ACID –BASE EQUILIBRIUM

(Analytical Chemistry I; Lecture 07)

Dr. Joel R. Salazar

Department of Chemistry
CENTRAL LUZON STATE UNIVERSITY
Equilibrium Constants for Weak Acids

Weak acid has Ka < 1

Leads to small [H3O+] and a pH of 2 - 7
Equilibrium Constants for Weak Bases

Weak base has Kb < 1

Leads to small [OH-] and a pH of 12 - 8
Relation of
Ka, Kb,
+
[H3O ] and
pH
Ionization Constants of Conjugate Acid-Base
Pairs
HA (aq) H+ (aq) + A- (aq) Ka
A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb
H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka
 Salts
• Salt: an ionic substance formed as a result of an acid–base
neutralization reaction.

E.g. NaCl is a salt from the reaction of HCl with NaOH.

– The properties of the salt will depend upon the strengths of the
acid and base that formed the salt.
E.g.1: determine the acid–base reaction that would produce
CH3COONa, NaCN, NH4Cl, (NH4)2CO3.
 Salt of WA + WB
• Determine Ka and Kb of acidic and basic portions of
salt.
• Largest K dominates to make solution either acidic
or basic.
• E.g. determine if 0.100 M NH4CN is acidic or basic.
• E.g. predict if 0.100 M C6H5NH3F is acidic or basic.
Qualitative predictions of pH for solutions of Salts for which
both cations and anions have acidic or basic properties

• Ka > Kb pH < 7 (acidic)

• Kb > Ka pH > 7 (basic)
• Ka = Kb pH = 7 (neutral)
Buffers:

• Solutions of a weak acid-

conjugate base pair.
• They are particularly
resistant to pH changes,
even when strong acid or
base is added.
 Which of the following are buffer systems?
(a) KF/HF (b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) HF 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 it conjugate acid
buffer solution
 Buffers

If a small amount of hydroxide is added to an equimolar

solution of HF in NaF, for example, the HF reacts with the
OH− to make F− and water.
 Buffers

If acid is added, the F− reacts to form HF and water.

 Buffer Calculations
Consider the equilibrium constant expression for
the dissociation of a generic acid, HA:

HA + H2O H3O + + A−

[H3O+] [A−]
Ka =
[HA]
 Buffer Calculations

Rearranging slightly, this becomes

[A−]
Ka = [H3O+]
[HA]
Taking the negative log of both side, we get
base
[A−]
−log Ka = −log [H3O+] + −log
[HA]
pKa
acid
pH
 Buffer Calculations
• So
[base]
pKa = pH − log
[acid]
• Rearranging, this becomes
[base]
pH = pKa + log
[acid]
• This is the Henderson–Hasselbalch equation.
 Henderson–Hasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic
acid, HC3H5O3, and 0.10 M in sodium lactate? Ka for
lactic acid is
1.4  10 .
−4
Henderson–Hasselbalch Equation

[base]
pH = pKa + log
[acid]
(0.10)
pH = −log (1.4  10−4) + log
(0.12)
pH = 3.85 + (−0.08)

pH = 3.77
 Henderson–Hasselbalch Equation
1. What is the pH of a buffer that is 0.25 M acetic
acid, CH3COOH, and 0.37 M sodium acetate? Ka =
1.75x10-5

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 pH Range/ preparation of buffer
• The pH range is the range of pH values over which a
buffer system works effectively = buffering capacity
• It is best to choose an acid with a pKa close to the
desired pH.
When Strong Acids or Bases Are Added
to a Buffer…
…it is safe to assume that all of the strong acid or base is
consumed in the reaction.
Addition of Strong Acid or Base to a
Buffer
1. Determine how the neutralization
reaction affects the amounts of the
weak acid and its conjugate base in
solution.
2. Use the Henderson–Hasselbalch
equation to determine the new pH of
the solution.
 Calculating pH Changes in Buffers
A buffer is made by adding 0.300 mol HC2H3O2 (Ka =
1.8x10-5) and 0.300 mol NaC2H3O2 to enough water
to make 1.00 L of solution. The pH of the buffer is
4.74. (a.) Calculate the pH of this solution after 0.020
mol of NaOH is added. (b.) Calculate the pH of this
after 0.020 mol of HCl is added
 Calculating pH Changes in Buffers

Before the reaction, since

mol HC2H3O2 = mol C2H3O2 −

pH = pKa = −log (1.8  10−5) = 4.74

 Calculating pH Changes in Buffers
The 0.020 mol NaOH will react with 0.020 mol of the acetic acid:

HC2H3O2(aq) + OH−(aq)  C2H3O2−(aq) + H2O(l)

HC2H3O2 C 2H 3 O 2− OH−
Before reaction 0.300 mol 0.300 mol 0.020 mol
After reaction 0.280 mol 0.320 mol 0.000 mol
 Calculating pH Changes in Buffers
Now use the Henderson – Hasselbalch equation to
calculate the new pH:
(0.320)
pH = 4.74 + log
(0. 200)
pH = 4.74 + 0.06

pH = 4.80
SAMPLE EXERCISE
Preparing a Buffer

How many grams of NH4Cl must be added to 2.0 L of

0.10 M NH3 to form a buffer whose pH is 9.00?(Assume
that the addition of NH4Cl does not change the volume
of the solution.) Kb = 1.8x10-5
SAMPLE EXERCISE continued
We now use the expression for Kb to calculate [NH4+]:

Thus, in order for the solution to have pH = 9.00, [NH4+] must equal 0.18 M. The number of moles of NH4Cl needed to
produce this concentration is given by the product of the volume of the solution and its molarity:

PRACTICE EXERCISE
Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (HC7H5O2) to
produce a pH of 4.00.
Answer: 0.13 M
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Homework:
1. The internal pH of muscle cell is 6.8. Calculate the
- -
[HPO4 /H2PO4 ] ratio in the cell. The second
dissociation constant of phosphoric acid is 6.31x10 . -8

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