Acid-Base Equilibria

• Common Ion Effect in Acids and Bases

• Buffer Solutions for Controlling pH
• Buffer Capacity
 Common Ion Effect
• Shift in the equilibrium position due to the
addition of an ion already involved in the
equilibrium process.
• An application of Le Châtelier’s principle.
 A Common Ion Effect

Consider the following equilibrium:

• HC2H3O2(aq) + H2O(l) ⇌ H3O+(aq) + C2H3O2-(aq)

• Adding NaC2H3O2 to the solution will shift the equilibrium to

the left because [C2H3O2-] increases; C2H3O2- is part of the
equilibrium system.
• This equilibrium shift causes [H3O+] to decrease and raise the
pH of the solution.
• Solutions containing a mixture of HC2H3O2 and NaC2H3O2
are less acidic than those solutions of HC2H3O2 alone, and
they are less basic than those of NaC2H3O2 alone.
 pH of weak acid and the Effect
of Common Ion
Consider the following solutions:
1. Calculate the pH of 1.00 M HC2H3O2 solution.
2. What is the pH of a solution that contains 1.00 M
HC2H3O2 and 0.50 M NaC2H3O2.
Solution-1:
Equilibrium: HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-(aq)

Initial [ ], M 1.00 0.00 0.00
Change, D[ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x x

 pH of Acetic Acid by itself.
• Solution-1:

[H   ][CH CO  ]
O x 22
[H
 3O3 ][CH 33CO22 ]
 x  -5 -5
K a a
K
[CH COOH] (1.00 - x )  1.8 x 10
1.8 x 10
[CH COOH]
3
3 (1.00-5 - x )
(1.00 x 1.8 x 10 )  4.2 x 10
-3

• By approximation, x = (1.00 x 1.8 x 10-5 )  4.2 x 10-3

• [H3O+] = x = 4.2 x 10-3 M,  pH = 2.37

 Acetic Acid-Acetate Equilibrium

Solution-2:

Equilibrium: HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-(aq)


Initial [ ], M 1.00 0.00 0.50
Change, D[ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x (0.50 + x)

 pH of Acetic Acid + Sodium Acetate

Solution-2:
 
[H O
3 O ][CH 3CO 2 ] ] (x
 )()(00.50 xx) )
KKa  3
[H ][CH 3 CO 2 
( x . 50 1.8
1.8xx10
10
-5
-5
a [CH
[CH3COOH]
COOH] (1.00
(1.00- -xx) )
3

By approximation,
x = (1.00/0.50)(1.8 x 10-5) = 3.6 x 10-5 M
[H+] = x = 3.6 x 10-6 M,  pH = 4.44

Solution containing HC2H3O2 and NaC2H3O2 is less acidic

than one containing only HC2H3O2 at the same concentration.
Solving Problems with Buffered Solutions
Buffering: How Does It Work?
Buffer Solutions
 Buffers
• Mammalian tissues in the resting state have a pH of
about 7.4
• In order to maintain the required pH in an invitro
biochemical experiment a buffer is always used
• The pH of a buffer is given by Henderson-
Hasselbalch equation:
pH= pKa + log [A-]
[HA]
 Buffers
• pKa= -log Ka

• Ka is the dissociation constant of the acid

• [A-] is the concentration of the base

• [HA] is the concentration of the acid

 Buffers
• A buffer consisting of a mixture of the weak
acid(CH3COOH) and its salt (CH3COONa+), will
undergo the following changes on the addition of
acid or base:

• If the base is added (OH) to the solution it will be

buffered by the following reaction with acetic acid:
CH3COOH + OHCH3COO- + H2O
So the pH will not change significantly
 Buffers
• If acid (H+) is added, it will be buffered by another
reaction, this time using the salt (CH3COO-):
CH3COO- + H+  CH3COOH
The pH will not alter significantly because the
CH3COOH formed is a weak acid
• Addition of more base increases A- and decreases
(HA) and this doesn’t alter the pH much until
[A-]>>>>[HA]
 Buffers
• The buffering power is greatest when pH=pKa , i.e.
when the acid and the salt are at the same
concentration
 pH of Buffer Solution:

1. 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:
• pH = pKa + log([C2H3O2-]/[HC2H3O2]
• pH = -log(1.8 × 10–5) + log(0.85/0.45)
• pH = 4.74 + 0.28 = 5.02
Calculate the pH of a buffer solution in the
previous example after adding 0.020 mol of solid
NaOH to a 1.0 L.

CH3COOH + OH- CH3COO- + H2O

Conc. (M) CH3COOH OH- CH3COO-

H 2O
Before 0.45 - 0.85 -
addition
During - 0.020 - -
addition
After (0.45 – 0.020) 0.020 (0.85 – -
addition 0.43 .0.020)
0.83
Acid dissociation table:

Conc CH3COOH H 2O CH3COO- H+

(M)
I 0.43 - 0.83 0
C -x - +x +x
E 0.43 - x - 0.83 + x x

[H+] = (1.8x10-5)(0.43) = 9.33x 10-6

0.83

pH = -log[9.33 x 10-6 ] = 5.03

2. Calculate the pH of a buffer consisting of 0.50 M
HF and 0.45 M F-

(a)Before (b) after addition of 0.40 g of NaOH to 1.0

L of the buffer.

Ka = 6.8 x 10-4 Na = 23; O =16; H =1

Ans.

a)pH = 3.12
b)pH = 3.14
 Characteristics of Buffer Solutions
1. Buffers contain relatively large amounts of the weak acids
(HA) and their conjugate base (A‫)־‬, (or weak bases and their
conjugate acids)
2. Buffer pH is determined by the pKa of the acid HA and the
molar ratio of the conjugate base to acid: [A‫]־‬/[HA].
3. Buffer pH changes very little because the ratio [A‫]־‬/[HA]
changes very little when a small amount of strong acid or
strong base is added.
4. [H3O+] in buffer solutions remains more or less constant:
Most of H+ from strong acid is absorbed by the conjugate
base A‫ ;־‬most of OH‫ ־‬added from strong base reacts with
acid HA in the buffer to yield A‫ ־‬and H2O.
 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.
 Some Common Buffers

Buffers pKa pH Range

• HCHO2 – NaCHO2 3.74 2.74 – 4.74
• CH3CO2H – NaCH3CO2 4.74 3.74 – 5.74
• KH2PO4 – K2HPO4 7.21 6.20 – 8.20
• CO2/H2O – NaHCO3 6.37 5.40 – 7.40
• NH4Cl – NH3 9.25 8.25 – 10.25

 Choosing a Buffer System
• The weak acid in buffer has pKa close to target pH.
• For example, KH2PO4 and K2HPO4 may be used to
buffer at pH ~ 7.5 (H2PO4‫ ־‬has pKa = 7.20)
• Phosphate buffer is most effective in the pH range
6.20 – 8.20; it has the highest buffering capacity at
about pH = 7.20.
 Making Buffer Solution:

2 . A phosphate buffer with pH = 7.40 is prepared using

KH2PO4 and K2HPO4. How many grams of KH2PO4
and K2HPO4, respectively, are needed to make 500.
mL of this solution? (H2PO4- has Ka = 6.2 x 10-8)
Steps:
(1) What is the molar ratio of [HPO42-] to [H2PO4-] in
the buffered solution?
(2) If [H2PO4-] = 0.20 M, what is [HPO42-]?
 Solutions to Buffer example #2

(1) Use Henderson-Hasselbalch equation:

• pH = pKa + log([HPO42-]/[H2PO4-])
• 7.40 = 7.21 + log([HPO42-]/[H2PO4-])
• log([HPO42-]/[H2PO4-]) = 7.40 – 7.21 = 0.19
• [HPO42-]/[H2PO4-] = 10 .19 = 1.55

(2) If [H2PO4-] = 0.20 M,

• [HPO42-] = 1.55 x 0.20 M = 0.31 M
 Solutions to Buffer example #2

(3) Moles of KH2PO4 needed =

500. mL x (1 L/1000 mL) x 0.20 mol/L = 0.10 mole
• Moles of K2HPO4 needed =
500. mL x (1 L/1000 mL) x 0.31 mol/L = 0.155 mole
• Grams of KH2PO4 needed =
0.10 mol x (136.086 g/mol) = 14 g
• Grams of K2HPO4 needed =
0.155 mol x (174.178 g/mol) = 27 g
Problem # 3:

An environmental chemist needs a carbonate buffer to

study the effects of the acid rain on limestone rich soil.
How many grams of Na2CO3 must she add to 1.5 L of
freshly prepared 0.20 M NaHCO3 to make the buffer? Ka of
bicarbonate = 4.7 x 20-11

Hint:

1) Use HH eqn to find molar ratio of base to acid

2) Find mole of NaHCO3
3) Find mole of Na2CO3
4) Find the mass of Na2CO3
you need molar mass of Na2CO3)
 Buffer Exercise #1

Indicate whether each of the following mixtures

makes a buffer solution. Explain.
(a) 50.0 mL of 0.20 M CH3CO2H + 50.0 mL of 0.20 M
NaCH3CO2;
(b) 50.0 mL of 0.20 M HC2H3O2 + 50.0 mL of 0.10 M NaOH;
(c) 50.0 mL of 0.20 M HC2H3O2 + 50.0 mL of 0.20 M NaOH;
(d) 50.0 mL of 0.20 M NaC2H3O2 + 50.0 mL of 0.20 M HCl;
(e) 50.0 mL of 0.20 M NaC2H3O2 + 50.0 mL of 0.10 M HCl

(Answer: (a) Yes; (b) Yes; (c) No; (d) No; (e) Yes)
 Buffer Exercise #2
Indicate whether each of the following solution
mixtures will make a buffer solution. Explain.
(a) 50.0 mL of 0.10 M NH3 + 50.0 mL of 0.10 M NH4NO3;
(b) 50.0 mL of 0.10 M NH3 + 50.0 mL of 0.10 M HNO3;
(c) 50.0 mL of 0.10 M NH3 + 25.0 mL of 0.10 M HNO3;
(d) 50.0 mL of 0.10 M NH4NO3 + 25.0 mL of 0.10 M NaOH;
(e) 50.0 mL of 0.10 M NH4NO3 + 50.0 mL of 0.10 M NaOH;

(Answer: (a) Yes; (b) No; (c) Yes; (d) Yes; (e) No)
 Buffer Exercise #3

An acetate buffer solution is prepared by mixing

35.0 mL of 1.0 M acetic acid and 65.0 mL of 1.0 M
sodium acetate. (a) What is the pH of this solution?
(b) If 0.010 mole of HCl is added to this solution
without altering its volume, what will be the pH of
the resulting solution? (Ka = 1.8 x 10-5)

(Answer: (a) pH = 5.01; (b) pH = 4.83 after adding 0.10 M HCl)

 Buffer Exercise #4

How many milliliters of each solution of 0.50 M

KH2PO4 and 0.50 M K2HPO4 are needed to make
100.0 mL solution of phosphate buffer with pH =
7.50? What are the final concentrations of K+, H2PO4-
and HPO42-, in the buffer solution?
(for H2PO4-, Ka = 6.2 x 10-8)

(Answer: (a) 33.9 mL of KH2PO4 + 66.1 mL of K2HPO4;

(b) [K+] = 0.83 M; [H2PO4-] = 0.17 M; [HPO42-] = 0.33 M)