speciation (HySS): a utility program for the investiga-
tion of equilibria involving soluble and partially soluble
species”. Coordination Chemistry Reviews. 184 (1): 311–
318. doi:10.1016/S0010-8545(98)00260-4.

6 External links
• “Biological buffers”. REACH Devices.

• Online pH buffer calculator

• Phosphate buffer
 5

7 Text and image sources, contributors, and licenses

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