What is TITRATION?

• It is an analytical technique which allows the quantitative determination

of a specific substance (analyte) dissolved in a sample.

• It is based on a complete chemical reaction between the analyte and a

reagent (titrant) of known concentration which is added to the sample.

• Fast, convenient, accurate, readily automated

• Volumetric titrimetry, gravimetric titrimetry, coulometric titrimetry

 ACID-BASE
(Neutralization)
TITRATION
ACID-BASE TITRATION (volumetric titrimetry)
• Process in which a standard reagent is added to a solution of an analyte
until the reaction between the analyte and reagent is judged to be
complete
ACID-BASE TITRATION
• Standard solution (titrant)
- Reagent of known concentration

Strong acids: HCl, HClO4, H2SO4

Strong bases: NaOH, KOH, Ba(OH)2
* Never use weak acids and bases
as titrants!

• Titrand
- Substance which is being analysed
in the titration
ACID-BASE TITRATION
• Equivalence point
- Reached when the amount of
added titrant is chemically
equivalent to the amount of
analyte in the sample

• End point
- Physical change associated with
the condition of equivalence
ACID-BASE TITRATION
• Titration error
- difference in the volume
between the equivalence point
and the end point

Et = Vep - Veq
Where Vep is the actual volume of reagent;
Veq is the theoretical volume to reach the
equivalence point
ACID-BASE TITRATION
• Indicators
- Added to the analyte solution to give an observable physical change
(end point)
- Weak organic acid or a weak organic base whose undissociated form
differs in color from its conjugate acid or its conjugate base form
(solvatochromic)
- Indicator pH range: pKa ± 1
Phenolphtalein indicator:
ACID-BASE TITRATION
• Standardization
- Concentration of a volumetric solution is determined by titrating it
against a carefully measured quantity of a primary or secondary
standard.
• Primary standard
- Highly pure compound that serves a reference material for titrimetric
method of analysis.
• Secondary standard
- Less pure than primary standards.
- Purity has been established by chemical analysis and that serves as the
reference material for a titrimetric method of analysis.
ACID-BASE TITRATION
• Standardization
- Concentration of a volumetric solution is determined by titrating it
against a carefully measured quantity of a primary or secondary
standard.
• Primary standard
- Highly pure compound that serves a reference material for titrimetric
method of analysis.
• Secondary standard
- Less pure than primary standards.
- Purity has been established by chemical analysis and that serves as the
reference material for a titrimetric method of analysis.
Primary standard
• Characteristics:
1. High purity
2. High stability
3. Low hygroscopicity
4. Large molar mass (to minimize weighing errors)
5. Non-toxic
6. Readily available and cheap
7. Reasonable solubility in the titration method

Examples: • Potassium hydrogen phthalate (usually called KHP)

• Sodium carbonate
Secondary standard
• Characteristics:
1. It has less purity than primary standard
2. Less stable and more reactive than primary standard
3. But its solution remains stable for a long time
4. Titrated against primary standard

Examples: • anhydrous sodium hydroxide (NaOH)

• potassium permanganate (KMnO4)
Calculating the Molarity of Standard Solutions
Problem 1:
Describe the preparation of 1.000 L of 0.0100 M AgNO3 (169.78 g/mol)
from the primary standard grade solid.

Problem 2:
Describe the preparation of 500 mL of 0.01000 M Na+ standard solution
from a primary standard Na2CO3 solid.

Problem 3:
How would you prepare 50.0 mL portion of standard solutions that are
0.00500 M, 0.00200 M, and 0.00100 M Na+ from 0.0100 M Na+ solution?
Calculating the Molarity of Standard Solutions
Problem 4:
Describe the preparation of the following:
a. 500 mL of 0.0750 M AgNO3 from the solid reagent.
b. 2.00 L of 0.325 M HCl, starting with 6.00 M solution of the reagent.
c. 750 mL of a solution that is 0.0900 M in K+, starting with solid
K4Fe(CN)6.
d. 600 mL of 2.00% (w/v) aqueous BaCl2 from a 0.500 M BaCl2 solution.
Calculating the Molarity from Standardization
data
Problem 5:
A 50.0 mL portion of an HCl solution required 26.5 mL of 0.009985 M
Ba(OH)2 to reach an endpoint with bromocresol green indicator.
Calculate the molarity of HCl.

Ba(OH)2 + 2HCl  BaCl2 + 2H2O

Calculating the Molarity from Standardization
data
Problem 6:
A 0.4512 g sample of primary standard grade Na2CO3 required 36.44 mL
of an H2SO4 solution to reach the endpoint in the reaction

CO32- + 2H+  H2O + CO2

What is the molarity of H2SO4?

Calculating the Molarity from Standardization
data
Problem 7:
A 0.1934 g sample of primary standard grade Na2CO3 required 15.44 mL
of an H2SO4 solution to reach the endpoint in the reaction

CO32- + 2H+  H2O + CO2

What is the molarity of H2SO4?

Calculating the Molarity from Standardization
data
Problem 8:
A sodium hydroxide solution of unknown concentration is titrated
against 0.8765 g KHP (Potassium acid phthalate, a monoprotic acid, MW
204.3 g/mol). 48.6 mL of the sodium hydroxide solution is required to
reach the endpoint of the titration. What is the concentration of the
unknown sodium hydroxide solution.
Calculating the Molarity from Standardization
data
Problem 9:
A 0.5000 g sample that assayed 94.6% Na2SO4 required 41.25 mL of
barium chloride solution.
Reaction: Ba2+ + SO42-  BaSO4(s)

Calculate the analytical molarity of BaCl2 in solution.

Calculating the Quantity of Analyte from
Titration data
Problem 10:
This sodium hydroxide solution in Problem 8 is then used to titrate an
unknown nitric acid sample. 25.0 mL of the nitric acid solution is
titrated. 32.8 mL of the sodium hydroxide solution is required to reach
the endpoint. What is the concentration of the nitric acid solution?
Calculating the Quantity of Analyte from
Titration data
Problem 11:
A 0.5627 g sample of iron ore is dissolved in acid. The iron is then
reduced to Fe2+ and titrated with 47.22 mL of 0.02224 M KMnO4
solution. Calculate the results of this analysis in terms of % Fe (55.847
g/mol) and % Fe3O4 (231.54 g/mol).

MnO4- + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4 H2O

Strong acid – Strong base Titration:
Titration curves
Plots of a
concentration-
related variable
as a function of
reagent volume
Strong acid – Strong base Titration

Case 1: Titration of Strong Acids with Strong Base

Titration Curve Region Major Constituent Equations / Comments

1. Initial point HCl only (analyte only)

HCl&NaCl (unreacted analyte&

2. Before equivalence point
salt)
3. Equivalence point NaCl& H2O (salt)

4. After equivalence point NaOH & NaCl (salt & excess base)
Generate the hypothetical titration curve for the titration of 50.00 mL of
0.0500 M HCl with 0.1000 M NaOH
1. Initial pt.
2. After addition of 10.00 mL of reagent
3. After addition of 25.00 mL of reagent
4. After addition of 25.10 mL of reagent

Seatwork: Construct a titration curve for the titration of 25.00 mL of

0.0920 M HCl with 0.00 mL, 15.00 mL, 23.00 mL, & 30.00 mL of 0.1000
M NaOH
Strong acid – Strong base Titration

Case 2: Titration of Strong Bases with Strong Acids

Titration Curve Region Major Constituent Equations / Comments

1. Initial point NaOH only (analyte only)

NaOH&NaCl (unreacted analyte&

2. Before equivalence point
salt)

3. Equivalence point NaCl & H2O (salt)

4. After equivalence point HCl & NaCl (salt & excess acid)
Calculate the pH during the titration of 50.00 mL of 0.0500 M NaOH with
0.1000 M HCl after the addition of the following volumes of reagent: 24.50
mL, 25.00 mL, 25.50 mL

Seatwork: Construct a titration curve for the titration of 25.00 mL of 0.0920 M

NaOH with 0.00 mL, 15.00 mL, 23.00 mL, & 30.00 mL of 0.1000 M HCl