Chapter 8

Monoprotic Acid-Base
Equilibria
• Ka
• Kb
• Fraction of dissociation
• Henderson-Hasselbalch eq.
• Buffer
• Buffer capacity
• Conjugated acid-base pair
 pH of a strong Acid & Base
Strong Acid
HBr + H2O H3O+ + Br-

pH of 0.10 M HBr ?

pH = -log[H+] = -log[0.10] = 1.00

Activity coefficient consideration

pH = -log[H+]g = -log[0.10][0.83] = 1.08
Strong Base
KOH K+ + OH-

pH of 0.10 M KOH ?

pOH = -log[OH-] = -log[0.10] = 1.00

pH + pOH = pKw = 14 at 25oC

pH = pKw – pOH = 14 – 1 = 13
The dilemma

KOH K+ + OH-

pH of 1.0 x 10-8 M KOH ?

pOH = -log[OH-] = -log[10-8] = 8.00

pH + pOH = pKw = 14 at 25oC

pH = pKw – pOH = 14 – 8 = 6.00 (acidic???)

The cure

pH of 1.0 x 10-8 M KOH ?

KOH K+ + OH-

H 2O H+ + OH-

Charge balance: [H+] + [K+] = [OH-]

Mass balance: [K+] = 1.0 x 10-8 M
Eq. constant: Kw = [H+][OH-] = 1.0 x 10-14 M
x
Kw = x(x + 1.0 x 10-8) = 1.0 x 10-14 M

Kw = x2+(1.0x10-8)x – (1.0x10-14) = 0

x = 9.6 x 10-8 M pH = -log [9.6 x 10-8] = 7.02

 Summary
Region 1
Complete
dissociation

Region 2

Region 3
Water almost never produces 10-7 M H+ and 10-7 M OH-

10-4M HBr, then pH = 4

From water(H2O) 10-10 M OH-, 10-10 M H+

What concentration of H+ and OH- are produced

by H2O dissociation in 10-2 M NaOH?

H 2O H+ + OH-

Any acid or base suppresses water dissociation

Why? Le Chatelier’s principle
 Weak Acids and Bases
[ H + ][ A- ]
HA H+ + A- Ka =
[ HA]
[ BH + ][OH - ]
B + H2O BH+ + OH- Kb =
[ B]

Conjugate pair: HA & A-, B & BH+

HA H+ + A-
A- + H2O HA + OH-

K w = K a Kb pK w = pK a + pK b
 Weak is Conjugated to Weak Basicity
increases
pKa(HA) = 4, then pKb(A-) = 10; A- is a weak base
pKa(HB) = 5, then pKb(B-) = 9; B- is a weak base
Acidity
increases

Conjugate of a strong acid (or base) is not a base (or an acid)

at all. (ex, HCl & Cl)
Using Appendix G

CH3NH3+, Ka = 2.3 x 10-11

CH3NH2, Kb = 1.0 x 10-14 / 2.3 x 10-11 = 4.3 x 10-4

 Weak-Acid Equilibria
[ H + ][ A- ]
HA H+ + A- Ka =
[ HA]
H 2O H+ + OH- K w = [ H + ][OH - ]

Charge balance: [H+] = [A-] + [OH-]

Mass balance: F = [A-] + [HA]
Eq. constant: Kw = [H+][OH-] = 1.0 x 10-14 M
+ -
[ H ][ A ]
Ka =
[ HA]
“Assumption: [H+] from acid dissociation >> [H+] from water dissociation”
[H+] ≈ [A-]
[ H + ][ A- ] x2
= = Ka Neglecting [H+] & [OH-] from H2O
[ HA] F-x
Ex> pH of 0.050 M o-hydroxybenzoic acid (Ka = 1.07 x 10-3)
[ H + ][ A- ] x2
= = Ka
[ HA] F-x
[ H + ][ A- ] x2
= = 1.0 ´ 10 -3
[ HA] 0.050 - x
-3
x = 6.80 ´ 10 M
pH = - log[6.80 ´ 10 -3 ] = 2.17
Check!

[H+] ≈ [A-] Neglecting [H+] & [OH-] from H2O

pOH = pK w - pH = 14 - 2.17 = 11.83

[OH-] = 10-11.83 = 1.47 x 10-12

Assumption is correct!
[H+] = 1.47 x 10-12
Fraction of Dissociation
- -
[A ] [A ]
a= -
=
[ HA] + [ A ] F

6.80 ´ 10 -3 M
a= = 0.136
0.0500 M

13.6 %
The Essence of a Weak-Acid Problem

When faced with the problem of finding the pH of a weak acid,

HA H+ + A- Neglecting [H+] & [OH-] from H2O

Initial F 0 0 [ H + ][ A- ] x2
Final F-x x
= = Ka
x [ HA] F-x

Ex> 0.100 M trimethylammonium chloride (pKa = 9.800)

2 2
x x
= = 10 -9.800
F - x 0.100 - x

x = 3.97 x 10-6 M pH = 5.40

 Weak-Base Equilibria
When faced with the problem of finding the pH of a weak base,

B + H2O BH+ + OH-

Initial F 0 0
Final F-x x x
Neglecting [H+] & [OH-] from H2O
[ BH + ][OH - ] x2
= = Kb
[ B] F-x
Fraction of Association
[ BH + ] [ BH + ]
a= +
=
[ B ] + [ BH ] F
Ex> pH of 0.0372 M cocaine ? (Kb=2.6 x 10-6)

[ BH + ][OH - ] x2
= = Kb
[ B] F-x
x2 x2
= = 2.6 ´ 10 -6 x = 3.1 x 10-4 = [OH-]
F - x 0.0372 - x

pOH = -log[OH-] = 3.51

pH = pKw -pOH = 14 - 3.51 = 10.49
 Conjugate Acids and Bases-Revisited
Ex> pH of 0.050 M sodium o-hydroxybenzoate (Ka=1.07 x 10-3)?

O O
C O- + H2 O C OH + OH-

OH OH

K w 1.0 ´ 10 -14 -12

K a Kb = K w Kb = =
K a 1.07 ´ 10 -5
= 9 . 35 ´ 10

+ - 2
[ BH ][OH ] x
= = Kb pH = pKw -pOH
[ B] F-x
= 14 – 6.17
= 7.83
x2 x2 -12
= = 9.35 ´ 10
F - x 0.050 - x
Ex> pH of 0.10 M ammonia? (pKa=9.244 in appendix G)

NH3 + H2O NH4+ + OH-

Kw 10 -14
K a Kb = K w Kb = = -9.244 = 1.75 ´ 10 -5
K a 10
+ - 2
[ NH 4 ][OH ] x
= = Kb
[ NH 3 ] F-x

x2 x2 -5
= = 1.75 ´ 10
F - x 0.10 - x

pH = pKw -pOH = 14 – 2.88 = 11.12

 pH Calculations

strong Acid & Base Weak-Acid

Weak-Base

Neglecting [H+] & [OH-] from H2O

[ H + ][ A- ] x2
= = Ka
[ HA] F-x

Neglecting [H+] & [OH-] from H2O

[ BH + ][OH - ] x2
= = Kb
[ B] F-x
 Buffers
Buffer = (weak) acid + its conjugate base
Resists changes in pH
when acids or bases are added or when dilution occurs.

Ex> Mixing a 0.100 M weak acid HA (pKa = 4.00)

and 0.100 M its conjugate base A-
[ H + ][ A- ] x2
HA H+ + A- = = Ka
[ HA] F-x
x
x = 3.1 x 10-3 M a = = 0.0311
F
[ HA][OH - ] x2
A- + H2O HA + OH- -
= = Kb
[A ] F-x
x = 3.2 x 10-6 M x
a = = 3.2 ´10 -6
F

[HA] ≈ FHA, [A-] ≈ FA-, when HA and A- are mixed together

 The Henderson-Hasselbalch Eq.

[ H + ][ A- ]
HA H+ + A- Ka =
[ HA]
-
+ [ A ]
log K a = log[ H ] + log
[ HA]
-
+ [ A ]
- log[ H ] = - log K a + log
[ HA]
[ A- ]
pH = pK a + log
[ HA]

When weak base B and its conjugated Acid

[ B]
pH = pK a + log
[ BH + ]
pKa of BH+
When [A-] = [HA], pH = pKa

[ A- ]
pH = pK a + log = pK a + log 1 = pK a
[ HA]
Ex> NaOCl in pH 6.20 solution. (pKa = 7.53),
then find [OCl-]/[HOCl]

HOCl H+ + OCl-

[OCl - ]
pH = pK a + log
[ HOCl ]
[OCl - ]
6.20 = 7.53 + log
[ HOCl ]

[OCl - ]
= 0.047
[ HOCl ]
A Buffer in Action

NH3 NH2

C C + H+
CH2OH CH2OH
HOH2C HOH2C
CH2OH CH2OH

“tris” = tris(hydroxymethyl)aminomethane

Ex> pH of 12.43g of tris + 4.67g of tris HCl in 1.00 L water

[ B] [12.43 / 121.136]
pH = pK a + log +
= 8.075 + log = 8.61
[ BH ] [4.67 / 157.597]
 Ex> Adding 12.0 mL of 1.00 M HCl to this buffer soln
0.1026 mole
[ B] [12.43 / 121.136]
pH = pK a + log +
= 8.075 + log = 8.61
[ BH ] [4.67 / 157.597]
0.0296 mole
Key factor: When a strong acid is added to a weak base,
both react completely to give BH+

mole of H+ from HCl: 12 x 10-3 x 1 = 0.0120 mole

[ B] [0.1026 - 0.0120]
pH = pK a + log +
= 8.075 + log = 8.41
[ BH ] [0.0296 + 0.0120]

Without buffering,
Adding 12.0 mL of 1.00 M HCl
1.00 L, pH 8.61 xL pH ?
1.012 L pH = 1.93
B neutralized the added acid,
BH+ neutralizes the added base
pH get affected through the log term.

[ B]
pH = pK a + log +
[ BH ]
 Buffer Capacity
dC b dCa
Buffer Capacity b= =
dpH dpH

• Maximum buffer capacity at pH = pKa

• Effective buffer range pKa ± 1

High [OH-]
Ex> Mixing 0.0383 mole A- and 0.9617 mole HA (pKa(HA)=5.00)
pH ?

Ex> Mixing 3.83 M, 10 mL A- and 9.617 mole, 100 mL HA

(pKa(HA)=5.00 pH ?

Ex> adding 0.0100 mole of OH- , then pH ?

Ex> adding 0.0100 mole of H+ , then pH ?

 Preparing Buffers
• pH pKa ± 1
• What buffer?
• Concentration (buffer capacity)
• Table 10-2, structures and pKa values for common buffers

Preparing a buffer in real life

1. Dissolve a measured amount of a weak acid (or base)
2. Adjust pH using concentrated OH- (or H+) with pH meter

Ex> 1.00 L of 0.100 M tris at pH 7.60 using solid tris HCl and
~1M NaOH

1. Dissolve 0.100 mole tris HCl in 800 mL water

2. Adjust pH to 7.60 monitoring using a pH meter with stirring
3. Add water to the final volume