Intensive Revision Program

of
Physical Chemistry

By : Brijesh Jindal Sir

KEY CONCEPTS
Oxidation Number :
It is the charge (real or imaginary) which an atom appears to have when it is in combination. It may be
a whole no. or fractional. For an element may have different values. It depends on nature of compound
in which it is present. There are some operational rules to determine oxidation number.
Stock's Notation :
Generally used for naming compounds of metals , some non-metals also. eg. Cr2O3 Chromium (iii)
oxide and P2O5 Phosphorous (v) oxide .
Oxidation :
Addition of oxygen , removal of hydrogen , addition of electro - negative element , removal of electro
- positive element , loss of electrons , increase in oxidation number (de-electronation) .
Reduction :
Removal of oxygen, addition of hydrogen, removal of electronegative element, addition of electro +ve
element, gain of electrons, decrease in oxid. no. (electronation).
Redox Reactions :
A reaction in which oxidation & reduction occur simultaneously .
Oxidising Agents :
(oxidants, oxidisors). They oxidise others, themselves are reduced & gain electrons. eg. O2, O3,
HNO3, MnO2, H2O2, halogens, KMnO4, K2Cr2O7, KIO3, Cl(SO4)3, FeCl3, NaOCl, hydrogen
ions.
[Atoms present in their higher oxidation state.]
Reducing Agents :
H2, molecular is weak but Nascent hydrogen is powerful . C, CO, H2S, SO2, SnCl2, Sodium thio
Sulphate, Al, Na, CaH2, NaBH4, LiAlH4 . They reduce others, themselves get oxidised & lose electrons.
Also called reductants or reducers .
[Atoms present in their lower oxidation state.]

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 Both Oxidising & Reducing Agents :
SO2 , H2O2 , O3 , NO2 , etc .
Balancing Of Equations :
(i) Ion - electron method
(ii) Oxidation number method
[Concept involved that in any chemical reaction e– cannot be produced so no. of e–s in O.H. & R.H.
should be same]
Oxidation Half Reaction : Na ¾® Na+ + e ¾ .
Reduction Half Reaction : F2 + 2 e ¾ ¾® 2 F ¾ .

EQUIVALENT CONCEPT
(A) Volumetric analysis :
This mainly involve titrations based chemistry. It can be divided into two major category.
(I) Non-redox system (II) Redox system

(I) Non – redox system

This involve following kind of titrations:
1. Acid-Base titrations
2. Back titration
3. Precipitation titration
4. Double indicator acid base titration

Titrimetric Method of Analysis : A titrimetric method of analysis is based on chemical reaction such as.
aA + tT ¾® Product
Where ‘a’ molecules of “analysis”, A, reacts with t molecules of reagent T.
T is called Titrant normally taken in buret in form of solution of known concentration. The solution of
titrant is called “standard solution”.
The addition of titrant is added till the amount of T, chemically equivalent to that of ‘A’ has been added.
It is said equivalent point of titration has been reached. In order to know when to stop addition of
titrant, a chemical substance is used called indicator, which respond to appearance of excess of titrant
by changing colour precisely at the equivalence point. The point in the titration where the indicator
changes colour is termed the ‘end point’. It is possible that end point be as close as possible to
the equivalence point.
The term titration refer’s to process of measuring the volume of titrant required to reach the end point.
For many years the term volumetric analysis was used rather than titrimetric analysis. However from a
rigorons stand point the term titrimetric is preferable because volume measurement may not be
confirmed to titration. In certain analysis, for example one might measure the volume of a gas.
We can adopt mole method in balanced chemical reactions to relate reactant and products but it is
more easier to apply law of equivalents in volumetric calculations because it does not require
knowledge of balanced chemical reactions involved in sequence. Law of equivalents refers to that,
equivalents of a limiting reactant is equal to equivalent of other reactant reacting in a chemical reaction
or equal to equivalents of products formed in reaction.

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 n-factor in non-redox system
n factor here we mean a conversion factor by which we divide molar mass of substance to get equivalent
mass and it depends on nature of substance which vary from one condition to another condition. We
can divide n-factor calculations in two category.
(A) when compound is not reacting.
(B) when compound is reacting.
Acid-Base titration
To find out strength or concentration of unknown acid or base it is titrated against base or acid of
known strength. At the equivalence point we can know amount of acid or base used and then with the
help of law of equivalents we can find strength of unknown.
Meq of acid at equivalence point = Meq of base at equivalence point

Back titration
Back titration is used in volumetric analysis to find out excess of reagent added by titrating it with
suitable reagent. It is also used to find out percentage purity of sample. For example in acid-base
titration suppose we have added excess base in acid mixture. To find excess base we can titrate the
solution with another acid of known strength.
Precipitation titration :
In ionic reaction we can know strength of unknown solution of salt by titrating it against a reagent with
which it can form precipitate. For example NaCl strength can be known by titrating it against AgNO3
solution with which it form white ppt. of AgCl.
So meq. of NaCl at equivalence point = meq of AgNO3 used = meq of AgCl formed
Double indicator acid-base titration:
In the acid-base titration the equivalence point is known with the help of indicator which changes its
colour at the end point. In the titration of polyacidic base or polybasic acid there are more than one end
(S) No colour point for each step neutralization. Sometimes one indicator is not able to give colour
change at every end point. So to find out end point we have to use more than one indicator. For
example in the titration of Na2CO3 against HCl there are two end points.
Na2CO3 + HCl ¾® NaHCO3 + NaCl
NaHCO3 + HCl ¾® H2CO3 + NaCl
When we use phenophthalein in the above titration it changes its colour at first end point when NaHCO3
is formed and with it we can not know second end point. Similarly with methyl orange it changes its
colour at second end point only and we can not know first end point. It is because all indicator changes
colour on the basis of pH of medium. So in titration of NaHCO3, KHCO3 against acid phenolphthalein
can not be used.
So we can write with phenolpthalein, if total meq of Na2CO3 = 1 then
½ meq of Na2CO3 = meq of HCl
with methyl orange,
meq of Na2CO3 = meq of HCl

Titration Indicator pH Range n factor

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 Na2CO3 Phenolphthalein 8.3 – 10 1
against acid
K2CO 3 Methyl orange 3.1 – 4.4 2

Note:
When we carry out dilution of solution, meq eq, milli mole or mole of substance does not change
because they represent amount of substance, however molar concentration may change.

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 EXERCISE

Single Correct:

1. Equivalent weight of carbon in CO and CO2 are in the ratio of :

(A) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) 1 : 4

2. The amount of wet NaOH containing 15% water required to prepare 70 litres of 0.5 N solution is :
(A) 1.65 kg (B) 1.4 kg (C) 16.5 kg (D) 140 kg

3. 28 NO3– + 3As2S3 + 4H2O  6AsO43– + 28NO + 9SO42– + 8H+.

What will be the equivalent mass of As2S3 in above reaction : (Molecular mass of As2S3 = M)

M M M M
(A) (B) (C) (D)
2 4 24 28

4. In the following reaction :

3Fe + 4H2O  Fe3O4 + 4H2, if the atomic weight of iron is 56, then its equivalent weight will be :
(A) 42 (B) 21 (C) 63 (D) 84

5. If 25 mL of a H2SO4 solution reacts completely with 1.06 g of pure Na2CO3, what is the normality of this acid solution
:
(A) 1 N (B) 0.5 N (C) 1.8 N (D) 0.8 N

6. 125 mL of 63% (w/v) H2C2O4 . 2H2O solution is made to react with 125 mL of a 40%(w/v) NaOH solution. The
resulting solution is: (ignoring hydrolysis of ions)
(A) neutral (B) acidic (C) strongly acidic (D) alkaline

7. A certain weight of pure CaCO3 is made to react completely with 200 mL of a HCl solution to give 224 mL of CO2 gas
at STP. The normality of the HCl solution is:
(A) 0.05N (B) 0.1 N (C) 1.0 N (D) 0.2 N

8. What volume of 0.05 M Ca(OH)2 solution is needed for complete conversion of 10 mL of 0.1 M H3PO4 into Ca(H2PO4)2?
(A) 10 mL (B) 5 mL (C) 20 mL (D) 40 mL

9. 22.7 mL of (N/10) Na2CO3 solution neutralises 10.2 mL of a dilute H2SO4 solution. The volume of water that must be
added to 400 mL of this H2SO4 solution in order to make it exactly N/10.
(A) 490.2 mL (B) 890.2 mL (C) 90.2 mL (D) 290.2 mL

10. 25 mL of a 0.1 M solution of a stable cation of transition metal Z reacts exactly with 25 mL of
0.04 M acidified KMnO4 solution. Which of the following is most likely to represent the change in oxidation state of
Z correctly :
(A) Z+ ® Z2+ (B) Z2+ ® Z3+ (C) Z3+ ® Z4+ (D) Z2+ ® Z4+

11. 4.9 g of K2Cr2O7 is taken to prepare 0.1 L of the solution. 10 mL of this solution is further taken to oxidise Sn2+ ion
into Sn4+ ion. If Sn4+ so produced is used in 2nd reaction to prepare Fe3+ ion from Fe2+, then the millimoles of Fe3+ ion
formed will be : (assume all other components are in sufficient amount) [Molar mass of K2Cr2O7 = 294]
(A) 5 (B) 20 (C) 10 (D) none of these

12. 10 gm sample of bleaching powder was dissolved into water to make the solution one litre. To this solution 35 mL of
1.0 M Mohr salt solution was added containing enough H2SO4. After the reaction was complete, the excess Mohr
salt required 30 mL of 0.1 M KMnO4 for oxidation. The % of available Cl2 approximately is (mol wt = 71)
(A) 10% (B) 12.7% (C) 7.1 % (D) 22%

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 13. In an experiment, 50 mL of 0.1 M solution of a salt reacted with 25 mL of 0.1 M solution of sodium sulphite. The half
equation for the oxidation of sulphite ion is :
SO32– (aq) + H2O  SO42– (aq) + 2H+ + 2e–
If the oxidation number of metal in the salt was 3, what would be the new oxidation number of metal :
(A) 0 (B) 1 (C) 2 (D) 4

14. HNO3 oxidises NH4+ ions to nitrogen and itself gets reduced to NO2. The moles of HNO3 required by 1 mole of
(NH4)2SO4 is :
(A) 4 (B) 5 (C) 6 (D) 2

15. How many litres of Cl2 at STP will be liberated by the oxidation of NaCl with 10 g KMnO4 in acidic medium: (Atomic
weight : Mn = 55 and K = 39)
(A) 3.54 (B) 7.08 (C) 1.77 (D) None of these

16. When tetracarbonylnickel(0) is heated, it dissociates into its components. If 5 moles of this compound is heated and
the resulting gaseous component is absorbed by sufficient amount of I2O5, liberating I2. What volume of 4M Hypo

solution will be required to react with this I2 : Ni(CO)4  Ni + 4CO

Ni(CO)4  Ni + 4CO
(A) 1 lit. (B) 2 lit. (C) 3 lit. (D) 4 lit.

17. One gram of Na3AsO4 is boiled with excess of solid KI in presence of strong HCl. The iodine evolved is absorbed
in KI solution and titrated against 0.2 N hypo solution. Assuming the reaction to be
AsO43– + 2H+ + 2I–  AsO33– + H2O + I2
calculate the volume of hypo consumed. [Atomic weight of As = 75]
(A) 48.1 mL (B) 38.4 mL (C) 24.7 mL (D) 30.3 mL

18. If 10 g of V2O5 is dissolved in acid and is reduced to V2+ by zinc metal, how many mole of I2 could be reduced by the
resulting solution, if it is further oxidised to VO2+ ions :
[Assume no change in state of Zn2+ions] (Atomic masses : V = 51, O = 16, I = 127)
(A) 0.11 (B) 0.22 (C) 0.055 (D) 0.44

19. During the disproportionation of Iodine to iodide and iodate ions, the ratio of iodate and iodide ions formed in
alkaline medium is :
(A) 1 : 5 (B) 5 : 1 (C) 3 : 1 (D) 1 : 3

20. When arsenic sulphide is boiled with NaOH, sodium arsenite and sodium thioarsenite are formed according to
reaction :
y
x As2S3+ y NaOH  x Na3AsO3 + x Na3AsS3 + H O. What are the values of x and y?
2 2
(A) 1, 6 (B) 2, 8 (C) 2, 6 (D) 1, 4

21 The number of moles of KMnO4 that will be needed to react completely with one mole of ferrous
oxalate in acid solution is,
(A) 3/5 (B) 2/5 (C) 4/5 (D) 1
22 The number of moles of KMnO4 that will be needed to react with one mole of sulphite ions in acidic
solution is
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1

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 23 The normality of 0.3 M phosphorus acid (H3PO3) is
(A) 0.1 (B) 0.9 (C) 0.3 (D) 0.6

24 One mole of calciums phosphide on reaction with excess of water gives

(A) one mole of phosphine (B) Two moles of phsophoric acid
(C) Two moles of phosphine (D) One mole of phosphorus pentoxide

25 An aqueous solution of 6.3 gm of oxalic acid dihydrate is made upto 250 ml. The volume of 0.1 N
NaOH required to completely neutralize 10 ml of this solution is
(A) 40 ml (B) 20 ml (C) 10 ml (D) 4 ml

26 In the standarization of Na2S2O3 using K2Cr2O7 by iodometry the equivalent mass of K2Cr2O7 is
M. Mass M. Mass M. Mass
(A) (B) (C) (D) Same as M. Mass.
2 6 3

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 SUBJECTIVE

1. 2.6 g of an element X is reacted with an aqueous solution containing NaOH and NaNO3 to yield Na2XO2 and
NH3. NH3 thus liberated is absorbed in 100 mL of 0.11 M H2SO4. The excess acid required 48 mL of 0.25M
NaOH for complete neutralisation. Find the atomic weight of X.

2. A 1 g sample of Fe2O3 solid of 55.2 percent purity is dissolved in acid and reduced by heating the solution
with zinc dust. The resultant solution is cooled and made upto 100 mL. 25 mL of this solution requires 17
mL of 0.0167 M solution of an oxidant for titration. Calculate the number of moles of electrons taken up by
one mole of the oxidant in the reaction of the above titration.

3. Potassium acid oxalate K2C2O4. 3H2C2O4 . 4H2O can be oxidized by MnO4– in acid medium. Calculate the
volume of 0.1 M KMnO4 reacting in acid solution with one gram of the acid oxalate.

4. A 3 mole mixture of FeSO4 and Fe2(SO4)3 required 100 mL of 2M KMnO4 solution in acidic medium. Find
the mole fraction of FeSO4 in the mixture.

5. A 1 g sample of H2O2 solution containing x % H2O2 by mass requires x cm3 of a KMnO4 solution for
complete oxidation under acidic conditions. Calculate the normality of KMnO4 solution.

6. 0.2828 g of iron wire was dissolved in excess dilute H2SO4 and the solution was made upto 100 mL. 20 mL
of this solution required 30 mL of N/30 K2Cr2O7 solution for exact oxidation. Calculate percent purity of Fe
in wire.

7. A solution of H2O2 labelled as ‘20 V' was left open. Due to this some, H2O2 decomposed and volume
strength of the solution decreased. To determine the new volume strength of the H2O2 solution, 10 mL of
the solution was taken and it was diluted to 100 mL. 10 mL of this diluted solution was titrated against 25
mL of 0.0245 M KMnO4 solution under acidic condition. Calculate the volume strength of the H2O2 solution.

8. How many mole of FeCl3 can be prepared by the reaction of 10 g KMnO4, 1.07 mole FeCl2 and 500 mL of
3 M HCl ? MnCI2 is the reduction product.

9. The reaction Cl2(g) + S2O32–  SO42– + Cl– is to be carried out in basic medium. Starting with 0.15
mole of Cl2, 0.01 mole S2O32– and 0.3 mole of OH¯, how many moles of OH¯ will be left in solution after
the reaction is complete. Assume no other reaction occurs.

10. An equal volume of a solution of a reducing agent is titrated separately with 1 M KMnO4 in acid, neutral and
alkaline media. The volumes of KMnO4 required are 20 mL in acid, 33.3 mL in neutral and 100 mL in
alkaline media. Find out the oxidation state of manganese in each reduction product. Give the balanced
equations for all the three half reactions. Find out the volume of 1 M K2Cr2O7 consumed, if the same volume
of the reducing agent is titrated in acid medium.

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 ANSWER KEY
OBJECTIVE

1. (C) 2. (A) 3. (D) 4. (B) 5. (D)

6. (A) 7. (B) 8. (A) 9. (A) 10. (D)

11. (C) 12. (C) 13. (C) 14. (C) 15. (A)

16. (B) 17. (A) 18. (A) 19. (A) 20. (A)

21. A 22. A 23. D 24. C 25. A

26. B

SUBJECTIVE

1
1. 65 2. 6 3. V = 31.5 mL 4.
3

5. 0.588 N 6. 99% 7. 17.15 V 8. 0.316

9. 0.2 10. +2, +4, +6, 16.67 mL

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