ACID BASE EQUILIBRIA AND

ACID BASE TITRATION

Aliya Nur Hasanah

Analytical Chemistry Laboratory
2015
Arrhenius (or Classical) Acid-Base Definition

An acid is a substance that contains hydrogen and dissociates

in water to yield a hydronium ion : H3O+

A base is a substance that contains the hydroxyl group and

dissociates in water to yield : OH -

Neutralization is the reaction of an H+ (H3O+) ion from the

acid and the OH - ion from the base to form water, H2O.

The neutralization reaction is exothermic and releases approximately

56 kJ per mole of acid and base.

H+(aq) + OH-(aq) H2O(l) H0rxn = -55.9 kJ

 Brønsted-Lowry Acid-Base Definition
An acid is a proton donor, any species that donates an H+ ion.
An acid must contain H in its formula; HNO3 and H2PO4- are two
examples, all Arrhenius acids are Brønsted-Lowry acids.

A base is a proton acceptor, any species that accepts an H+ ion.

A base must contain a lone pair of electrons to bind the H+ ion;
a few examples are NH3, CO32-, F -, as well as OH -.
Brønsted-Lowry bases are not Arrhenius bases, but all Arrhenius
bases contain the Brønsted-Lowry base OH-.

Therefore in the Brønsted-Lowry perspective, one species donates a

proton and another species accepts it: an acid-base reaction is a
proton transfer process.

Acids donate a proton to water

Bases accept a proton from water

Molecular model: The reaction of an acid
HA with water to form H3O+ and a conjugate base.

Acid Base Conjugate Conjugate

acid base
STRONG AND WEAK ACIDS

 The reaction of an acid with its solvent (typically

water) is called an acid dissociation reaction.
 Acids are divided into two categories based on
the ease with which they can donate protons to
the solvent.
 Strong acids, such as HCl, almost completely
transfer their protons to the solvent molecules.
• In this reaction H2O serves as the base.
•The hydronium ion, H3O+, is the conjugate acid of H2O, and the chloride
ion is the conjugate base of HCl.
•It is the hydronium ion that is the acidic species in solution, and its
concentration determines the acidity of the resulting solution.
• We have chosen to use a single arrow in place of the double arrows to
indicate that we treat HCl as if it were completely dissociated in aqueous
solutions.
 Weak acids, of which aqueous acetic acid is one
example, cannot completely donate their acidic
protons to the solvent.
 Instead, most of the acid remains undissociated,
with only a small fraction present as the
conjugate base.

The equilibrium constant for this reaction is called an acid

dissociation constant, Ka, and is written as
STRONG AND WEAK BASES
 Just as the acidity of an aqueous solution is a
measure of the concentration of the hydronium
ion, H3O+
 the basicity of an aqueous solution is a measure
of the concentration of the hydroxide ion, OH–.
 The most common example of a strong base is
an alkali metal hydroxide, such as sodium
hydroxide, which completely dissociates to
produce the hydroxide ion.
 Weak bases only partially accept protons from
the solvent and are characterized by a base
dissociation constant, Kb.
 Example :
the base dissociation reaction and base
dissociation constant for the acetate ion are
Amphiprotic Species
 Some species can behave as either an acid or a
base. (called amphiprotic species)
 Example :
the following two reactions show the chemical
reactivity of the bicarbonate ion, HCO3 –, in
water.
Salts of Weak Acids and Bases

The salt of a weak acid is a bronsted base, which will accept protons.
It ionizes in water to form hydroxide ion and the corresponding undissociated acid.
OAc- + H2O HOAc + OH-
The HOAc here is undissociated and therefore does not contribute to the pH. This
ionization is also known as hydrolysis of the salt ion. Because it hydrolyzes, sodium
acetate is a weak base (the conjugate base of acetic acid).
Equilibria for the Bronsted bases are treated identically to the weak bases :
[HOAc] [OH-] = Kb

[OAc-]
 The product of Ka of any weak acid and Kb of its
conjugate base is always equal to Kw.
Ka.Kb = Kw
For any salt of weak acid, HA that ionizes in water :
A - + H2O HA + OH-
[HA] [OH-] = Kw
[A-] Ka

OH- concentration can be solve using :

[OH-] = Kw/Ka. [A-]

 Example :

Calculate the pH of 0,1 M solution of sodium

acetate, Ka = 7.6 x 10-5???

Answer :
[OH-] = Kw/Ka. [A-]

= (1.0 x 10-14/7.6 x 10-5). 0,1 M

= 7.6 x 10-6 M
pOH = -log[OH-]
pH = 14-pOH
= 8.89
Similar equation can be derived for salts of weak bases. These are
bronsted acids (give protons) and ionizes in water :

BH+ + H2O B + H3O +

[B] [H3O+] = Kw
[BH+] Kb

We can solve concentration for hydrogen ion :

[H+] = Kw/Kb. [BH+]

Example :

Calculate the pH of 0.25 M solution ammonium chloride, Kb = 1.75 x 10-5

Answer :

[H+] = (1.0 x 10-14 / 1.75 x 10-5) x 0.25M = 1.2 x 10-5 M

pH = -log [H+] = -log 1.2 x 10-5 = 5 – 0.08 = 4.92

 Buffer
 A buffer is defined as a solution that ressist change in
pH when a small amount of an acid or base is added or
when the solution is diluted.
 Usefull for maintaining the pH for a reaction at an
optimum value
 Consist of : Mixture of a weak acid and its salt or a weak
base and its salt
 Consider an acetic acid-acetate buffer. The acid
equilibrium that governs this system is

HOAc H+ + OAc-
Since we have added a supply of acetate ions to the system
(from sodium acetate), the hydrogen ion concentration is no
longer equal to the acetate ion concentration.

The hydrogen ion concentration is :

[H+] = Ka. ([HOAc]/[OAc-])

Taking the negative logarithm of each side of this equation, than

inverting the last log term it becomes :

pH = pKa + log ([Oac-]/[HOAc])

This is called Hendersson-Hasselbach equation

 The Buffer Capacity of a buffer is the number of
moles of strong acid or strong base that 1 L of the
buffer can absorb without changing pH by more than
1.

Maximum buffer
cappacity occur when the
concentration of acid and
conjugate base are equal
Example :
Calculate the pH of a buffer that is 0.020 M in NH3 and 0.030
M in NH4Cl.
What is the pH after adding 1.00 mL of 0.10 M NaOH to 0.10
L of this buffer?
Answer :
The acid dissociation constant for NH4+ is 5.70 x 10–10; thus the initial
pH of the buffer is
Adding NaOH converts a portion of the NH4+ to
NH3 due to the following reaction

Since the equilibrium constant for this reaction

is large, we may treat the reaction as if it went
to completion. The new concentrations of
NH4+ and NH3 are therefore
For mixture of weak base and its salt. Example is
the equilibrium for the ionization of ammonia is :
NH3 + H2O NH4+ + OH-

The equation for determining the pH would be:

pOH = pKb + log ([salt]/[base])
Example :
The basicity constant Kb for ammonia is 1.75 x 10-5 at 25oC. Calculate the pH and
pOH for 1.0 x 10-3 M solution of ammonia

Answer :

NH3+ H2O NH4+ + OH -

1.75 x 10-35= [NH4+] [OH-] / [NH3]

= [x] [x] / 1.00 x 10-3
X = 1.32 x 10-4 M = [OH-]
pOH = - log 1.32 x 10-4
= 3.88
pH = 14- 3.88 = 10.12
ACID BASE TITRATION
Strong Acid Versus Strong Base
 Acid base titration involves a neutralization reaction
 Titration curve is constructed for end point detection
 The titrant is always a strong acid or strong base
 The analyte may be either strong acid or base or weak acid
or base
 The equivalence point is where the reaction is theoretically
complete
 Titration Curve for 100 mL of
0.1 M HCl versus 0.1 M NaOH
pH
14

12

10
Phenolphthalein Transition range
8

0
0 20 40 60 80 100 120 140 mL NaOH
Equation Governing a Strong Acid (HX) or
Strong Base (BOH) Titration

Fraction Strong Acid Strong Base

F
Titrated
Present Equation Present Equation

F=0 HX [H+]=[HX] BOH [OH-]=[BOH]

0<F<1 HX/X- [H+]=[remainin BOH/B+ [OH-]=[remaining

g HX] BOH]

F=1 X- [H+]=Kw B+ [H+]=Kw

F>1 OH-/X- [OH-]=[excess H+/B+ [H+]=[excess

titrant] titrant]
 Dependence of the magnitude of the end
point break on concentration

HCl 1.0 M vs NaOH 0.1 M

14
HCl 0.01 M vs NaOH 0.01 M
12 HCl 0.001 M vs NaOH 0.001 M

10
Phenolphthalein Transition range
8
Bromothymol blue Transition range
6

4 Methyl orange Transition range

0
0 20 40 60 80 100 120 140
 Detection of The End Point: Indicator

 The point at which the reaction is observed

to be complete is called end point
 The selection of indicator become more
critical as the solution become more dilute
 The goal is for the end point to coincide
with the equivalence point
Indicator
 Indicator of acid base titration is a weak acid or weak base that highly
colored
 The color of the ionized form is markedly different from that of the
unionized form
HIn = H+ + In-
Red Blue
 Henderson-Hasselbalch equation
In 
pH  pK In  log
HIn
 Your eye can generally discern only one color if it is 10 times as intense
as the other
Indicator
1
pH  pK In  log
10 pH=pKIn - 1
10
pH  pK In  log pH=pKIn + 1
1

 Most indicator require transition

range of about two pH units
 The pKa of the indicator should be
close to the pH of the equivalence
point
Colour change
and molecular
model of
phenolftalein
Weak Acid Versus Strong Base
 The curve is flattest and the buffering capacity the greatest at the midpoint

14

12

10 Ka =10-10

8 Phenolphthalein Transition range

Ka =10-8
6

4 Methyl red Transition range

Ka =10-4
2

0
0 20 40 60 80 100 120 140
Equation Governing a Weak Acid (HA)
or Strong Base (BOH) Titration

Fraction F Weak acid

Titrated
Present Equation

F=0 HX [H+]=Ka M

0<F<1 HX/X- [H+]=Ka CHA/CA-

F=1 X- [OH-]=Kw/Ka CA-

F>1 OH-/X- [OH-]=[excess

titrant]
 Strong acid are actually good buffers,
except their pH change with dilution
 Weak acid titration require careful
selection of the indicator
 Acid weaker than pKa = 8 must be
titrated in non aqueous solvent
ASSIGNMENT

Calculate the pH at 0, 10, 35, and 50 mL of titrant in the

titration of 35 mL of 0.1 M HA (Ka=2x10-5) with 0.1 M
NaOH