The Henderson-Hasselbalch Equation

1. The Henderson-Hasselbalch Equation

the significance of pH
the predominant solution species
2. The significance of pH in solutions which contain
many different acid/base pairs
3. Diprotic Acids
4. Triprotic Acids
Example - calculating concentrations of all
phosphate containing species in a solution
of KH2PO4 at known pH
5. pH buffer solutions
- choosing the conjugate acid/base pair
- calculating the pH
 Henderson-Hasselbalch Equation

[H+] [A-]
HA = H+ + A- Ka =
[HA]

An especially convenient form of the equilibrium equation is obtained by

re-writing the equilibrium expression using logs -
[A-]
log10 Ka = log10 [H+] + log10
[HA]
[A-]
- pKa = - pH + log10
[HA]

pH = pKa + log10 [A-] Henderson-Hasselbalch

[HA] Equation
 Use of the Henderson-Hasselbalch Equation

In most practical cases, the pH of the solution is known either from

(1) direct measurement with a pH meter
(2) use of a pH buffer in the solution
When the pH is known, the H.-H. Equation is much more
convenient to use than the equilibrium constant expression. It
immediately gives the ratio of concentrations of all conjugate
acid/base pairs in the solution.

pH = pKa + log10 [A-] Henderson-Hasselbalch

[HA] Equation

measured or known (from calculate ratio of

set by buffer tabulations) (base/acid) concentrations
 pKa and the Dissociation of Weak Acids

For any conjugate acid/base pair,

HA = H+ + A-

[A-]
pH = pKa + log10
[HA]

[base] [A-]
Note that pH = pKa when = =1
[acid] [HA]

because log10 (1) = 0

 The Use of pH plots

mostly Mostly
CH3COOH pKa=4.75 CH3COO-

0 7 14
pH
CH3COOH = H+ + CH3COO- pKa = 4.75

When pH < pKa, acetic acid is mostly protonated.

When pH > pKa, acetic acid is mostly deprotonated.

When pH = pKa, concentrations of the protonated

and deprotonated forms are equal.
 pH, pKa and % Dissociation

When the pH = pKa, half the conjugate acid/base pair

is in the protonated form,
half is de-protonated.

If the pKa = 4.7 (as for acetic acid):

At pH 4.7 [CH3COO-] / [CH3COOH] = 1 (equal)

pH 5.7 [CH3COO-] / [CH3COOH] = 10 (mostly de-protonated)
pH 3.7 [CH3COO-] / [CH3COOH] = 0.1 (mostly protonated)
 An Exercise in % Dissociation

A 0.050 M acetic acid solution is made pH 7.00 with added NaOH.

Find [CH3COOH], [CH3COO-], and [H+] in this solution.

[CH3COO-]
pH = pKa + log10
[CH3COOH]

7.00 4.75 ratio = 1.80

Thus, [CH3COO-] ≈ 0.050 M

[CH3COOH] ≈ 2.8 x 10-4 M

most of the acetic acid is dissociated

(% undissociated is 0.56%)
 How to Use the [base] / [acid] Ratio

[base]
pH = pKa + log10
[acid]
[base]
pH = pKa + log10 (r) where r=
[acid]

[acetic acid] + [acetate] = 0.050 M eqn 1

[acetate] / [acetic acid] = r eqn 2

[acetate] = r * [acetic acid] subst. in eqn 1

[acetic acid] (1 + r) = 0.050 M

[acetic acid] = 0.050 M / (1 + r) = 2.8 x 10-4 M

[acetate] = 0.050 M - 2.8 x 10-4 M ≈ 0.050 M

 Summary: Significance of the pH

1. The solution may contain many conjugate

acid/base pairs (biological solutions usually do).
In order to reproduce a sample, you need to
reproduce the pH. This guarantees that all
conjugate acid/base pairs will have the same ratio
of protonated/deprotonated concentrations as in
the original sample.

2. When the pH is known, you can readily calculate

the ratio of (protonated/deprotonated) forms of
any acid for which you know the pKa.
 Ratio of protonated and deprotonated species

Knowledge of the pH completely determines the state of

protonation / deprotonation of every Bronsted conjugate acid/base
pair in solution.

An example:
A solution at pH 6.9 contains lactic acid (pKa = 3.9). Is lactic acid
predominantly in the protonated form or the deprotonated form
(lactate ion)?
Ans: Predominantly deprotonated. The ratio
[Lac-]/[HLac] = 103
 Diprotic Weak Acid - H2CO3

H2CO3 = H+ + HCO3- pKa1 = 6.4

HCO3- = H+ + CO32- pKa2 = 10.3

pKa1=6.4 pKa2=10.3
mostly mostly mostly
H2CO3 HCO3- CO32-

0 7 14
pH
 Triprotic Weak Acid - H3PO4

H3PO4 = H+ + H2PO4- pKa1 = 2.12

H2PO4- = H+ + HPO42- pKa2 = 7.21
HPO42- = H+ + PO43- pKa3 = 12.67

pKa1=2.12 pKa2=7.21 pKa3=12.67

mostly mostly mostly mostly
H3PO4 H2PO4 -
HPO4 2-
PO43-

0 7 14
pH
 Effect of pH on Solution Composition: H3PO4

pKa1=2.12 pKa2=7.21 pKa3=12.67

mostly mostly mostly mostly
H3PO4 H2PO4 -
HPO4 2-
PO43-

0 7 14
pH

Problem:
A solution is prepared by dissolving 0.100 mole of NaH2PO4 in water to produce
1.00 L of solution. The pH is then adjusted to pH 8.50 with NaOH.
What are the concentrations of H3PO4, H2PO4-, HPO42-, PO43-, and H+?
 Calculating the Concentrations

[base]
pH = pKa + log
[acid]

(1) Apply H-H eqn to [H2PO4-] and [HPO42-] using pKa2 :

8.50 = 7.21 + log10 ( [HPO42-] / [H2PO4-] )

This gives [HPO42-] / [H2PO4-] = 20

(2) Apply H-H eqn to [H3PO4] and [H2PO4-] using pKa1 :

8.50 = 2.12 + log10 ( [H2PO4-] / [H3PO4] )

This gives [H2PO4-] / [H3PO4] = 2.4 x 106

(3) Apply H-H eqn to [PO43-] and [HPO42-] using pKa3 :

8.50 = 12.67 + log10 ( [PO42-] / [HPO42-] )

This gives [PO43-] / [HPO42-] = 6.8 x 10-5
 Answers to the Exercise

pKa1=2.12 pKa2=7.21 pKa3=12.67

mostly mostly mostly mostly
H3PO4 H2PO4 -
HPO42- PO43-

0 7 14
solution
pH

Ans: [HPO42-] = 0.95 x10-1 M [PO43-] = 1.6 x10-4 * [HPO42-]

[H2PO4-] = 0.047 x10-1 M [H3PO4] = 2.0 x106 * [H2PO4-]

[H3O+] = 3.2 x10-8 M

 Problem

(a) Calculate the pH of a 500 mL solution prepared from:

0.050 mol of acetic acid and 0.020 mol sodium acetate.

HAc = H+ + Ac- pKa = 4.75

?
[Ac-]
pH = pKa + log10
[HAc]

4.75 ?
?
 Problem

(b) Suppose that 0.010 mol NaOH is added to

the buffer of part (a). What is the pH?

HAc + OH- = H2O + Ac- pKa = 4.75

(0.020 + 0.010) / 0.50

[Ac-]
pH = pKa + log10
[HAc]
4.63 4.75 (0.050 - 0.010) / 0.50

As long as the buffer capacity is not exceeded, the change

of pH is small, in this case, 4.35 to 4.63
 pH Buffers

1. pH buffers resist a change in pH upon addition of small

amounts of either acid or base.
2. Buffer solutions should contain roughly equal concentrations of a
conjugate acid and its conjugate base.
3. The conjugate acid/base pair of the buffer should have a pKa that
approximately equals the pH.

For example: a buffer will result from mixing

0.1 M acetic acid and 0.1 M sodium acetate.

Added OH- is neutralized Added H+ is neutralized

by the conjugate acid by the conjugate base

OH- + HC2H3O2 = H2O + C2H3O2- H+ + C2H3O2- = HC2H3O2

 pH of Buffer Solutions

Problem:
Prepare a pH 5.00 buffer using sodium acetate and acetic acid

[base]
pH = pKa + log10
[acid]
5.00 4.75
ratio [base]/[acid] = 1.78

Any solution with this composition (i.e., this ratio of base / acid),
will form a buffer, but higher concentrations provide higher
buffering capacity. For example, one could use
0.178 M sodium acetate + 0.100 M acetic acid
 Exercises with Buffers

Use the data in Table 10.2 to design buffers at:

pH 6.9
pH 9.3
pH 3.6

Find the weight of solid compounds you would use to

produce 100 mL each buffer.
Choosing a Weak Acid/Base Pair for a Buffer

6.9