Chemistry of Solutions

202-NYB-05
Lecture 9

pH of Weak Acid Solutions

Calculate the pH of 1.00 M HF solution Ka = 7.2x10-4.
Weak acid
Major components: HF(aq), H2O(l)
Major contributor of H+
HF(aq) H+(aq) + F-(aq) Ka = 7.2x10-4

H2O(l) H+(aq) + OH-(aq) Kw = 1.0x10-14

Set up an equilibrium ICE table

pH of Weak Acid Solutions

HF(aq) H+(aq) + F-(aq)
[Initial] 1.00 M 0.00 M 0.00 M
[Change] -x +x +x
[Equil.] 1.00-x x x
1.00 M 2.7x10-2 M 2.7x10-2 M
[H+][F-] (x)(x)
Ka = = = 7.2x10-4
[HF] 1.00-x
Can solve using the quadratic equation However Valid if
1.00-x ≈ 1.00 because Ka is so small x x100% < 5%
x = 2.7x10-2 M [HF]o

pH = -log[H+] = -log(2.7x10-2) = 1.57 3

1
 Solving Weak Acid Equilibrium
Problems
1. List the major species in the solution.
2. Choose the species that can produce H+, and write balanced
equations for the reactions producing H+.
3. Using the values of the equilibrium constants for the
reactions you have written, decide which equilibrium will
dominate in producing H+.
5. Write the equilibrium expression for the dominant
equilibrium.
6. List the initial concentrations of the species participating in
the dominant equilibrium.
7. Define the change needed to achieve equilibrium; that is,
define x.

Solving Weak Acid Equilibrium

Problems
8. Write the equilibrium concentrations in terms of x.
9. Substitute the equilibrium concentrations into the
equilibrium expression.
10. Solve for x the “easy” way, that is, by assuming that [HA]0
– x about equals [HA]0.
11. Use the 5% rule to verify whether the approximation is
valid.
12. Calculate [H+] and pH.

pH of Weak Acid Solutions

Calculate the pH of 0.100 M HOCl solution Ka = 3.5x10-8.
Weak acid
Major components: HOCl(aq), H2O(l)
Major contributor of H+
HOCl(aq) H+(aq) + OCl-(aq) Ka = 3.5x10-8

H2O(l) H+(aq) + OH-(aq) Kw = 1.0x10-14

Set up an equilibrium ICE table

2
 pH of Weak Acid Solutions
HOCl(aq) H+(aq) + OCl-(aq)
[Initial] 0.100 M 0.00 M 0.00 M
[Change] -x +x +x
[Equil.] 0.100-x x x
0.100 M 5.9x10-5 M 5.9x10-5 M
[H+][OCl-] (x)(x)
Ka = = = 3.5x10-8
[HOCl-] 0.100-x
Can solve using the quadratic equation However Valid if
0.100-x ≈ 0.100 because Ka is so small x
x100% < 5%
[HOCl]o
x= 5.9x10-5 M
pH = -log[H+] = -log(5.9x10-5) = 4.23 7

pH of Mixtures of Weak Acid Solutions

Calculate the pH of 1.00 M HCN (Ka = 6.2x10-10) & 5.00 M
HNO2 (Ka = 4.0x10-4) solution. What is [CN-] at equilibrium?
Weak acids
Major components: HCN(aq), HNO2(aq), H2O(l)
HCN(aq) H+(aq) + CN-(aq) Ka = 6.2x10-10
Major contributor of H+
HNO2(aq) H+(aq) + NO2-(aq) Ka = 4.0x10-4

H2O(l) H+(aq) + OH-(aq) Kw = 1.0x10-14

Set up an equilibrium ICE table

pH of Mixtures of Weak Acid Solutions

HNO2(aq) H+(aq) + NO2-(aq)
[Initial] 5.00 M 0.00 M 0.00 M
[Change] -x +x +x
[Equil.] 5.00-x x x
5.00 M 4.5x10-2 M 4.5x10-2 M
[H+][NO2-] (x)(x)
Ka = = = 4.0x10-4
[HNO2] 5.00-x
Can solve using the quadratic equation However Valid if
5.00-x ≈ 5.00 because Ka is so small x
x100% < 5%
[HNO2]o
x = 4.5x10-2 M
pH = -log[H+] = -log(4.5x10-2) = 1.35 9

3
 Continued
Solve for [CN-]

HCN(aq) H+(aq) + CN-(aq) Ka = 6.2x10-10

[Initial] 1.00 M
4.5x10-2 M
[Change] -x
[Equil.] 1.00M -x
[H+][CN-]
≈ 1.00M Ka = = 6.2x10-10
[HCN]
Because weak acid and Ka
is small
1.00 M
[CN-] = 1.4x10-8 M

10

Percent Dissociation

Percent dissociation = amount dissociated (M) x 100%

initial concentration (M)

Generally, the percent dissociation increases as a

weak acid becomes more dilute.

11

Percent Dissociation
Compare percent dissociation for 2.00 M and 0.300 M
acetic acid. Ka = 1.8x10-5 Weak acid
Major components: HC2H3O2(aq), H2O(l)

HC2H3O2(aq) H+(aq) + C2H3O2-(aq)

[Initial] 2.00 M 0 0
[Change] -x x x
[Equil.] 2.00 –x x x Check 5% rule
≈ 2.00 M
[H+][C2H3O2-]
x = 6.0x10-3 Ka = = 1.8x10-5
[HC2H3O2]
12

4
 Percent Dissociation
Compare percent dissociation for 2.00 M and 0.300 M
acetic acid. Ka = 1.8x10-5 Weak acid
Major components: HC2H3O2(aq), H2O(l)

HC2H3O2(aq) H+(aq) + C2H3O2-(aq)

≈ 2.00 M 6.0x10-3 M 6.0x10-3 M
≈ 0.300 M 2.3x10-3 M 2.3x10-3 M
[H+]
% dissoc. = [HC H Oeq ] x 100%
2 3 2 o

= 6.0x10-3 M x 100%
= 0.30%
2.00 M = 0.77%
13

Percent Dissociation
Explanation of dilution effect on % dissoc.
HA H+ + A-
[HA] = [HA]o – x ≈ [HA]o [H+] = [A-] = x
[H+][A-] (x)(x)
Ka = =
[HA] [HA]o
Dilute by factor of 10 [H+]new = [A-]new = x/10
[HA]new = [HA]o/10
[H+][A-] (x/10)(x/10)
Q= = = Ka / 10
[HA] [HA]o/10
Q < Ka
14

Percent Dissociation
Lactic Acid
A 0.100 M aqueous solution of lactic acid is 3.7%
dissociated. What is Ka? Weak acid

Major components: HC3H5O2(aq), H2O(l)

HC3H5O2 (aq) H+(aq) + C3H5O2-(aq)
[Initial] 0.100 M 0 0
[Change] -x x x
[Equil.] 0.100 –x x x
≈ 0.100 M [H+][C3H5O2-]
Ka =
[HC3H5O2]
15

5
 Percent Dissociation
Lactic Acid
A 0.100 M aqueous solution of lactic acid is 3.7%
dissociated. What is Ka? Weak acid

Major components: HC3H5O2(aq), H2O(l)

HC3H5O2 (aq) H+(aq) + C3H5O2-(aq)
≈ 0.100 M x x
x = 3.7x10-3 M
[H+] x 100%
% dissoc. =
[HC3H5O2]
x x 100% = 3.7% [H+][C3H5O2-]
0.100 Ka = = 1.4x10-4
[HC3H5O2]
16

Bases
Brønsted-Lowry definition
A base is a proton acceptor.

Strong base,
NaOH(s) Na+(aq) + OH-(aq) complete dissociation

All hydroxides of the group 1A are strong bases. LiOH, NaOH,

KOH…..
Hydroxides of the group 2A are also strong bases. Ca(OH)2, Ba(OH)2,
Sr(OH)2….. Note these produce 2 moles of OH- / mole base.
These also have low solubility.

17

Bases
Calculate the pH of 5.0x10-2 M NaOH at room
temperature.
Major species in solution: Na+(aq), OH-(aq), H2O(l)

[OH-] = 5.0x10-2 M
[H+] = Kw / [OH-] = 1.0x10-14 / 5.0x10-2 = 2.0x10-13

pH = -log[H+] = 12.70

18

6
 2015-02-17

Bases
Bases do not necessarily contain OH-

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

base

Still increases [OH-] in solution

19

Bases
B(aq) + H2O(aq) BH+(aq) + OH-(aq)
Base Acid Conjugate Conjugate
acid base
Kb always refers to the reaction
[BH+][OH-]
Kb = of a base with water.
[B]

20

Exercise
Butyric acid is a weak acid that can be found in spoiled butter.
The compound has many uses in synthesizing other flavors.
The Ka of HC4H7O2 at typical room temperatures is 1.5  10–5.
What is the pH of a 0.20 M solution of the acid?

1. 5.52
2. 4.82
3. 2.76
4. –0.70

21

7
 Exercise
A 0.35 M solution of an unknown acid is brought into a lab.
The pH of the solution is found to be 2.67. From this data,
what is the Ka value of the acid?

1. 6.1  10–3
2. 1.3  10–5
3. 7.5  10–4
4. 2.1  10–3

22

Exercise
Two weak acids, HA and HB are placed in separate solutions so
that their molarities are the same. Which, if either, would have
the larger value for Ka if the pH of the HA solution were lower
than the pH of the HB solution?

1. HA has the larger Ka.

2. HB has the larger Ka.
3. The Ka of HA = Ka of HB.
4. My answer would actually just be a guess, does more
information need to be given?

23

Next Time

• Chapter 14
– Sections 14.6 & 14.7

24