Chapter 11

Titrations: Taking
Advantage of
Stoichiometric Reactions

Titrimetric methods include a large and

powerful group of quantitative procedures
based on measuring the amount of a
reagent of known concentration that is
consumed by the analyte. Titrimetry is a
term which includes a group of analytical
methods based on determining the
quantity of a reagent of known
concentration that is required to react
completely with the analyte.

There are three main types of titrimetry: volumetric titrimetry,

gravimetric titrimetry, and coulometrtic titrimetry.

Volumetric titrimetry is used to measure the volume of a solution

of known concentration that is needed to react completely with the
analyte.

Gravimetric titrimetry is like volumetric titrimetry, but the mass is

measured instead of the volume.

Coulometric titrimetry is where the reagent is a constant direct

electrical current of known magnitude that consumes the analyte;
the time required to complete the electrochemical reaction is
measured.

The benefits of these methods are that they are rapid, accurate,
convenient, and readily available.

Defining Terms

Standard Solution
Titration
Equivalence Point
Back- Titration

Defining terms
Standard Solution: A reagent of a known concentration which is used in
the titrimetric analysis.

Titration: This is performed by adding a standard solution from a

buret or other liquid- dispensing device to a solution of the analyte
until the point at which the reaction is believed to be complete.

More Defining Terms

Equivalence Point: Occurs in a titration at the point in which the
amount of added titrant is chemically equivalent to the amount
of analyte in a sample.
Back- Titration: This is a process that is sometimes necessary in
which an
excess of the standard titrant is added, and the amount of the excess is
determined by back titration with a second standard titrant. In this
instance the equivalence point corresponds with the amount of initial
titrant is chemically equivalent to the amount of analyte plus the amount
of back- titrant.

Equivalence Points and

End Points
One can only estimate the equivalence point by observing a
physical change associated with the condition of
equivalence.

End point: The point in titration when a physical change occurs

that is associated with the condition of chemical equivalence.

Indicators are used to give an observable physical change (end point) at

or near the equivalence point by adding them to the analyte. The
difference between the end point and equivalence point should be very
small and this difference is referred to as titration error. To determine
the titration error: Et= Vep - Veq
Et is the titration error

Vep is the actual volume used to get to the end point

Veq is the theoretical value of reagent required to reach the end point

Primary Standards

A primary standard is a highly purified compound that serves as a reference

material in all volumetric and mass titrimetric properties. The accuracy
depends on the properties of a compound and the important properties are:

1. High purity

2. Atmospheric stability

3. Absence of hydrate water

4. Readily available at a modest cost

5. Reasonable solution in the titration medium

6. Reasonably large molar mass

Compounds that meet or even approach these criteria are few, and only a few
primary standards are available.

Standard Solutions
Standard solutions play a key role in
titrimetric methods.
Desirable Properties of Standard Solutions:
1.
Sufficiently stable
2.
React rapidly with analyte
3.
React completely with analyte
4.
Endure a selective reaction with analyte

Example of titration and set up

http://wine1.sb.fsu.edu/chm1045/notes/Aqueous/Stoich/Aqua02.htm

Example: Calculating the Molarity of Standard Solutions

Describe the preparation of a 5.0 L of 0.10 M Na2CO3 (105.99 g/mol)
from the primary standard solution.

Amount Na2CO3 = n Na2CO3 (mol) = Volume solution x c Na2CO3 (mol/ L)

= 5 L x 0.1 mol Na2CO3 = 0.5 mol Na2CO3
L
Mass Na2CO3 = mNa2CO3=0.5 mol Na2CO3 x 105.99 g Na2CO3 =53 g Na2C
mol Na2CO3

he solution is prepared by dissolving 53 g of Na2CO3 in water and diluting to 5 L

Example: Calculating the Molarity using different

algebraic relationships
How would you prepare 50mL portions of standard solutions that are
0.005 M, 0.002 M, and 0.001 M in a standard 0.01 M Na+?
To solve this the relationship Vconcd x cconcd = Vdil x cdil
Vconcd = Vdil x cdil = 50mL x 0.005 mmol Na+ /mL = 25mL
cconcd
0.01mmol Na+ /mL
To produce 50mL of 0.005 M Na+, 25mL of the concentration solution
should be diluted to 50mL.

How to deal with titration

data

e following two examples show the two types of volumetric calculations.

The first involves computing the molarity of solutions that have been
ndardized against either a primary standard or another standard solution
e second example involves calculating the amount of analyte in a sampl
from titration data.

Example: Molarity of solutions that have been

standardized

A 50mL volume of HCl solution required 29.71mL of 0.01963 M

Ba(OH)2 to reach an end point with bromocresol green indicator.
Calculate the molarityof the HCl.
Stoichiometric ratio= 2 mmol HCl/ 1 mmol Ba(OH)2
Amount Ba(OH)2 = 29.71 mL Ba(OH)2 x 0.01963 mmol Ba(OH)2
mL Ba(OH)2
Amount HCl = (29.71 x 0.01963) mmol Ba(OH)2 x 2 mmol HCl
1 mmol Ba(OH)2
C HCl = (29.71 x 0.01963 x 2) mmol HCL
50mL solution
= 0.023328 mmol HCl = 0.0233M
mL solution

Example: Amount of analyte in sample from

titration
Titration of 0.2121 g of pure Na2C2O4 (134 g/mol) required 43.31
mL of KMnO4. What is the molarity of the KMnO4 solution?
Stoichiometric ratio = 2 mmol KmnO4/ 5 mmol Na2C2O4
Amount Na2C2O4= 0.2121 g Na2C2O4 x 1 mmol Na2C2O4
0.134 g na2C2O4
Amount KMnO4 = 0.2121 mmol Na2C2O4 x 2 mmol KMnO4
0.134
5 mmol Na2C2O4
C KMnO4 = ( 0.2121 x 2) mmol KMnO4
0.134
5
= 0.01462M
43.31 mL KMnO4

Example: Computing analyte

concentrations from titration data
A 0.8040g sample of an iron ore is dissolved in acid. The iron is then
reduced to Fe2+ and titrated with 47.22mL of 0.02242 M KMnO4
solution. Calculate the results of this analysis in terms of percent Fe
(55.847 g/mol).
Stoichiometric ratio = 5 mmol Fe2+/ 1 mmol KMnO4
Amount KMnO4 = 47.22mL KMnO4 x 0.02242 mmol KMnO4
mL KMnO4
Amount Fe2+ = (47.22 x 0.02242) mmol KMnO4 x 5 mmol Fe2+
1 mmol KMnO4
Mass Fe2+ = (47.22 x 0.02242 x 5) mmol Fe2+ x 0.055847 g Fe 2+
mmol Fe2+
% Fe2+ = (47.22 x 0.02242 x 5 x 0.055947) g Fe 2+ x 100% = 36.77%
0.8040 g sample

Titration Curves

Example of a sigmoidal titration curve once calculations

of data have been computed.

www.psigate.ac.uk/newsite/ reference/plambeck/chem1/p01173.htm

References

Skoog, D., West, D., Holler, F.J., & Crouch,

S. (2000). Analytical Chemistry: An
Introduction. 7th ed. Thomson Learning,
Inc: United States of America.
http://wine1.sb.fsu.edu/chm1045/notes/A
queous/Stoich/Aqua02.htm
www.psigate.ac.uk/newsite/
reference/plambeck/chem1/p01173.htm
http://www2.hmc.edu/~karukstis/chem21
f2001/tutorials/tutorialStoichiFrame.html