Chapter 15:

Acid / Base Chemistry

15.3 pH Changes in Acid-Base
Reaction Systems

pH curves

A pH curve is a graph showing the continuous change

in pH during a titration (an acid-base reaction)
Inv. 15.3 Demonstration pH curves
Titration of NaOH and Na2CO3 with HCl

14
pH
7

0
vol. of titrant (HCl) added (mL)

Titration Terminology
(Gr.11)

Titration the progressive transfer of a solution

from a buret (called the titrant) into a measured
volume of another solution (called the sample).

Equivalence point the volume of titrant required to

neutralize the sample (# mol acid = # mol base).

Endpoint the pH at the equivalence point of a

titration.

Indicator a chemical which is added to the sample

that changes colour at the equivalence point of a
titration.

Buffering region a horizontal region of the pH

curve where pH is not changing significantly.

Interpreting pH curves
Titration of NaOH with HCl

14
buffer region
pH
7

endpoint
X

titrant

equivalence point

equivalence point volume

buffer region
0
0
10
20
30
volume of titrant added (mL)

40

Which is the titrant?

Take 2 titrations involving NaOH and HCl

pH

pH

vol. of titrant

HCl is titrant
(pH high to low)

vol. of titrant
NaOH is titrant
(pH low to high)

Choosing an Indicator

pH curves are used to determine which indicator(s) are suitable

for a particular titration
The goal is to get an indicator that changes colour in the same
region as the endpoint of your titration

14
pH
7

Titration of NaOH with HCl

unsuitable: alizarin yellow (too early)
good indicators: bromothymol blue,
litmus and phenol red
unsuitable: orange IV (too late)

0
vol. of titrant (HCl) added (mL)

Multiple Endpoints
Titration of Na2CO3 with HCl

14
endpoint 1

pH

X
endpoint 2
equivalence point volume 1

4
0

X equivalence point volume 2

0
10
20
30
volume of titrant added (mL)

40

Choosing Indicators for

Multiple Endpoints

14

Titration of Na2CO3 with HCl

endpoint 1 - metacresol purple (7.4-9.0)

pH

X
endpoint 2 methyl orange (3.2-4.4)

4
0

X
0
10
20
30
volume of titrant added (mL)

40

Interpreting Endpoints

The Bronsted-Lowry 5-step method can be used

to write proton-transfer reactions that explain the
endpoints on a pH curve

In general, we only observe distinct endpoints on

a pH curve when a proton has been quantitatively
transferred from an acid to a base; incomplete
reactions are not observed

The number of endpoints that are observed

represent the number of proton transfer reactions
between B-L acids and B-L bases in a titration

Using the B-L 5-Step

Method
to Explain Endpoints

14

Titration of NaOH with HCl

pH

7
X
we can write a proton transfer
reaction to explain this endpoint

0
10
20
30
volume of titrant added (mL)

40

Writing B-L Equations

to Explain Endpoints
To

explain the endpoint observed for

the titration of NaOH with HCl, we
use the B-L 5-step method:

SA
A
Na + OH H 3O +
Cl - H2O

SB
B
B

Endpoint:

H+

H3O + + OH -

2 H2O

Using the B-L 5-Step

Method
to Explain Endpoints

14

Titration of NaOH with HCl

pH
7

H 3O + + OH -

2 H 2O

0
0
10
20
30
volume of titrant added (mL)

40

Polyprotic Acids and Bases

Polyprotic acids are those which can donate

more than one proton; in most cases, it is
equal to the number of hydrogens in the
chemical formula
E.g. H2SO4 : can donate 2 protons
E.g. H3PO4 : can donate 3 protons

Polyprotic bases are those which can accept

more than one proton; in most cases it is
equal to the magnitude of the charge on the
anion
E.g. CO3 2- : can accept 2 protons
E.g. PO4 3- : can accept 3 protons

Method
to Explain Polyprotic
Endpoints
Titration
of Na2CO3 with HCl

14

pH

4
0

endpoint 1

endpoint 2

0
10
20
30
volume of titrant added (mL)

40

Writing B-L Equations

to Explain Polyprotic
Endpoints

To explain the first endpoint observed for

the titration of Na2CO3 with HCl, we will
use the B-L 5-step method:

SA
A
Na + CO3 2H 3O +
Cl - H2O

SB
B
B

H+

Endpoint 1: H3O + + CO3 2-

H2O + HCO3 -

Writing B-L Equations

to Explain Polyprotic
Endpoints

To explain the second endpoint, we must consider

not just the original entities, but those entities that
were consumed in the first reaction and entities that
were created in the first reaction

Na +

CO3 2-

SA
H 3O +

Cl B

A
H 2O
B

A
HCO3 SB

H+

Endpoint 2:

H3O + + HCO3 -

H2O + H2CO3

Method
to Explain Polyprotic
TitrationEndpoints
of Na2CO3 with HCl

14

H3O+ + CO3 2-

H2O + HCO3 -

pH
4

H3O+ + HCO3 -

0
0
10
20
30
volume of titrant added (mL)

40

H2O + H2CO3

Other Polyprotic Systems

Consider the titration of phosphoric acid,

H3PO4, with sodium hydroxide, NaOH:
11
X

pH
X

endpoint 1

0
Vol. of NaOH (mL)

endpoint 2

Other Polyprotic Systems

To

explain the first endpoint observed

for the titration of H3PO4 with NaOH,
we use the B-L 5-step method:

SA
A
H3PO4
Na +
OH - H2O

SB
B
H+

Endpoint 1: H3PO4 + OH -

H2O + H2PO4 -

Other Polyprotic Systems

To explain the second endpoint, we must consider

not just the original entities, but those entities that
were consumed in the first reaction and entities that
were created in the first reaction

H3PO4

Na +

OH SB

A
H 2O

SA
H2PO4 -

H+

Endpoint 2:

H2PO4 - + OH -

H2O + HPO4 2-

Other Polyprotic Systems

The B-L method suggests there is the possibility of a third

endpoint:

H3PO4

Na +

OH SB

A
H2O

H2PO4 -

SA
HPO4 2-

However, because it was not observed in the pH curve, it must

mean the reaction was not quantitative, therefore we must
write it with a double arrow
H+
> 50%

Endpoint 3:

(not observed)

HPO4 2- + OH -

H2O + PO4 3-

Other Polyprotic Systems

Consider the titration of phosphoric acid, H3PO4,

with sodium hydroxide, NaOH:
11

HPO42- + OH H2PO4- + OH-

H2O + PO43- (not observed)

H2O + HPO42-

pH
X

H3PO4 + OH -

0
Vol. of NaOH (mL)

H2O + H2PO4 -

Homework:

Answer Q. 24-29 p.539-540.