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.
where pH is not changing significantly.

Buffering region a horizontal region of the pH curve

Interpreting pH curves

Titration of NaOH with HCl

14 buffer region titrant

pH

endpoint

equivalence point

equivalence point volume buffer region

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

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

HCl is titrant (pH high to low)

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 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)

14 pH 7

Multiple Endpoints

Titration of Na2CO3 with HCl

14
endpoint 1

pH

8
endpoint 2

X
equivalence point volume 1

4
0 0

X equivalence point volume 2

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 0

X
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

endpoint

we can write a proton transfer reaction to explain this

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 H3O + Cl - H2O SB B B

Endpoint: H3O

+ OH

2 H2O

Using the B-L 5-Step Method to Explain Endpoints

14

Titration of NaOH with HCl

pH

H3 O

+ OH

2 H2 O

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

Using the B-L 5-Step Method to Explain Polyprotic Endpoints

Titration of Na2CO3 with HCl

14

pH

endpoint 1

4
0 0

endpoint 2

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 2H3O + Cl - H2O SB B B

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 SA Na
+

A
+

A HCO3 SB
-

CO3

2-

H3O

Cl B

H2O B

Endpoint 2:

H3O

+ HCO3

H2O + H2CO3

Using the B-L 5-Step Method to Explain Polyprotic Endpoints

Titration of Na2CO3 with HCl

14

H3O+ + CO3

2-

H2O + HCO3 -

pH 4 0 X
H3O+ + HCO3
-

H2O + H2CO3

10 20 30 volume of titrant added (mL)

40

Other Polyprotic Systems

Consider the titration of phosphoric acid, H3PO4, with sodium hydroxide, NaOH: 11

X
pH

endpoint 2

X
0

endpoint 1

Vol. of NaOH (mL)

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

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 A H3PO4 Na
+

SA H2PO4 B
-

OH SB
H
+

H2O B

Endpoint 2:

H2PO4 - + OH

H2O + HPO4 2-

Other Polyprotic Systems

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

A
H3PO4 Na
+

SA
H2PO4 B
-

OH SB

H2O B

HPO4 B

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
-

H2O + PO43- (not observed)

H2PO4- + OH-

H2O + HPO42-

pH

X
0

H3PO4 + OH

H2O + H2PO4

Vol. of NaOH (mL)

Homework:

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