Volumetric Calculations Using

Normality and Equivalent Weight

The normality of a solution expresses the number of
equivalents of solute contained in 1 L of solution or the
number of milliequivalents in 1 mL. The equivalent and
milliequivalent, like the mole and millimole, are units for
describing the amount of a chemical species.

1
Volumetric Calculations Using
Normality and Equivalent Weight
The equivalent and milliequivalent, however, are defined so
that we may state that, at the equivalence point in any
titration,
no. meq analyte present = no. meq standard reagent added
or
no. eq analyte present = no. eq standard reagent added

2
The Definitions of Equivalent
and Milliequivalent
 The amount of a substance contained in one equivalent
can vary from reaction to reaction.
 The weight of one equivalent of a compound can never be
computed without reference to a chemical reaction in
which that compound is, directly or indirectly, a
participant.
 The normality of a solution can never be specified without
knowledge about how the solution will be used.

3
Equivalent Weights in
Neutralization Reactions
One equivalent weight of a substance participating in a
neutralization reaction is that amount of substance (molecule,
ion, or paired ion such as NaOH) that either reacts with or
supplies 1 mol of hydrogen ions in that reaction. A
milliequivalent is 1/1000 of an equivalent.
The relationship between equivalent weight (eqw) and the
molar mass (M) is straightforward for strong acids or bases and
for other acids or bases that contain a single reaction hydrogen
or hydroxide ion.

4
Equivalent Weights in
Neutralization Reactions
For example, the equivalent weights of potassium
hydroxide, hydrochloric acid, and acetic acid are equal to
their molar masses because each has but a single reactive
hydrogen ion or hydroxide ion. Barium hydroxide, which
contains two identical hydroxide ions, reacts with two
hydrogen ions in any acid/base reaction, and so its
equivalent weight is one half its molar mass:

5
Equivalent Weights in
Neutralization Reactions
The situation is more complex for acids or bases that contain
two or more reactive hydrogen or hydroxide ions with
different tendencies to dissociate. With certain indicators,
for example, only the first of the three protons in phosphoric
acid is titrated:

With certain other indicators, a color change occurs only

after two hydrogen ions have reacted:

6
Equivalent Weights in
Neutralization Reactions
For a titration involving the first reaction, the equivalent
weight of phosphoric acid is equal to the molar mass; for
the second, the equivalent weight is one half the molar
mass. (Because it is not practical to titrate the third proton,
an equivalent weight that is one third the molar mass is not
generally encountered for H3PO4.) If it is not known which of
these reactions is involved, an unambiguous definition of the
equivalent weight for phosphoric acid cannot be made.

7
Equivalent Weights in
Oxidation/Reduction Reactions
The equivalent weight of a participant in an
oxidation/reduction reaction is that amount that directly or
indirectly produces or consumes 1 mol of electrons. The
numerical value for the equivalent weight is conveniently
established by dividing the molar mass of the substance of
interest by the change in oxidation number associated with
its reaction. As an example, consider the oxidation of oxalate
ion by permanganate
3+ 2- 7+ 2-
ion: 4+ 2- 1+ 2-

8
Equivalent Weights in
Oxidation/Reduction Reactions
In this reaction, the change in oxidation number of
manganese is 5 because the element passes from the +7 to
the +2 state; the equivalent weights for MnO4– and Mn2+ are
thus one fifth their molar masses.
Each carbon atom in the oxalate ion is oxidized from the +3
to the +4 state, leading to the production of two electrons by
that species. Therefore, the equivalent weight of sodium
oxalate is one half its molar mass.

9
Equivalent Weights in
Oxidation/Reduction Reactions
It is also possible to assign an equivalent weight to the
carbon dioxide produced by the reaction. Since this
molecule contains but a single carbon atom and since that
carbon undergoes a change in oxidation number of 1, the
molar mass and equivalent weight of the two are identical.
It is important to note that in evaluating the equivalent
weight of a substance, only its change in oxidation number
during the titration is considered.

10
Equivalent Weights in Precipitation
and Complex Formation Reactions
The equivalent weight of a participant in a precipitation or a
complex formation reaction is that weight which reacts with
or provides one mole of the reacting cation if it is univalent,
one-half mole if it is divalent, one-third mole if it is
trivalent, and so on. It is important to note that the cation
referred to in this definition is always the cation directly
involved in the analytical reaction and not necessarily the
cation contained in the compound whose equivalent weight
is being defined.

11
Sample Problem No. 1
Define equivalent weights for AlCl3 and BiOCl if the two
compounds are determined by a precipitate on titration
with AgNO3:
Solution:
AlCl3 (aq) + 3AgNO3 (aq) Al(NO3)3 (aq) + 3AgCl (s)
Al3+ + 3Cl- + 3Ag+ + 3NO3- Al3+ + 3NO3- + 3AgCl (s)
3Cl- + 3Ag+ 3AgCl(s)

12
Sample Problem No. 1
 
Define equivalent weights for AlCl3 and BiOCl if the two
compounds are determined by a precipitate on titration
with AgNO3:
Solution:

13
Sample Problem No. 1
Define equivalent weights for AlCl3 and BiOCl if the two
compounds are determined by a precipitate on titration
with AgNO3:
Solution:
BiOCl (aq) + AgNO3 (aq) BiONO3 (aq) + AgCl (s)
BiO++ Cl- + Ag+ + NO3- BiO+ + NO3- + AgCl (s)
Cl- + Ag+ AgCl(s)

14
Sample Problem No. 1
 
Define equivalent weights for AlCl3 and BiOCl if the two
compounds are determined by a precipitate on titration
with AgNO3:
Solution:

15
The Definition of Normality
 
The normality, N, of a solution is the number of
milliequivalents of solute contained in 1 mL of solution or
the number of equivalents contained in 1 L.

16
Some Useful Algebraic
Relationships
 

17
Calculation of the Normality of Standard
Solutions
 
Example #1: Describe the preparation of 5.000 L of 0.1000 N
Na2CO3 (105.99 g/mol) from the primary-standard solid,
assuming the solution is to be used for titrations in which
the reaction is
CO32- + 2H+ H2O + CO2
Solution:

18
Calculation of the Normality of Standard
Solutions
 
Example #1: Describe the preparation of 5.000 L of 0.1000 N
Na2CO3 (105.99 g/mol) from the primary-standard solid,
assuming the solution is to be used for titrations in which
the reaction is
CO32- + 2H+ H2O + CO2
Solution:

19
Calculation of the Normality of Standard
Solutions
 
Example #1: Describe the preparation of 5.000 L of 0.1000 N
Na2CO3 (105.99 g/mol) from the primary-standard solid,
assuming the solution is to be used for titrations in which
the reaction is
CO32- + 2H+ H2O + CO2
Solution:

Thus, dissolve 26.50 g of Na2CO3 in water and dilute to 5.000

L. 20
Calculation of Normalities from
Titration Data
 
Example #2: Exactly 50.00 mL of an HCl solution required
29.71 mL of 0.03926 N Ba(OH)2 to give an end point with
bromocresol green indicator. Calculate the normality of the
HCl. Note that the molar concentration of Ba(OH)2 is one
half its normality, that is,

Solution:

21
Calculation of Normalities from
Titration Data
 
Example #2: Exactly 50.00 mL of an HCl solution required
29.71 mL of 0.03926 N Ba(OH)2 to give an end point with
bromocresol green indicator. Calculate the normality of the
HCl.
Solution:

22
 Calculation of Normalities from
Titration Data
 
Example #2: Exactly 50.00 mL of an HCl solution required 29.71
mL of 0.03926 N Ba(OH)2 to give an end point with bromocresol
green indicator. Calculate the normality of the HCl.
Solution: no. meq HCl = no. meq Ba(OH)2

23
 Calculation of Normalities from
Titration Data
 
Example #2: Exactly 50.00 mL of an HCl solution required 29.71
mL of 0.03926 N Ba(OH)2 to give an end point with bromocresol
green indicator. Calculate the normality of the HCl.
Solution:

24
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
The molecular equation is

Na2C2O4(aq) + KMnO4(aq) + H2SO4(aq)  Na2SO4(aq) + K2SO4(aq)

+ MnSO4(aq) + H2O(l) + CO2 (g)

25
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
The ionic equation is

2Na+ + C2O42- + 2K+ + MnO4- + 8H+ + 3SO42-  2Na+ + SO42- + 2K+ +

SO42- + Mn2+ + SO42- + 4H2O + 2CO2

26
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
The net ionic equation is

2Na+ + C2O42- + 2K+ + MnO4- + 8H+ + 3SO42-  2Na+ + SO42- + 2K+ +

SO42- + Mn2+ + SO42- + 4H2O + 2CO2

27
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
The net ionic equation is

C2O42- + MnO4- + 8H+  Mn2+ + 4H2O + 2CO2

28
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
The reduction half-reaction is
7+ 2- 1+ 2-

MnO4- + 8H+ + 5e-  Mn2+ + 4H2O

29
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?

The oxidation half-reaction is

3+ 2- 4+ 2-

C2O42-  2CO2 + 2e-

30
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol) was
titrated with 43.31 mL of KMnO4. What is the normality of the
KMnO4 solution?

The overall reaction is

(MnO4- + 8H+ + 5e-  Mn2+ + 4H2O) x 2

(C2O42-  2CO2 + 2e-) x 5

31
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol) was
titrated with 43.31 mL of KMnO4. What is the normality of the
KMnO4 solution?

The overall reaction is

2MnO4- + 16H+ + 10e-  2Mn2+ + 8H2O

5C2O42-  10CO2 + 10e-

32
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?

The overall reaction is

2MnO4- + 16H++ 5C2O42-  2Mn2+ + 8H2O + 10CO2

33
 Calculation of Normalities from
Titration Data
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
2MnO4- + 16H++ 5C2O42-  2Mn2+ + 8H2O + 10CO2
Solution: At the equivalence point in the titration:
no. meq Na2C2O4 = no. meq KMnO4

34
 Calculation of Normalities from
Titration Data
 
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
Solution:

35
 Calculation of Normalities from
Titration Data
 
Example #3: A 0.2121-g sample of pure Na2C2O4 (134.00 g/mol)
was titrated with 43.31 mL of KMnO4. What is the normality of
the KMnO4 solution?
Solution:

36
Calculation of the Quantity of
Analyte from Titration Data
Example #4: A 0.8040-g sample of an iron ore was dissolved
in acid. The iron was then reduced to Fe2+ and titrated with
47.22 mL of 0.1121 N (0.02242 M) KMnO4 solution. Calculate
the results of this analysis in terms of (a) percent Fe (55.847
g/mol) and (b) percent Fe3O4 (231.54 g/mol). The reaction of
the analyte with the reagent is described by the equation

37
 
Example #4: A 0.8040-g sample of an iron ore was dissolved in
acid. The iron was then reduced to Fe2+ and titrated with 47.22
mL of 0.1121 N (0.02242 M) KMnO4 solution. Calculate the
results of this analysis in terms of (a) percent Fe (55.847
g/mol) and (b) percent Fe3O4 (231.54 g/mol). The reaction of
the analyte with the reagent is described by the equation

Solution:
(a) At the equivalence point, we know that
no. meq KMnO4 = no. meq Fe2+ = no. meq Fe3O4

38
  Example #4: A 0.8040-g sample of an iron ore was dissolved in acid. The iron was
then reduced to Fe2+ and titrated with 47.22 mL of 0.1121 N (0.02242 M) KMnO4
solution. Calculate the results of this analysis in terms of (a) percent Fe (55.847
g/mol) and (b) percent Fe3O4 (231.54 g/mol). The reaction of the analyte with the
reagent is described by the equation

Solution:

◦ = 36.77%

39
  Example #4: A 0.8040-g sample of an iron ore was dissolved in acid. The iron was
then reduced to Fe2+ and titrated with 47.22 mL of 0.1121 N (0.02242 M) KMnO4
solution. Calculate the results of this analysis in terms of (a) percent Fe (55.847
g/mol) and (b) percent Fe3O4 (231.54 g/mol). The reaction of the analyte with the
reagent is described by the equation

Solution:

40
Calculation of the Quantity of
Analyte from Titration Data
Example #5: A 0.8040-g sample of an iron ore was dissolved
in acid. The iron was then reduced to Fe2+ and titrated with
47.22 mL of 0.1121 N (0.02242 M) KMnO4 solution. Calculate
the results of this analysis in terms of (a) percent Fe (55.847
g/mol) and (b) percent Fe3O4 (231.54 g/mol). The reaction of
the analyte with the reagent is described by the equation

41
Calculation of the Quantity of
Analyte from Titration Data
Example #5: A 0.4755-g sample containing (NH4)2C2O4 and
inert compounds was dissolved in water and made alkaline
with KOH. The liberated NH3 was distilled into 50.00 mL of
0.1007 N (0.05035 M) H2SO4. The excess H2SO4 was back-
titrated with 11.13 mL of 0.1214 N NaOH. Calculate the
percentage of N (14.007 g/mol) and of (NH4)2C2O4 (124.10
g/mol) in the sample.

42
  Example #5: A 0.4755-g sample containing (NH4)2C2O4 and inert
compounds was dissolved in water and made alkaline with KOH. The
liberated NH3 was distilled into 50.00 mL of 0.1007 N (0.05035 M)
H2SO4. The excess H2SO4 was back-titrated with 11.13 mL of 0.1214
N NaOH. Calculate the percentage of N (14.007 g/mol) and of
(NH4)2C2O4 (124.10 g/mol) in the sample.
Solution:
At the equivalence point, the number of milliequivalents of acid and
base are equal. In this titration, however, two bases are involved:
NaOH and NH3. Thus,

43
  Example #5: A 0.4755-g sample containing (NH4)2C2O4 and inert
compounds was dissolved in water and made alkaline with KOH. The
liberated NH3 was distilled into 50.00 mL of 0.1007 N (0.05035 M)
H2SO4. The excess H2SO4 was back-titrated with 11.13 mL of 0.1214
N NaOH. Calculate the percentage of N (14.007 g/mol) and of
(NH4)2C2O4 (124.10 g/mol) in the sample.
Solution:

44
  Example #5: A 0.4755-g sample containing (NH4)2C2O4 and inert
compounds was dissolved in water and made alkaline with KOH. The
liberated NH3 was distilled into 50.00 mL of 0.1007 N (0.05035 M)
H2SO4. The excess H2SO4 was back-titrated with 11.13 mL of 0.1214
N NaOH. Calculate the percentage of N (14.007 g/mol) and of
(NH4)2C2O4 (124.10 g/mol) in the sample.
Solution:

= 10.85%

45
Example #5: A 0.4755-g sample containing (NH4)2C2O4 and inert
compounds was dissolved in water and made alkaline with KOH. The
liberated NH3 was distilled into 50.00 mL of 0.1007 N (0.05035 M)
H2SO4. The excess H2SO4 was back-titrated with 11.13 mL of 0.1214
N NaOH. Calculate the percentage of N (14.007 g/mol) and of
(NH4)2C2O4 (124.10 g/mol) in the sample.
Solution:
The number of milliequivalents of (NH4)2C2O4 is equal to the number
of milliequivalents of NH3 and N, but the milliequivalent weight of
the (NH4)2C2O4 is equal to one half its molar mass. Thus,
mass (NH4)2C2O4 = (50.00 x 0.2007 – 11.13 x 0.1214) meq x 0.12410
g/2 meq

46
  Example #5: A 0.4755-g sample containing (NH4)2C2O4 and inert
compounds was dissolved in water and made alkaline with KOH. The
liberated NH3 was distilled into 50.00 mL of 0.1007 N (0.05035 M)
H2SO4. The excess H2SO4 was back-titrated with 11.13 mL of 0.1214
N NaOH. Calculate the percentage of N (14.007 g/mol) and of
(NH4)2C2O4 (124.10 g/mol) in the sample.
Solution:
percent (NH4)2C2O4
=
= 48.07%

47
Exercises
1. Find the normality of a solution containing 6.34 g of ascorbic acid in 250.0 mL if the relevant
half-reaction is

Ans. 0.288 N
2. How many grams of potassium oxalate should be dissolved in 500.0 mL to make a 0.100 N
solution for titration of MnO4-? Ans. 4.15 g

48
Exercises
3. A solution containing 25.0 mL of oxalic acid required 13.78 mL of 0.041 62 N KMnO 4 for
titration, according to the reaction below. Find the normality and molarity of the oxalic acid.

Ans. 0.022 94 equiv/L; 0.011 47 M

4. A 50.0-mL sample of calcium hydroxide solution required 19.50 mL of a 0.1050 N hydrochloric
acid solution to neutralize it. Calculate the amount of Ca(OH)2 in 100 mL of the solution (%w/v).
Ans. 0.152 g per 100 mL
5. Answer Questions and Problems nos. 1 to 6 found in page 75 of your book.

49