Acid-Base Equilibria

Chapter 17

1
 Acid –Ionization Equilibria
• Weak acids and weak bases only partially dissociate; their strengths are experimentally
determined in the same way as strong acids and bases by determining the electrical
conductivity.
• The reaction of a weak acid (or base) with water is the same as discussed in previous
• section.

• Consider the reaction:

[H3O ][ A  ]
HA(aq)  H2O(l)  H3O (aq)  A  (aq) Ka 
[HA ]
– Hydronium ion concentration must be determined from the equilibrium expression.
• Relative strengths of weak acids can be determined from the value of the equilibrium
constant.
– Large equilibrium constant means strong acid
– Small equilibrium constant means weak acid

E.g. determine which acid is the strongest and which the weakest.
Acid Ka
HCN 4.9x1010
HCOOH 1.8x104
CH3COOH 1.8x105
HF 3.5x104
 Determining K from pH
• Ka determined if pH and CHA known.
– Use the equilibrium expression for the acid.
E.g. Determine the equilibrium constant of acetic acid if the pH of a 0.260 M
solution was 2.68. Determine [H3O+]; [HA]; and [A].

HA(aq)+H2O(l)  H3O+(aq) + A(aq)

Initial conc 0.100 M 0 0
 to Equil. x +x +x
Equil. 0.100 M  x +x +x

– Strategy
• Calculate the [H3O+] from pH; this is x in the table above.
• The rest of the quantities are obtained from the bottom row.
 Calculating Equilibrium Concentrations in Weak–acid
Solutions
• pH determined if Ka and Ca known; for the dissociation of acetic
acid:
CH3COOH(aq)  H 2O(l)  H3O (aq)  CH3COO (aq) [H3O ][CH3COO ]
Ka 
[CH COOH]
3
 1.8x105
2H2O(l)  H3O (aq)  OH (aq) K w  [H3O ][OH ]
 1.00x1014

– [H3O+]total = [H3O+]CH3COOH + [H3O+]H2O.

– [H3O+]total  [H3O+]CH3COOH.
• The total hydronium ion concentration is often equal to the
contribution from the weak acid which is usually a lot stronger acid
than water.
• The total hydronium ion concentration is needed for the equilibrium
calculation.
 pH from Ka and Ca
E.g. Calculate the pH of 0.100M acetic acid. Given pKa = 4.76
CH3COOH(aq)+H2O(l)  H3O+(aq)+ CH3COO(aq)
Initial conc 0.100 M 0 0
 to Equil. x +x +x
Equil. 0.100 M  x +x +x
Method I:
x2
• Substitute into equilibrium equation to get  1.75x10  5 
0.100  x
• x2 + 1.75x105x  1.75x106 = 0.
• Solve using quadratic equation (see book).
Method 2
• Assume x << CHA. Then x = (KaCHA)1/2.
• Check (confirm assumption to be correct)
– Analytical concentration should be: Ca = 100x[H3O+]
Method 3 method of successive approximations.
• As in Method 2; then
• x = (Ka(CHA  x1))1/2; repeat if necessary.
E.g. Calculate pH of 0.0200M lactic acid if its Ka = 8.4x104M.
 % Dissociated (also called % Ionized) Weak Acids

• % ionization – a useful way of expressing the strength of an acid or base.

– 100% ionized a strong acid.
– Only partial ionization occurs with weak acids.
HA(aq)+ H2O(l)  H3O+(aq)+ A(aq)
Initial conc CHA 0 0
 to Equil. x +x +x
Equil. CHA  x +x +x
x
% Ionization   100%
CHA
E.g. determine the % ionization for 0.100 M, 0.0100 M, 0.00100M HCN if Ka = 4.9x1010.
– Solution: determine x for each and sub into definition above. Check assumptions.

CHA  K a 1/ 2
% Ionization   100%
CHA
1/ 2
 K 
  a   100%
• C
Notice % ionization increases withdilution.
HA 
 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.
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses the ionization of

a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

8
 pH of weak acid and the Effect of
Common
Consider the following solutions:
• Calculate the pH of 1.00 M HC2H3O2 solution.
• 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, [ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x x

 pH of Acetic Acid by itself.

• Solution-1:

[H 3O  ][CH 3CO 2 ] x2
Ka    1.8 x 10-5
[CH 3COOH] (1.00 - x )

• 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, [ ], M -x +x +x
Equilm. [ ], M (1.00 – x) x (0.50 + x)


 pH of Acetic Acid + Sodium Acetate

Solution-2:

[H 3O  ][CH 3CO 2 ] ( x )(0.50  x )
Ka    1.8 x 10-5
[CH 3COOH] (1.00 - x )

By approximation,
x = (1.00/0.50)(1.8 x 10-5) = 3.6 x 10-6 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?
Buffering: How Does It Work?
Buffer Solutions
 Henderson–Hasselbalch Equation
• HA(aq) ⇌ H+(aq) + A-(aq);
[ H  ][ A  ]
• Ka =
[ HA]
• pH = pKa + log([A–]/[HA])
• For a particular buffer system, solutions
with the same [A–]/[HA] ratio have same pH.
 pH of Buffer Solution: example #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
 Characteristics of Buffer Solutions

• Contain weak acids or weak bases and their

corresponding conjugate partners (common ions).
• Resist changes in pH.
• Buffering capacity depends on concentrations of
weak acid or weak base and their common ions.
• Effective pH buffering range ~ pKa  1
 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: example #2

A phosphate buffer with pH = 7.40 is prepared

using KH2PO4 and K2HPO4.
(a) What is the molar ratio of [HPO42-] to
[H2PO4-] in the buffered solution?
(b) If [H2PO4-] = 0.20 M, what is [HPO42-]?
(c) 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)
 Solutions to Buffer example #2

(a) 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-] = 100.19 = 1.55

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

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

(c) 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
 Consider mixture of salt NaA and weak acid HA.

NaA (s) Na+ (aq) + A- (aq) [H+][A-]

Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
-] pH = pKa + log
[A [acid]
-log [H+] = -log Ka + log
[HA]

[A-]
pH = pKa + log pKa = -log Ka
[HA]
27
What is the pH of a solution containing 0.30 M HCOOH and
0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log
[0.30]
= 4.01

HCOOH pKa = 3.77

28
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
29
 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

30
Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution
(b) HBr is a strong acid
not a buffer solution
(c) CO32- is a weak base and HCO3- is its conjugate acid
buffer solution

31
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of 0.050
M NaOH to 80.0 mL of the buffer solution?
NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]

start (moles) 0.029 0.001 0.024

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

+]
0.028 0.025 [0.25]
[NH4 = [NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28] 32