Henderson-Hasselbalch Equation

The Henderson-Hasselbalch equation allows us one method to approximate the pH of a buffer solution. The basic equation is
as follows:
[A−]
pH ≈ pKa +log10 (1)
[HA]

Lawrence

Derivation for Buffers from Weak Acids

For a weak acid HA and its conjugate base A−:

HA+H2O ⇋ H+ +A−
which has an acid ionization constant Ka. The Henderson-Hasselbalch approximation is derived from this acid ionization
constant.

Ka = (2)

−log10 Ka = −log10 (3)

−
[A ]
−log10 Ka = −log10[H+]−log10
(4)
[HA]
[A−]
(5)
pKa = pH −log10
[HA]

pH = pKa +log10 (6)

Equation 6 is formulated in terms of equilibrium concentrations in solution. Since HA is a weak acid and weakly dissociates and
we can introduce two approximations

[HA] ≈ [HA]i (7)

and

[A−] ≈ [A−]i (8)

Hence, we can use the initial concentrations rather than equilibrium concentrations because
[A−][A− pKa +log10 i≈ pKa
+log10 ] = pH (9)

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 [HA]i [HA]

Derivation for Buffers from Weak Bases

Similarly, for a weak base B and its conjugate acid HB+:

B+H2O ⇋ OH− +HB+ (10)

which has an base ionization constant Kb. The Henderson-Hasselbalch approximation for basic buffers is derived from this base
ionization constant.

[OH−][HB+] Kb =

[B]
(11)
[OH−][HB+]
−log10 Kb = −log10
(12)
[B]
[HB+]
−
−log10 Kb = −log10[OH ]−log10 (13)
[B]
[HB+] (14)
pKb = pOH −log10
[B]
[HB+] (15)
pOH = pKb +log10
[B]
Note that B is a weak base and does not dissociate completely and we can say [B] ≈ [B]i and [HB+] ≈ [HB+]i . Hence, we can use
the initial concentrations because

Example

References
1. "Henderson-Hasselbalch Equation: Its History and Limitations," Henry N. Po and N. M. Senozan, J. Chem. Educ., 2001, 78
(11), p 1499
2. National Academy of Sciences (U.S.) Biographical memoirs. City of Washington, 1945. Vol. XXIII, 2d memoir.
3. Petrucci, et al. General Chemistry: Principles & Modern Applications. 9th ed. Upper Saddle River, New Jersey 2007.

Contributors
Gurinder Khaira and Alexander Kot (UCD)

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