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Buffers

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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) or
strong base (right)>
-
dilute HCl is adjusted changes the pH by several
-
to pH 5.00. units.
-

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 acid acid salt 24/11/2022
Buffer= weak +

weak base + basic salt.

C
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 5.00. little.

The acetate buffer is made by mixing 1 M Acetic acid CH3COOH ( a weak

-

acid) with 1-
M CH3COONa (Sodium Acetate) (which provides the
conjugate base, CH3COO-).

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How a Buffer Works

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

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

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

O
Added OH- reacts with 0
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.

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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

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Relative Concentrations of Buffer Components

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

[CH3COO-][H3O+] [CH3COOH]
Ka = [H3O+] = Ka x
[CH3COOH] [CH3COO-]

Since Ka is constant, the [H3O+] of the solution depends

on the ratio of buffer component concentrations.
[HA]
If the ratio increases, [H3O+] decreases.
[A-]
[HA]
If the ratio decreases, [H3O+] increases.
[A-]

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and base
L e
Calculating the Effect of Added
00 H3O+ or OH- on Buffer pH
Calculate the pH:
(a)
C
Of a buffer solution consisting of 0.50 M CH3COOH and 0.50 M >
x
CH3COONa

↳
(b) After adding 0.020 mol of solid NaOH to 1.0 L of the buffer
solution

-
(c) After adding 0.020 mol of HCl to 1.0 L of the buffer solution in (a).

Ka of CH3COOH = 1.8 x 10-5. (Assume the additions cause a

negligible change in volume.)

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
19-7 a reaction table, and calculate the new [H3O+].

SOLUTION: (a) 0:
Of a buffer solution consisting of 0.50 M CH3COOH and 0.50 M
CH3COONa
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO
I -(aq) + H O+(aq)
3

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 M and [CH3COO-] = 0.50 + x ≈ 0.50 M

O
gig
[CH3COOH]
x = [H3O+] = Ka x ≈ 1.8x10-5 x 0.50 = 1.8x10-5 M
[CH3COO-] 0.50

Checking the assumption:

O
pH = -log(1.8x10-5) = 4.74

1.8x10-5 M x 100 = 3.6x10-3% (< 5%; assumption is justified.)

0.50 M
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(b) After adding 0.020 mol of solid NaOH to 1.0 L of the buffer solution

(b) [OH−]added =
-o0.020 mol
1.0 L soln
= 0.020 M OH−

Setting up a reaction table for the stoichiometry:

Concentration (M) 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 (M) 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

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

[CH3COOH] = 0.48 – x ≈ 0.48 M and [CH3COO-] = 0.52 + x ≈ 0.52 M
[CH3COOH]
x = [H3O+] = Ka x ≈ 1.8x10-5 x 0.48 = 1.7x10-5 M
[CH3COO-] 0.52

&
pH = -log(1.7x10-5) = 4.77 4.78

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-
(c) After adding 0.020 mol of HCl to 1.0 L of the buffer solution in (a).
0.020 mol
(c) [H3O+]added = = 0.020 M H3O+
1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (M) 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 (M) 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

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

[CH3COOH] = 0.52 – x ≈ 0.52 M and [CH3COO-] = 0.48 + x ≈ 0.48 M

x = [H3O+] = Ka x [CH3COOH]
[CH3COO-]

0.52
≈ 1.8x10-5 x = 2.0x10-5 M
0.48

pH = -log(2.0x10-5) = 4.70
& 4.41,.

Note that this buffer resists changes in pH from

additions of either strong acid or strong base!
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The Henderson-Hasselbalch Equation

HA(aq) + H2O(l) A-(aq) + H3O+(aq)

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

[HA]
-log[H3O+] = -logKa – log
[A-]

pH = pKa + log [A- ]

[HA]

when [base] = [acid], [base]

pH = pKa + log &
the pH of the buffer solution [acid]
equals the pKa of the acid.
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Henderson-Hasselbach Equation:

[ A− ]
pH = pK + log
[ HA]
• When acid or base added to buffered system
C
with a pH near pK (remember that when pH=pK ↑

HA and A- are equal), the pH will not change

much
• When the pH is further from the pK, additions of
acid or base will change the pH a lot

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Henderson–Hasselbalch Equation
Problem:
-
What is the pH of a buffer that is 0.12 M in lactic acid,

-
HC3H5O3, and 0.10 M in sodium lactate? Ka = 1.4 10−4.
-
Ka =
[H3O+] [A−]
[HA]
[base]& conjugate.
pH = pKa + log
[acid]
(0.10)
pH = −log (1.4 10−4) + log
(0.12)
pH = 3.85 + (−0.08)
Acids

pH = 3.77 and
Bases

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pH of Buffer Solution
• What is the pH of a buffer solution that is 0.45 M acetic acid (HC2H3O2)
-

and 0.85 M sodium acetate (NaC2H3O2)? The Ka for acetic acid is 1.8 ×
-

10–5.

• Solution:
[base]
pH = pKa + log
[acid]

• pH = -log(1.8 × 10–5) + log(0.85/0.45)

• pH = 4.74 + 0.28 = 5.02

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Study Check

Ra
The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH
-

of a buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?

-

HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

-

log (1.8 10-5)

x
log
+

(,)

4:74
=

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

17

Solution

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH of a

buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

STEP 1 State the given and needed quantities.

ANALYZE Given Need

THE [HC2H3O2] = 1.0 M pH of solution
PROBLEM [C2H3O2−] = 1.0 M
Equation
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

18

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Solution

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH of a

buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

STEP 2 Write the Ka expression and rearrange for [H3O+].

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

19

Solution

The Ka for acetic acid, HC2H3O2, is 1.8 10–5. What is the pH

of a buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

STEP 3 Substitute [HA] and [A−] into the Ka expression.

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

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Solution

The Ka for acetic acid, HC2H3O2, is 1.8 10–5. What is the pH

of a buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)

STEP 4 Use [H3O+] to calculate pH.

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

21

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 e n

to resist pH changes.
-

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Buffering Capacity
• How much H3O+ or OH- the buffer can absorb without
significantly changing its pH.

• Depends on the concentrations of HA and A‫־‬.

• High [HA] and [A‫ ]־‬lead to large buffering capacity.

->
• Optimal buffering occurs when [HA] = [A‫;]־‬
• Ratio [A–] / [HA] ~ 1 strong resist to change when either
H3O+ or OH– is added.

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The relation between buffer capacity and pH change.

When strong base is
added, the pH increases
least for the most
concentrated buffer.

high
(buffer] pH-
remaine
-

high

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

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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.

[HA]
The closer 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.

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Concept Map

General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake

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