TITRIMETRIC METHODS

TITRIMETRIC METHODS
Lecture Content
• Acid Base Reactions and Titration
• Redox Reactions and Titration
 Acid Base Reactions and Titration
Titration
Volumetric titrimetry involves measuring the volume of a solution of known
concentration that is needed to react essentially completely with the analyte.
Gravimetric titration differs only in that the mass of the reagent is measured instead
of its volume.
A standard solution (or a standard titrant) is a reagent of known concentration that
is used to carry out a titrimetric analysis.
Analyte is a constituent of the sample which is to be studied by quantitative
measurements or identified qualitatively.
Sample is a substance or portion of a substance about which analytical information is
required.
Reagent is a chemical used to produce a specified reaction in relation to an analytical
procedure.
Standard is the pure analyte or a substance containing an accurately known amount
of it which is used to calibrate an instrument or to standardize a reagent solution.
 Acid Base Reactions and Titration
Titration
Principle of titration:
Titration is a quick, accurate, and widely used way of measuring the amount of a
substance in solution.

A titration is performed by adding exactly the volume of a standard solution (a

solution of exactly known concentration) needed to react with an unknown quantity
of a second substance.

The standard solution is called titrant. The volume of titrant needed for the titration
is carefully measured by means of a buret.

If the volume and concentration of the titrant are known, the unknown quantity of
the substance titrated can be calculated.

Chemical reaction of a titration may be represented as: 𝑎𝐴 + 𝑏𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Acid-Base Reactions and Titration
 Acid Base Reactions and Titration
Titration
It is sometimes necessary to add an excess of the standard titrant and then
determine the excess amount by back-titration with a second standard titrant. The
amount of the standard titrant is chemically equivalent to the amount of analyte
plus the amount of the second standard titrant.

An equivalent point in a titration is a theoretical point reached when the amount of

added titrant is chemically equivalent to the amount of analyte in the sample.

A primary standard is an ultrapure compound that serves as the reference material

for a titrimetric method of analysis.***

A secondary standard is a compound whose purity has been established by

chemical analysis and that serves as the reference material for a titrimetric method
of analysis.***
 Acid Base Reactions and Titration
Titration
In a standardization, the concentration of a volumetric solution is determined by
titrating it against a carefully measured quantity of a primary or secondary standard
or an exactly known volume of another standard solution.

The standard solutions used in neutralization titrations are strong acids or strong
bases because these substances react more completely with an analyte, and they
therefore provide sharper end points (HCl, HClO4, H2SO4, NaOH and KOH).

Weak acids and bases are never used as standard reagents because they react
incompletely with analyte.

Acid/base indicator is a weak organic acid or a weak organic base that used to
indicate the acidity or alkalinity of water.
Acid-Base Reactions and Titration
Acid-Base Reactions and Titration
 Acid-Base Reactions and Titration
Titrating a strong acid with a strong base

Titration curves for HCl with

NaOH.

Curve A: 50.0 mL of 0.0500 M

HCl with 0.1000 M NaOH.

Curve B: 50.00 mL of 0.000500

M HCl with 0.001000 M NaOH
 Acid-Base Reactions and Titration
Titrating a strong acid with a strong base
 Acid-Base Reactions and Titration
Titrating a strong base with a strong acid

Titration curves for NaOH

with HCl.

Curve A: 50.0 mL of 0.0500

M NaOH with 0.1000 M
HCl.

Curve B: 50.00 mL of
0.00500 M NaOH with
0.0100 M HCl
 Acid-Base Reactions and Titration
Titrating a weak acid with a strong base

Titration curves for acetic

acid with NaOH.

Curve A: 0.1000 M acid with

0.1000 M base.

Curve B: 0.001000 M acid

with 0.001000 M bse.
 Acid-Base Reactions and Titration
Titrating a weak acid with a strong base
 Acid-Base Reactions and Titration
Titrating a weak base with a strong acid
 Acid-Base Reactions and Titration
Titration indicator

The effect of acid strength on titration

curves.
Each curve represents the titration of
50.00 mL of 0.1000 M acid with
0.1000 M base.
 Acid-Base Reactions and Titration
Calculation involved:

𝐶1 𝑉1 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1

=
𝐶2 𝑉2 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 2

C = concentration
V = volume
33 mL of 3 M Hydrochloric acid is titrated with sodium
hydroxide to form water and sodium chloride. How many mmols
of sodium hydroxide are consumed in this reaction?

1. Balance the reaction:

HCl + NaOH → H2​O + NaCl

2. check no. of mole in reaction. 1 : 1

3. Convert the molarity into a number of moles

𝐶1 𝑉1 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (𝐻𝐶𝑙)

=
𝐶2 𝑉2 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (𝑁𝑎𝑂𝐻)

(3)(33/1000)/C2V2 = 1/1
C2V2 = 0.099 mol
= 99 mmols
50 mL of 0.50M barium hydroxide are required to fully titrate a 100mL solution of
sulfuric acid. What is the initial concentration of the acid?

1. Balance the reaction equation:

Ba(OH)2 (aq) + H2SO4 (aq) → BaSO4 (s) + 2H2O (l)

2. check no. of mole in reaction. 1 : 1

3. Convert the molarity into a number of moles

𝐶1 𝑉1 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (Ba(OH)2)

=
𝐶2 𝑉2 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (H2SO4)

(0.5)(50/1000)/C2(100/1000) = 1/1
C2 = 0.25M
10mL of 0.50M calcium hydroxide is required to titrate 50mL, hydrochloric acid.
What is the initial concentration of the acid?

1. Balance the reaction equation:

Ca(OH)2 + 2HCl → CaCl2 + 2H2O

2. check no. of mole in reaction. 1 mole Ca(OH)2 : 2 moles HCl

3. Convert the molarity into a number of moles

𝐶1 𝑉1 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (Ca(OH)2)

=
𝐶2 𝑉2 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒 (HCl)

10
0.5 (1000) 1
50 =
𝐶2 (1000) 2

0.005 1
=
0.05𝐶2 2

C2 = 0.2 M
 Redox Reactions and Titration
Oxidation/reduction reactions (redox)
In an oxidation/reduction reaction, electrons are transferred from one reactant to
another (or redox reaction).
Ared + Box ↔ Aox + Bred

Example: Oxidation of iron(II) ions by cerium(IV) ions;

𝐶𝑒 4+ + 𝐹𝑒 2+ ↔ 𝐶𝑒 3+ + 𝐹𝑒 3+
In this reaction, an electron is transferred from 𝐹𝑒 2+ to 𝐶𝑒 4+ to form 𝐶𝑒 3+ and
𝐹𝑒 3+ ions (𝐹𝑒 2+ is oxidized by 𝐶𝑒 4+ ; 𝐶𝑒 4+ is reduced by 𝐹𝑒 2+ )

𝐶𝑒 4+ : an oxidizing agent (oxidant)- a substance that has a strong affinity for

electrons

𝐹𝑒 2+ : a reducing agent (reductant)- a species that easily donates electrons to

another species
 Redox Reactions and Titration
Oxidation/reduction reactions
Half-reactions: to show which species gains and loses electrons

Reduction of 𝐶𝑒 4+ : 𝐶𝑒 4+ +𝑒 − ↔ 𝐶𝑒 3+

Oxidation of 𝐹𝑒 2+ : 𝐹𝑒 2+ ↔ 𝐹𝑒 3+ +𝑒 −

Balancing half-reactions: the number of atoms of each element as well as the net
charge on each side of the equation must be the same.
 Fe2+

Fe2+
The two balanced half reactions are:
CH3CH2OH + H2O → CH3COOH + 4H+ + 4e−

Cr2O72- + 14H+ + 6e−→2Cr3+ + 7H2O

The first equation is multiplied by 3 and the second by 2,
giving 12 electrons in each equation:

Simplifying the water molecules and hydrogen ions gives

final equation:
mL
Question:

A solution contains both iron(II) and iron(III) ions. A 50.0 mL

sample of the solution is titrated with 35.0 mL of 0.00280 M
KMnO4, which oxidizes Fe2+ to Fe3+. The permanganate ion is
reduced to manganese(II) ion. Another 50.0 mL sample of
solution is treated with zinc metal, which reduces all the
Fe3+ to Fe2+. The resulting solution is again titrated with
0.00280 M KMnO4, this time 48.0 mL is required. What are
the concentrations of Fe2+ and Fe3+ in the solution?
Solution:
1) The chemical equation of interest is this:
5Fe2+ + 8H+ + MnO4¯ ---> 5Fe3+ + Mn2+ + 4H2O
The stoichiometric relationship:
5 mole of Fe2+ : 1 mole of MnO4¯

2) Calculate moles of Fe2+ reacted:

Given: 35.0 mL of 0.00280 M KMnO4 oxidizes Fe2+ to Fe3+

(0.00280 mol / L) (0.0350 L) = 0.000098 mol of MnO4¯

(0.0000980 mol MnO4¯) (5 mol Fe / 1 mol MnO4¯) =
0.000490 mol Fe(II)
(3) Determine the TOTAL iron content. For this, we will use
the second 50.0 mL sample after it has been treated with
zinc. Since all the Fe3+ has been reduced to Fe2+, we can
determine how much iron was in the second 50.0 mL sample.
(0.00280 mol / L) (0.0480 L) = 0.0001344 mol of MnO4¯
(0.0001344 mol MnO4¯) (5 mol Fe / 1 mol MnO4¯) =
0.000672 mol of total Fe

4) Determine Fe(III) in solution and its molarity:

0.000672 mol - 0.000490 mol = 0.000182 mol
0.000182 mol / 0.050 L = 0.00364 M

5) Determine molarity of Fe(II):

0.000490 mol / 0.050 L = 0.0098 M