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Volumetric Assignment

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VOLUMETRIC ANALYSIS
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Chemical analysis is kept under two heads
i) Qualitative ii) Quantitative
1.Qualitative:- Which involves the detection or identification of the constituents in
the given substance or mixture of substances.
2.Quantitative:- Which deals with the actual estimation of an element or a com-
pound or a radical present in the given sample. Of the various methods of quantitative
estimations, volumetric is one of them. It involves the measurement of volumes of the
solutions of reacting substances. From the measured volumes of solutions of the two
and knowing the concentration of one, the concentration of the other can be calcu-

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lated using appropriate mathematical formulae.

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Titration:- The process of adding one solution from the burette to another present in
the conical flask until the reaction is completed.
Titrant:- The solution taken in the burette.
Titrate:- The solution taken in the conical flask.

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End Point:- The point in a titration usually indicated by a change of colour of an

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indicator at which a particular reaction is completed.

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Indicator:- The substance, by a sharp colour change indicates the completion of a
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chemical reaction,
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1.When KMnO4 is used as the tittant in a redox reaction itself acts as an indicator.
(It is a self indicator)
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2. When Fe2+ vs K2Cr2O7 titration is carried out diphenylamine is the indicator and it
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gives violet colour at the end point due to the oxidisation of the indicator
zC
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2 NH N N +2H
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en

diphenylamine diphenylbenzedine violet


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3. In case of Iodo and Iodimetric titrations starch is the indicator that forms blue
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coloured complex with Iodine


4. When a chloride is titrated against AgNO3, Potasium chromate (K2CrO4) is use as an
idicator
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5. Acid-Base indicators............ refer page 6


Different types of titration:-
i) Acid-base titration or Neutralisation titration:- Involve the titrations of solutions
of acids against solutions of bases or vice versa.[Leading to the formation of salt and
water]
ii) Redox titration:- Which involve the titrations of solutions of oxidants against the
solutions of reductants or vice versa.
iii) Iodometric:- It involves the titration of liberated iodine in a quantitative reaction
against standard solutions of reducing agents such as sodium thiosulphate.
iv) Iodimetric:- Titrations involving standard solutions of iodine.
[Iodo - and Iodi - are also part of Redox titrations]
Chemistry >>1<<
Volumetric Assignment
v) Precipitation titrations: During the titration the precipitation of a particular com-
ponent occurs.

ex: BaC 2 H2SO4 BaSO4 2HC ; AgNO3 NaC AgC NaNO3 etc.
Note:- Chemical reactions are represented by means of balanced chemical equations.
In a balanced equation the number of moles of the reacting substances might differ,
but the number of equivalents of reacting substances will remain the same. i.e. one
equivalent of one substance completely reacts with one equivalent of another
substance
For a given reaction:-
n1 A n 2 B n 3 C n 4 D

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eq. of A eq. of B eq. of C eq. of D

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or meq of A meq of B meq of C meq of D
(Equal volumes of equinormal solutions react completely)
Equivalent Mass:- Equivalent mass of a substance depends upon the nature of the

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chemical reaction in which the substance takes part. The equivalent mass of sub-

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stance expressed in grams is known as gram equivalent mass. One gram equivalent

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mass is one equivalent.

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Equivalent mass is that much mass of a substance which can combine with or can be
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replaced by 1.008 parts by mass of hydrogen or 8 parts by mass of oxygen or 35.5 parts

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by mass of chlorine
Equivalent Masses of Various Substances:- j
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Atomic Mass
a) Equivalent mass of an Element ...........
Valence
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M.Mass of the acid


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b) Equivalent Mass of an acid ....................


Basicity
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Acids have basicity which is the number of replaceable Hydrogen atoms.


or
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Basicity of an aicd is the number of H+ ions furnished by a molecule of an acid


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M.Mass of the base


c) Equivalent mass of a base ...................
acidity
Bases have acidity which is the number of replaceable hydroxyl ions.
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or
Acidity is the number of hydroxyl ions furnished by a molecule of a base
M.Mass of the salt
d) Equivalent Mass of a salt ...................
Total No.of units of ve or ve ch arg es
e) Equivalent Mass of an oxidizing agent:
An oxidizing agent is one that oxidises the other self undergoing reduction. It accepts
electrons
M.Mass of the O.A
Equivalent mass
No.of moles of Electrons accepted by one mole of it
f) Eq. Mass of reducing agent ..........
A reducing agent is one that reduces the other self undergoing oxidasation
It gives out electrons
Chemistry >>2<<
Volumetric Assignment

M.Mass of the R.A


Equivalent mass
No.of moles of Electrons given out by one mole of it
Formula weight of an ion
g) Equivalent Mass of an ion .........
Ch arg e carried by the ion
Molecular mass of acidic salt
h) Equivalent mass of an acidic salt ......
No.of replaceable H atoms in it

M.Mass
i) Equivalnet Mass of a basic salt............
No.of replaceable OH ions of it

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atomic mass
j) Equivalent mass of an elemenet
valence

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Solution:- A solution is a homogeneous mixture of two or more components. If there
are only two components it is said to be a binary solution. The one which is relatively
lower in concentration is said to be the solute and the other one is the solvent. The
concentrations of the solutions are expressed in different ways.

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Different ways of expressing concentrations:

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1. Molarity (M):- Number of moles of the solute present per litre of the solution or

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number of millimoles present per mL of the solution.
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In case w grams of solute of molecular mass W is present in V - mL of the solution,
then
w 1000
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Molarity, M .
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W V
In case the mass of V - mL of solution is x-grams and the density of the solution is d
irc

g/mL, then
zC
ar R

w 1000.d
M .
W x
Ne E
en

2. Normality(N):- Number of equivalents of solute present per litre of solution or


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number of milli equivalents present per mL of solution.


In case w g of solute of equivalent mass E is dissolved in V - mL of solution
AS

w 1000
N .
E V
Normality = Molarity Z,
M

M.Mass
where Z - is the valence factor
Eq.Mass
Molarity M.Mass
Normality
Eq.Mass
Eq. mass Normality = M.Mass Molarity
Note:- Normality and Molarity are temperature dependent.
3. Molality(m):- Number of moles of solute present per 1000g of solvent.
In case w g of solute of M.Mass M is dissolved in X g of solvent, then
w 1000
then molality m .
M X
Chemistry >>3<<
Volumetric Assignment
4. Mole fraction (x):- It is the ratio between the number of moles of a particular
component to the total number of moles of various components in the mixture. If a
given mixture contains
n1 moles of 1st component
n2 moles of 2nd component
n3 moles of 3rd component and so on
Total number of moles, n = n1 + n2 + n3 + ...........
n1
mole fraction of 1st , x1
n
n2
mole fraction of 2nd, x 2

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and so on
n

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Sum of the mole fractions of the various components in a solution is always equal one.
Molality and mole fraction are temperature independent.
Ex:- A given sample of Urea is of 4.5 molal. Find the molefraction of Urea
[M.M of Urea = 60 and density of water: 1.0 g/mL

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Solution:-

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Urea = 4.5 moles

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Mass of water = 1000 g 55.5 moles

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Total number of moles = 55.5 + 4.5 = 60

4.5
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Molefraction of Urea = 0.075
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60
le,

5. Parts per million:- It is used to express the concentration of a solution when the
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solute is present in a very samll amount in solution. ppm is the number of parts of
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solute present per one million parts of solvent.


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Mass of solute
Amount of a solute in solution in terms of ppm 106
Mass of solvent
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Amounts of solute and solvent are to be expressed in the same units i.e. either in
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grams, milligrams, kgs etc


Example:-
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A sample of seawater contains 5.8 moles of Bromide ion in 10 3 kg. Calculate the
concentration of Bromide ion in ppm (At. mass of Bromide = 80)
Solution:
103 kg 106 g
106 g contains 5.8 moles
5.8 moles of Bromide ion 5.8 80 = 464g
Concentration of Bromide ion in ppm = 464
Example:-
A given sample of seawater contains Lithium ion and its concentration is 1.9 ppm.
Calculate the number of moles of Lithium ion present in 10 kg of water (At. mass of
Lithium = 7)

Chemistry >>4<<
Volumetric Assignment
Solution:-
concentration of Li+ = 1.9 ppm
106 g of seawater contains 1.9g of Lithium ion

1.9 104
+ 4
mass of Li in 10 kg i.e. 10 g of seawater = 6
1.9 102 g
10

2 1.9 10 2
1.9 10 g moles 2.7 10 3 moles of Li+
7
6. Percentage (w/v):- Mass of solute in grams present per 100 mL of solution

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Ex:- 10% of solution by (w/v) i.e., 100 mL solution contains 10g of solute
7. Percentage(w/w):- Mass of solute in grams present per 100g of solution.

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Ex:- 98% by mass i.e., every 100g of solution contains 98g of solute
In case percentage by mass of solute and density(d) of the solution are given, then

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% 10 d

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molarity, M

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M.Mass of solute

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8. Percentage (v/v):- Volume of solute in mL per 100 mL of the solution.
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Ex:- 20% by volume i.e., every 100 mL solution contains 20 mL solute
Strength of solution = Normality Eq. Mass .....g/L
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Strength of solute = Molarity M.Mass ...........g/L
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Standard solution:-
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A solution of known concentration is said to be a standard solution.


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Exactly a known mass of a sample is dissolved and the solution is made upto a
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specified volume and normality or molarity is calculated.


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A normal solution is a standard solution. But a standard solution need not always be a
normal solution
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Primary standard substance:-


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Any substance used for preparing such a standard solution as said above is known as a
primary standard substance and it should satisfy the following criteria:
a) Available in pure crystalline form.
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b) neither hygroscopic nor efflorescent.


c) inert to atmosphere i.e. no reaction with atmospheric gases such as CO2 or O2 etc.
d) having high equivalent mass or molecular mass
e) readily soluble in water.
f) its solution should be stable over a period of time.
A few examples of primary standard substances that satisfy the above conditions are:

COOH
a) | .2H 2 O b) Na2CO3 c) KCl d) K2Cr2O7 etc
COOH

Chemistry >>5<<
Volumetric Assignment

Secondary standard substance:- Any substance that doesnt satisfy the above condi-
tions is treated as a secondary standard substance.Different substances will have
different reasons for not being considered as primary standard substances
Ex:-
KMnO4 - cannot be used as a primary standard since.
a) it is difficult to get it absolutely free from MnO2
b) Also solutions of KMnO4 get contaminated with MnO2 over a period of time.
NaOH is not a primary standard substance since it is hygroscopic. Like wise
Na2S2O3.5H2O is efflorecent in nature. HCl is a gas. FeSO4 undergoes areal oxidation
etc

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Equivalence formula:-

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Equal volumes of equinormal solutions react completely with one another.
If N1 is the normality of 1st solution and V1 be its volume
N2 is the normality of the 2nd solution and V2 is its volume

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N1V1

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no. of equivalents present in V1 mL solution =
1000

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N2 V2
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similarly for the second solution =

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1000
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Since number of equivalents of the reacting substances are same
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N1 V1 N2 V2
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or V1N1 = V2N2
1000 1000
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no of meq of 1st = no of meq of 2nd


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b) V1M1 = V2M2 is meant for dilution and also for such of the solutions where equivalent
mass of a substance is equal to its molecular mass.
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Hydrogen ion - indicators:-


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These are also kown as acid base indicators or pH-indicators. These substances
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change their colours depending upon the pH of the medium to which they are added.
They are generally weak organic acids or weak organic bases. Phenolphthalein is a
weak organic acid.The ionised form of phenolphthalein gives pink colour and unionised
form gives no colour. Similarly, methyl orange is a weak organic base. Its ionised form
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gives pale orange colour and unionised form gives yellow colour.


H In
HIn

[H ][In ]
K ln
[HIn]
where Kln is known as indictor constant [Dissociation constant of indicator]
[HIn]
[H ] K ln
[In ]
[HIn]
log[H ] log K ln log
[In ]

Chemistry >>6<<
Volumetric Assignment

[In ] [In ]
pH pK ln log or log pH pK ln
HIn HIn
Thus the ratio of the two forms is dependent upon the pH of the solution.
[In ]
If 10, pH pK ln 1
HIn
[In ] 1
If , pH pK ln 1
HIn 10
Thus pH = pKln 1 and it is known as pH- range of the indicator
Thus the working pH range of any indicator is roughly two units around pKln value.

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Each indicator shows distinctly different colours below pKln - 1 and above pKln + 1.

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With in the range of two units it is a mixed colour and one cannot identifie the
completion of titration
pH range of phenolphthalein is 8.3 to 10.2
Below 8.3, it gives no colour and above 10.2, it gives pink colour.

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Similarly, for methylorange the pH range is 3.3 to 4.9

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Below 3.3, it gives pale orange and above 4.9, it gives yellow colour

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Methyl red 4.4 to 6.2 (Red and Yellow) Thymol Blue: 8.0 to 9.6 (yellow and blue)

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The suitability of an indicator for a given acid base titration is judged from
i) pH - range of the indicator. j
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ii) pH of the resulting solution when the neutralization is completed


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Ex:- a) When a strong acid is neutralised by a strong base, the pH of the resulting
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solution is 7.
zC
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b) When a weak acid is neutralised by a strong base, the pH of the resulting is


greater than 7 due to the hydrolysis of the salt formed [salt of St. Base Vs Weak acid]
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c) When a weak base is neutralised by a strongacid, the pH of the resulting is


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less than seven due to the hydrolysis of the salt formed [salt of weak base Vs st. Acid]
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d) The titration of a weak acid Vs weak base gives no sharp transition and hence no
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suitable indicator
Hydrogen peroxide as a volumetric Reagent:-
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Hydrogen peroxide (H 2O2) is a unique inorganic compound that it acts both as an


oxidizing agent as well as a reducing agent both in acidic as well as in alkaline me-
dium.
The relevant reactions are:

As a oxidizing agent: H 2 O2 2H 2e 2H 2 O (acidic medium)

O2 H H 2 O 2e 3OH (Basic medium)

as a reducing agent: H 2 O2 O 2 2H 2e (Both acidic as well as in basic medium)

M .Mass 34
Eq. mass 17
No.of electrons given out or accepted by it 2

Chemistry >>7<<
Volumetric Assignment
It is too difficult to get 100% pure hydrogen peroxide. The concentration of H2O2 solu-
tion is expressed in terms of volume strength, such as 10V, 15V, 100V etc.
A 10V hydrogen peroxide means - one mL solution contains that much mass of hydro-
gen peroxide which on decomposition gives out oxygen that measures 10 mL at NTP.

2H2O2 2H2O O2
2 34g 22400mL at NTP

2 34 10
Mass of H2O2 that gives 10 mL of Oxygen = g
22400

2 34 10

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i.e. 1 mL solution contains: g of H2O2
22400

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2 34 10 1000
Mass of H2O2 in 1000 mL solution = g
22400

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2 34 10 1000

a
Molarity 0.891

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22400 34

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Normality = 2 0.891 = 1.782 and % by mass = 3.03
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w
10V H 2O 2 0.891M 1.782N 3.03%
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Based upon this one can calculate the concentration of solutions of different
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volume strength
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As an oxidizing agent:-
To a solution of Hydrogen peroxide excess of KI when added in acid medium, iodide is
zC
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oxidized to free iodine and the liberated iodine is titrated against standard sodium
thiosulphate solution.
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en

O.A : Hydrogen peroxide and R.A: potasssium Iodide.


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T

H 2 O2 2H 2I 2H 2 O I 2
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I2 2Na 2 S2 O3 Na 2 S4 O6 2NaI

I 2 2S2 O 32 S4 O 62 2I
M

No. of meq of H2O2 meq of Iodine meq of Na2S2O3


As a reducing agent:-
Acidified KMnO4 Vs H2O2
O.A. : Acidified KMnO4
R.A. : Hydrogen peroxide
[MnO 4 8H 5e Mn 2 4H 2 O] 2
[H 2 O2 O 2 2H 2e ] 5
Add: 2MnO 4 6H 5H 2O 2 2Mn 2 8H 2 O 5O 2

No. of meq of MnO 4 meq of H2O2

Chemistry >>8<<
Volumetric Assignment
Solved Examples:
A bottle of H2O2 solution is labelled as x - volume. 25 mL of the this solution is trans-
ferred into a 250 mL volumetric flask and the solution is made upto the mark. To 20 mL
of this solution excess of KI is added in acid medium and the liberated iodine required
25 mL of 0.1N sodium thiosulphate. Find the value of x.
Solution:-
no of meq of thio = 25 0.1 = 2.5
20 mL of dilute solution contains 2.5 meq of H2O2
2.5 250
no of eq of H2O2 in 250 mL of made up solution 31.25
20

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i.e, 25 mL of bottle solution contains 31.25 meq.
no. of meq per mL solution is the normality

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31.25
Normality of bottle solution = 1.25
25
1.782 N solution of H2O2 10V

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10 1.25
The volume strength of 1.25 N solution of H2O2

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7.0

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1.782

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x = 7.0
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Example:-2.

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1.0g sample of H2O2 solution containing x percent of H2O2 by mass requires x mL of
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KMnO4 in acid medium for oxidation. Calculate the normality of KMnO4 solution.
Solution:-
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le,

1 x
mass of H2O2 in 1g sample 0.01 g
irc

100
zC

Eq mass of H2O2 = 17
ar R

0.01x 103
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meq of H2O2
17
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Let the normality of KMnO4 = N


no. of meq. of KMnO4 = x N
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0.01x 103
xN or
17
M

10
N 0.588
17
BOTH KMnO4 AND K2Cr2O7 ACT AS OXIDIZING AGENTS IN ACIDIC MEDIUM.
For acidifying KMnO4:

i) HCl cannot be used since Cl is oxidised by MnO4

ii) HNO3 cannot be used since HNO3 itself is an oxidizing agent.


iii) Only H2SO4 is used to acidify KMnO4
For acidifying K2Cr2O7:
i) HNO3 cannot be used since itself is an oxidizing agent.
ii) Either HCl or H2SO4 can be used for acidifying K2Cr2O7
Chemistry >>9<<
Volumetric Assignment

SOME USEFUL IMPORTANT CHEMICAL REACTIONS IN VOLUMETRIC ANALYSIS


1. KMnO4 acts as an oxidizing agent in acidic, alkaline or even in neutral medium and
the relevant reactions are:
acid medium: MnO4 8H 5e Mn2 4H 2O

M.Mass 158
Eq. Mass 31.6
5 5
2. Alkaline medium or neutral medium:
2 KMnO4 2 KOH 2 K 2 MnO4 H 2O (O ) ...................(A)
MnO4 e MnO42

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[ Reduction product is K2MnO4 and there is only one electron transfer and hence for
this step, equivalent mass and molecular mass are same for KMnO4]

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2K 2 MnO4 2H 2O 2MnO2 4KOH 2(O) .......................(B)
........................................................................................
2KMnO4 H 2O 2MnO2 2KOH 3(O) (on adding A & B)

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........................................................................................

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Or Ionically: MnO 4 2H 2 O 3e MnO 2 4OH

Vi A
M.Mass 158

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Eq. Mass of KMnO4 in alkaline or neutral medium 52.66
3 3
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(Reduction product of MnO4 is MnO2)
3. Reaction between acidified KMnO4 Vs SO2
2KMnO4 3H 2SO4 K 2SO4 2MnSO4 3H 2O 5(O)
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SO 2 O H 2 O H 2SO4 5
irc

2KMnO4 5SO2 2H2 O K 2SO4 2MnSO4 2H 2SO4


zC
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(or) 2MnO4 5SO2 2 H 2O 5SO42 2 Mn2 4 H

2MnO 4 5SO 32 6H 2Mn 2 5SO 24 3H 2 O


Ne E
en

meq of KMnO4 meq of SO2


B
T

M.Mass M.Mass
AS

Eq. Mass of KMnO4 = ; Eq. mass of SO2


5 2
4. Acidified KMnO4 Vs oxalic acid
MnO4 is the oxidizing agent and oxalic acid is the reducing agent
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MnO 4 8H 5e Mn 2 4H 2O

COO 2
| 2CO2 2e
COO
Equalising the number of electrons and on adding
2
2MnO 4 5COO
| 16H 2Mn 2 10CO2 8H 2 O
COO

M.Mass M.mass
Eq. mass of oxalic acid and that of KMnO4 =
2 5
Meq of KMnO4 meq of oxalic acid
Chemistry >>10<<
Volumetric Assignment
5. Acidified KMnO4 Vs Hydrogen peroxide
Oxidizing agent = KMnO4
Reducing agent = H2O2
2KMnO4 3H 2SO4 K 2SO4 2MnSO4 3H 2O 5(O)
5[H2 O2 H 2O O]
Add: 2 KMnO4 3H 2 SO4 5 H 2O2 K 2 SO4 2 MnSO4 8 H 2O 5O2

[MnO 4 8H 5e Mn 2 4H 2 O] 2

[H 2 O2 O 2 2H 2e ] 5

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2MnO 4 5H 2 O 2 6H 2Mn 2 8H 2 O 5O 2

EM
M.Mass M.Mass
Eq. Mass of H 2 O 2 and that of KMnO4
2 5
meq of H 2O2 meq of KMnO4

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6. Acidified KMnO4 Vs KI

a
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MnO4 - is the oxidizing agent

Vi A
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I - is the reducing agent
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[MnO 4 8H 5e Mn 2 4H 2 O] 2

[2I I 2 2e ] 5 j
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le,

2MnO 4 16H 10I 2Mn 2 8H 2O 5I 2


irc

Eq. mass of KI = M. Mass


7. Acidified KMnO4 Vs Fe2+
zC
ar R

MnO -4 8H 5e Mn 2 4H 2 O
Ne E
en

5Fe 2 5Fe 3 5e
B
T

MnO 4 8H 5Fe 2 Mn 2 5Fe 3 4H 2 O


AS

The ferrous is either from ferrous sulphate [FeSO 4.7H 2O] or ferrous ammonium
sulphate [FeSO 4.(NH4)2SO4.6H2O] which are the reducing agents.
Eq. mass of ferrous sulphate or ferrous ammonia sulphate corresponds to the respec-
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tive molecular masses (Since there is only one electron transfer)


8. KMnO4 oxidizes HCl, HBr and HI to free halogen in acid medium.
2KMnO4 3H 2SO4 10HX K 2SO4 2MnSO4 8H2 O 5X 2
(or) 2MnO 4 16H 10X 2Mn 2 8H 2O 5X 2
9. KMnO4 oxidizes HCl to free chlorine as per the eq.
2 KMnO4 16 HC 2 KC 2MnC 2 5C 2 8H 2O
10. KMnO4 oxidizes sodium thiosulphate to sodium sulphate in neutral medium:
3Na 2 S2 O3 8KMnO 4 H 2O 3Na 2SO 4 8MnO 2 3K 2SO 4 2KOH
M.Mass M.Mass
Eq. mass of KMnO 4 and Eq. mass of Na 2 S2 O3
3 8
Chemistry >>11<<
Volumetric Assignment
11. KMnO4 oxidizes As2O3 to ortho arsenic acid in acid medium.
4MnO 4 5As2 O 3 12H 9H 2 O 4Mn 2 10H 3 AsO 4
As2 O3 is the reducing agent
M.Mass M.Mass
Eq. mass of KMnO 4 and Eq. mass of As2 O3
5 4
Number of meq KMnO4 = number of meq of As2O3
12. KMnO4 reacts with MnSO4 in neutral medium as per the eq:
2KMnO4 3MnSO4 2H2 O K 2SO4 5MnO2 2H 2SO4
KMnO4 is the oxidizing agent
MnSO4 is the reudcing agent

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M.Mass M.Mass
Eq. mass of KMnO4 and Eq. mass of MnSO4
3 2

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(It is an example of comproportionation reaction)

13. 2KMnO4 (s) K 2 MnO4 + MnO2 + O2
1 mole of O2 4 equivalents and 2 moles of KMnO4 4 equivalents

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a
M.Mass
Eq. Mass of KMnO4

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2

Vi A
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14. Acidified KMnO4 Vs H2S
AC
KMnO4 is the oxidizing agent

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H2S is the reducing agent
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2KMnO4 3H2SO4 5H2S K 2SO4 2MnSO4 8H2 O 5S
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le,

(or) 2MnO 4 16H 5S2 2Mn 2 8H 2 O 5S


irc

H2S O H2 O S (or) S2 S 2e
zC
ar R

M.Mass 34
Eq. mass of H 2S 17
2 2
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en

15. MnO2 Vs oxalic acid in acidic medium


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T

MnO2 is the oxidizing agent


AS

oxalic acid or oxalate ion is the reducing agent


MnO 2 4H 2e Mn 2 2H 2 O
C2 O24 2CO 2 2e
M

..................................................................
MnO2 4 H C2O42 Mn2 CO2 H 2O
......................................................................
M.Mass M.Mass
Eq. mass of MnO2 ; Eq. mass of oxalic acid
2 2
16. a) MnO2 Vs HCl b) KI Vs Cl2 and c) I2 Vs Na2S2O3
a) MnO2 4 HC MnC 2 2 H 2O C 2
Oxidizing agent MnO2 and reducing agent Chloride ion
M.Mass
Eq. mass of MnO 2
2

Chemistry >>12<<
Volumetric Assignment

b) 2KI C 2 2KC I 2
M.Mass
Eq. mass of KI
1
M.Mass atomic mass
Eq. mass of C 2 or
2 1
Iodide is oxidized by chlorine i.e. chlorine is the oxidizing agent
c) 2Na 2 S2 O3 I 2 Na 2 S4 O6 2NaI
Reducing agent = Na2S2O3
Oxidizing agent = I2
M.Mass
Eq. mass of Na 2 S2O3 and Eq. mass of Iodine = its atomic mass

Y
1
Meq of MnO2 meq of Cl2 meq of I2 meq of Na2S2O3

EM
17. MnO2 Vs Ferrous Sulphate:
MnO 2 2Fe 2 4H Mn 2 2Fe 3 2H 2O
M.Mass M.Mass
Eq. mass of FeSO4 and Eq. mass of MnO2

D
1 2

a
18. MnO2 Vs H2O2 in acid medium:

ad
MnO2 is reduced to Mn2+ by H2O2 in presence of an acid

Vi A
aw
MnO 2 H 2 O2 2H Mn 2 2H 2 O O 2
AC
ay
M.Mass M.Mass
Eq.mass of MnO 2 and Eq. mass of H2O2
2 j 2
19. Acidified K2Cr2O7 Vs SO2
IIT

K2Cr2O7 acts as an oxidizing agent while SO2 acts as a reducing agent.


le,

K 2 Cr2 O7 4H 2SO4 K 2 SO 4 Cr2 (SO 4 )3 4H 2 O 3(O)


irc

3SO2 3(O) 3H2 O 3H2SO4


zC
ar R

------------------------------------------------------------------
K 2 Cr2 O7 H 2 SO 4 3SO2 K 2SO 4 Cr2 (SO 4 )3 H 2 O
Ne E
en

------------------------------------------------------------------
B
T

M.Mass M.Mass
Eq. mass of K 2Cr2 O7 and that of SO 2
AS

6 2
20. Potassium dichromate Vs sulphite in acid medium:
[Sulphite gives SO2 in presence of dil. acids and the redox reaction (19) is given here in
M

the ionic form)


Cr2 O 72 3SO 32 8H 2Cr 3 3SO 24 4H 2 O
b) Dichromate with H2S in acid medium
K 2Cr2O7 4H2SO4 K 2SO4 Cr2 (SO4 )3 4H2O 3(O)
3H2S 3(O) 3H2O 3S
---------------------------------------------------------------------------------
add: K 2Cr2O7 4H2SO4 3H2S K 2SO4 Cr2 (SO4 )3 7H2O 3S
--------------------------------------------------------------------------------
21. Acidified K2Cr2O7 Vs KI
KI -acts as a reducing agent and K2Cr2O7 as the oxidizing agent
Cr2O72 6I 14H 2Cr 3 3I2 7H2O
Chemistry >>13<<
Volumetric Assignment
22. Acidified K2Cr2O7 oxidizes oxalic acid to CO2
Cr2O72 3COO2 14H 2Cr 3 7H2O 6CO2
|
COO
23. Sn2+ is oxidized to Sn4+ and also Sn is oxidized to Sn4+ by acidified potassium dichro-
mate
a) Cr2O72 14 H 3Sn 2 2Cr 3 3Sn 4 7 H 2O

b) 2Cr2 O 72 3Sn 28H 4Cr 3 3Sn 4 14H 2 O



24. 4K 2 Cr2 O 7 (s) 4K 2 CrO 4 Cr2 O 3 3O 2
M.Mass
Eq. mass of K 2Cr2 O 7
3

Y
25. H2O2 acts both as an oxidizing as well as a reducing in both acidic as well as alka-
line medium and the relevant reactions are:

EM
As Oxidizing agent Reducing agent
a) acidic medium Acidic as well as in alkaline medium

H2O2 2H 2e 2H2O

D
a
ad
b) alkaline medium H2O2 O2 2H 2e

Vi A
aw
O2H H2O 2e 3OH when it acts as reducing agent total oxygen is
AC
ay
given out by H2O2 only
j
In all these cases, the equivalent mass of H 2 O2
M.Mass 34
17
2 2
IIT

26. H 2O2 Vs Cl2 gas


le,

when chlorine gas is passed through H2O2, it is reduced to a chloride


irc

H 2 O2 2H O 2 2e
zC
ar R

C 2 2H 2e 2HC
................................................. H2O2 - reducing agnet
Ne E
en

H2 O2 C 2 2HC O2 Cl2 - oxidizing agent


B
T

..................................................
meq of Cl2 = meq of H2O2
AS

27. H2O2 Vs SO2 in alkaline medium:


H2O2 acts as an oxidizing agent in alkaline medium and oxidizes SO2 to SO24 as per the
equation
M

(H2O2 oxidizes sulphites to sulphates)


SO 2 H 2 O2 2OH SO 42 2H 2 O( )
M.Mass M.Mass
Eq. mass of SO 2 ; Eq. mass of H 2 O 2
2 2
Meq of SO2 meq of H2O2
28. H2O2 Vs Sn2+
H2O2 is reduced by Sn2+ giving Sn4+ and H2O: [H2O2 is the oxidizing agent]
Sn 2 Sn 4 2e
H 2 O2 2e 2H 2H 2 O
...........................................................
H 2 O2 Sn 2 2H Sn 4 2H 2 O
............................................................
Chemistry >>14<<
Volumetric Assignment
29. a) NH 2 OH 3H 2 O 2 HNO3 4H 2 O
[NH2OH is the reducing agent and H2O2 is oxidising agent]
M.Mass 33 M.Mass
Eq.mass of hydroxylamine 5.5 and that of H2 O 2
6 6 2
30. H y dr azi n e (N 2H4) Vs Fe3+ :
Ferric iron oxidizes hydrazine to nitrogen (Hydrazine is the reducing agent)
2N 2 N 2 4e
4Fe 3 4e 4Fe 2
...............................................
4Fe 3 2N 2 4Fe 2 N 2

Y
or 4Fe3 N2 H 4 N 2 4Fe2 4H

EM
M.Mass 32
Eq. mass of hydrazine 8
4 4
31. Hydroxylamine acts as a reducing agent and reduces ferric iron to ferrous

D
4Fe 3 2NH 2OH N 2 O H 2 O 4Fe 2 4H

a
ad
M.Mass 33

Vi A
Eq. mass of hydroxylamine 16.5

aw
2 2
32. KIO3 Vs KI in acid medium:
AC
KI acts as a reducing agent and KIO3 oxidizing agent
KIO3 5KI 6HC 6KC 3I 2 3H 2O
(or) IO 3 5I 6H 3I 2 3H 2 O
j ay
IIT
le,

M.Mass
Eq. mass of KIO3
irc

5
Eq. mass of KI = molecular mass
zC
ar R

(This is also an example of comproportionation reaction)


33. KClO3 Vs KI in acid medium:
Ne E
en

CO 3 6I 6H C 3I 2 3H 2 O
B
T

KI ............reducing agent
KClO3 ..................... as an oxidizing agent
AS

M.Mass
Eq. mass of KCO3
6
M

34. Chlorate Vs Ferrous sulphate in acid medium


CO 3 6Fe 2 6H C 6Fe 3 3H 2 O
M.Mass
Eq. mass of chlorate and Eq. mass of FeSO4 = Molecular Mass.
6
35. On passing chlorine gas through Fe2+ solution, ferrous gets oxidised to Ferric
C 2 2 Fe2 2C 2Fe3
36. Chlorate Vs SO2 in acid medium
CO 3 3SO 2 3H 2 O C 3H 2 SO 4

M.Mass M.Mass
Eq. mass CO3 , Eq. mass of SO 2
6 2

Chemistry >>15<<
Volumetric Assignment
37. HIO3 Vs SO2:
SO2 reduces HIO3 to free iodine
2HIO3 5SO2 4H 2 O H 2SO 4 I 2
M.Mass
Eq. mass of HIO3
5
M.Mass
Eq. mass of SO 2
2
38. CuSO4 Vs KI
In the absence of mineral acids, copper sulphate oxidizes iodide to free iodine and
it is a quantitative reaction.
CuSO4 is the oxidating agent and I is the reducing agent

Y
2CuSO 4 4KI Cu 2 I 2 2K 2 SO 4 I 2
or 2Cu 2 2I 2Cu I 2

EM
Eq. mass of CuSO4 = M. Mass
The liberated iodine can be titrated against sodium thiosulphate
Meq. of CuSO4 = meq. of Iodine = meq. of sodium thiosulphate

D
39. When H2S gas is passed through aqueous solution of Iodine, free sulphur is

a
formed

ad
Vi A
(i) H 2 S I 2 2HI S (ii) H 2 S Br2 S 2HBr

aw
I2 Oxidises H2S to S Br2 oxidizes H2S to sulphur.
AC
40. Nitric acid oxidizes H2S to S on passing H2S through nitric acid solution

ay
2HNO 3 3H 2 S 4H 2 O 2NO 3S
M.Mass
j M.Mass
Eq. mass of HNO3 ; Eq. mass H 2 S
IIT

3 2
le,

41. Free iodine is oxidized to iodic acid by nitric acid


irc

10HNO 3 I 2 10NO 2 2HIO 3 4H 2 O


zC

M.Mass atomic mass


ar R

Eq. mass of HNO3 and Eq. mass of Iodine


1 5
Ne E

42. Equivalent mass of HNO3 (M.M = 63) in the following reaction is


en

3Cu 8HNO 3 3Cu(NO 3 )2 2NO 4H 2 O


B
T

8M 8 63
84
AS

Ans :
6 6
Out of 8 nitrogens present in + 5 oxidation state only two are undergoing reduction
to NO(ON :+2). Hence 6 electrons are transferred out of 8 moles
M

43. a) Ozone liberates iodine from KI :


2KI O 3 H 2 O 2KOH I 2 O 2
M.Mass M.Mass 48
Eq. mass of KI and Eq. mass of O3
1 2 2
Meq of O3 = meq of KI
b) Ozone oxidizes moist iodine to iodic acid
I 2 5O3 H 2 O 2HIO3 5O 2
atomic mass M.Mass
Eq. mass of Iodine = and Eq. mass of Ozone =
5 2

Chemistry >>16<<
Volumetric Assignment
44. Carbon monoxide content in air can be estimated by its reaction with I2O5 liber-
ating Iodine as per the equation:
5CO I 2 O5 I 2 5CO 2
The liberated Iodine is titrated against standard sodium thiosulphate solution
2Na 2 S2 O3 I 2 Na 2 S4 O6 2NaI
Meq of Thio meq of I2 meq of CO
M.Mass
Eq. mass of CO
2
45. Equivalent mass of sodium bromate (NaBrO3) in the following reactions:
M.Mass
a) BrO3 6H 6e Br 3H2 O and Eq. mass of BrO 3 =
6

Y
b) 2BrO3 12H 10e Br2 6H2 O

EM
M.Mass
Eq. mass =
5
46. Na2SeO3 Vs KBrO3
Selenites which are the salts of selenious acid are oxidixed to selenates as per the

D
equation :

a
ad
SeO23 2BrO3 10H SeO42 Br2 5H2 O

Vi A
aw
M.Mass M.Mass
Eq. mass of KBrO3 and Eq. mass of Na 2 SeO3
AC
5 2

ay
47. BrO3 Vs AsO2 : (Bromate Vs Arsenite)
BrO3 AsO2 H2 O Br AsO34 H
j
IIT
le,

M.Mass M.Mass
Eq. mass of BrO3 and Eq. mass of AsO 2
6 2
irc

48. Arsenious oxide is used in the laboratory for the titration against iodine and the
zC

relevant reaction
ar R

As2 O3 2I 2 2H 2 O As2 O 5 4HI


Ne E
en

H AsO
3 3 I 2 H 2 O H 3 AsO 4 2HI
B
T

[ The titration is carried out in presence of sodium bicarbonate that neutralises HI,
AS

HI NaHCO 3 NaI H 2 O CO 2 otherwise HI will undergo dissociation that effect the


titration].
M.Mass Atomic mass
Eq. mass of As2 O3 and Eq. mass of Iodine =
M

4 1
49. In acid medium Na2HAsO4 or As2O5 liberates I2 from KI and the liberated iodine
can be titrated against sodium thiosulphate
Na 2 HAsO 4 2HI Na 2 HAsO 3 I 2 H 2 O
M.Mass
Eq. mass of Na 2 HAsO 4
2
50. HCl Vs NaOH [Neutralization titration]
strong acid Vs Strong base and NaOH solution in the burette
Indicator : Either phenolphthalein or methyl orange or any indicator that has a pH
range 4.3 to 9.7
End point with phenolphthalein : from colorless to pink
End point with methyl orange : from orange to yellow
Chemistry >>17<<
Volumetric Assignment
51. Na2CO3 Vs HCl [Neutralization]
There are two steps in this reaction
Na 2 CO3 HC NaHCO 3 NaC
NaHCO3 HC NaC H 2 O CO 2
.............................................................
Na 2 CO3 2HC 2NaC H 2 O CO 2
.............................................................
M.Mass
Eq. mass of Na 2 CO3
2
Indicator : Methyl orange
HCl in the burette
End point : From yellow to orange

Y
52. Na2CO3 Vs HCl
Indicator : Phenolphthalein

EM
HCl in the burette
The two steps are
Na2 CO3 HC NaHCO3 NaCl ...........(i )
Na 2 HCO 3 HC NaC CO 2 H 2 O ........(ii)

D
a
when the 1st step is over the pink colour of the indicator disappears

ad
Vi A
i.e. NaH CO 3 is an acidic salt and the pH of the solution decreases by the time the 1st

aw
step is over and it is below the pH range of the indicator phenolphthalein (8.0 to 10.2)
AC
i.e. the acid HCl used corresponds to half of Na2CO3. [NaHCO3 behaves like a weak

ay
acid towards phenolphathalein]
53. Sodium hydroxide Vs Oxalic acid [ Neutralization]
NaOH solution in the burette
j
IIT

M.Mass
le,

Eq. mass of oxalic acid =


2
irc

NaOH solution in the burette


Indicator : It is a weak acid Vs strong base titration
zC
ar R

Hence phenolphthalein is used


End point from colourless to pink
Ne E
en

COONa
54. a) Sodium hydroxide Vs monosodium oxalate
B
T

COOH
It is a neutralization titration
AS

NaOH solution in the burette


NaOH COOH COONa H 2 O
COONa COONa
M

M.Mass
Eq. mass of C2 O 4 HNa
1
(There is only one acidic hydrogen)
COOH
b) When is titrated against acidified KMnO4, it is a redox titration.
COONa

COOH 2
M.Mass COO
2C O2 2e
Eq. mass of =
COONa 2 COO

Chemistry >>18<<
Volumetric Assignment

55. Equivalent mass of Ferrous oxalate as a reducing agent


FeC2 O 4 Fe3 2CO2 3e
one mole of Ferrous oxalate gives out three moles of electrons
molecular mass
Eq. mass of ferrous oxalate =
3
Note: As a salt one mole of Ferrous sulphate corresponds to two equivalents
56. Equivalent mass of Ferric oxalate as a reducing agent
Ferric oxalate : Fe 2 COO 6
Ferric ion does not undergo further oxidation . Only oxalate ion undergoes oxida-
tion
2

Y
COO
3 6CO 2 6e
COO

EM
Every one molecule of ferric oxalate gives out six electrons
molecular mass
Eq. mass of Ferric oxalate =
6

D
Note: As a salt one mole of ferric oxalate corresponds to six equivalents

a
Disproportion Reaction and Calculation of equivalent masses:

ad
Vi A
It is a type of chemical reaction in which same compound is simultaneously re-

aw
duced as well as oxidized
AC
Eg:- 2CuC Cu CuC 2

ay
This reaction involves oxidation of one molecule
Cu Cu2 e
j
IIT

and reduction of the other


le,

Cu e Cu
irc

57. HCHO disproportionates in presence of OH as:


zC

_
OH
HCOO CH3OH
ar R

2HCHO
C0 C2 2e
Ne E
en

C0 2e C2
B
T

There are two carbon atoms involved and they have exchanged two electrons.
AS

2 M.Mass of HCHO
Eq: mass of HCHO = M.Mass
2
58. The reaction of chlorine with hot and concentrated solution of NaOH or KOH [an
M

alkali]
3C 2 6OH 5C CO3 3H2O
C C 5 5e (ox)
5C 5e 5C (red)
6 at mass of chlorine 6 35.5
Eq: mass
no.of electrons exchanged 5
3 M.Mass of chlorine 6 71

no.of electrons exchanged 5

Chemistry >>19<<
Volumetric Assignment

59. 3MnO24
OH
MnO2 2MnO4
3 M.Mass 3 M.Mass
Eq:- mass of manganate
no.of electrons exchanged 2
60. Available oxygen:
What is meant of Available oxygen in Pyrolusite?
Ans: The volume of oxygen which MnO2 liberates when heated with conc. H2SO4 is called
available oxygen.
2MnO2 2H2SO4 2MnSO4 2H2 O O2
Every one mole of oxygen is given by two moles of MnO2.
i.e. 87g MnO2 gives 16g oxygen. Based on the amount of oxygen liberated when pyrousite

Y
is heated with conc. H2SO4, MnO2 content in pyrolusite can be calculated.

EM
61. Hg5, (IO6)2 mercuric iodate when titrated with KI in acid medium liberates Iodine
and the liberated Iodine is titrated against sodium thiosulphate.
Hg5 (IO6 )2 34KI 24HC 5K 2 HgI 4 8I 2 2KC 12H 2 O

D
[I 2 2Na 2 S2 O3 2NaI Na 2 S4 O6 ] 8

a
ad
1 mole of Hg5(IO6)2 = 8 moles of I2 = 16 moles of Na2S2O3.

Vi A
aw
62. Available Chlorine:
AC
It is that much amount of chlorine which liberates an equivalent quantity of Iodine

ay
from KI when bleaching powder is suspended in water or in an acid.
CaOC 2 H2 O Ca(OH)2 C 2 j
or
IIT
le,

CaOC 2 2CH 3COOH (CH 3COO)2 Ca H 2O C 2 etc.


irc

From the amount of chlorine liberated, percentage of available chlorine in bleaching


zC

powder can be calculated.


ar R

63. Strength of solution (g/L) = Molarity Molar mass


Ne E
en

64. Strength of the solution (g/L) = Normality Eq. mass


65. Normality Eq. mass = molarity Molecular mass
B
T
AS

******
M

Chemistry >>20<<
Volumetric Assignment
Assignment 1
Solve The Following (short answer questions):-
1. Calculate the number of equivalents present in
a) 0.5L of 0.2N b) 1.5L of 4.5N solution
c) 0.5L of 0.4N solution d) 5L of 0.5N solution
Ans: (a) 0.1, b) 6.75, c) 0.2, d) 2.5
2. 100mL of 0.1N HCl, 200m of 0.2N HCl and 200mL of 0.3N H 2SO4 are mixed together
what is the resulting normality of the solution ?
Ans :0.22N
3. 10mL of 0.5N HCl and 20mL of 0.4M H2SO4 are mixed together and the total volume
made to one litre. What is the final normality of the solution ? What is the conc. of

Y
sulphate ion ?

EM
Ans : 0.021N & 0.008 M
4. H2SO4 solution has a density of 1.198g /mL and it is 27.0% by mass. Calculate normality,
molarity and molality
Ans :N = 6.6 and M = 3.3

D
a
5. The molality of a solution of acetone in water is 1.64. How many grams of acetone are

ad
Vi A
dissolved in 3.5kg of water ?

aw
Ans :332.92
AC
6. What mass of KNO3 must be weighed to make 100 mL of an aqueous solution containing

ay
0.79mg of K+ per mL
Ans :0.203 g j
IIT

7. It is required to prepare 26% by mass of aqueous solution of Ca(OH)2. How many grams
le,

of each is required ?
irc

Ans :74g of water and 26g of Ca(OH)2


8. Calculate the volume in mL of FeSO 4. 7H2O solution containing 16.68g in 500mL
zC
ar R

required to reduce 1.58 g of KMnO4 in acid medium


Ans :416.6 mL
Ne E
en

9. A solution is a mixture of sulphuric acid and oxalic acid. 25mL of this solution required
B
T

41.66mL of 0.12N base for neutralization. Also 25mL of this solution required 62.5mL
of 0.02N KMnO4 for oxidation. Calculate the individual normalities of H2SO4 and oxalic
AS

acid. Also calculate the mass of each acid present per litre.
Ans : H2SO4 = 0.1N & oxalic acid = 0.05N
10. What volume of 95% alcohol by mass (d = 0.809g/mL) must be used to prepare 150mL
M

of 30.0% by mass of alcohol (d = 0.957 g/mL)


Ans : 56.0 cm3
11. 10.0 mL of sulphuric acid of density of 1.85 g/mL are diluted to one Liter and 10mL of
this solution required 34.65mL of deci-normal sodium hydroxide solution for titration.
Find the percentage by mass of the original solution of H2SO4.
Ans :91.77%
12. What volume in mL of KMnO4 solution containing 7.9g in one litre will oxidize completely
the oxalic acid present in 125 mL of 0.1 M oxalic acid ?
Ans : 100 mL
13. What volumes of 12N and 1.5M H2SO4 must be mixed to give 4L of 4.5N solution ?
Ans :0.67L of 12N HCl and 3.33L of 1.5M H2SO4

Chemistry >>21<<
Volumetric Assignment
14. Find the equivalent mass of H3PO4 in the reaction
Ca (OH )2 H3 PO4 CaHPO4 2 H 2O [M.Mass of H3PO4 is M]

M . Mass
Ans :
2
15. 12.6g HNO3, 8g of NaOH and 3.7g of Ca(OH)2 are dissolved in water and the solution is
made to 500 mL. Find out whether the solution is acidic or basic. What would be the
conc. w.r.t. it ?
Ans : Solution is Basic 0.2N
16. a) 0.5g of metal on combustion formed only one oxide of mass 0.666g. What is the
equivalent mass of the metal ?

Y
b) 0.24g of metal on oxidation forms 0.4g of the metal oxide. What is the equivalent
mass of the metal?

EM
Ans :a) 24 b) 12
17. Calculate the molarity, molality and mole fraction of ethyl alcohol in a solution of total
volume of 95mL obtained by mixing 50mL ethyl alcohol and 50mL water. Density of

D
water = 1.0 g/mL and that alcohol 0.789g/mL

a
ad
Ans : M = 9.1 ; m = 17; x = 0.23

Vi A
18. What volume of ammonia gas at NTP is to be passed through 10 mL of 0.8N H2SO4 for

aw
complete neutralisation ?
AC
ay
Ans :179.2 mL
19. j
Calculte mass of MnO2 that is reduced by 50 mL 0.08N oxalic acid in presence of dilute
H2SO4 ? The unbalanced equation is MnO2 H H 2C2O4 CO2 H 2O Mn2
IIT
le,

Ans :0.174 g
irc

20. Calculate the mass of KMnO4 to be dissolved in 250mL of the solution so that one mL is
equivalent to 5.00mg of iron in FeSO4 ?
zC
ar R

Ans :0.707g
Ne E
en

21. The density of 4.0 M solution of acetic acid (M. M : 60) in water is 1.24 g/mL. Calculate
the mole fraction of the acetic acid
B
T

Ans : 0.0672
AS

22. Derive the formula for the volume of water V 2, which must be added to V1 mL of a
concentrated solution of molarity M1 to give a solution of concentration M2
V1(M1 M2 )
Ans : V2
M

M2
23. What volume of hydrogen at NTP is needed to reduce 125g of MoO 3 to pure metal ?
At. mass of Mo = 96
Ans :58.3L
24. What is the molarity of H 3PO4 solution 40mL of which is neutralized by 120mL of
0.321N NaOH ?
Ans : 0.321 M
25. Calculate the volume in mL of 0.5M H2SO4 required to react with 0.5g of CuCO3.
Ans : 8.097mL
26. The molality of 1M solution of sodium nitrate is 0.858 mol/kg. What is the density of
the solution ? (M. M of NaNO3 = 85.0)
Ans :1.249 g/mL
Chemistry >>22<<
Volumetric Assignment
27. If 32.5 mL of 0.26N standard base neutralises 1.2g of a dibasic acid, what is the
molecular mass of the acid ?
Ans : 284
28. A sample of Na2CO3. H2O weighing 0.62g is added to 100mL of 0.1N sulphuric acid. Will
the solution be acidic, alkaline or neutral ?
Ans :Neutral

W 1
29. Show that molarity (M) and molality (m) of a solution are related by d M
1000 m
where d density of solution in g/mL; W molecular mass of solute.
30. What volume of conc. H2SO4[d = 1.835g / mL] of 93.2% by mass is required to make up
to 500mL of 3.0N acid ?

Y
Ans : 43.48mL
31. Calculate the number of molecules of H 2SO4 present in 250mL of 98% by mass of

EM
sulphuric solution. Density of solution is 1.84 g/mL
Ans : 4.6 N0
32. 0.5g of fuming H 2SO 4 is diluted with water. When it is tritrated against NaOH, it
required 26.7ml of 0.4N solution for its complete neutralization. What is the percentage

D
a
of free SO3 in the sample of OLEUM.

ad
Vi A
Ans : 20.8%

aw
33. One mole of SO2Cl2 is dissolveld in water and the acidic solution formed is neutralised
AC
by Ca(OH)2 Find the moles of Ca(OH)2 required for neutralization.

ay
Ans : 2
34.
j
One litre of 0.2M NaOH, when exposed to air has absorbed 25 m moles of CO 2 forming
Na2CO3. Find the concentration of NaOH and Na2CO3 in the resulting solution.
IIT
le,

Ans: NaOH: 0.15M, Na2CO3 : 0.025M


irc

Assignment- II
zC
ar R

CHOOSE THE CORRECT ALTERNATIVE(single option)


01. The normality of 15 V Hydrogen peroxide solution is
Ne E
en

1) 1.2 2) 1.78 3) 2.673 4) 3.56


B

02. In the reaction 2 KMnO4 5SO2 2 H 2O K 2 SO4 2 MnSO4 2 H 2 SO4


T

the equivalent mass of SO2 is (M.Mass:64)


AS

1) 8 2) 16 3) 32 4) 64

MnO2 H 2O2 4 H Mn2 2 H 2O O2 , the reducing agent is


M

03.
1) MnO2 2) H2O2 3) H 4) None

04. 6 MnO4 5 As2 O3 12 H 9 H 2O 4 Mn 2 10 H 3 AsO4


The equivalent mass of As2O3 is
M .Mass M .Mass M .Mass M .Mass
1) 2) 3) 4)
4 5 2 1
05. H3 PO4 is a tribasic acid and one of its salts is NaH2 PO4 . The volume of 1.0N NaOH
needed to convert 24 g of NaH2 PO4 [ M .Mass :120] exactly into Na3 PO4 is
1) 400 ml 2) 300 ml 3) 200 ml 4) 100 ml
06. The mass of one atom of a divalent metal is 6.664 10 23 . The equivalent mass of the
metal is
1) 40 2) 30 3) 20 4) 10
Chemistry >>23<<
Volumetric Assignment
07. 0.75g of a metal combines with oxygen to from 1.0g of the metal oxide. The equivalent
mass of the metal is
1) 12 2) 24 3) 36 4) 48
08. 0.135g of a trivalent metal liberates 168mL of Hydrogen measured at NTP when
reacted with dil HCI. The atomic mass of the metal
1) 27 2) 18.0 3) 9.0 4) 24
09. The number of moles of ferrous oxalate required to react with 94.8g of KMnO4 in
presence of dil H2 SO4 [ M .M of KMnO4 158]
1) 2.5 2) 1.0 3) 5.0 4) 7.5
10. KMnO4 acts as an oxidizing agent in neutral medium and sodium thiosulphate gets
oxidized as per the equation
3 Na2 S2O3 8 KMnO4 H 2O 3 Na2 SO4 8 MnO2 5K 2 SO4 2 KOH
If the molecular mass of sodium thiosulphate is 248, mass of hypo needed to prepare

Y
500 mL of 0.2N solution
1) 31.0g 2) 4.65g 3) 3.1g 4) 24.8 g

EM
11. The molecular mass of H3 PO4 is 98 and that of Mg(OH )2 is 58. The mass of phosphoric
acid required to neutralise 7.25g of magnesium hydroxide is
1) 32.66g 2) 16.33g 3) 8.165g 4) 14.5g
12. The normality and molarity of perhydrol are
1) 8.91 and 26.73 2) 17.82 and 8.91 3) 26.73 and 17.824) 26.73 and 8.91

D
a
13. In hot alkaline medium Br2 disproportionates as per the equation

ad
Vi A
3 Br2 6OH 5 Br BrO3 3 H 2O.

aw
AC
The equivalent mass of Br2 , if its molecular mass is ' M '

1)
M
2
2)
M
3
j 3)
3M
5
ay 4)
5M
3
IIT
le,

14. Observe the reaction H3 PO4 Ca(OH )2 CaHPO4 2 H 2O . Pick out the wrong statement
irc

1) Equivalent mass of H3 PO4 is 49


zC

2) The resulting mixture needs 1 mole of KOH for complete neutralization


ar R

3) CaHPO4 is an acidic salt


Ne E
en

4) One mole of Ca(OH )2 is neutralized by half a mole of H3 PO4


B
T

15. In the reaction H2 SO4 NaOH NaHSO4 H 2O . The equivalent mass of H2 SO4 is
AS

M .Mass M .Mass M .Mass M .Mass 2


1) 2) 3) 4)
2 4 1 3
M

16. The molarity of H3 PO4 , 40 mL of which is neutralised by 120mL of 0.321N sodium


hydroxide is
1) 0.6 M 2) 0.4 M 3) 0.2 M 4) 0.321 M
17. Two acids H2 SO4 and H3 PO4 are neutralised by the same amount of alkali when
sulphate and dihydrogen phosphate are formed respectively. The ratio between the
number of moles of two acids
1) 1:2 2) 2:3 3) 1:3 4) 3:1
18. 42mL of 0.5N KOH are needed to neutralise 1.0g of the acid present in 100mL of
solution. If the acid is dibasic, the molecular mass of the acid is
1) 95.2 2) 119 3) 47.6 4) 142.85
19. The number of moles of MnO4 that will react with one mole of oxalic acid in acid
medium
1) 0.2 2) 0.4 3) 0.6 4) 1.67
Chemistry >>24<<
Volumetric Assignment
20. The molecular mass of KMnO4 is M . Its equivalent mass when it is converted into
K 2 MnO4 .in basic medium
M 2M M
1) M 2) 3) 4)
3 3 2
21. The number of millimoles present in 1.5L of 0.3N H3 PO4
1) 150 2) 45 3) 450 4) 90
22. The equivalent mass of a trivalent metal is 3.50. The molecular mass of its chloride
(at.mass of chlorine : 35.5)
1) 46.0 2) 81.5 3) 152.5 4) 117.0
23. Cupric ion reacts with Iodide as per the equation: 2Cu2 4I Cu2 I 2 I 2 . The equivalent
mass of copper as per this reaction

Y
At.mass At.mass At.mass At.mass
1) 2) 3) 4)

EM
2 1 3 4
24. The number of moles of KMnO4 needed to oxidise two moles of Ferrous to Ferric in
acid medium
1) 2 moles 2) 1 moles 3) 0.4 mole 4) 0.04 mole

D
a
25. In a metal chloride, the mass of metal and chlorine are in the ratio of 1:2. The

ad
equivalent mass of the metal is

Vi A
1) 35.5 2) 17.75 3) 71.5 4) 106.5

aw
26. 6L of 1N HCl and 4L of 2N HCl are mixed to get 10L of the resulting solution. The
AC
ay
normality of the resulting solution is
1) 6.0N 2) 7.0 3) 7.4 4) 8.2
27.
4 K 2 Cr2O7
j
4 K 2CrO4 2Cr2O3 3O2 . The equivalent mass of K 2Cr2O7 is
IIT
le,

M .Mass M .Mass M .Mass M .Mass


1) 2) 3) 4)
2 3 1 4
irc

28. The equivalent mass of any substance is that much amount that combines with
1) 0.5 mole of oxgen 2) 0.25 mole of oxygen
zC
ar R

3) 2.0g of hydrogen 4) one mole of chlorine


29. One gram of a metal oxide is reduced to 0.67g of metal. The equivalent mass of the
Ne E
en

metal is
B
T

1) 34 2) 16 3) 68 4) 32
30. The mass of 8.0g of a metal on complete combustion has increased by 40%. The
AS

equivalent mass of the metal


1) 28 2) 32 3) 40 4) 20
31. The number of equivalents that one mole of H2 S corresponds to when it is converted
M

to SO2 is
1) 2 2) 4 3) 6 4) 8
32. For a given mixture of NaHCO3 and Na2CO3 , vol of HCl required is ' X ' mL with
phenolphthalein as indicator and a further ' Y ' mL is required using methyl orange.
Hence vol of HCl required to neutralise only NaHCO3 is
1) 2x 2) x/2 3) y x 4) ( y 2 x )
33. A given mixture of NaOH and Na2CO3 required ' X ' mL of HCl using phenolphthalein
as indicator and a further ' Y ' mL using methyl orange as indicator. The vol. of HCl
needed for the neutralisation of only NaOH is
1) y 2 x 2) x 2 y 3) x y 4) 2x y

Chemistry >>25<<
Volumetric Assignment
34. A mixture of NaOH and NaHCO3 required ' X ' mL of HCl using phenolphthalein as
indicator and a further ' Y ' mL using methyl orange. The vol. of HCl for the
neutralization of NaHCO3 only.
1) X 2) Y 3) X Y 4) Y X
35. The molality of H2 SO4 solution is 9. The mass of H2 SO4 present in 1000g of H2 SO4
solution
1) 882g 2) 9.0g 3) 900g 4) 468.65g
36. One molar solution of H3 PO2 corresponds to 2N when
1) it is neutralised to form H 2 PO2 2) it is oxidised to H 3 PO3
3) it is reduced to PH3 4) it disproportional to H 3 PO3 and PH3

Y
37. KMnO4 and H2O2 both will liberate Iodine from an Iodide in acid medium. 0.5 mole of

EM
KMnO4 and one mole of H2O2 are separately treated with excess of an Iodide in acid
medium. The mass of iodine liberated is
1) More by KMnO4 2) Less by KMnO4

D
a
ad
3) Equal in both the cases 4) Data is Insufficient

Vi A
aw
38. The number of milli equivalents of Na2 S present in 250mL of 0.048M solution when it
AC
ay
acts as a reducting agent as per the equation. 8OH S 2 SO42 4 H 2O 8e
1) 24 2) 48 3) 96 4) 192
39.
j
The molarity of NO3 ion in the resulting solution when 2L of 3M AgNO3 and 3L of 1M
IIT
le,

BaCl2 are mixed.


irc

1) 1.2M 2) 1.8M 3) 0.4 4) 0.5


40. 9.8g of H2 SO4 and 4.0g of NaOH are taken together in a volumetric flask and solution
zC
ar R

is made up to one litre. The resulting solution is


Ne E
en

1) 0.1M w.r.t NaOH 2) 0.1M w.r.t H2 SO4


B
T

3) 0.1N w.r.t H2 SO4 4) 0.05N w.r.t NaOH


41. In the reaction MnO2 4 HCl MnCl2 Cl2 2 H 2O, the equivalent mass of MnO2 is
AS

( M . Mass 87)
1) 87 2) 43.5 3) 29 4) 21.75
M

42. In the reaction SO2 2 H 2 S 3S 2 H 2O, the equivalent mass of SO2 and H2 S are
1) 64 and 34 2) 32 and 17 3) 16 and 17 4) 32 and 34
43. The equivalent mass of H2 SO4 in the following reaction: (M.M. of H2 SO4 : 98)

8 H H 2 SO4 4 Zn H2 S 4 Zn 2 4 H 2O
1) 98 2) 49 3) 24.5 4) 12.25

44. As per the reaction 8 H H 2 SO4 8e H 2 S 4 H 2 , the molarity of 4N H2 SO4 is
1) 2.0 2) 1.0 3) 0.5 4) 4.0
45. Density of organic solvent is 0.8 g/mL and 100mL of the solvent is made to one litre
by adding water of density 1g/mL. If the molecular mass of organic solvent is 40, the
molality is
1) 1.0 2) 2.2 3) 3.3 4) 4.4

Chemistry >>26<<
Volumetric Assignment
Assignment III
Subjective Question along with solutions:-
1. A mixture of pure K2Cr2O7 and KMnO4 weighing 0.84g was treated with excess of KI
in acidic medium. The Iodine liberated required 120mL of 0.15 M of sodium
thiosulphate. What is the percentage of each in the mixture ?
Solution:-
Out of 0.84g mixture of K2Cr2O7 & KMnO4, x g is K2Cr2O7
KMnO4 = (0.84 - x)
x 1000 (0.84 x)
120 0.15
49 316
On solving, % K2Cr2O7 = 90.8

Y
2. 2.8g of an ammonium salt was heated with excess of NaOH solution and the evolved
gas is passed into 150mL of 0.25M H2SO4. The left out acid required 63.0 mL of 0.5 N

EM
NaOH for complete neutralisation. Calculate the percentage of ammonia in the salt.
Solutin:-
H2SO4 taken = 150 0.25 2 = 75 meq
NaOH used for excess of H2SO4 = 63 0.5 = 31.5 meq

D
meq of H2SO4 reacted with NH3 = meq of NH3 liberated

a
[Ammonium salt releases ammnia gas when reacted with an alkali:

ad
Vi A
NH 4 OH H 2 O NH 3 ]

aw
AC
meq of NH3 = 75 - 31.5 = 43.5

ay
% NH3 = 26.4
3. 12.53 mL of 0.0509 M SeO 2 reacted with 25.52mL of 0.1M CrSO 4 solution. In the
j
reaction chromium is oxidised to Cr3+. To what oxidation state selenium is converted
IIT

in the reaction ? Write the redox change for the SeO2


le,

Solution:
Equating the number of meq:
irc

25.52 0.1 1 = 12.53 0.0509 Z, where Z is the valence factor of selenium


zC

valence factor of CrSO4 is one


ar R

25.53 0.1
Z 4
Ne E
en

12.53 0.0509
B
T

Se 4 4e Se 0
selenium goes to zero oxidation state
AS

4. One litre of mixture of O 2 and O 3 at STP was allowed to react with an excess of
acdified solution of KI. The iodine liberated required 40mL of M/10 sodium thiosulphate
solution. What is the mass percentage of ozone in the mixture ? Ultraviolet radiation
M

of wavelength 300nm can decompose ozone. Assuming that one photon can decom-
pose one molecule of ozone how many photons would have been required for the
complete decomposition of ozone in the original mixture ?
Solution:- Total volume of O2 and O3 = 1000 mL at NTP
meq O3 meq I2 meq thio = 40 0.1 = 4
vol equivalent of O3 = 11, 200 mL
1000 meq 11, 200 mL
11200 4
Hence volume that corresponds to 4 meq 44.8 mL
1000
% mass of O3 in the mixture = 6.44g
no. of photons no of ozone molecules in 44.8 mL at NTP
1.2 1021

Chemistry >>27<<
Volumetric Assignment
5. 25mL of a solution of Na2CO3 having specific gravity of 1.25 g / mL required 32.9 mL of
a solution of HCl containing 109.5g of the acid per litre for complete neutralisation.
Calculate the volume of 0.84N H2SO4 that will be completely neutralised by 125g of
Na2CO3 solution
Solution:
109.5
Normality of HCl = 3
36.5
32.9 3
32.9 3 = 25 N and N of Na2CO3 = 3.948
25
125
125g of Na2CO3 solution = 100mL
1.25

Y
3.948 100
vol. of H2SO4 = 470 mL

EM
0.84
6. A solution contains a mixture of sulphuric acid and oxalic acid 25mL solution re-
quired 35.5mL of 0.1M NaOH for neutralisation and another 25mL solution required
23.45mL of 0.02M KMnO4 for the oxidation of oxalic acid. Calculate the molarity of the

D
solution w.r.t. sulphuric acid and oxalic acid.

a
ad
Solution:

Vi A
aw
Total no. of meq of H2SO4 and oxalic acid = 35.5 0.1 = 3.55
AC
meq of oxalic acid = 23.45 0.1 = 2.345

ay
meq of H2SO4 = 3.55 2.345 = 1.205
N of H2SO4 = 0.0482 0.0241M j
IIT

2.345
le,

N of oxalic acid = 0.0938 0.0465M


25
irc

7. To a 25mL of H 2O2 solution, excess of acidified solution of potassium iodide was


zC

added. The iodine liberated required 20 mL of 0.3N solution thiosulphate solultion.


ar R

Calculate the volume strength of hydrogen peroxide solution.


Ne E
en

Solution:
B

meq of H2O2 in 25 mL meq of I2 meq of thio = 20 0.3 = 60


T

6
AS

Normality of H2O2 0.24


25
1.782 N H2O2 10V
M

Hence volume strength of 0.24N H2O2 1.347V



8. In basic solution CrO42 oxidises S2O32 to SO 24 forming Cr OH 4 . How many millilitres
of 0.15M Na2CrO4 solution are required to just react with 50.0 mL of 0.25M Na2S2O3
solution.
Solution:
Oxidation number of chromium, decreases from +6 to +3 while that of sulphur in-
creases from +2 to +6
0.15 3 V = 50 0.25 8

50 0.25 8
Hence volume of Na2CrO4 solution 222.2 mL
0.15 3

Chemistry >>28<<
Volumetric Assignment
9. Ten grams of a sample of bleaching powder is extracted with water and the solution
is made to one litre. 25mL of this solution is added to 50mL of N/14 Mohrs salt
solution containing enough H2SO4. After the reaction, the whole solution required 22
mL of KMnO4 solution containing 2.257g of KMnO4 in one liter for complete oxidation.
Calculate the percentage of available chlorine in the sample of bleaching powder
Given : C 2 2Fe 2 2C 2Fe 3
MnO4 8H 5e Mn 2 4H2 O
Solution:-
2.257
N of KMnO4 = 0.0714
31.6
meq of KMnO4 = 0.0714 22 = 1.571

Y
1
Total meq of mohrs salt = 50 3.571
14

EM
meq of chlorine liberated meq of Mohrs salt utilized
= 3.571 1.571 = 2.0
2000 meq of chlorine 71g and hence mass of 2 meq of chlorine = 0.071g

D
0.071 1000

a
Mass of chlorine given by 10g bleaching powder = 2.84g

ad
25

Vi A
Available chlorine = 2.84 10 = 28.4 %

aw
10. One litre of an acidified solution of KMnO4 containing 15.8 g of KMnO4 is decolourised
AC
ay
by passing SO2 gas. If SO2 is produced by heating iron pyrites (FeS2), what would be
the mass of iron pyrites required to produce the necessary amount of SO2 gas ?
Solution:- j
IIT

15.8 1000
le,

meq of KMnO4 meq SO2 500


31.6
irc

500 meq of SO2 16g


zC
ar R

4FeS2 11O2 2Fe2O3 8SO2


one mole of FeS2 (120g) on heating gives 2 moles of SO2 (124g)
Ne E
en

Mass of FeS2 required to give 16g of SO2 = 15 g


B
T

11. Calculate the volume of HNO3 (specific gravity 1.08) containing 9.0% by mass of the
acid required to oxidise the iron in 2.0 g of FeSO4. 7H2O (M.M. 278) in presence of
AS

dilute sulphuric acid as per the equation. Also what is the equivalent mass of HNO3
Given: 6FeSO4 2 HNO3 3H 2 SO4 3Fe2 ( SO4 )3 2 NO 4 H 2O
Solution:
M

1.08 10 9
Normality or molarity of HNO3 = 1.543
63
278g of FeSO4.7H2O 1000 meq
1000 2
2 g of Ferrous surphate meq
278
1000 2
1.543 V
278
M.Mass
Vol of HNO3 = 4.66 mL and equivalent mass of HNO3 =
3

Chemistry >>29<<
Volumetric Assignment
12. A 2.0g sample of a mixture containing sodium carbonate, sodium bicarbonate and
sodium sulphate is heated till the evolution of CO2 ceases. The volume of CO2 at 750
mm Hg pressure and at 298K is measured to be 123.9mL. A 1.5g of the sample
requires 150mL of M/10 HCl for complete neutralization. Calculate the percentage
composition of the components of the mixture.
Solution:-
Due to heating only NaHCO3 gets converted into Na2CO3 giving out carbondioxide


2NaHCO3 Na 2 CO 3 H 2 O CO 2 and Na 2CO3 no change

750 123.9 w
0.0821 298
760 1000 44

Y
on simplifying w mass of CO2 = 0.22g

EM
0.22 2 84
mass of NaHCO3 that gives 0.22g CO2 = 0.84g
44
1.5g mixture requires 150 mL HCl

D
a
2.0 g mixture requires 200 mL of HCl

ad
Vi A
x 0.84 20

aw

53 84 1000
AC
ay
x = ( 0.02 0.01)53 = 0.53
2g mixture contains 0.53g og Na2CO3 j
IIT

% of Na2CO3 = 26.5
le,

% of NaHCO3 = 42 and remaining Na2SO4


irc

13. An aqueous solution containing 1.612g of oxalic acid required 96mL 0.25N KMnO 4 in
zC

H2SO4 medium for its complete oxidation. Find the percentage purity of oxalic acid.
ar R

Solution:-
Ne E
en

63 24
B
T

meq of KMnO4 meq of oxalic acid 96 0.25 = 24 1.512g


1000
AS

since 63 g of oxalic acid 1000 meq

1.512 100
purity of oxalic acid = 93.8%
M

1.612
14. A mixture of 0.527g containing Na 2CO3 and NaHCO 3 and some inert impurities is
titrated against 0.109M HCl requiring 15.7mL to reach the phenolphthalein end point
and a total of 43.8mL to reach the modified methyl orange end point. What is the
percentage of Na2CO3 and NaHCO3 in the mixture
Solution:-
Total volume of HCl of 0.109N = 43.8 mL
volume of HCl meant for Na2CO3 = 15.7 2 = 31.4 mL
Eq. mass of Na2CO3 = 53 and that of NaHCO3 = 84
meq of Na2 CO3 = 31.4 x 0.109

Chemistry >>30<<
Volumetric Assignment

31.4 0.109 53 100


% of Na2CO3 = 34.42
1000 0.527
volume of HCl meant for NaHCO3 = 12.4 mL
meq of NaHCO3 = 12.4 0.109

12.9 0.109 84 100


% of NaHCO3 in the mixture = 21.54
1000 0.527
15. 0.32g sample of KI is mixed with 1.1 millimoles of K2CrO4 to which 25mL of 5N H2SO4
is added, and the iodine liberated is boiled off and the solution is now mixed with
excess of pure KI and the iodine liberated now required 14mL of 0.1N sodium
thiosulphate solution. Calculate the purity of original KI solution.

Y
Solution:-

EM
Iodine is liberated by acidified K2Cr2O7 as per the equation:
Cr2O72 14H 6I 2Cr 3 7H2O 3I2

D
K 2CrO4 .......
K 2Cr2O7

a
ad
1.1 m mol 0.55 m mol 3.3meq [ since z = 6 for K2Cr2O7]

Vi A
aw
meq of iodine liberated by pure KI = 14 0.1 = 1.4
AC
ay
meq of K2Cr2O7 utilized by impure KI = 3.3 1.4 = 1.9

I I e j
IIT

1 mole of KI 1 eq 1000 meq 167 g


le,
irc

1.9 167
1.9 meq of KI 0.317g
1000
zC
ar R

0.317 100
purity of orginal KI = 99.17%
Ne E
en

0.32
B
T

16. H2O2 decomposes on warming to give oxygen according to the equation


AS

2H 2O2 (aq) 2 H 2O O2 ( g ) , under such conditions when one mole of oxygen occupies
24dm3. If 100mL of H2O2 solution of molarity x produces 3dm3 of oxygen, find x.
Solution:-
M

As per the given condition.


24 L of oxygen is given by 2 moles of hydrogen peroxide

23 1
number of moles that gives 3L of oxygen = 0.25
24 4
i.e. 0.25 moles of H2O2 are present in 100 mL of solution

0.25 1000
Molarity 2.5
100
17. 2.0g of the carbonate of a divalent metal is dissolved in 50 mL of 1N HCl. Excess of
acid required 100mL of 0.1N NaOH for complete neutralisation. Find the atomic mass
of the metal.

Chemistry >>31<<
Volumetric Assignment
Solution:-
meq reacted with 2 g of MCO3 = 50 - 10 = 40
40 meq 2g
Hence mass of MCO3 that corresponds to 1000 meq = 50 g
M.Mass of carbonate = 100 & atomic mass of metal = 40
18. 5.45g of impure sample of KI is added to a solution containing 2.3g of As2O5 in acid
medium. The liberated iodine is boiled off and to this solution excess of pure KI is
added. The liberated iodine required 80mL of sodium thiosulphate solution that con-
tains 12.4g in 500mL solution. Find the percentage purity of original sample of potas-
sium iodide. M. Mass of Na2S2O3 = 248
Solution:

Y
As2 O5 4I 4H As2 O3 2I 2 2H2 O

EM
1mole of As2O5 230g 4 equivalents
Eq. mass of As2O5 = 57.5 1000 meq.
12.4 g of Na2S2O3 in 500 mL corresponds to 0.1M.

D
Meq of Iodine liberated by pure KI(second part) = 80 0.1 = 8

a
2.3g As2O5 40 meq

ad
Vi A
meq of As2O5 utilized by KI present in impure sample of KI = 40 8 = 32

aw
167 32
AC
32 meq of KI 5.344g [since 167g of KI 1000 meq]

ay
1000

% of KI in impure sample =
5.344 100 j
98.05
5.45
IIT
le,

19. An aqueous solution containing 0.10g KIO3 (m Mass : 214.0) was treated with excess
of KI solution. The solution was acidified with HCl solution. The liberated iodine
irc

consumed 45.0mL of thiosulphate solution to decolourise the blue starch iodine


complex. Calculate the molarity of the sodium thiosulphate solution.
zC
ar R

Solution:-
Ne E
en

IO3 5I 6H 3I2 3H 2 O [comproportionation reaction]


B
T

meq of I2 liberated meq of Na2S2O3 used = 45 N


where N - Normality of thio solution
AS

127 45N
mass of I2 = g
1000
M

As per the equation


214g of KIO3 liberats = 3 254g of Iodine
3 254 0.1
Iodine liberated by 0.1g of KIO3 =
214
127 45N 3 254 0.1

1000 214
N = 0.0623
20. A 0.5g sample of MnO2 is treated with HCl liberating chlorine. The liberated chlorine
is passed through KI solution and 30.0 mL of 0.1M Na2S2O3 are required to titrate the
liberated iodine. Calculate the percentage of MnO2 in the sample (At.mass of Mn= 55)
Solution:
MnO2 4HC MnC 2 2H2O C 2

Chemistry >>32<<
Volumetric Assignment

2KI C 2 2KC I2
2Na 2S2O3 I2 2NaI Na 2S4O6
meq of MnO2 meq Cl2 meq I2 meq of thio = 30 0.1 = 3
87
Eq. mass of MnO2 = 43.5
2
43.5 3
mass of MnO2 = 0.1305g
1000
0.1305 100
percentage of MnO2 in the sample 26.1
0.5
The ion An+ is oxidized to AO3 by MnO

Y
2+
21. 4 where by MnO4 changes to Mn . In case 2.68
10-3 moles of An+ requires 1.61 10-3 moles of MnO

EM
4 , find the value of n
Solution:
A n A 5

D
MnO4 Mn2

a
ad
Z 2.68 10-3 = 1.61 10-3 5; where z is valency factor of An+

Vi A
Z = 3 and hence n = 2

aw
22. In case 150 mL of K2Cr2O7 is treated with KI in acid medium, the liberated iodine
AC
required 76.0 mL of 0.12N Na2S2O3, find the strength of dichromate solution(M.Mass of

ay
K2Cr2O7 = 294) .GIve the relevant reactions
Solution: j
Cr2 O72 6 I 14 H 2Cr 3 3 I 2 7 H 2 O
IIT
le,

I2 2Na 2 S2O3 2NaI Na 2S4 O6


irc

meq of Cr2 O72 meq I2 meq of Na2S2O3 76 0.12 = 9.12


zC
ar R

9.12
Normality of Cr2O72 =
Ne E
en

150
B
T

9.12 49
strength = 2.98g / L
150
AS

23. 1.9g of a sample of copper ore is digested and Cu2+ is obtained in aqueous medium. It is
treated with excess KI and the iodine liberated needed 15.12 mL of 0.15M Na 2S2O3
solution. Find the percentage of copper content by mass in the sample. Give the
M

necessary reactions.
Solution:-
2Cu2 4I Cu2I2 I2
2Na 2S2O3 I2 2NaI Na 2S4O6
meq of copper = 15.12 0.15 = 2.268
63.5 2.268
mass of copper =
1000
63.5 2.268 100
% copper in the sample = 7.5
1000 1.9

Chemistry >>33<<
Volumetric Assignment

24. A sample of air of 25L containing CO is passed over heated I 2O5 to convent CO to CO2 as
per the equation I2 O5 5CO 5CO2 I 2 . The liberated iodine is collected into a vessel
that contains 13 mL of 0.02M sodium thiosulphate soluton.The left out Na2S2O3 needed
12 mL of 0.005N pure Iodine solution. Based on this information find the number of
moles of CO present per litre of air
Solution:-
Initial number of meq of thio = 13 0.02 = 0.26
Left out thio = 0.06
meq of thio consumed by iodine = 0.2
meq of Iodine liberated by CO = 0.2
1000 meq of Iodine 127g
127 0.2

Y
mass of Iodine liberated =
1000

EM
127 0.2 5
moles of CO that liberated I2 = 5 10 4
1000 254

5 104
moles of CO persent per litre of air = 2 105

D
25

a
25. 1.333g sample of Ferric oxalate (M.M. : 376) required for its complete oxidation of V mL

ad
Vi A
of 1M KMnO4 in acid medium. Find the value of V

aw
Solution:
AC
1000 1.333 6

ay
V 5 1 or V = 4.25 mL
376
26. j
Equal volumes of a reducing agent when titrated against 1M KMnO4, needed 20 mL in
acidic, 33.3 in neutral and 100 mL in alkaline media. If MnO 2+
4 is reduced to Mn in acid
IIT
le,

medium, to what state MnO


4 is reduced in alkaline and neutral media.
irc

Solution:-
When equal volumes of reducing agents are titrated,
zC
ar R

meq of MnO 4 in acidmedium meq in Neutral meq in alkaline


Ne E
en

20 5 33.3 Z1 100 Z2
Valence factor in neutral medium = 3
B
T

valency factor in alkaline medium = 1


In alkaline medium Mn+7 is reduced to Mn+6 and in neutral medium Mn+7 is reduced
AS

to Mn+4
27. 1.0g sample of solid Fe2O3 of 55.2% pure is dissolved in an acid and reduced by heating
the solution with zinc dust. The resulting solution is cooled and made to 100.0mL.
M

25mL, of this solution requires 17.0mL of 0.017M solution of an oxidant for the titra-
tion. Calculated the number of electrons taken up by the oxidant in the above tritration.
Solution:
mass of Fe2O3 in 1g sample = 0.552g
2Fe3 Zn Zn2 2Fe2
i.e. Ferric is reduced to ferrous and Ferrous solution is titrated against the oxidant
Valence factor of the oxidant = Z
no. of meq present in 25 mL of the made up solution = 17 0.017 Z
Hence meq in 100 mL solution = 17 0.017 4Z
0.552 112 1000
4 17 0.017 Z or Z = 6
56 160
Number of electrons transferred = 6

Chemistry >>34<<
Volumetric Assignment
28. 1.8 g sample containing Arsenic is dissolved by heating in HNO 3 and then treated with
HI. The liberated iodine required 35.6 mL of 0.32 M sodium thiosulphate for complete
titration. Determine the percentage of Arsenic in the sample. (At.mass of Arsenic= 75)
Given : As 5 HNO3 H 3 AsO4 5 NO2 H 2O and H3 AsO4 2 HI H3 AsO3 H 2O I 2
Solution:
meq of H3AsO4 meq I2 meq thio 35.6 0.32 = 11.40
11.4 37.5
Arsenic content in 11.4 meq of H3AsO4 0.428g
1000
0.428 100
% Arsenic in the original sample 23.7
1.8
29. One litre of pure oxygen measured at NTP when passed through an ozoniser and the

Y
resulting gaseous mixture has liberated iodine from aqueous KI. If the iodine liberated
needed 75mL of 0.2N thiosulphate solution, find the final volume of the ozonised oxy-

EM
gen under the same condition.
Solution:- 3O2 2O3
meq Ozone meq I2 meq thio 75 0.2 = 15

D
O3 2I 2H I 2 H 2O O2

a
ad
1000 meq of ozone 11, 200 mL of NTP

Vi A
aw
11200 15
15 meq 168mL
AC
100

ay
168 mL of ozone is formed out of 252 mL of oxygen

30.
j
Hence final volume of the mixture = 1000 252 + 168 = 916 mL
What is the equivalent mass of H3PO2 when it disproportionates to PH3 and H3PO3 as
IIT
le,

per the equation : 3 H3 PO2 PH 3 2 H 3 PO3


Solution:
irc

1 3 3
zC

3H3 PO2 PH3 2H3 PO3


ar R

2P 1 2P 3 4e
Ne E
en

P 1 4e P 3
B
T

(Four electrons are exchanged among three phosphorus atoms)


AS

3 M.Mass
Eq. mass =
4
31. Find the equivalent mass of phosphorus when it disproportionates as per the reaction
M

P4 3NaOH 3H 2O PH 3 3NaH 2 PO2


Solution:
3 1
P40 3NaOH 3H 2 O PH 3 3NaH 2 PO 2
1
P 0 3P 3e

P0 3e P3
Three electrons are exchanged among four phosphorus atoms
4 atomic mass 4 31
Eq. mass = 41.33
3 3

Chemistry >>35<<
Volumetric Assignment
32. 8.5g of bleaching powder is suspended in water and it is made to 500 mL.25 mL of this
is transferred into a conical flask to which HCl and excess of KI solution are added.
The liberated iodine required 22.2mL of 0.14M sodium thiosulphate solution. Find the
percentage available chlorine in the given sample of bleaching powder.
Solution:
CaOC 2 H2 O Ca(OH)2 C 2
C 2 2KI 2KC I 2
I 2 2Na 2 S2 O3 2NaI Na 2S4 O 6
meq of Na2S2O3 meq of I2 meq of Cl2 22.2 0.14 = 3.108
meq of chlorine given by 25 mL suspension = 3.108
meq of chlorine given by 500 ml = 3.108 x 20 = 62.16

Y
62.16 35.5
mass of chlorine 2.2g
1000

EM
2.2 100
% of Available chlorine 25.96
8.5
33. There are two samples of HCl acid of normalities 0.24 and 0.38 and you are given one
litre each of the solution

D
a
a) What volumes of each of these two are to be mixed to get maximum volume of

ad
0.29N HCl

Vi A
aw
b) What volumes of the two are to be mixed to get maximum volulme of 0.36N HCl ?
Solution:
AC
ay
a) 1L of 0.24 + 555.5 mL of 0.38N
b) 1L of 0.38N + 166.6 mL of 0.24 N
34. j
With phenophthalein as indicator 25mL of a solution containing Na2CO3 and NaHCO3
required 11.36 mL of 0.11 N HCl for titration. The resulting solution required a further
IIT
le,

39.77 mL of 0.11 N HCl for titration using methyl orange. Calculate in grams of each
component in one litre of the solution
irc

Soltion:
Vol of HCl required for Na2CO3 = 11.36 2 = 22.72 mL
zC
ar R

22.72 0.11 53
mass of Na2CO3 in one litre 5.3g [Eq. mass of Na2CO3 = 53]
Ne E
en

25
volume of HCl required for NaHCO3 = 39.77 - 11.36 = 28.41 mL
B
T

28.41 0.11 84
AS

Mass of NaHCO3 in 1 Litre = 10.5 g [Eq. mass of NaHCO3 = 84]


25
35. 1.60g of pyrolusite mineral is digested with 50mL of 0.5M oxalic acid and some sulphuric
acid. The left out oxalic acid solution is made to 250mL and 25mL of this solution
M

required 26mL of 0.123N KMnO 4 solution. Calculate the percentage of MnO 2 in the
given sample of pyrolusite.
Solution:
MnO2 4H 2e Mn2 2H2O and MnO4 8H 5e Mn2 4H2O

COO2 2CO2 2e
|
COO
Initial meq of oxalic acid = 50 0.5 2 = 50
meq of oxalic acid left out = 26 0.123 10 = 32
meq of oxalic acid oxidized by MnO2 meq of MnO2 present in pyrolusite = 18
Equivalnet mass of MnO2 = 43.5
43.5 18 100
% MnO2 in the sample = 48.8
1000 1.6
Chemistry >>36<<
Volumetric Assignment

36. An oxide of a metal contains 40% by mass of oxygen. It is converted into the chloride of
the metal by a series of steps. Find the percentage of chlorine in the sample ?
Solution:
% age oxygen in metal oxide = 40 5 equivalents
metal = 60% 5 equivalents
60
eq. mass of metal = 12
5
Eq. mass of metal chloride = 12 + 35.5 = 47.5
35.5 100
% of chlorine in the metal chloride = 74.7
47.5
37. A sample of hydrazine sulphate (N2H6SO4) is dissolved in 100 mL of solution. 10mL of
this solution is made to react with excess of ferric chloride solution and warmed to

Y
complete the reaction. The ferrous ion formed required 20 mL of 0.02 M permanganate
solution. Find the an amount of hydrazine sulphate in one litre of the solution

EM
Given : N 2 H 4 4 Fe3 N 2 4 Fe 2 4 H

MnO4 5Fe2 8 H Mn2 5Fe3 4 H 2O

D
Solution:

a
As per the equation

ad
Vi A
meq of MnO 2+
4 meq of Fe meq of N2H4

aw
meq of MnO2 in 100 mL solution = 20 0.02 5 10 = 20
AC
ay
Eq. mass of N2H6SO4 = 32.5
20 32.5 1000 j
Mass of N2H6SO4 = 6.5g / L
1000 100
IIT

38. A 10mL sample of hydroxylamine sample is diluted to one litre and 50mL of this diluted
le,

solution is boiled with excess of ferric iron. The resulting solution required 12mL of
irc

0.02M KMnO 4 solution for its complete oxidation of ferrous to ferric. Calculate the
mass of hydroxylamine in one litre of the original sample.
zC
ar R

Given : 2 NH2 OH 4 Fe3 N 2O( s) 5Fe3 4 H 2O


Ne E
en

MnO4 5 Fe 2 8 H Mn 2 5 Fe3 4 H 2O
B
T

Solution:
meq of KMnO4 meq of Fe2+ meq of NH2OH in 50 mL
AS

meq of KMnO4 = 12 0.02 5 = 1.2


1.2 1000
meq of NH2OH in 1000 mL made up solution = = 24
50
10 mL original sample contains 24 meq
M

Normality = 2.4
Eq mass of NH2OH = 16.5
16.5 2400
Hence strength of original sample of NH2OH 39.6g / L
1000
39. How many litres of HCl gas measured at 300 C and 745 torr are required to prepare
1.25L of a 3.5M solution of hydrochloric acid ?
Solution:
number of moles of HCl gas present in 1.25L = 1.25 3.5 = 4.375
PV = nRT
4.375 0.0821 303 760
V 111.05L
745

Chemistry >>37<<
Volumetric Assignment
40. The formula mass of an acid is 82. A solution of 100 mL of the acid containing 58.5g of
it per litre is completely neutralized by 190.3mL of NaOH solution that contains 30g of
it in one litre. Find the basicity of the acid.
Solution:
Normality of NaOH = 0.75
meq of acid in 100 mL = 190.3 0.75
meq of acid in 1000 mL = 190.3 0.75 10 = 1427.25
mass of 1427.25 meq = 58.5 (given)
58.5 1000
mass of 1000 meq = 41 = Eq. mass of the acid
1427.25
M.Mass 82
Basicity of acid = eq.Mass = 2
41

Y
Assignment IV

EM
Assertion & Reason Type:-
a) A and R are true and R is the correct explanation of A
b) A and R are true and R is not the correct explanation of A

D
a
c) A is true but R is false d) A is false but R is true

ad
01. Assertion:- To 100 mL of 1M HCl solution on adding enough water to make it one litre,

Vi A
the solution gets diluted

aw
Reason:- The number of m.moles of HCl remains the same
AC
ay
02. Assertion:- H2O2 is an inorganic compound that acts as an oxidizing as well as reducing
agent in both acidic as well as in alkaline medium.
j
Reason:- When H2O2 acts as a reducing agent the oxygen given out is totally from H2O2
IIT

only
le,

03. Assertion:- Both Cu2+ and Fe3+ liberate Iodine from aqueous KI. One mole each of Cu2+
irc

and Fe3+ liberate same number of moles of Iodine in separate experiments from KI
Reason:- The change in the oxidation number of each metal ion is by one unit only.
zC
ar R

04. Assertion:- Every one mole of ferric oxalate corresponds to six equivalents while acting
as reducing agent.
Ne E
en

Reason:- Every one mole contains three oxalate ions that give six moles of electrons.
B
T

05. Assertion:- When a mixture of NaOH and Na 2CO 3 is titrated against HCl using
phenolphthalein the pink colour disappears when total NaOH is neutralised and Na2CO3
AS

is converted into NaHCO3


Reason:- NaHCO3 behaves like a weak acid to wards phenolphthalein.
06. Assertion:- The reaction between KIO3 and KI in acidic medium is an example of a
M

redox reaction.
Reason:- It is an example of dispropartionation reaction
07. Assertion:- The titration of As2O3(aq) against the solution of Iodine is to be carried out
in presence of NaHCO3
Reason:- NaHCO3 is needed to neutralise the acid HI formed in the process
08. Assertion:- The reaction between chlorine and hot and concentrated NaOH is an example
of disproportionation reaction
Reason:- In a disproportionation reaction the same compound is simultaneously oxidized
as well as reduced.
KEY
01. b 02. b 03.a 04. a
05. a 06. c 07.a 08. a
Chemistry >>38<<
Volumetric Assignment

Assignment V
Subjective Question ( Integer Answer Type ):-
01. The number of moles of NaH2PO4 required to neutralize 4.0 g of NaOH is found to be
x 102. Find x
Ans :x = 5
02. Given : MnO4 8 H 5Fe2 Mn2 5Fe3 4 H2O The volume of KMnO 4 solution in mL
containing 31.6g per litre that reacts with 5.56g of FeSO47H2O is x 10.Find the value
of x (Given M.M of KMnO4 is 158 and that of FeSO47H2O = 278)
Ans :x = 2
03. How many moles of oxalic acid are required to reduce K2Cr2O7 present in 6000mL of

Y
0.5M solution in acidic medium ?
Ans :9.0 moles

EM
04. The mole fraction of a solute in 4.5 molal aqueous solution is x 0.025. Find x
Ans :x = 3
05. 0.5g of a metal on combustion forms 0.66g of the metal oxide. Hence the equivalent

D
mass of the metal is A2. Find the value of A

a
ad
Ans : A = 5

Vi A
aw
06. 1.0g of a metal combines with oxygen to form 1.074g of metal oxide. If the specific heat
of the metal is 0.0593 Cal/g/K, find the valency of the metal
AC
ay
Ans : 1
j
07. A given sample of oleum is labelled as 109% of sulphuric acid. The percentage of free
SO3 in the sample is z 10. Find the value of z?
IIT

Ans : z = 4
le,

08. The number of millimoles of H 3PO4 present in 2.5L of 0.6N solution of the acid is
irc

z 100. Find the value of z


Ans: z = 5
zC
ar R

09. As per the equation:


Ne E
en

KIO3 5KI 6HC 6KC 3I2 3H2O , the equivalent mass of KIO 3 is obtained by
B
T

dividing the molecular mass by z. Find the value of z


Ans: z=5
AS

10. 10 mL of H2O2 solution of volume strength X required for its complete oxidation 10 mL
of 0.891N KMnO4. Hence find the value of X
Ans: X=5
M

11. 0.225g of an acid of molecular mass 90, required 50 mL of 0.2N NaOH solution. Find
the basicity of the acid
Ans: 2
12. A solution of specific gravity 1.6g/mL is 67% by mass of an acid. The percentage by
mass of the same acid when 100 mL of the above solution is diluted to 300 mL with
specific gravity of 1.19g/mL is x 10. Find the value of x
Ans: 3

Chemistry >>39<<
Volumetric Assignment

ASSIGNMENT - VI
MULTI-MATCHING TYPE:-
01. COLUMN - I COLUMN -II
Redox reaction Mole ratio of reductant
(unbalanced) and oxidant
COO H
Fe2 CO2 Mn2
A) Fe2 COO KMnO4
P) 5 : 1
3

H
B) Fe KMnO4 Fe3 Mn2 Q) 2 : 1

OH
C) KI MnO4 MnO2 IO3 R) 5 : 6

Y
D) Na 2S2O3 I2 NaI Na 2S4O6 S) 1 : 2
02. COLUMN - I COLUMN -II

EM
oxidation reaction(unbalanced) Eq. mass of the compound
4 M.Mass
A) Fe(CN)6 Fe3 6CO2 6NO3 P) eq.mass
6
M.Mass

D
a
B) Cu3P Cu2 H3PO4 Q) eq.mass
3

ad
Vi A
M.Mass
R) eq.mass

aw
C) NH2OH HNO3 H2O
11
AC
M.Mass

ay
D) Fe(COO)2 Fe 3 CO2 S) eq.mass
61
03. COLUMN - I
jCOLUMN -II
compound valence factor (z)
IIT
le,

COO
A) Fe2 COO
irc

P) As a salt, z = 6
3
zC

B) Al2(SO4)3 Q) As a reducing agent, z = 6


ar R

C) Ba(MnO4)2 R) As a salt, z = 2
Ne E

D) Ferrous oxalate S) As an oxidizing agent


en

in acid medium, z = 10
B
T

T) As a reducing agent, z = 3
04. COLUMN - I COLUMN -II
AS

compound valence factor(z)


A) KMnO4 P) As a salt, z = 1
B) K2Cr2O7 Q) As a oxidizing agent
M

in acid medium, z = 6
COOH
C) R) As a reducing agent, z = 2
COOH
COOH
D) S) As a salt, z = 2
COONa
T) As an oxidizing
in acid medium, z = 5
KEY:

01. A R; B P;C S; D Q 02. A S;B R;C P; D Q

03. A PQ; B P;C RS; D RT 04. A P, T;B Q, S; C R;D P,R

Chemistry >>40<<
Volumetric Assignment
COMPREHENSIONS
Comprehension:-I
The mass percentage of MnO 2 in the given sample of pyrolusite was determined by
reacting it with As2O3 in acid medium. A sample of 0.3g was ground and boild with 75
mL of 0.0125M As2O3 solution. On completing the reaction the solution is cooled and
titrated against 2.4 102 M KMnO4 and it required 12.5 mL of the solution to reach
the end point (At mass of As = 75, Mn = 55)
Answer the following:-
01. The equivalent mass of As 2O3 in the reactions with MnO 2 as well as KMnO 4 in acid
medium.
a) 198 b) 99 c) 49.5 d) 24.75
02. Number of equivalents of As2O3 reacted with acidified KMnO4

Y
a) 1.5 b) 1.5 103 c) 0.15 d) 1.5 102

EM
03. Percentage of MnO2 in the given sample of pyrolusite
a) 24.4 b) 32.6 c) 65.2 d) 16.3
Comprehension:-II

D
Hydrogen peroxide solution (20 mL) reacts quantitatively with a solution of KMnO4 (20

a
mL) acidified with dilute H 2SO 4. The same volume of the KMnO 4 solution is just

ad
Vi A
decolourised by 10 mL of MnSO4 in neutral medium simultaneously forming a dark

aw
brown precipitate of hydrated MnO2. The brown precipitate is dissolved in 10 mL of 0.2
AC
M sodium oxalate under boiling condition in the presence of dilute H2SO4.

ay
Answer the following:
04. Mass of MnO2 formed
a) 4.35g b) 0.174 g
j
c) 0.348g d) 3.44 g
IIT
le,

05. As per the reaction between KMnO 4 and MnSO 4 in neutral medium, the equivalent
mass of KMnO4 (M. Mass of KMnO4 = M)
irc

M M M
zC

a) b) M c) d)
ar R

3 5 2
06.Molarity of H2O2 solution
Ne E
en

a) 0.2 b) 0.4 c) 0.8 d) 0.1


B
T

Comprehension:-III
A 3.0 g sample containing Fe3O4, Fe2O3 and an inert impure substance is treated with
AS

excess of KI solution in presence of dilute H2SO4.The entire iron is converted to Fe2+


along with the liberation of iodine. The resulting solution is diluted to 100 mL. A 20 mL
of the dilute solution requires 11 mL of 0.5 M Na2S3O3 solution to reduce the iodine
M

present.A 50 mL of the diluted solution after complete extraction of iodine required


12.8 mL of 0.25 M KMnO4 solution in dilute H2SO4 medium for the oxdation of Fe2+.
Answer the following:-
07. Total no of meq of Iron present
a) 27.5 b) 32.0 c) 13.75 d) 16
08. Mass of Fe3O4 present in the given sample
a) 2.088 g b) 1.044 g c) 3.132 g d) 0.522 g
09. Percentage by mass of Fe2O3 in the given sample
a) 24.15 b) 12.05 c) 49.33 d) 89.6
KEY:
01. c 02. b 03. b 04.b
05. a 06. d 07. b 08. b 09. c

Chemistry ***** >>41<<