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Before the development of electronic view of reactions, oxidation was defined as:
A reaction which leads to the addition of oxygen or electronegative element to a
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substance or removal of hydrogen or electropositive element from a substance.
For example:
2Mg(s) + O ( ) 2MgO(s)
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S(s)+ O ( ) SO ( )
CH ( ) + 2O ( ) CO ( ) + 2H2O(l)
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Mg(s) + F ( ) MgF ( )
2K4[Fe(CN)6] +H2O2 2K3 [Fe(CN)6](aq.) + 2KOH(aq.)
cr
A close study of the above reactions reveals that in first two reactions, oxygen is
being added. In the next two reactions addition of oxygen as well as removal of
hydrogen is taking place. In the last but one reaction an electronegative element
fluorine is being added, while in the last reaction an electropositive element
potassium is removed from K4Fe(CN)6 [potassium ferrocyanide] when it is
converted into K3Fe(CN)6 [potassium ferricyanide].
Similarly reduction was defined as:
A reaction which leads to the removal of oxygen or electronegative element
from a substance, or addition of hydrogen or electropositive element to a
substance.
For example:
2HgO(s) 2H ( ) + O ()
Let us now examine the following chemical reaction with the help of concepts of
oxidation and reduction which we have just gone through.
2HgCl ( .) + SnCl ( .) Hg2Cl ( ) + SnCl ( .)
(mercuric chloride) (stannous chloride) (mercurous chloride (stannic chloride)
or calomel)
We find that conversion of SnCl2 into SnCl4 leads to the addition of
electronegative element chlorine to SnCl2. Hence SnCl2 is oxidized to SnCl4.
Simultaneously conversion of HgCl2 into Hg2Cl2 leads to the addition of
electropositive element mercury to HgCl2. Hence HgCl2 is reducing to HgCl2. It
means oxidation and reduction always occur simultaneously in all oxidation
reduction reactions. Hence a new word REDOX was coined for this class of
chemical reactions.
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2. Modern Concepts for Redox reactions
i. Redox reactions in terms of election transfer reactions (electronic concept)
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Let us examine the following reaction
2Na(s) + Cl ( ) 2Na+Cl-(s) Sodium chloride (ionic compd.)
Here we see that two Na atoms are converted into two Na+ with the loss
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of two electrons i.e. one electron per atom as is clear from their electronic
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configurations
Na (atom) Na (ion)
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(ls , 2s p , 3s ) e (ls , 2s p )
On the other hand these two electrons are taken up by two chlorine atoms
to form two chloride ions i.e. each Cl atom gains a electron which is clear
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it is acceptor of electron(s)
Reducing agent: means which reduces others but itself is oxidized, hence
it is donor of electron(s)
Let us understand a redox reaction with the help of following experiment.
Take a beaker containing some Cu(NO3)2 aqueous solution into it. The
color of the solution is blue due hydrated Cu2+ ions. Now place a Zn rod in
it. Wait for some time. What do you observe? Look in the reddish
deposition of metallic copper on the zinc rod. The overall reaction can be
represented by the following ionic equation.
Zn(s) + Cu2+(aq.) (Blue) Zn2+(aq.)(Colorless) + Cu(s)(reddish)
This is obviously a redox reaction which can be further represented by
following two half reactions
Zn(s) Zn2+(aq.) +2 (oxidation)
Cu2+(aq.)+2 Cu(s) (reduction)
Therefore, in this reaction Zn is behaving as reducing agent and Cu 2+ as
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oxidizing agent.
ii. Concept of oxidation numbers ee
Another method to deal with redox reactions is with the help of oxidation
number or oxidation state of the species involved.
Oxidation number (also called oxidation state) of an element is defined as
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the charge calculated per atom with the help of a set of rules. These rules
are formulated on the basis that in a covalent bond, the shared electrons
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K [Fe[-2+0 = -2](CO)4]
Thus oxidation number of iron in the complex K2[Fe(CO)4] is equal to -2.
x. Except for the elements covered in the above rules, for all elements
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belonging to p block of the periodic table (from Boron family to
Halogens) the possible oxidation numbers for an element can be from +n
to n-8 where n means the group number. Since sulphur (S) belongs to VI th
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group of the periodic table hence it can have oxidation numbers from -2 to
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After studying all the above rules now we are in a position to define
the following terms in terms of oxidation number.
OXIDATION: means an increase in the oxidation number of the element in the given
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substance.
Thus if in a reaction K2MnO4 is converted into K2MnO4, we see that oxidation number of
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Mn increases from +6 to +7. Hence it becomes a case of oxidation.
REDUCTION: means decrease in the oxidation number of the element in the given
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MnO MnO
substance for example
+7 +4
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OXIDIZING AGENT OR OXIDANT: means a reagent which can increase the oxidation
number of an element in a given substance. For example in acid medium KMnO 4
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b) Comproportionation
It is reverse of disproportionation In such a reaction two species with the
same element in different oxidation states form a product in which the
element is in an intermediate oxidation state. For example
Ag ( .) + Ag ( ) 2Ag ( .)
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ideas related to MOLE.
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In SI system, mole (symbol, mol) was introduced as seventh base quantity for
the amount of a substance.
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One mole is the amount of a substance that contains as many particles or
entities as there are atoms in exactly 12g of the C 12 isotope. Since the mass of a C12
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Thus number of moles for any mass of a substance can be calculated using the
formula
However if the substance is in the atomic state then molar mass means atomic mars
(atomic weight) and if in the form of ion then molar mars means molar mars of the
ion.
Therefore:
88
88g of CO2(g) means = 2 mole CO2
44
58.5
58.5g of NaCl means = 1 mole NaCl
58.5
[Atomic mass Na = 23, Cl = 35.5]
238
238g of MnO 4 means = 2 mole MnO 4
119
[Atomic mass: Mn = 55, O=16] and so on.
At the same time we must not forget that 1 mole of a gas occupies 22.4L volume at
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273 K temp. and 1 atm. pressure (NTP)
With this much knowledge, we are in a position to apply mole concept to any
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chemical reaction provided we have a balanced chemical equation representing that
reaction.
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Consider a reaction:
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The answer is that it tells us for example for the above equation (or
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This is the mole concept. Thus with its help if we know the number of moles of one
substance we can calculate the number of moles of the other substance needed to
react with it or to be produced when reaction is complete.
The following numerical illustrations will make the use of mole concept further clear.
1. A solution containing 2.68 x 10-3 moles of An+ ions require 1.61 x 10-3 moles
of MnO 4 for oxidation of An+ into AO 3 in acid medium. Calculate the value of
n.
Solution As is clear from the text of the question that here MnO 4 is oxidizing agent
oxidizing A n+ into AO 3 . Further we have already learnt that in acid medium MnO 4
is reduced into Mn2+. Hence we can write the following two half equations, balance
them and add to get the net balanced equation for the complete reaction.
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Multiply equation (1) by (5-n) and (2) by 5 and add them so as to cancel out the
electrons. Thus we get
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[8(5-n)-30]H+ + (5-n) MnO 4 + 5An+ (5-n) Mn2+ + 5AO 3 + [4(5-n)-15] H2O.
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number of moles of A n 5
ac
=
number of moles of MnO 4 (5 - n)
cr
2.68 x 10 -3 5
=
1.61 x 10 -3
(5 - n)
NOTE: Just to save the time, there is no need to write the entire balanced equation,
pick up the molar coefficients of the species for which we want to apply mole
concept.
Solution: The half reactions and hence their equations are, assuming that metal (m)
is reduced from +3 to + state.
(3- ) e + M3+ M+ x 2
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no. of moles or mmoles of M 3 2
=
no. of moles or mmoles of SO 2 - (3 - x)
3 ee
Since from the question we have
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No. of m.moles of M3+ = 0.1 x 40 = 4
and No. of m.moles of SO 2 = 0.1 x 20 = 2
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3
ac
4 2
We have = solving this we get =2 or +2
2 (3 - x)
cr
Where valence factor means the number of electrons lost or gained per molecule or
ion in the balanced half equation for reducing or oxidizing agent respectively.
Further do not forget for any solution of an oxidizing or reducing agent that
Normality = molarity x uf
no. of equivalents = no. of moles x uf
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Solution: Since the balanced half equation for the conversion of MnO 4 into Mn2+ in
acid medium is: ee
5 e + 8H++ MnO 4 Mn2+ + 4H2O
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Hence valence factor for MnO 4 becomes 5
55 64 119
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However if we wish to calculate equivalent weight for the molecular form K MnO 4 ,
then since K is not involved in oxidation or reduction, hence it becomes a spectator
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39 x 2 52 x 2 16 x 7
Equivalent weight of K2Cr2O7 = 6
= 49 Ans.
2 16 x 2
Hence equivalent weight of H2O2 = 2
= 17 Ans.
H2O2 O2 + 2H+ + 2 e
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2 16 x 2
Equivalent weight = 2
= 17 Ans. ee
Part (iii) Here we wish to study some typical calculations involving compounds like
H2O2, hypo, bleaching powder etc. involved in some redox reactions.
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H2O2
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important thing about its aqueous solution is the style of expressing its
concentration which is known as volume strength of H2O2 solution
For example a 20 volume solution of H2O2 means1 litre of such a solution will
liberate 20L of O2(g) at NTP according to the following reaction:
1. 25mL of H2O2 solution were added to excess of acidified solution of KI. The I 2
so liberated required 20mL of 0.1M Na2S2O3 solution for titration. Calculate
the volume strength of H2O2. Also write the reactions involved.
Solution Reactions:
1 m mole
2 2
I2 + 2S2O 3 S4O 6 + 2I
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20mL
0.1M ee
m moles = 2
m mole 1
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' V'
molarity = 11.2 where V is volume strength
V
0.04 = 11.2
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The chemical reactions involved are ee
CaOCl2 + 2CH3COH Ca(CH3COO)2 + Cl2 + H2O
2 2
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Calculation
Let the molarity of hypo solution used is , and its volume used in titration be V
cr
mL.
XxV
moles of Hypo consumed = 1000
XV
Then according to mole concept moles of I2 must be half of this i.e. 2000 and these
XV x 71
must be equal to moles of Cl2 Hence mass of Cl2 liberated = g
2000
XV71
W(g) bleaching powder gives Cl2 = 2000 g
X x V x 71 X x V x 3.55
% of Cl2 = 2000 x W x 100 = W
.
We can directly apply this formula provided such data are given as is clear from the
following numerical illustration.
X x V x 3.55
% Cl2 = W
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Calculation of % of free SO3 in oleum (H2S2O7) solution
from which it becomes desirable to calculate free SO 3 present in that. Let us solve
the following question to understand it.
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Solution A 109% H2SO4 means that if we take 100g of such a oleum solution and
add to that 9g H2O. In other words 9g H2O must combine with free SO3 present in
oleum.
80
% (w/w) of SO3 in the given sample of oleum = 18 ( -100) [ >100]
We know that hard water does not give sufficient lather with soap. Hardness
is due to the presence of salts of Ca and Mg. further the temporary hardness is due
to the presence of bicarbonates of Ca and Mg while permanent is due the presence
of sulphates and chlorides of Ca & Mg.
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The extent of hardness in water is expressed in terms of degree of hardness
which is defined as: ee
the number of parts of CaCO3 equivalent to various calcium and magnesium
salts present in a million parts of water by mass.
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Thus it is expressed in ppm (w/w) unit. Let us solve the following numerical to
understand it.
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Further since molecular weights of MgSO4 and CaCO3 are 120 and 100 respectively
hence we can say that
120g MgSO4 is equivalent to 100g CaCO3
12g MgSO4 will be equivalent to 10g CaCO3
Degree of hardness in the given sample of water = 10 ppm. AnS