Unit 2

Acid-Base Titration

Dr Priti Jain
Asst Prof
DPSRU
Aqueous Acid –Base Titration

Theory of acid and base

Theory of Indicators, Choice of indicator,

Mixed Indicator
Neutralization or titration curves
ACID vs BASE
• A matter of taste

• Acid: from the Latin word acere, which means

"sour."
All acids taste sour.

• Base: All bases taste bitter. They usually feel

slippery, like soap (which is basic!)
Arrhenius Theory

Acid- a substance which yields hydrogen ion (H+) ion in aqueous medium.
E.g- HCl

Base- a substance which yields hydroxy (OH-) ion in aqueous medium. E.g-
NaOH

This theory does not explains the behavior of acid and bases in non aqueous
media

Lowry –Bronsted theory:proton theory of acids and bases,

Acid is a substance capable of yielding a proton, while base is substance

capable of accepting a proton

E.g. HA acid ↔ H+ + B base

• when an acidic substance loses a proton, it
forms a base, called the
conjugate base of an acid, and when a basic
substance gains a proton, it forms an acid
called the conjugate acid of a base.

In the equation the ammonium ion (NH+4 ) is the acid conjugate to the base
ammonia, and the chloride ion (Cl-) is the base conjugate to hydrochloric acid.
Conjugate acid-Base Pair
The pair of substance which by virtue of their mutual ability either
gain or lose of proton
 Not only molecule but
also anions and cations
can act as acid and bases
 In A-B titration an acid
will not release a proton
until a base capable of
accepting is not present
A1 + B2 B1 + A2

HCl+ NH3 Cl- + NH4+

Lewis Theory: generalized explanation of acids and
bases based on structure and bonding.
Acid- a species that can accept a pair of electron

Base-a species that can donate a pair of electron

• Titration Basics
– Titration = addition of a measurable volume of a known solution
(titrant) to an unknown solution until it is just consumed
– Use the stoichiometry of the reaction of the known and unknown to
calculate the concentration of the unknown solution
– A pH curve shows the change in pH versus volume of titrant as the
titration proceeds

pH meter can be used to monitor

pH during the titration

An acid-base indicator can be used

to signal reaching the equivalence point

First Derivative Curve

Shows where change is greatest
 Titrant: the standard solution of known molarity in the burette
that is being added to the solution in the flask. This is more often
the acid than the base.
 Analyte: the solution in the flask of unknown concentration.
Usually the base. Also called as Titrand
 Indicator: a compound that is added in small amounts (a few
drops) in acid-base titrations. It changes color over a certain pH
range, and indicates the end of the titration. This range should be
matched with pH at which you expect your solutions to reach the
equivalence point.
 Endpoint: the point at which the titration is stopped, when the
indicator permanently changes color. Traditionally, this is the
point when the titration is stopped, where the number of moles of
titrant is equal to the number of moles of analyte, or some
multiple thereof (as in di- or tri- protic acids)
 Equivalence point (neutralization or endpoint): the point (in mL
of solution added) at which the number of moles of acid equal the
number of moles of base.
 Half-equivalence point: the point (in mL of solution added) at
which the number of number of moles of acid (or base) added is
half the number of moles of base (or acid) present in the solution
Titration Curve / Neutralization Curves
 A titration curve is a plot of pH vs. the amount of titrant
added. Typically the titrant is a strong (completely)
dissociated acid or base.
 Such curves are useful for determining endpoints and
dissociation constants of weak acids or bases.
 Helps in selection of Indicator which will give smallest
titration error
 pH can be determined at various stages during the
titration using potentiometric method
Strong Acid-Strong Base Titration
Curve
HCl +NaOH NaCl + H O 2

H+ + OH- H O 2

 A titration of 50 ml of 0.1N HCl with 0.1N NaOH

 As titration proceeds more and more H+ of HCl will combine with
OH- of NaOH.
 This means concentration of H+ will go on decreasing and pH will
increase.
 When 50 ml of NaOH has been added, neutralization reaction
between acid and base is just complete. At this stage reaction
mixture will be neutral (pH=7)
 pH before any NaOH is added pH= - log [H+]
0.1N HCl i.e [H+]= 0.1 g ion/ litre (pH= 1)
 pH after addition of 10 ml of NaOH

40 ml acid will be left, 10 ml will react with base. Total volume will be 60 ml

NHCl X 60 = 40 X 0.1 i.e NHCl = 0.0667 N

This means 0.0667g eq of HCl is present per litre

i.e. [H+]= 0.0667 (pH= 1.18)

When 20% titration is complete the pH rises from 1-1.18

 pH after addition of 20 ml of NaOH

30 ml acid will be left, 20 ml will react with base. Total volume will be 70 ml

NHCl X 70 = 30 X 0.1 i.e NHCl = 0.0428 N

This means 0.0428g eq of HCl is present per litre

i.e. [H+]= 0.0428 (pH= 1.37)

When 40% titration is complete the pH rises from 1-1.37

Continued……..
 pH after addition of 50ml of NaOH
Reaction is just complete i.e. equivalence point has reached
Now the mixture contains only salt and water and it will be neutral with
pH 7

 pH after addition of 50.1ml of NaOH

50 ml has been reacted with acid, so 0.1 ml is present in excess. Total

volume of reaction mixture 100.1ml

i.e 0.1 ml of 0.1 N NaOH has been diluted to 100 ml

Therefore normality of NaOH can be calculated as

NNaOH = 0.1 X 0.1 / 100 = 10-4 N

This means 10-4g eq of NaOH is present per litre of solution

i.e [OH-] = 10-4 g ion per litre

Continued…….. [OH-] = 10-4 g ion per litre

We know that [H+] [OH-] = 10-14

[H+] = 10-14 / [OH-] i.e 10-14 / 10-4

Therefore, [H+] = 10-10 g ion per litre

- (log 10-10)= 10 i.e pH of the solution will be 10

 When the volume of NaOH is increased from 0.0 to 49.9 ml,
increase in pH is from 1-4, by 3 unit
 When the volume further increases from 49.9-50.0 ml , pH sharply
increases from 4-7, by 3 unit
 When volume increase from 50.0-50.1ml, pH again increases form
7-10
 After the addition of 49.9 ml of NaOH 99.8% reaction is complete
and and pH is 4. If some indicator shows colour at this pH then
titration error will be 0.2%. Similarly, if an indicator shows colour
change at pH 10 then the titre value will be 50.1 instead of 50ml.
Therfore error will be 0.2%
 Any indicator which show colour change between 4-10 can be used
 Features of the Strong Acid-Strong Base
Titration Curve

 The pH starts out low, reflecting the high [H3O+] of the strong
acid and increases gradually as acid is neutralized by the
added base.

 Suddenly the pH rises steeply. This occurs in the immediate

vicinity of the equivalence point. For this type of titration the
pH is 7.0 at the equivalence point.

 Beyond this steep portion, the pH increases slowly as more

base is added.
Weak Acid-Strong Base Titration Curve

 The initial pH is higher.

 The rate of increase in pH during the titration is greater
 A gradually rising portion of the curve, called the buffer
region, appears before the steep rise to the equivalence
point.
 The pH at the equivalence point is greater than 7 due to
hydrolysis of salt
 The steep rise interval is less pronounced.
Hpr vs NaOH

CH3COOH vs NaOH
 Weak Base -Strong Acid Titration Curve

1. The initial pH is above 7.00.

2. A gradually decreasing portion of the curve, called the buffer

region, appears before a steep fall to the equivalence point.

3. The pH at the equivalence point is less than 7.00.

4. Thereafter, the pH decreases slowly as excess strong acid is

added.
NH4OH + HCl  NH4Cl+ H2O

NH4Cl + H2O  NH4OH +

H+
Weak Acid -Weak Base Titration Curve
0.1 M CH3COOH + 0.1 M NH4OH  CH3COONH4 + H2O

CH3COONH4 + H2O  CH3COOH + NH4OH

 Inflection on the pH neutralization curve is very small near the

eq point
Eg. In above titration pH near the Eq point slowly rises from 6-8.
If pH rise near Eq point is less than 2 , it is very difficult to
judge the colour change, and results can not be obtained. This
could be a major problem in dilute solutions.
 Change in pH during entire titration is very gradual, therefore
end point cannot be detected by ordinary indicator. Mixed
indicators are used
 It is better to avoid titration of WA-WB
• Define Mixed Indicators?
• With ordinary acid base indicators, the color change is not sharp and
abrupt, but it extends over 2 units of pH. However, sometimes, it is
desirable to have sharp color change over a narrow and selected range of
pH. This can be achieved by the use of mixture of indicators whose pK ind
values are close together and the overlapping colors are complementary at
an intermediate pH value.
• For example:
A mixture of 3parts of phenolphthalein and 1 part of naphtholphthalein
shows a change in color from pale rose to violet at pH = 8.9. The mixed
indicator is useful for the titration of phosphoric acid to diprotic stage.
Similarly, a mixture of 3 parts of thymol blue and 1 part of cresol red shows
change in color from yellow to violet at pH = 8.3. This mixed indicator is
useful for the titration of CO32- to HCO3– stage.
• Universal Indicators?
A Universal Indicator is defined as a mixture having
many indicators of wide pH range. To obtain universal
indicators, many indicators are mixed( though it
behave as a single indicator) so that they can have a
change in color over a wider pH range.
Limitation of Universal Indicator is that it can not be
used if we are looking for very precise and accurate
quantitative titration. Therefore it can be used only
for determining approximate pH of a solution.
Q1. Suppose 25.66 mL (or 0.02566 L) of 0.1078 M
HCl was used to titrate an unknown sample of
NaOH. What mass of NaOH was in the sample?

Q2. What mass of Ca(OH)2 is present in a sample if it

is titrated to its equivalence point with 44.02 mL
of 0.0885 M HNO3?
• A1.
• # mol HCl = (0.02566 L)(0.1078 M) = 0.002766 mol HCl We also
have the balanced chemical reaction between HCl and NaOH:
• HCl + NaOH → NaCl + H2O So we can construct a conversion factor
to convert to number of moles of NaOH reacted:
• 0.002766 mol HCl ×1 mol NaOH/1 mol HCl=0.002766 mol NaOH
Then we convert this amount to mass, using the molar mass of
NaOH (40.00 g/mol):
• 0.002766 mol NaOH×40.00 g NaOH/1 mol NaOH=0.1106 g NaOH
A2.
• Q3. What mass of H2C2O4 is present in a sample
if it is titrated to its equivalence point with
18.09 mL of 0.2235 M NaOH? The balanced
chemical reaction is as follows:
H2C2O4 + 2NaOH → Na2C2O4 + 2H2O

0.182g