Buffers and the Common-ion Effect

A buffer works through the common-ion effect.

Acetic acid in water dissociates slightly to produce some

acetate ion:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
acetic acid acetate ion

If NaCH3COO is added, it provides a source of

CH3COO- ion, and the equilibrium shifts to the left.
CH3COO- is common to both solutions.

The addition of CH3COO- reduces the % dissociation of

the acid.
 Table 17.1 The Effect of Added Acetate Ion on the
Dissociation of Acetic Acid

[CH3COOH]init [CH3COO-]added % Dissociation* [H3O+] pH

0.10 0.00 1.3 1.3x10-3 2.89

0.10 0.050 0.036 3.6x10-5 4.44

0.10 0.10 0.018 1.8x10-5 4.74

0.10 0.15 0.012 1.2x10-5 4.92

[CH3COOH]dissoc
* % Dissociation = x 100
[CH3COOH]init
 How a Buffer Works

The buffer components (HA and A-) are able to consume

small amounts of added OH- or H3O+ by a shift in
equilibrium position.

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+

(aq)
Added OH- reacts with Added H3O+ reacts with
CH3COOH, causing a shift to CH3COO-, causing a
the right. shift to the left.

The shift in equilibrium position absorbs the change in

[H3O+] or [OH-], and the pH changes only slightly.
 Figure 17.3 How a buffer works.

Buffer has more HA after Buffer has equal Buffer has more A- after
addition of H3O+. concentrations of A- and HA. addition of OH-.

H3O+ OH-

H2O + CH3COOH ← H3O+ + CH3COO- CH3COOH + OH- → CH3COO- + H2O

Figure 17.1 The effect of adding acid or base to an unbuffered
solution.

A 100-mL sample of The addition of 1 mL of strong acid (left)

dilute HCl is adjusted or strong base (right) changes the pH by
to pH 5.00. several units.
 Figure 17.2 The effect of adding acid or base to a buffered
solution.

A 100-mL sample of The addition of 1 mL of strong acid (left)

an acetate buffer is or strong base (right) changes the pH very
adjusted to pH little.
5.00.
The acetate buffer is made by mixing 1 M CH3COOH ( a weak acid) with
1 M CH3COONa (which provides the conjugate base, CH3COO-).
Relative Concentrations of Buffer Components

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

[CH3COO-][H3O+] [CH3COOH]
Ka = [H3O ] = Ka x
+
[CH3COOH] [CH 3COO-]
Since Ka is constant, the [H3O+] of the solution depends
on the ratio of buffer component concentrations.
[HA]
If the ratio increases, [H3O+] increases.
[A-]
[HA]
If the ratio decreases, [H3O+] decreases.
[A-]
 Sample Problem 1 Calculating the Effect of Added H3O+ or
OH- on Buffer pH
PROBLEM: Calculate the following pH values(K of CH COOH = 1.8 x
a 3
10-5 , assume the additions cause a negligible change in
volume.)
(a) pH of a buffer solution consisting of 0.50 mol/L CH3COOH and
0.50 mol/L CH3COONa
(b) pH after adding 0.020 mol of solid NaOH to 1.0 L of the buffer
solution
(c) pH after adding 0.020 mol of HCl to 1.0 L of the buffer solution in
(a).

PLAN: We can calculate [CH3COOH]init and [CH3COO-]init from the

given information. From this we can find the starting pH. For (b) and (c)
we assume that the added OH- or H3O+ reacts completely with the
buffer components. We write a balanced equation in each case, set up
a reaction table, and calculate the new [H3O+].
 Sample Problem 1
SOLUTION: (a)
Concentration(mol/L) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Initial 0.50 - 0.50 0

Change −x - +x +x
Equilibrium 0.50 - x - 0.50 + x x
Since Ka is small, x is small, so we assume
[CH3COOH] = 0.50 – x ≈ 0.50 mol/L and [CH3COO-] = 0.50 + x ≈ 0.50 mol/L
[CH3COOH] ≈ 1.8x10-5 x 0.50
= 1.8x10-5 mol/L
x = [H3O+] = Ka x [CH3COO-] 0.50
Checking the assumption: pH = -log(1.8x10-5) =
4.74
1.8x10-5 mol/L x 100 = 3.6x10-3% (< 5%; assumption is justified.)
0.50 mol/L
 Sample Problem 1

(b) [OH−] added = 0.020 mol = 0.020 M OH−

1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (mol/L) CH3COOH(aq) + OH-(aq) → CH3COO-(aq) + H2O(l)

Initial 0.50 0.020 0.50 -

Change -0.020 -0.020 +0.020 -
Equilibrium 0.48 0 0.52 -

Setting up a reaction table for the acid dissociation, using new initial [ ]:
Concentration (mol/L) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Initial 0.48 - 0.52 0

Change −x - +x +x
Equilibrium 0.48 - x - 0.52 + x x
Sample Problem 1

Since Ka is small, x is small, so we assume

[CH3COOH] = 0.48 – x ≈ 0.48 mol/L and [CH3COO-] = 0.52 + x ≈ 0.52 mol/L
[CH3COOH] 0.48
≈ 1.8x10-5 x = 1.7x10-5 mol/L
x = [H3O ] = Ka x
+
[CH3COO-] 0.52
pH = -log(1.7x10-5) = 4.77
 Sample Problem 1

(c) [H3O+]added = 0.020 mol = 0.020 M H3 O+

1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (mol/L) CH3COO-(aq) + H3O+(aq) → CH3COOH(aq) + H2O(l)
Initial 0.50 0.020 0.50 -
Change -0.020 -0.020 +0.020 -
Equilibrium 0.48 0 0.52 -

Setting up a reaction table for the acid dissociation, using new initial [ ]:
Concentration(mol/L) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Initial 0.52 - 0.48 0

Change −x - +x +x
Equilibrium 0.52 - x - 0.48 + x x
Sample Problem 1

Since Ka is small, x is small, so we assume

[CH3COOH] = 0.52 – x ≈ 0.52 mol/L and [CH3COO-] = 0.48 + x ≈ 0.48 mol/L
[CH3COOH] ≈ 1.8x10-5 x 0.52 = 2.0x10-5 mol/L
x = [H3O+] = Ka x
[CH3COO-] 0.48
pH = -log(2.0x10-5) = 4.70
The Henderson-Hasselbalch Equation
HA(aq) + H2O(l) A-(aq) + H3O+(aq)

[H3O+][A-]
Ka = [H3O+] = K a x
[HA]
[HA] [A-]

[HA]
-log[H3O ] = -logKa – log
+
[A-]

[base]
pH = pKa + log
[acid]
 pKa concepts

Ionization = the process in which ions are formed

from neutral compounds;

Dissociation = the separation of the ions of an

electrovalent compound as a result of the action
of a solvent (usually water)
For a weak acid, which dissociates as follows:

HA ↔   H+ + A-
                                                                                                  
An interesting and extremely useful relationship between
pH and pKa can be obtained simply by taking logarithms
(to the base 10) of the previous equation:

log10Ka = log10[H+] + log10[A- ] - log10[HA]

Therefore
             -log10[H+] = -log10Ka + log10[A-] - log10[HA]

Note: log a – log b = log (a/b)

giving the Henderson-Hasselbalch equation:                                     
 Using pKa and pH relationship
• By using pKa values, we are able to express the
strength of an acid (i.e. its tendency to dissociate)
with reference to the pH scale.
• If Ka is large, then pKa will have a low numerical
value. E.g.,
Hydrochloric acid, HCl has a pKa = -3
Acetic acid, CH3COOH has a pKa = 4.77
• A strong acid is one which is largely, or completely,
dissociated, and which therefore has a high Ka value
(and low pKa).
• A weak acid is one that is only slightly dissociated in
solution, and has a low Ka value.
 if we consider the situation where the acid
is one-half (50%) dissociated,
or where
[A-] = [HA]
(that is 50% negatively charged and 50% uncharged)
then, substituting in the
Henderson-Hasselbalch Equation 

pH = pKa + log(A-/HA)

pH = pKa + log(1)

Therefore pH = pKa + 0

and                   pH = pKa
 Buffer Capacity

The buffer capacity is a measure of the “strength” of

the buffer, its ability to maintain the pH following addition
of strong acid or base.

The greater the concentrations of the buffer

components, the greater its capacity to resist pH
changes.
The closer the component concentrations are to each
other, the greater the buffer capacity.
Figure 17.4 The relation between buffer capacity and pH change.

When strong base is

added, the pH increases
least for the most
concentrated buffer.

This graph shows the final pH values for four different buffer solutions after
the addition of strong base.
 Buffer Range

The buffer range is the pH range over which the buffer is

effective.
Buffer range is related to the ratio of buffer component
concentrations.
The closer [HA] is to 1, the more effective the buffer.
[A ]
-

If one component is more than 10 times the other, buffering

action is poor. Since log10 = 1, buffers have a usable
range within ± 1 pH unit of the pKa of the acid
component.
Sample Problem 2 Using Molecular Scenes to Examine Buffers

PROBLEM: The molecular scenes below represent samples of

four HA/A- buffers. (HA is blue and green, A- is green,
and other ions and water are not shown.)

(a) Which buffer has the highest pH?

(b) Which buffer has the greatest capacity?
(c) Should we add a small amount of concentrated strong acid or
strong base to convert sample 1 to sample 2 (assuming no
volume changes)?
Sample Problem 2

PLAN: Since the volumes of the solutions are equal, the scenes
represent molarities as well as numbers. We count the particles
of each species present in each scene and calculate the ratio
of the buffer components.

SOLUTION:
[A-]/[HA] ratios: sample 1, 3/3 = 1; sample 2, 2/4 = 0.5; sample 3,
4/4 = 1; and sample 4, 4/2 = 2.
Sample Problem 2

(a) As the pH rises, more HA will be converted to A-. The scene with
the highest [A-]/[HA] ratio is at the highest pH. Sample 4 has
the highest pH because it has the highest ratio.

(b) The buffer with the greatest capacity is the one with the [A-]/[HA]
closest to 1. Sample 3 has the greatest buffer capacity.

(c) Sample 2 has a lower [A-]/[HA] ratio than sample 1, so we need to

increase the [A-] and decrease the [HA]. This is achieved by
adding strong acid to sample 1.
 Preparing a Buffer
• Choose the conjugate acid-base pair.
– The pKa of the weak acid component should be close
to the desired pH.
• Calculate the ratio of buffer component
concentrations.
pH = pKa + log
[acid]
[base]
• Determine the buffer concentration, and calculate the
required volume of stock solutions and/or masses of
components.
• Mix the solution and correct the pH.
Sample Problem 3 Preparing a Buffer

PROBLEM: An environmental chemist needs a carbonate buffer of

pH 10.00 to study the effects of the acid rain on
limsetone-rich soils. How many grams of Na2CO3 must
she add to 1.5 L of freshly prepared 0.20 mol/L NaHCO3
to make the buffer? Ka of HCO3- is 4.7x10-11.
PLAN: The conjugate pair is HCO3 - (acid) and CO32- (base), and we
know both the buffer volume and the concentration of HCO 3-.
We can calculate the ratio of components that gives a pH of
10.00, and hence the mass of Na2CO3 that must be added to
make 1.5 L of solution.

SOLUTION:
[H3O+] = 10-pH = 10-10.00 = 1.0x10-10 mol/L
[CO 2-][H O+]
3
HCO (aq)
-
2 + H O(l)
3 H
3 O (aq) + CO (aq)
+ 2- 3 Ka 3
[HCO3-]
=
Sample Problem 17.3 Preparing a Buffer

Ka[HCO3 -] (4.7x10-11)(0.20)
[CO32-] = = = 0.094 mol/L
[H 3O ]
+ 1.0x10 -10

Amount (mol) 2- 0.094 mol CO 2-

needed = 1.5 L soln x 3
of CO3
1 L soln
= 0.14 mol CO3
2-

0.14 mol Na2CO3 x 105.99 g Na2CO3 = 15 g Na2CO3

1 mol Na2CO3

The chemist should dissolve 15 g Na2CO3 in about 1.3 L of 0.20 mol/

L NaHCO3 and add more 0.20 mol/L NaHCO3 to make 1.5 L. Using a
pH meter, she can then adjust the pH to 10.00 by dropwise addition of
concentrated strong acid or base.
 Sample Problem 4 Calculating the pH of a buffer

PROBLEM: A first year university student working in a lab is asked

to prepare a buffer by adding 5.00mL of 5.0 mol/L
NaOH
To 100.0 mL of 0.50 mol/L HCOOH. What will be the pH of
the resulting buffer solution?(Ka HCOOH= 1.8 ×10-4)
PLAN: Knowing the amount of strong base(NaOH) and the weak acid
(HCOOH), we can calculate the remaining amount of weak acid
and the formed conjugate base(HCOO-) in solution. Knowing
Ka Of the acid and using Henderson Hasselbalch equation, we
can find the pH of the buffer in solution
SOLUTION: HCOOH(aq) + NaOH(aq) → Na+HCOO-(aq) + H2O(l)

After dilution,
[NaOH]initial = 5.0 mol/L x 5.00 mL = 0.238 mol/L
105.0 mL
 Sample Problem 4

[HCOOH]initial = 0.50 mol/L x 100.0 mL = 0. 476 mol/L

105.0 mL
HCOOH(aq) + NaOH(aq) → Na+HCOO-(aq) + H2O(l)

Initial 0.476 0.238 0 -

Change – 0.238 – 0.238 +0.238 -

Equilibrium +0.238 0 +0.238 -

[HCOO-] 0.238mol/L
pH = pKa + = -log 1.8 ×10 + log
-4
log [HCOOH] 0.238 mol/L

= 3.74
 17.2 Acid-Base Indicators

An acid-base indicator is a weak organic acid (HIn)

whose color differs from that of its conjugate base (In-).

The ratio [HIn]/[In-] is governed by the [H3O+] of the

solution. Indicators can therefore be used to monitor the
pH change during an acid-base reaction.

The color of an indicator changes over a specific,

narrow pH range, a range of about 2 pH units.

©2013 McGraw-Hill Ryerson Limited

17-31
 Figure 17.5 Colors and approximate pH range of some
common acid-base indicators.
pH

©2013 McGraw-Hill Ryerson Limited

17-32
 Fig 17.6 An acid-base titration

17-28 ©2013 McGraw-Hill Ryerson Limited

 Figure 17.7 The color change of the indicator bromthymol blue.

pH < 6.0 pH = 6.0-7.5 pH > 7.5

©2013 McGraw-Hill Ryerson Limited

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