Pyridine is mixed with hydrocyanic acid to give the

equilibrium:
C5H5N (aq) + HCN (aq) ⇆ C5H5NH+ (aq) + CN- (aq)

Given that the pKb for pyridine is 8.77 and the pKa for
hydrocyanic acid is 3.46, the equilibrium will favor the:

a) Reactants To text in your answer, send

b) Products ’GZSB A,B,etc' to (613) 777-0647

Acid-Base Equilibria 34
Pyridine C5H5N serves as a solvent and as a
base in many organic syntheses. It has a pKb
of 8.77. What is the pH of 0.10 mol/L pyridine?

Acid-Base Equilibria 35
Acid-Base Equilibria 36
The percent hydrolysis of a 0.735 mol/L solution of a
weak acid is 12.5%. Calculate the pH and pOH of this
solution.

Acid-Base Equilibria 37
Sodium hypochlorite is the active ingredient of household
laundry bleach. What is the pH of 0.20 mol/L NaClO?

Acid-Base Equilibria 38
Polyprotic acid:
• An acid with more than one ionizable proton.
• Each dissociation step has a different value for Ka

H2CO3 + H2O D HCO3– + H3O+ Ka1

HCO3– + H2O D CO32– + H3O+ Ka2

• Assume the first reaction is 100% complete before next

reaction starts
• Therefore, the first reaction reaches equilibrium (Ka1), and
this equilibrium is the initial state for the second
dissociation reaction (Ka2).
Acid-Base Equilibria 39
Oxalic acid (H2C2O4) is the simplest diprotic carboxylic acid.
Calculate the equilibrium values of [H2C2O4], [HC2O4-] and
[C2O42-] and find the pH of a 0.150 M oxalic acid solution.
Ka1 = 5.6x10-2, Ka2 = 5.4 x 10-5.

First check to see if the assumptions

we normally use will be valid:

Acid-Base Equilibria 40
We will need to use: −b ± b 2 − 4ac
x=
2a

a= b= c=

Second dissociation reaction:

Acid-Base Equilibria 41
Chapter 14:
39, 41, 43, 47 (a and c), 61 (a and b)

Chapter 15:
17, 27, 29, 33, 38, 39, 41, 43, 53, 59, 62, 73, 76, 80, 81,
82, 83, 86

Acid-Base Equilibria 42
Buffers
Acid-Base Titrations

Precipitation Reactions

Aqueous Equilibria 1
• The function of a buffer is to resist changes in the pH of a
solution when either H+ or OH- is added.
• Consists of a conjugate acid-base pair
• Could be comprised of either:
i. A weak acid and its conjugate base
ii. A weak base and its conjugate acid

ered
tb uff
n o

buffer
ed
+ 1 mL
strong acid
pHAqueous Equilibria
5 solution 2
Suppose we add a strong acid (e.g. HCl) to a weak acid (HA) at
equilibrium with its conjugate base in water:

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

The strong acid will dissociate completely:
HCl (aq) + H2O (l) → H3O+ (aq) + Cl- (aq)
Instead of lowering the pH of the solution, the H3O+ from this acid
will react with A- to push the equilibrium towards HA.

The amount that is left over after reaction with A- is controlled by Ka:
Ka = [A-][H3O+] [H3O+] = Ka[HA]
[HA] [A-]

• If the [A-] >> [H3O+], almost all H3O+ will react with the buffer.
• The amount left to decrease the pH of the solution will be very
small.
Aqueous Equilibria 3
Suppose we add a strong base e.g. sodium hydroxide:
NaOH (aq) → OH- (aq) + Na+ (aq)

Instead of raising the pH of the solution, the OH- from

this base will react with…

• If the [HA] >> added [OH-], almost all OH- will react with the
buffer.
• The amount left to increase the pH of the solution will be very
small.
Aqueous Equilibria 4
Calculate the pH of a buffer consisting of 0.50 M HF and 0.45
M F-. (Ka = 6.8 x 10-4)
Approach: Use the same approach that we have used for
any equilibrium question.

1) Write the balanced chemical reaction.

HF (aq) + H2O (l) D F- (aq) + H3O+ (aq)

2) Set up the ICE table:

HF F- H3O+
Initial 0.50 M 0.45 M 10-7
Change
Equilibrium
Aqueous Equilibria 5
3) Can we make any simplifying assumptions?

[H3O+]o

[HF]eq

[F-]eq

4) Write the equation for Ka:

5) Solve for [H3O+], pH

Aqueous Equilibria 6
When calculating the pH of a buffer we always start with the
equilibrium reaction. For acid this is:
HA(aq) + H2O(l) A-(aq) + H3O+(aq)
[H3O+][A-] [HA]
Ka = [H3O+] = Ka x
[HA] [A-]
If we take the logarithm of both sides:
[HA]
-log[H3O+] = -logKa – log
[A-]

[A-] Allows us to calculate pH of

pH = pKa + log a buffer if we know the
[HA] equilibrium concentrations
of A- and HA.
Aqueous Equilibria 7
According to the Henderson-Hasselbalch equation,
when [HA] = [A-], the pH is equal to:

A. 1
B. 0
C. -pKa
D. pKa

To text in your answer, send ’HZSB A,B,etc' to

Aqueous Equilibria (613) 777-0647 8
After addition of a strong acid or base to a buffer, deal with
neutralization first, then equilibrium.
1) Neutralization reaction after addition of:
A strong base
HA (aq) + OH- (aq) → A- (aq) + H2O (l)
or
A strong acid
A- (aq) + H3O+ (aq) → HA (aq) + H2O (l)

2) Equilibrium reaction for:

Base ionization
A- (aq) + H2O (l) D HA (aq) + OH- (aq)
or
Acid dissociation
HA (aq) + H2O (l) D A- (aq) + H3O+ (aq)
Aqueous Equilibria 9
Calculate the pH of 1.0 L of the HF buffer from slide 5
after the addition of 0.40 g of NaOH.
1) Write the balanced chemical reaction for the
neutralization reaction.
HF (aq) + OH- (aq) → F- (aq) + H2O (l)
2) How much HF and F- is left after addition of OH-?

HF OH- F-
Initial 0.50 M 0.01 M 0.45 M
Change
Final

Aqueous Equilibria 10
3) Now set up the Hendersen-Hasselbalch equation for:

HF (aq) + H2O (l) D F- (aq) + H3O+ (aq)

[A-]
pH = pKa + log
[HA]

How much did the pH change by when this base was added?

How much would the pH change by if this base was added to

water?

Aqueous Equilibria 11