Volumetric Analysis

Raju Bhattarai
 Terms used in volumetric Analysis
Equivalent weight : It is defined as the no. of parts by weight of a chemical substance
which combines with or is displaced by 1.008 parts of hydrogen, 8 parts by weight of
oxygen or 35.5 parts by weight of chlorine.
Basicity: The number of replaceable hydrogen atoms present in a mole of an acid is called
Basicity of an acid.
Acidity: The number of replaceable hydroxyl ion present in a mole of base is called acidity
of a base.
Titration: The process in which the concentration of unknown solution is determined with
the help of standard solution by using suitable indicator is called titration.
Normality: The number of gram equivalents of a solute dissolved in a liter of a solution is
called its normality. It is denoted by N.
Normal solution(1N):The solution containing one gram equivalent of solute present in a
liter of solution is called normal solution.
Molarity: The number of moles of a solute dissolved in a liter of a solution is called its
Molarity. It is denoted by M.
Acidimetry: The process of determining the strength of acid in a solution,
by titrating against known strength of base in presence of suitable indicator is
called acidimetry.
Alkalimetry: The process of determining the strength of base in a solution,
by titrating against known strength of acid in presence of suitable indicator is
called alkalimetry.
Redox Titration : The titration in which oxidation and reduction takes place is
known as redox titration. For Example: titration between KMnO4 and Oxalic
acid
Titrant :The solution of known concentration usually taken in a burette is called
titrant.
Titrand: The solution of unknown concentration usually taken in a conical flask
is called titrand.
Indicator: A chemical substance which indicates the end point of reaction by
changing color is called Indicator. Eg: methyl orange, litmus paper etc.
Equivalence point : The point at which the number of gram equivalent of titrant
is equal to the number of gram equivalent of titrand is called equivalence point .
It is also called theoretical end point.
End point : The point at which the reaction is completed which is indicated by
the change of color of indicator is called end point. It is also called practical end
point.
Titration error :The difference between end point and equivalence point is called
titration error.
Normality factor :The normality factor of a solution is defined as the ratio of
actual weight of solute taken to the theoretical weight of solute to be taken.
Normality factor(f)  = weight of solute taken /weight of solute to be taken
Primary standard substances: The substance whose standard solution can be
prepared directly by weighing fixed amount of solute in fixed volume of solution
is known as primary standard substances.
E.g.: Oxalic acid crystals, Na2CO3(anhydrous), K2Cr2O7, AgNO3, etc.
Requisites for substance to be a primary standard substance
• it should be available in pure state,
• its composition should be constant during storage and weighing,
• should be soluble in water and not be decomposed by water
• should have high equivalent weight to minimize weighing error and
• should not be hygroscopic or deliquescent.
Primary standard solution : The solution prepared by directly weighing fixed
amount of primary standard substance in fixed volume of solution is known as
primary standard solution.
E.g. : Oxalic acid solution , K2Cr2O7
Secondary standard Substance : The substance whose standard solution can’t be prepared
directly by weighing is called secondary standard solution.
For E.g. KMnO4 , NaOH. etc
Secondary standard Solution : The solution prepared from secondary standard substance and
the actual strength is determined by titrating with primary standard solution are secondary
standard solution.
For E.g. KMnO4 Solution , NaOH solution, HCl solution ,H2SO4 solution. etc
Normality Equation : During chemical reaction, substances react in definite ratio of their
equivalent weight. Hence principle of volumetric analysis is supposed to be based on chemical
equivalent (eq. wt) of substance. During complete reaction,
No. of gm equivalent of acid=No. of gm equivalent of base -------(i)
Normality of acid =  ( No. of gm eq. of acid ) / (volume of acid solution (in litre))
so, No. of gm equivalent of acid= Normality for acid X volume of acid solution (in lit)
Similarly.
No of gm equivalent of base= Normality for base X volume of base solution (in lit)………(ii)
Let us represent normality for acid by N1, Normality of base by N2 and v1 and v2 be their
From equation (i) and (ii) we get
V1N1=V2N2
• Selection of Indicator in acid –Base Titration
A chemical substance which indicates the end point of reaction by changing color is called Indicator. Eg: methyl
orange, litmus paper etc. An acid – base titration is usually of four types and each sets a definite criteria for
selection of indicators. The selection of indicator should be done in a such a way that the equivalence point of
titration should coincides the pH range of an indicator. The selection of suitable indicator on different types of acid –
base titration can be explained on the basis of titration curve(pH curve)
a. Titration involving strong acid and strong base:
In this type of titration ,The pH curve is shown by ABCD where the equivalence point lies in pH range of 3-11 . Hence
both phenolphthalein or methyl orange can be used.
b. Titration involving strong acid and weak base:
In this type of titration the equivalent point lies on the pH range of 3 to 8 and pH curve is shown by ABGH . So,
indicator like methyl orange can be used . 
c. Titration involving strong base and weak acid:
The titration has equivalent point in the pH range of 6 to 11 and and pH curve is shown by EFCD . Hence, indicator
like phenolphthalein can be used.
d. Titration involving weak acids and weak base.
Since, there is no sharp change in pH, accurate measurement of end point in this case is not shown by indicators.
Generally such type of titration in not conducted.
 Questions
1. Distinguish between end point and equivalence point of a titration.
2. X g of metal (equ wt =12) was completely dissolved in 100 cc of N/2 HCl. The
volume was then made up to 500 mL. 25 mL of the diluted acid required 17.5
mL of N/10 NaOH for complete neutralization. Find the value of X.
Ans =0.18g
3. Define the following terms
4. (a) gram/liter (b) normality (c) decinormal solution (d) molarity (e) molality
(f) normality factor
5. Define acidimetry? A solution of Conc. HCl contains 38 % of acid by mass.
(i)What is the molarity of the solution if the density of the solution is 1.19 g/cc
and ans:12.38
(ii) what is the volume of HCl required to neutralize 1 L of 0.1 M NaOH solution?
Ans: 8.077
6. Define the term normality and normality factor.
7. Define normality and molarity and write the relation between them.
8. A commercial sample of sulphuric acid has specific gravity of 1.8. 10 mL of this
acid was diluted to1 L with water. 10 mL of diluted acid required 30 mL of N/10
NaOH for complete neutralization. Calculate the purity of the acid. Ans: 82%
9. Calculate the normality and molarity of 5% NaOH solution ans:1.25
10.Which of the following is has high concentration
11. i) 60 g /l of NaOH and 2M NaOH solution ii) 5.3 g/l of Na2CO3 and N/5 Na2CO3.
12.How is indicator choosed in acid base titration? 0.8 g of a divalent metal was
dissolved in 100 ml of 1.28 N HCl. After the metal was carefully dissolved the
mixture was diluted to 200 ml. 50 ml of the diluted acid required 54.6 ml of 0.22
N NaOH for complete neutralization. Calculate the atomic weight of metal.
Ans:20
13.Calculate the weight of 90% pure CaCO3 required to react with 2liters of 0.1N
HCl solution. Ans : 11.11
14.Define semi-normal solution. 3 g of a trivalent metal was completely
dissolved in 750ml of 1NHCl. The resulting solution required 1000 ml of
N/2 NaOH for complete neutralization. Find the atomic mass of metal.
Ans:36
15.What volume of 5% NaOH solution is required to neutralize 2 liters of
decinormal HCl solution? Ans: 160 ml
16.X g of metal (eq.wt=12) react with 20 ml of N(f=0.95)acid. Calculate the
value of X. Ans :0.228 g
17.If 20ml of 0.5 N NaOH is mixed with 30 ml of 0.3 N HCl. Will the
resulting solution acid ,basic or neutral. Ans :Basic 0.02
18.Calculate the weight of anhydrous sodium carbonate required to make
250ml of N/20 solution. Ans: 0.6625 g
19.What volume of N/2 and N/10 HCl must be mixed to give 2 litre of N/5
HCl ? Ans: 0.5,1.5L
20.What volume of 12 M NaOH and 2M NaOH should be mixed to get 2
litre of 9M NaOH solution. Ans: 1.4,0.6
21. 28.4 g of NaOH was added to 20 cc of 2N H2SO4 solution and the volume
was diluted to one litre .Predict whether the dilute solution is acidic, basic or
neutral .Also calculate the resulting strength of diluted solution in g/l.
Ans: basic, 26.8
22. Calculate the resulting normality of solution prepared by mixing 20ml of
0.8M NaOH with 25 ml of 0.4M H2SO4. Ans:0.089
23. 1 g of ordinary sample of limestone dissolved in 16.6 cc of 0.92N HCl leaving
some sandy residue. Calculate the percentage of pure CaCO3 in the sample.
Ans: 76.36%