CHAPTER 7

OXIDATION-REDUCTION REACTIONS

There are many different kinds of chemical reactions, some of which have
been discussed in the previous chapter. One very important class of chemical
reaction deserves special study and these are oxidation-reduction reactions.
Oxidation-reduction reactions arc defined according to various concepts.

1. The Classical Concept : According to the classical concept,

oxidation" simply means the addition of oxygen to elements or compounds.
This was the original idea about oxidation and likewise the word "reduction" was
used to indicate the removal of oxygen from a compound. The definitions were
further extended to include other electronegative and elcuropositive , atoms or
groups as well as the removal and addition of hydrogen to make the terms more
gener-ahzed.

(a) Addition of oxygen :

2Mg + 02 = 2MgO

2CO + 02 = 2CO2

(b) Addition of electronegative elerneni or group .-

2FeCl 2 + C12 heat - 2FcC13

heat
SnC1 2 + C12 SnC14
Cu + S h"_ CuS
190 D41RODUCnON TO MODERN INORGANIC C1 IEMISTRY

Hydrogen peroxide oxidizes an acidified solution of ferrous sulphate to ferric

of SO4-2 radical :
sulphate increasing the proportion

2FeSO4 + H2SO4 + H 202 = Fe2(SO4)3 + 21-120

(c)Removal of hydrogen :

When H 2S is passed into an acidified solution of potassium dichromate, it is

oxidized to sulphur:
-1-12, S
H2S

i.e., H2S +K2Cr207+HCI ) S + CrC13 + KCI +H20

Chlorine is evolved when HCl is heated with Mn02. Here HCI is oxidized
to chlorine :
-H2_4
2HCI C12

i. e., 4HCI + Mn02 ^Le-81

1 MnC1 2 +C12 + 21-120

(d)Reinoval of electropositive elefftent or group :

Potassium iodide is oxidized to iodine by the action of hydrogen peroxide.

Here K* is removed from KI :

K __^
2KI + H202 2KOH +12

Potassium ferrocyanide is oxidized to potassium ferricyanide by removal of

K+
K I
K4FC(M6 K3Fe(CM6

It can now be easily seen that the definition of the term "reduction" will be

just the reverse of that of "oxidation" from the classical point of view.

T he term "reduction" may be illustrated by the following reaction.

(a) Addition of hydrogen :

2N 2 + 31-1 2 2NHj

S + H2 H2S
In the above reactions N and S are reduced to NH3 and H 2 S respectively by
addition of H2-
 0XIDMION -REDUC- M)N REAC-11ONS 191

(b)Addition of eleciropositive element or group :

on
Mercuric chloride is reduced to mercurous chloride heating with mercury.

Here the electropositivc Hg is added to HgC12:

Hg 2CIe + Ill; -4 H92Cl2

(c)Removal of oxygen :

CUO -:^' Cu

i. e., when hydrogen is passed over heated CuO, it is reduced to Cu by

removal of oxygen. Thus,

CuO + H2 = Cu + H20

Similarly, Fc.203 + 3C = 217e + 3CO

Fe203 is reduced to iron by removal of oxygen on heating with carbon.

(d)Removal of electronegative element or group

FeC13 FcCl2

This can happen in presence of

FcC13 is reduced to FeC12 by removal of Cl.
zinc in acid solution or by means of SnC12. Thus,

2FeCI 3 + SnC12 = 2FeCl 2 + SnCl4

Similarly, CUSO4 + Fe = Cu + FcSO4

CuSO4 is reduced to copper by removal O f SO4-2 by Fe.

2. Valence state Concept : It will be observed that the oxidation-

reduction reactions take place with changes in the valence state of certain atom in
the compounds undergoing the reaction. Thus when ferrous chloride is oxidized

to ferric choloride, the valence state of iron is increased from divalent to

trivalent. Similarly, when H-2S is oxidized to elementary sulphur, the valence

state of sulphur is increased from -2 to zero and when CuO is reduced to Cu, the
valence state of copper is decreased from +2 to zero. On the basis of valence
state, therefore, the following simplified definitions for oxidation and reduction

may be put forward:—

Oxidation is a chemical reaction which involves change of valence state in

the positive direction.

 192 NTRODUCUON TO MODERN INORGXNIC C1 1EMBIRY

Reduction is a chemical reaction which involves change of valence state in

the negative direction.

3. The Electronegativity Concept : Elcuronegativity is defined as

the tendency for an atom in a molecule to attract electrons. During oxidation-
reduction reaction it can be observed that certain atoms in the compounds
undergo decrease or increase of cleuronegativity value. During oxidation there is
always a decrease in the elcuronegativity of an atom, whereas reduction involves
increase of clectronegativity value. Substances having high electronegativity act
as oxidizing agent such as fluorine, halogen, oxygen etc. Substances having low
values of eleuronegativity act as reducing agent, such as hydrogen, sodium,
potassium etc.

4. Ttfe Charge Concept : Since the terms clectropositive and

eleuronegative elements have been used in the classical concept of oxidation-
reduction reactions. The following procedure may be adopted to illustrate the
phenomena :—

When ferrous salt is oxidized to ferric salt, it can be seen that Fe' is
converted to Fe *3 . Similarly, when copper is converted to copper sulphate,
CUSO 4, the charge on copper increases from zero to +2. When H2S is oxidized
Jo elementary sulphur, the charge on sulphur is changed from –2 to zero.
— *3
(Reduction) Fe' Fe (oxidation)
(Reduction) Cu' Cu +1 (oxidation)

(Reduction) S-2 S' (oxidation)

Naturally, when the reaction takes place in the reverse manner i. e.,to the
left, this indicates reduction. Hence the following definition :

Oxidation is a process which involves increase of positive charges on an

element or removal of negative charges.

Reduction is a process which involves increase of negative charges or

decrease of positive charges on an element.

If we examine this definition of oxidation-reduction reaction it is not quite

clear as to how this increase of positive charges or removal of ncgative charges
occurs. Obviously, there is no mechanism to consider direct addition of positive
 0XIDMION-REDUMON REACHONS 193

charges to an atom by chemical reaction. Oxidation-reduction reaction is best

explained on the basis of electron transfer process as given by the electronic
concept.

5. The Electronic Concept : When ferrous chloride is oxidized to

ferric chloride by chlorine in aqueous solution, Fc* l is converted 10 FC'3 and C11'
is changed to Cl-. Similarly, the oxidation of magnesium to MgO involves the
change of' Mg to Mg,2 and of 011 to 0-2. The only way to account for this
change is by means of electron transfer process. The electrons in the outermost
energy level, i. c., valence electrons in an atorn undergo changes during the
chemical reaction. The electrons in the outermost cncriy level may be lost or
be
electrons may gained depending upon the electronic arrangements of the atom.
Thus when Mg 1 is oxidized to Mg+2, the two electrons in the outermost energy
level, 2s 2 , are lost. Similarly, oxidafion of FcO to Fe +2 is due to the loss of two
electrons from 4s energy level. Subsequent oxidation of Fe *1 to Fc` is due to
the loss of one electron from 3d level which originally contains 6 electrons,
i. e., 3d 6 which has tendency to lose one electron to become 3d 5 which, now,
half-filled represents a stable electronic arrangement.

Now we can give a generalized definition of oxidation :

Oxidation is a process which involves loss of c1ccurons by an atom or an

ion.

Similarly, reduction can be attributed due' to the gain of electrons by an

atom. Thus when oxygen is reduced to 0-2, or Fc *3 is reduced to Fc *2 and
subsequently to Fe, the entire process can be easily explained on the basis of
gain of electrons by an atom or an ion.
An oxidizing agent is one that accepts electrons and is thereby reduced. A
reducing agent is one that gives electrons and is Lhcrchy oxidized. Therefore, in
oxida jon-redUCLion reactions, clectrons are irmisferi-cd frorn the reducing agent to
the oxidizing agent. The oxidation-reduction reactions (also known as redox
reactions) are complementary and take place simultaneously. Consequently,
oxidation (the loss of electrons ) and reduction (the gain of electrons) must
always accompany each other in a reaction. In other words, if a given reaction
involves an oxidation ' it must also involve a reduction. Thus the reaction
between Mg and oxygen
—13
194 -ISIRY
INTRODUCTION TO MODERN NORG&NIC C1 IEM

2Mg 0 + 002 = 2Mg +10-2 or 2MgO

Hence, MgO is oxidized t o Mg,2 by loss of two electrons and oxygen 0 0 is

reduced to oxide 0-2 ion. Mg is the reducing agent and 02 is acting as an
oxidizing agent.

In the reaction between Zn and C USO4 Solution , metallic copper is deposited

and some of the zinc rapidly dissolves :

Zn o + Cu+2SO4 -2 = Cu O + Zn*2 SO4 -2

Notice that the SO4 -2 ion does not undergo any change in this oxidation-
reduction reaction. The zinc metal is oxidized from Zn O to Zn +2 ion obviously by
loss of two electrons. The copper ion, Cu +2 , is reduced to Cu o by the gain of
these two electrons. Here ZnO is oxidized and acts as the reducing agent and Cu*2
is reduced and acts as oxidizing agent.

It may be mentioned here that this is the simplest and at the same time
most comprehensive theory of oxidation-reduction reactions that has ever been
put forward.
be
The simple explanation of clectron transfer may readily demonstrated
with test tube experiment.

Oxidation-reduction reactions according to the electronic concept is

essentially an electrical phenomenon. This means that it should be possible to
be
accomplish oxidation-reduction simply means of electric energy. The
chemical reactions, therefore, can be made to occur by passing electricity through
solutions of ions :
'lectric--,
2Na'Cl_ 2Na' = Cl'2
cruucnt

Thus, where Na* is reduced to Na O and Cl — is oxidized to C1 1 and, therefore,

represented as,

Na +e cathode — Nal

anode, 1)
20 - - e '
Cl
k - 12
 0MAT1ON-RIDUCTIO N REAC11ON'S
195

Thus electrolysis is a simple electron transfer reaction. These oxidation-

reduction reactions do not occur spontaneously but take place only if electrical

energy is supplied.

Not only oxiation-reduction can be accomplished by electric current but

proper arrangements of an
also, vice versa, electricity can be generated by
oxidation -reduction reaction. Thus the reverse reaction,

2Na' + CI -2 = 2Na' + Cl_

Cl — , takes place
where Na O is oxidized to Na + and C10 is reduced to
spontaneously and spontaneous oxidation-reduction reactions of this sori, which

involve the loss and gain of electrons, can actually be used as a means of

generating electric current. The arrangements require that electrons lost by Nao

and gained by C12 pass through a conducting wire during the ox idation -reduction
reaction between the two, thereby we can produce a source of electric current.

Similarly, the reactions between Zn and H2SO4 or CUSO4 solutions produce

electric current by the same mechanism of electron transfer from Zn to H' ions

or Cu *2 ion respectively.

Important application of the oxidation-reduction reactions have been made in

connection with the manufacture of dry cells, storage batteries and other type of

appliances for producing electricity.

Oxidation State and Oxidation Number

Whe n the electrons in the outermost energy level (or valence electrons) are

removed from an atom during a chemical reaction, the atom is said to be in a

positive oxidation state. Similarly, when an atom takes up electron during a

chemical reaction, the atom is said to be in a negative oxidation state. The

number of electrical charges on an atom is known as the Oxidation Number.

Thus in the reaction,

Mg, + CI '2 = M9*2 Cl-Cl-,

the oxidatw^ number of Mg undergoes a change from zero in the free state to +2
and the oxidation lumber of chlorine changes from zero in the free state to — I. It
m'ncrallY the oxidation number of an element
may be noted that during oxj,!a' i­
is increased and during reduction the oxidation number is decreased. A substance
 196 LN'TRODUCTION TD MODIRN INORGANIC CIIE.WS-TRY

that causes an increase in the oxidation number of another substance is called an

oxidizing agent. A substance that causes a decrease in the oxidation number of
another substance is called a reducing agent.

Assignment of Oxidation Number

In connection with oxidation-reduction reaction it is convenient to adopt a

generalization in order to assign the correct value for the oxidation number of an
clement in a compound. Oxidation-reduction reactions arc important in
I
chemistry, and writing of balanced equations of these reactions often involves
cumbrous process by trial and error method. But the writing of equations has
been, for the most part, simplified by adopting the use of oxidation numbers and
their changes which occur during oxidation-reduction reactions. The following
rules for assigning oxidation number arc generally followed :—
(1) Neutral atoms and molecules have zero oxidation number.

(2) When atoms of different elements are present in a molecule, the more
clecLronegative atoms will have a negative oxidation number and the less
clectronegative atoms have positive oxidation number. Thus,

Na"Cl -1 , H*10-1, H2*'O-I, N ­ 3 H,+ I

Ca*2S-2, 1 * 'Cl– ', Na*111-1

Generally metallic atoms in a compound have positive oxidation number

and non-mctallic atoms in a compound have negative oxidation number.

(3) Hydrogen. is +I when combined with non-metal and –1 when combined

with metals.

(4) Oxygen is –2 except in peroxides when it is – 1.

(5) The oxidation number of a compound is always zero. It is determined by

the sum of oxidation numbers of the individual atoms, each multiplied by the
number of atoms of the clement present in the molecule.

In a given compound the sum of the positive oxidation numbers is equal to

the sum of the negative oxidation numbers and since the molecule as a whole is
neutral, the algebraic sum of the positive and negative oxidation numbers is
zero.
 0XIDA11ON-REDUCHON RFAC-11ON'S 197

Thus knowing the oxidain numbers of some of the well-known elements in

a compound, the oxidation number of the unknown can be calculated. For

instance, in H 2SE)4, The oxidation number of H is +1 and that of oxygen is -2;

the oxidation number of sulphur is easily found out

H, S 0,

2(+1) + x + 4(-2) = 0

2 + x - 8 = 0

x +6 (oxidation No. of S in H2SO4

Similarly, in the case of KNO3 the oxida6on number of N can be calculated as

follows :

K N 0,

+1 + x + 3(-2) = 0

+1 +x-6 = 0 or x = +5

Some clement may exist in several oxidation states and can have several
oxidation numbers. Thus nitrogen can have oxidation states :

-3, -2, -1, 0, +1, +2, +3, +4, +5. as in the following compounds
-3 -2 -1 +1 +2 +3 +4 +5
N H, N,H, NH2OII ^' N 20 NO N 203 NO2 N 205

Similarly, chlorine has oxidation numbers +7, +5,+3, +1, 0 and -1, as in,
+ I o -I
HC10
+7 4 HC103
+5 +3
HC102 HCIO HCI
C12

Rules for Writing of Equations involving Oxidation-Reduction

Reactions

There arc various methods for writing the oxidadon-reduction equafions and

one of the most convenient procedures for balancing such equations is based

upon the transfer of electrons. This involves consideration of the change in the

oxidation numbers of the elements undergoing oxidabon-reduction reactions. The

following simple rules provide a convenient means to write the oxidation-
reduction equations in the balanced and completed forms.

Rule 1. Indicate the oxidation numbers of each clement in the oxidizing

and reducing agents in both the states respectively.

198 , TO MODOLN NORGANIC CHENUSIRY
LNIRODUCTION

Rule 2. Note the elements which undergo a change in the oxidation

numbers during the reaction and indicate the electrons gained and lost by them.

Rule 3. Use H * ions to form undissociated molecules bf water where

necessary.
Rule 4. Use H 2 0 molecules in order to form higher oxygen containing

product during oxidation.

Rule 5. Make total number of electrons accepted by the oxidizing agent

equal to the total number of electrons given by the reducing agent.

Rule 6. Complete the equation by providing appropriate missing ionic

species to form molecules after adding both the sides of the equation and

cancelling out equal terms.

Various types of oxidation-reduction reactions have been selected to

illustrate the application of the above rules. 't may be noted that all the rules
may not always be required to write oxidation-reduction equations. Which of the

rules will be applicable could be easily determined.

Example 1. Ferrous chloride is oxidized by chlorine to ferric chloride.

Writing the change in ferrous chloride and chlorine we get,

Cl^ + 2e 2CI-

Fe+3 + 2CI-
Fe+ 2Cl2- -e

Since the loss and gain of electrons during the process must be equ ', the second

part has to be multiplied by 2 :

C12 + 2e 2CI-

2Fe+2CI,- -2e 2Fe+3 + 4Cr

2Ee3 + 6CI-
By adding 2Fg.Cl2 + C12
or 2FcCl,
2FeC12 + C12
'Me equation is obtained in the completed and balanced form.

Example 2. H 2 S is oxidized to H2SO4 when passed into a concentrated

aqueous solution of bromine.

 0XIDA]ION-REDUC110N RI : A(:IIONS 199

Here bromire acts as an oxidixing agent; hence it accepts one electron per
atom and is reduced to bromide. When H 2 S is oxidized to H2SO4 the oxidation

number of S is changed fioin —2 to +6 by loss of 8 electrons.

is
Now, we find thaL a higher oxygen conuning substance Y12SO4 formed

by oxidation of li 2 S which has no oxygen atom. Hence 4 oxygen atoms in

H 2 SO 4 Will require the use of 4 molecules of H 2 0. Thus we write two half-

reaction underlining the symbols of those elements which undergo change in the

reactions :

Br2 + 2e 213r
.1 +6

H 2 S_2_8e+4H 2O H2SO4 + 8H+

The loss and gain of electrons must be equal. Hence the upper haff-reaction
be
is to multiplied by 4 :

4 Ar, + 8e 8B_r (1)

11 2_a-2 - 8e + (2)
411 20 H2SO4 + 811+

On adding (I)and (2) we have,

4 Br2 + H 2S + 4 H 20 = H 2SOI + 8H * + 8Br-

Completing, 4 Br2 + H 2S + 4 H 20 = H2SO4 8HBr

Example 3. Potassium dichromate oxidizes potassium iodide in acid

solution liberating iodine :

+2+12-14 +3 +1
K2Cr2O7 +6e 2Cr + 2K + 7 0-2 (1)

^ki —2e + 2K'- (2)

Now, 7 0-2 require 1411 + ions to form 7H 2 0 and, therefore, l4H + is to be

introduced in the half -reaction in (1) ; and in order to make the number of'
 200 IN-IRODUCHON TONIODINN NORGANICCI IFMISIRY

electron lost and gained equal, the half-reaction (2) is to be multiplied by 3. Thus
we get,

K2Cr2O7 + 6c = 2CrII + 2K +I + 7 0-2

7 0-2 + 14YI + = 7H20

6 Kl— 6e = 31 2 + 6K+I

On adding and cancelling equal tenns,

K 2 Cr 2 O 7 + 6KI + 14H * = 2Cr +3+ 8K * ' + 7l`l2O + 312

The above equation is almost complete, except the requirement arising out
of the use of H * ions. The H I ions can come from an acid. Generally the acid
used is HCI or H2SO4 and hence the anionic portion for the various cations will

depend upon the acid used. HCI will gave chlorides and H 2 SO 4 Will form

sulphates. Thus the complete equation is automatically derived :

K2Cr2O7 + 6KI + 14HCI 2CrC'3 + 8KCI + 7H 20 + 31 2 or, in the case of

[I'SO"

K 2 Cr 2 O 7 + 6KI + 7H 2 SO 4 Cr2(SO4)3 + 4K2SO4 + 7H 20 + 312

Example 4. Potassium permanganatc oxidizes 1'2S in aqueous solution

and sulphur is liberated

+1 7 -8
K Mn 0 4+ 5e Mn+2 + K +I + 4 0-2 (1)
+1_2
H 2S — 2e 2H+ + SO (2)

Now 40 -2 require 8H + to form 4H 2 0 and, therefore 8H+ is 'to be introduced

in (1) and we get,

K^
,LnO4 + 5e K+1 + Mn +2 + 40-2

-2
40 + 8H + 4H20

+1-2
H2S — 2e 2H+ + aO

Multiplying (1) by 2 and (2) by 5 in order to make the loss and gain of
electrons equal, we have,
 OXIDA ' 110,N-REDUCTION REAMIONS 201

2K MnO4 + I Oe = 2K+' + tLn+2 + 8 0-2

-2
80 + 161-1 1= 81-120

5 H 2a- l0e = IOH + + 5 aO

On adding, cancelling equal terms and adjusting the species involved we

have,

2KMnO 4 + 5H§ + 6H + = 2K + ' +2Mn*2 + 5a + 8 H20-

In order to complete the equation, again it is required to supply the anionic

species which will obviously depend upon the acid used. Generally, the acid used

is H2SO4 because HC1 is oxidized by KMn0 4 and HNO3 itself is an oxidizing

agent besides an acid.

Hence the complete equation is:

2KMnO4 + 51-12S + 3H2SO4 = K2SO4 + 2MnSO4 + 5S + 81-120

to
Example 5. Hot and concentrated nitric acid oxidizes CuS CUSO4 and

NO2 is evolved :
.1 +5 +4
-2
H NO 3 + C = NO2 + H +1 + 0
6
2 (2)
4^- -8c + 4H 20 = etl^04+g^
2
One 0- requires 2H + for conversion to H 20 and again (1) has to be

multiplied by 8 in order to make the loss and gain of electrons equal. Thus,

8HNO 3 + 8C = 8NO2 + 8H + + 8 0-2

80-2 + 1611 + = 81-120

CuS - 8e + 41-1 20 = CUSO4 + 8H+

On adding and cancelling equal terms,

8H N-0 3 + CUa = 8NOI + CUSO4 + 41-120

The equation is complete without further adjustment.

Example 6. The oxidation of sodium thiosulphate by iodine

Na2S203 is converted to Na2S406 (sodium tctrathionate) 1 2' is converted to

iodide !-.
202 LVIRODUCHONIMMODERN LNORGANIC CHEMISIRY

Taking +] as the oxidation number of Na and -2 as the oxidation n umber 1)f

oxygen, the average oxidation number of each S in

Na2SO3 is +2 and that the
average oxidation number of each S atom in Na2 S406 is 2!. Hence,

'4
Na§2()3 Na2 10406

Thus each S atom of thiosulphate loses ^clectron for oxidation to

tetrathionatc. 4 S atoms in tetrathionate must come from 2 molecules of

thiosulphate. Hence the total change in oxidabon number of S is from 2 (+4)

+8 to 4 x 21 = + 10
2

2N a2920, - 2e = N,2+§'40, , 2Na+

and 12 + 2e = 21-

Adding, 2Na 2S 2O3 + 12 = Na2S406 + 2Na I

Equivalent Weights of Oxidizing and Reducing Substances in

Reactions

The fundamental definition of equivalent weight is as follows:—

The equivalent weight of a substance is that weight which combines with or

displaces 1.008 parts by weight of hydrogen or 8.000 parts by weight of oxygen.

This fundamental definition may be extended and modified to the following

definition which seems to be applicable to all ordinary cases.

The gramme-equivalent weight of a substance taking part in chemical

reaction is the number of grams of the substance associated with the transfer of
N electron or proton or with the neutralization of N negative or posiLive charge
(N is the Avogadro's Number). N may be conveniently replaced by I or unity

which gives the same result. In acid-base reaction where neutralization reacdons
occur, protons (H') are transferred from the acid to the base and the number of
protons transferred determines the equivalent weight of the acid or the
base.
 OVDA11ON-REDUCnON RrACIIONS 203

The changes in the oxidation numbers of some of the important oxidizing

and reducing substances are given in Table 6- 1.

Table 6.1. Change In the oxidation numbers of some oxidizing and

reducing reagents.

Effective Oxidation No. of Change New oxida- Change

Reagents elements nwnber of electrons due to tion number in oxi-
effective involved redox of effective dation
element reaction element number

KMnO4 (acid) Mn +7 +5e Mn+2 +2 5

KMnO4 (alk) Mn +7 Ae K2MnO4 +6 1

KMn04 (neutral) Mn +7 +3e MnO2 +4 3
+6 +3e cr+3 +3 3 per CT
K2Cr2,()7 Cr
atom
Cl +5 +6e Cr, -1 6
KCI03
Ce(SO4)2 Ce +4 Ae Ce,3 +3 1

NaCIO Cl +1 +2e Cr, -1 2

H 2 02(redn.) 0 -I -2e 02 0 1 per 0
1 atom
0 -1 +2e 0-2 -2 per 0
B 202(oxn)
atom

FeCl, Fe +3 Ae Fe+2 +2 1

S -2 -2e S 0 2
H2S
S -2 -8e H2SO4 +6 8
H2S
SnC12 Sn +2 -2e Sn^4 +4 2
C +3 -le CO2 +4 1 per C
H2C204
atom
+4 -2e so4-2 +6 2
S02 S
KI I -I -le 12 0 1 per I
1 atom
H 0 -le H+1 +1 per H
th
atom

CU 0 -2e CU+2 +2 2
Cu
Zn Zn 0 -2e Zn+2 +2 2
1 0 -le per I
12
atom
204 LNIRODUC-nOIN TO MODFILN LNORGAMC CHEMIRY

Thus in the reaction,

HCI + NaOH = NaCI + H20,

N protons (6-023 x 1023) are transferred from HCI to NaOH. The g. equivalent
weights of HCI or NaOH are, therefore, equal to one mole (36-5g.) of HCI and
one mole (40-0g) of NaOH. When one mole of H2SO4 reacts with 2 moles of
NaOH in the reaction:

H2SO4 + 2NaOH = Na2SO4 + 21-120,

we have 2N protons transferred from H2SO4 to NaOH. hence one grarnme-
equivalent of H 2SO 4 is equal to g. mole divided by 2, i.e., 98-0/2 = 49-0.

When silver nitrate reacts with sodium chloride, silver chloride is

precipitated out according to the reaction,

AVNO3— + Na+CI— = Ag+CI— + Na+NO3—

or, Ag+ + Cl— = Ag+Cl-

The gramme-equivalent weights of AgNO3 and NaCl are calculated from the
number of charges neutralized electrically in the reaction. Here I positive charge
of Ag+ and I negative charge of Cl — are neutralized. Hence the gramme-
equivalent weight of AgNO 3 and that of NaCI are equal to one mole of AgNO3
and NaCI (169-89g. and 58-46 g.) respectively. In the case of precipitation of
BaSO 4 (i.e., Ba+2+ SO4 -2 = Ba+2SO 4-2) one mole of Ba *2 ion reacts with one
mole of SO4-2; 2 positive charges and 2 negative charges are neutralized. Hence
the gram me-equ i valent weight of BaC1 2 will be one-half the gramme-formula
weight and that of Na2SO4 is also one-half the molecular weight.

In the case of oxidation-reduction reactions which always involve transfer of

electrons from the substance oxidized to the substance reduced, the equivalent
weights are easily calculated. The grain me-equi valent weight of an oxidizing or
reducing substance is the weight which loses or gains I electron during the
process. It may also be put as the weight of the substance which undergoes a
change of one unit in the oxidation number of the effective element in the
substance. In other words, the gramme-equivalent weight may be obtained by
dividing the molecular weight by the total number of electrons transferred or
from the total change in oxidation number . Thus,
 OXIDAMN-REDUCFION REACnONI S 205

KMn0
+7 4 + 5e Mn+2

The change in oxidation number of Mn is 5 or the number of electrons accepted

by Mn in KMnO4 is also 5. Hence the gramme-cquivalent weight of KMn04 for
this reaction is equal to the molecular weight divided by 5, i.e., 158.02/5
31.63g. Similarly,
K2Cr207 + 6e ) 2Cr+3

Thus the effective element Cr accepts 6 electrons to change from +6 to +3 state.

(The total charge on Cr in K2Cr2O7 is 2 x +6 = +12 and 2Cr ,3 has the tow
charge = 2 x +3 = +6. Hence a change of +12 to +6 involves the gain of 6
electrons.) The change in oxidation number is of 6 units. The gramme-equivalent
weight of K2Cr2O7 for the reduction to Cr*3 state is, therefore, equal to the
molecular weight divided by 6. That is, 294.22/6 = 49 -037 g.
Similarly, the equivalent-weight of Na2C204 may be calculated from the
reaction

gi4_
1_014 — 2e ) 262

The total change in he oxidation number of carbon is from (2 x +3)= +6 to

(2 x +4) = +8. This can be accomplished by the loss wi - electrons. The total
change in electron number is also 2. Hence the gram me-cquivalcnt weight of
Na2C204 for this reaction is the molecular weight divided by 2.

The normality of an oxidizing or reducing agent is defined as :

No. of electrons gained or lost by I g. mole
Normality =
I litrc of solution

Oxidation-Reduction Potential (Electrode Potential)

Oxidation potential or redox potential is the direct consequence of electron

transfer phenomenon of ox idation- reduction reaction. It has been mentioned that
electric current can be generated by carrying out oxidation-reduction reactions.
When two electrodes are immersed in a solution containing oxidation-reduction
system and then connected by a wire, a current flows through the wire from the
anode to the cathode. 'Me use of the reactions as a source of electrical energy is
possible only if the reactions taking part in the redox reaction are not permitted
to come into direct contact. If the reactants come into direct contact, the energy
206 IN'FRODUCT1ONTO MODERN INORGANIC CHEMSIRY

is liberated as heat energy rather than as electrical energy. The conditions for the
generations of electricity are that the cell assembly must have both the electron
path between the electrodes via the metallic wire and also the ion path through
the solutions. The ion path is generally created via a porous membrane or by
suitable connections by a bridge containing ionic solution. The oxidation
process always takes place at the anode and reduction at the cathode. It is
obvious, therefore, that a chemical reaction involving oxidation-reduction
generates electric potential commonly known as redox potential. The values of
the redox potentials for the oxidation-reduction system have been determined in
most cases and are of great theoretical and practical value. The details of these
descriptions may be found in advanced text books on electrochemistry but an
elementary qu,-,Iitative treatment with respect to the applications of oxidation
potential to understand the chemical reactions is given here briefly.

Considering the equations :

Zn + Cu* 2 = Zn,2 + CU

and Cu + 2Ag+ = Cu *2 + 2Ag

we know that the above reactions do take place and we say that Zn is more
electropositive than Cu, and Cu is more electropositive than Ag and hence the
elec troposi Live metals in solutions are replaced by more electropositive metals.
The term "electropositive " of a metal means the "driving force" with which the
metal tends to give up the valence electrons to form a positive ion. Thus the
electropositivity of Zn means the driving force, also known as "Solution
Pressure", with which the reaction Zn = Zn *2 + 2e takes place. Now, when the
driving force is exerted during a reaction, energy must be spent. This means that
energy is spent when Zn changes to Zn* 2 in the reaction Zn = Zn +2 +2e. Thus
be
the effective energy content of Zn +2 must less than that of Zn atoms. This
effective energy content of a system is known as the "free energy" of the system.
The free energy originates from the resultant (or product) of the heat content and
tendency for the heat energy to be spent. A system of lower heat content but a
higher tendency to spend it will have a higher free energy than one which has a
largcr heat content but less tendency to spend it. ne difference between free
energy of Zn and Zn' 2 is called the change in the free energy that occurs when
reaction Zn = Zn' 2 + 2e takes place. The change in free energy provides the
 0XlDA"110N-lW)UC7II0N Rl-!A(:IIO.NS 207

driving force of the reaction and makes it go. The driving force of a reaction is
referred to as "Potential". The reactions involving oxidation, therefore, involves
"Oxidation Potential". The oxidation potent4d, therefore, represents the change
in the free energy of reaction. The values of oxidation potential is expressed in
volts. More generally the driving force is known as "electrode potential" (EO).
The potential of a standard hydrogen electrode is arbitrarily considered to be zero.
The standard hydrogen electrode is made by bubbling H2 gas at a pressure of I
atmosphere over platinizcd platinum immersed in a solution of H' ions of I M
concentration.

To determine the electrode potential of any element, an clecLro-chernical cell

is set up consisting of a strip of the clement (say Zn) in contact with a I M
solution (of Zn 12 ions). This is known as the half-ccli and a standard hydrogen
electrode is the other half-cell. The two half-ccils connected by a salt bridge (KCI
solution in a gel of agar) is shown in Fig. 7-1.

%.:/
e e—I
Salt bridge Cathode
Anode KCI agar

I Qbn
o 0-
-a-
Z n+ -0-
-0-
-7 _W±7 00
0- 0-
—0- -0-
0
___00 0-
00
00 Pt 0 0-
0 00
_0 0 0 0-
-Z

Zinc electrode Hydrogen electrode

Zn -4 Zn+2 + 2e- 2H+ + 2e- ­4 H2
Fig. 7-1. Electrode Potential
This bridge allows the ions to migrate through it but does not allow the
3olutions to come in contact. On connecting the two half-cells with a voltmeter,
208 LNIRODUCTION TO MODLRN LNORGANIC C1 1EMISIRY

we can measure the potential difference of the cell as a whole. Each half-cell
the
has equilibrium reaction :

1­1 2 ^^21­1* +2e

Zn 4z^^ Zn +2 + 2e

Because Zn has a greater tendency to go into solution as Zn +2 , the zinc acquires a

higher electron density than the Pt of hydrogen electrode. Hence the greater

electron pressure or electrode potential of Zn causes the electrons to flow to the

hydrogen electrode through the wire connection. The flow of electrons from Zn

to H increases the electron density at the hydrogen electrode and the equilibrium

is shifted to the left causing H + ions to be reduced to H2 :

H 2 ^— 2H* + 2e

At the same time the clecbron density at the Zn-clectrode is decreased, and the
equilibrium is shifted to the right and more Zn is oxidized to Zn* 2 ions :

Zn --) Zn 12 + 2e

This difference in potential is measured by a voltmeter and is 0.76 volts. The

the
force causing electrons to move from the Zn-clecLrode to the H-clecLrode is
called the electromotive force (E.M.F.) and is 0-76 volts. The Zn-clecLrode is the

negative electrode (cathode) because its electron density is higher than that of

H-electrode which is the positive electrode (anode). Since the potential of

H-elecLrode is zero, we can say that the potential of Zn-clectrode is above 0-76

volt than that of H-clectrode. In other words, the sign of Zn-clectrode is positive,
i.e., + 0-76 volts.

The over-all reaction in the Zn—H cell is one of oxidation and rcduction :

Anodic oxicIaLion— Zn --) Zn' 2 + 2e

Cathodic reduction— 2H* + 2e —* H2

Cell reaction— Zn + 2H + —^ Zn +2 + H2
 OXLDAIION-REDUCMON REACTIONS 209

The cell is represented as :

-C
Zn I Zn-2 (I M) I I H- (I M) H 2 (Pt) I atm

The Electromotive Series of the Elements

By measuring the electrode potentials of different metals, where ion

concentrations are I Molar as in the case of Zn, the metals (or elements) can be

arranged in accordance with the decreasing potentials. This series is known as the
Electromotive Series or E. M. F. series of elements. The potential of
H 2 !^—
_ 2H* +2e has been arbitrarily assumed to be zero and there are negative

values of the potentials for some metals also as shown in Table 7-2. For

instance, when Cu metal in contact with CU*2 is made the other electrode of

a cell containing standard H-clectrode, it is found that H has a greater tendency

to form H + ions than does Cu. Consequently, electrons flow from the H-
electrode to the Cu-clecLrode. The electrode processes are :

Anodic oxidation H2 2H* + 2c

Cathodic reduction Cu *2 + 2c Cu

Cell reaction + CU'2 ;^^ Cu + 2H+

H2

The E.M.F. of the cell,

H PO I atm I H'(1 M) Cu'2(l M) I Cu

has been measured by a voltmeter to be = 0.34 Volts (cc]] reversed)

The zero potential of H-electrode is above this figure of 0.34. Hence the

electrode potential of Cu-electrode is —0.34 volt with respect to the H-electrode.

The electrode reactions given in Table 7.2 represent reversible reactions.

This indicates that under one set of conditions a metal, say, Cu atoms, will

give up electrons to form Cu 12 ions, while under another set of conditions CU+2
ions will pick up electrons to give Cu atoms. This is the case with all the

—14
210 INTRODUCFJON TO MODERN INORGANIC CHEMISTRY

Table 7.2. E.MF. Series on Oxn-Redn. Potentials.

Elements Electrode
Reduced Elecoutie O)a&zed
f— reaction form potential
(volts)

Potassium K K'+e +292

Calcium Ca Ca .2 + 2e +276
Sodium Na Na+ + e +2-71
Magnesium Mg ^2 +2e +2-34
Mg
Aluminium Al A1+3 + 3e * 1-67
Manganese Mn Mn +2 + 2e * 1-05
Zinc Zn Zn +2 .+ 2e * 0.76
Chromium Cr Cr+3 + 3e +051
Iron Fe Fe +2 + 2e +044
Cadmium Cd Cd +2 + 2e +0.40
Cobalt Co C0+2 + 2e +0-28
Nickel Ni Ni+2 +2e +0.25
Tin Sn Sn*2 + 2e +0.14
Lzad Pb Pb+2 + 2e +013
Hydrogen H2 2H + +2c -0-00

Copper CU CU+2+2e -0-34

Iodine 21- 12 + 2e -053

Silver Ag Ag + +e -0-80
MencuTy Hg +2 +2e -0-85
H9
Bromine
213r- Br2 + 2e - 1-06

Platinum Pt Pt+2+2e - 120

Oxygen 21420 02 +4H + +4e - 1-23
Chlorine 2C1- C12 + 2e - 136

Gold Au Au+ +e - 1.68

Fluorine 21' F2 + 2e -2.85
 OXIDAMIN-REDUC-11ON REA(MONS 211

electrode processes. The equations given indicate that the substance on the left is
being oxidized and is acting as a reducing agent. The substances on the right side
of the equation are formed and the reactions are proceeding to the right. When the
reactions proceed to the left, the substances on the right side are acting as
oxidizing agents.

The substances on the top of the table 7.2 are strongest reducing agents and
the substances at the bottom are the weakest reducing agents. Thus the lower the
oxidation potential, the weaker the reducing ability of the element. The elements
at the bottom of table in the right side of the equilibrium equations are the
strongest oxidizing agents. Thus the lower the oxidation potential, the stronger
the oxidizing ability of the oxidizing agent.

Uses of the E.M.F. Series

The oxidation potential values in the E.M.F. series of elements can be used
to determine whether or not a reaction will take place. The most important uses
may be mentioned as follows :—
(1) The metal with high electrode potential at the top of the series are good
reducing agents. They are the metals most easily oxidized by removal of
electrons. They have low electron affinities, low ionization potentials and low
electronegativities.

(2) The elements with negative electrode potentials are good oxidizing
agents when in the oxidized form, i.e., when the metals are in the form of ions
and non-metals are in the form of neutral atoms or molecules.
(3) A reducing agent with a higher potential will reduce any oxidizing agent
with a lower potential. The wider the potential differcoce, the more vigorous will
be the reaction. This gives rise to the displacement reaction. To illustrate the
application of the rules, the example of the reaction
Zn + 2Ag+ = Zn +2 + 2Ag

may be mentioned. The electrodes involved have the following potentials:—

Zn = Zn 12 + 2e .. .. + 0.76 volts

Ag = Ag+ + e .. .. – 0.80 volts

212 ]NTRODUC`nON TO MODERN INORGANIC CHEMIS7RY

Therefore, Zn will be oxidized to Zn 12 by Ag* , and Ag+ will be reduced to

Ag by Zn. It means that Ag will be displaced from a solution of, say, AgNO3,

by adding Zn metal to the solution (dipping a strip of Zn to the solution of

AgNO3)- Similarly, H2 may be prepared by displacement reactions from an acid

containing H I ions by means of metals which occur above H in the E.M.F.
scries. Metals with a high positive potential liberate hydrogen from acids with

explosive violence and metals with low positive potential liberate hydrogen at a
reasonable speed. The displacement reactions are generally applicable and any

element will displace other which follows it in the E.M.F. series.

There are two types of cells which make use of oxidation-reduction reactions

for generating electficity. They are :—

1. The Primary Cells : These are irreversible cells. The electrodes and

electrolytes cannot be restored to their original states once they have been

consumed for the production of current by the application of an external electrical

potential. The "dry cell" is a primary cell and reactions are irreversible.

2. The Secondary Cells : In these cells the chemicals used and the

electrodes may be regenerated after they have been consumed in producing

electricity. This is done by passing a direct current of electricity to flow in the

reverse direction of the discharge. This is called recharging the cell. T71e "lead
storage battery or accumulators" is an example of secondary cells.

The Dry Cell : The container of the chemicals in this cell is made of Zn
which serves as one of the electrodes and is separated from the chemicals by

lining with porous paper. A carbon rod in the centre of the cells is the other
electrode. The space around the carbon rod contains a mixture of NH4CI, Mn02,
a
ZnC12 and some saw-dust, all moistened with H20 in the form of thick paste.

The cells is sealed from top by shellac or pitch. When the dry cell generates
electfic current, Zn goes into solution as Zn 12 ions and electrons accumulate on
Zn making it a negative electrode. NI-14 + ions is reduced at the carbon electrode.

Anode reaction : Zn —^ Zn* 2 + 2e

Cathode reaction 2NH4+ + 2e —^ 2NH 3 + H2

Overall reaction Zn + 2NH, 1 -4 Zn+2 + 2NH 3 + H2

Mn02 oxidizes H2, otherwise it will collect and stop the reaction :

11
 OXIDATION - RE DUCTION RFACTIONS 213

H2 + Mn0 2 + 2H + = Mn *2 + 2H20

The entire reaction :

2NH4* + Mn0 2 + Zn = 2NH 3 + MnO + H20 + Zn+2

NH3 formed is taken up by ZnC1 2 forming the complex Zn(NH3)4C]2-

The voltage of the dry cell is generally 1-5 volts.

The Lead Accumulator (Storage cell) : The electrodes of lead storage

battery consist of two lead plates. The negative plate consists of a spongy lead
supported on grid made of Pb-Sb alloy. The positive pole is
Pb02 supported in a
similar grid. The electrolyte is H2SO4-

When the battery produces current, the following reaction takes place.

At the lead plate :

Pb + SO4-2 = ASO4 + 2e El = 0.356 volts

(oxidation)
At the Pb02 plate :
.4
PbO2 + SO4-2 + 4H + + 2e = ASO4 +2H20

(Reduction) Eo = 1.685 volts

Electrons flow from the lead electrodo through the external circuit and enter the
lead dioxide electrode. The positively charged lead dioxide is the cathode and the
lead electrode is the anode.

Recharging of lead accumulator is done by passing electrons through the cell in

the reverse direction by applying an external potential. The lead electrode is now
made the cathode. The reaction is :

PbSO4 + 2e ---> Pb + SO4-2 (reduction)

PbO2 electrode is made positive and the oxidation reaction is:

PbSO4 + 21­120 = Pb02 + 4H+ + So^-2 + 2e (oxidation)

Thus the two processes may be written as

-2 discLaTg
Pb-plate reaction : Pb 4 q04 PbSO4+ 2e
cl;arge

Pb0 2 -plate reaction :

214 DZIRODUCI`10N TD MODERN LNORGAINIC Cl IEMISTRY

PbO2 + 4H+ + So -2
4
+ 2e discharge
— PbSO4 + 21-120
charge

The overall reaction:

Pb + Pb02 + 4H + + SO4-2 discharge 2PbSO 4 + 21-120

CZ-ge

H2SO4 consumed is replenished from time to time.

QUESTIONS AND PROBLEMS

I . Explain oxidation and reduction.

2. Explain what happens when :—
(a) S02 is passed into a solution of Iodine.
(b) A solution of Na2S203 is added to acidified K 2Cr2O7 solution to which KI
had been added.
(c) Iodine reacts with a solution of Na2S203-
3. Explain the meaning of the term "oxidation state".
4. Define oxidation and reduction in terms of change of oxidation number. What are
oxidising and reducing agents ?
5. What are oxidation numbers of nitrogen in each of the following compounds?
N20, NO, N203, N204 , HNO2, N143, NH4CI, NA, NH20H and AIN -
6. Calculate the equivalent weight of the oxidising and reducing agents in the
folloiwing reactions in term of the molecular weights of the respective
compounds taken as M :—

(a) H202 + KMn04 + H' --+ Mn +2 + H20 + 02,

(b) Zn + H+ + NO3- -4 Zn+2 + N20 + H20,
+2 +Fe+3 + "20.
(c) K2Cr2()7 + Fe + H + -4 2CT+3 + 2K+
7. What is meant by oxidation-reduction potentials ? How this can be applied for
determining the feasibility of chemical reactions ?
8. Write the equations of the following reactions :—
(a) Chlorine is passed into a solution of ferrous chloride.
 0MAIION-REDUCTFION RFACTIONS 215

(b) H2S is passed into a neutral solution of KMn04,

(c) Nitric acid is passed Over heated copper.
(d) CuS is heated with strong HNO3
(e) KBr03 reacts with KI in acid solution.
reacts
M KMn04 with Na 2C2 04 in acid solution.
(g) H202 reacts with KI in neutral solution.
(h) Cr(OH)3 reacts with H202 in presence of NaOH
(i) HCI is dropped over KMn04,

9. What is meant by the electromotive series of elements? What are the

applications if this series ?
10. How do you use electromotive series in the preparation
of some elements?
11. Complete and balance the following chemical equations
(a) H2S + KMnO4 + H2SO4
(b) As2S3 + HNO3 + H20 —+
(c) SnCl2+H2SO3+HCl—^

(d) CT13 + KOH + C12

12. Write notes on :-

(a) Oxidation and reduction

(b) Oxidation states and oxidation number of elements
13. Give the modem concept of oxidation and reduction , How can you prove

experimentally that oxidation and reduction generate electricity ?

14. Discruss with examples (and equation) the disproportionation reactions and
oxidat ion-reduction reactions. Mention their significance in chemistry.
15. Write explanatory note on Electronic Concept of oxidation and reduction.
16. Write note on variable oxidation states.
17. Discuss : Transfer of electrons occur during oxidation-reduction reaction.
18. Discuss the oxidation states of iron and chromium.
 CHAPTER 8

OXIDES AND HYDROXIDES

The chemical facts concerning this important class of compounds have now
been coffelated with electronic arrangements, the ionic sizes, the oxidafibn states,
electronegativity and bonding systems involved in the oxides and hydroxides of
the elements.
Compounds containing oxygen as a constituent are most abundant and
widely distributed. Among these, oxides of elements (other than halogen and
noble metals) are by far the most important from the points of view of
chemistry.
OXIDES
Oxides are binary compounds of oxygen and other elements. Oxides of all
elements are known:-
The large number of oxides which are formed by various elements are Sub-
divided into various classes. The classification is based upon two different
considerations:-
A. Classification based upon reactions.
B. Classification based upon their structures and bonding systems.

A. Classification of Oxides based on reactions:

(a) Basic oxides, (b) Acidic oxides (c) Amphoteric oxides, (d) Neutral oxides,
(c) Sub-oxides (f) Saline oxides (g) Nonstoichiometric oxides (h) Peroxides.
(a) Basic oxides : This class includes the normal oxides of most metals.
They are derived from the metallic elements and their properties depend upon the
degree of electropositive character of the metal. Basic oxides form salt and water
 OXIDES AND I IYDROXIDrS 217

with acids, Basic oxides when soluble in water produce aqueous solutions of
bases. For instance , Na2O, CaO, MgO., FC203 etc. are basic oxides. The ionic
oxide are generally basic. The smaller the positive charge and larger the size of
the element forming the oxide, the greater is the basic character, Thus K+ forms
a strong basic oxides than Mg+2 ion, Oxides of elements having low
electronegativity values are more basic than those having high electroncgativity
values. Thus CaO is more basic than Al203

Method of Formation of Basic Oxides

(i) The alkali metals take up oxygen from the air and are converted into
oxides. The alkali metal oxides, however, are generally prepared by heating
excess of the alkali metal with oxygen in vacuo having :
heated in
Na + 02 Na20 + Na
vacuo
(Excess) Excess Na removed
(ii) The alkaline earth metal oxides are generally prepared by strongly
heating their hydroxides, carbonates and nitrates, e.g.

heat , CaO + CO2

CaCO3 8120

(iii) Heavy metal oxides are generally prepared by heating the metal or lower
oxides in air. They are also formed by heating the hydroxides, carbonates,
nitrates etc. For instance,
heat , C60
CU + 02
+ 02 heat ,
CU20 Cuo
Cu(OH)2 heat ) CuO + H20

2Cu(NO3)2 heat 2CuO + 4NO2 + 02

CUC204 heat , CUO + CO2 + CO

Reactions :
(i) Basic oxides react with acids to form salts and water
Na2O + 2HC1 = 2NaCl + H20
CaO + 2HCl = CaC12 + H20
FeO + H2SO4 = FeSO4 + H20
218 D41RODUCFION TO MODERN INORG/LNIC G IENIUSTRY

(ii) Some of the basic oxides produce hydroxides with water and when
soluble they are extensively dissociated to give strong alkaline reactions :
aq.
Na20 + H 20 2 NaOH Na* +OH-

aq.
CaO +H 20 Ca (OH)2 Ca+2 + 20H—

(iii) Oxides of the teavy metals are decomposed to metal when heated with
carbon or hydrogen :

Fe203 + 2C = 2 Fe + CO2 + CO

Fe203 + 3H 2 = 2 Fe + 3 H20
But the alkali and alkaline earth metal oxides do not undergo above
reactions.

(iv) Some of the oxides of less electropositive elements are easily

decomposed by beat into metal and oxygen:
heat )
2 A920 4 Ag + 02
or light

2 HgO teat-+ 2 Hg + 02

(b) Acidic oxides : The acidic oxides are generally derived from non-
metals. They react with bases to form salt and water, and sometimes only salt.
They are anhydrides of the respective acids and their hydroxides are oxyacids. For
instance, S02, S03, N 20 5 , P 20 5 , B203 etc. are some of the acidic oxides.
Elements with high elearonegativity values form acidic oxides.

Acidic oxides are also formed by metals which can exert a high oxidation
state by losing a number of electrons and thus combine with several oxygen
atoms. Thus Cr0 3, Sn02, W0 3, M003, etc. are examples of metallic acidic
oxides. Elements having both metallic and nonmetallic properties, i e.,
metalloidic elements, also produce oxides which are acidic, such as, AS203,
Sb 20 3, Si02, etc.

Both the non-metallic and metallic acidic oxides when soluble in water are
extensively hydrolysed and produce acidic reactions.
 OXIDISANDIIYDROXDES 219

Reactions :
(i) The acidic oxides react with water to give the respective acids:

S02 + H 20 = H2SO3
so, + H 20 = H2SO4

N 20 5 + H20 = 2HNO3

P205 + 31-1 20 = 2H3PO4

CO2 + H 20 = H2CO3
B203 + 31-1 20 = 21-131303

Cr03 + H20 = H2CrO4

W03 + H20 = H2WO4

M003 + H20 = H2MOO4

AS203 + 31-120 21-13AS03

) H3ASO4
Sb203 + H 20 H3SbO3
H3SbO4
(ii) Acidic oxides combine with bases to form salts and water. Thus,
CO2 + Ba(OH)2 BaCO3 + H20
S02 + 2NaOH Na2S03 + H20
N205 + NaOH NaNO3 + H20
(c) Amphoteric oxides : The amphoteric oxides react with both -acids
and alkalies and, therefore, exhibit both acidic and basic properties. Thus, Al203,
ZnO, SnO, Cr203 etc. are examples of amphotcric oxides. These oxides are
generally insoluble in water and dissolve readily in an acid or a base.

Reactions :
(i) With acids these form salt and water. Thus,
Al203 + 6 HCI = 2 AIC13 + 3 H20
ZnO + 2 HCI = ZnC12 + H20
SnO + 2 HCI = SnCl2 + H20
Cr203 + 6 HCI = 2 CrC13 + 3 H20
220 MRODUCHON TO MODERN INORGANIC CI IEMISIRY

(ii) The same oxides react with alkalis to give salt and water. Thus,
Al203 + 2 NaOH = 2 NaAJ02 + H20
ZnO + 2 NaOH = Na2ZnO2 + H20
SnO + 2 NaOH = Na2SnO2 + H20
Cr203 + 2 NaOH = 2 NaCr02 + H20

(d) Neutral oxides : The neutral oxides combine neither with acids nor
with bases to form salts. They do not give acidic or basic reactions. Thus, H20,
CO, N20, NO ctc. are examples of neutral oxides.

(e) Sub-oxides : The sub-oxides or protoxides generally contain less

number of oxygen atoms than what is actually required for the formation of
normal oxides. Thus, Pb20, Ag4O, Cu4O, Pd20 etc. are examples of sub-oxides.

(f) Saline oxides : The saline oxides -are so called because they behave
like salts. These are also known as compound oxides and mixed oxides since
these may be assumed to be a combination of more than one oxide. Thus,
AU 20 2, Fe 304, Pb 3 04, Mn 3 04, NO2 etc. are examples of saline oxides. They are
generally formed by combination of a basic oxide with an acidic oxide. Ferroso-
ferric oxide, FC304, may be considered as a combination of FeO and Fc203, and
with acids it gives salts of both ferrous and ferric ions. Mixed-metal oxides are
known as spinels having special types of crystal structures.
Similarly, red lead, Pb304, is composed of PbO and Pb02 and Mn304, is
composed of MnO and Mn0 2 . NO2 is a mixed anhydride of N 20 3 and N205-
These combinations may be represented as follows:
AU202 = 2AuO
Fe304 = FeO.Fe2 O3 or Fe Fe204

Pb304 = 2PbO.PbO 2 or PbPb204

Mn304 = 2MnO.MnO2orMnO.Mn2O3orMnMn2O4

4NO2 = N203-N205

(g) Nonstoichiometric oxides : There are also many oxides which are
known as nonstoichiometric oxides. These are generally formed by metals
having variable oxidation states. Thus ferrous oxide probably never has the
 OXIDFS AND I rfDROXIDES 221

composition FeO, but usually something in the range FcO 0.9 to FcOO,95

depending on the manner of preparation.

(h) Peroxides : These are oxides which contain more oxygen combined

to an element than what is necessary for its highest oxides according to the

periodic law. In terms of the oxidation states of oxygen, peroxides contain

oxygen in – ^.and –1 oxidation states. The most common oxidation sate of

oxygen in normal oxides is-2. Exceptions are 0 217 2 and OF2-

Classification or Peroxides Based on Reactions

Peroxides have been classified into the following groups on the basis of

their reactions :—

(1) Basic Peroxides.

(ID Acidic Peroxides.

(111) Neutral Peroxides.

(1) Basic Peroxides : The basic peroxides when soluble in water produce
hases. Na 2 0 2, K0 2, Ca0 2, Ba02 are examples of water-soluble basic peroxides.

Pb0 2, Bi 205, Mn02 etc. are, however, not true basic peroxides, because the

oxygen content does not exceed that of the normal typical oxides. But these are
classified as basic peroxides, because these react with acids to produce salts of the
basic oxides of PbO, B'203 and MnO respectively.

Reactions :

(i)Basic peroxides react with water to form hydrogen peroxides or oxygen in

addition to bases :

Na202 + 2 H20 = 2 NaOH + H202

2 Na202 + 2 H20 = 4 NaOH + 02

(ii) With sulphuric acid these peroxides always give oxygen

2 MnO 2 + 2 H2SO4 = 2 MnSO 4 + 2 H 20 + 02

(iii)With hydrochloric acid, chlorine is always evolved :

BaO2 + 4 HCI = BaC1 2 + 2 H20 + C12

Mn0 2 + 4 HCI = MnC12 + 2 H 20 + C12

222 MRODUCTION TD MODIRN WORGANIC CI [ENUSTRY

Chlorine evolved is equivalent to the excess amount of oxygen present in the

basic oxides. This amount of oxygen is generally known as the "available
oxygen" of the peroxides.

(iv) The basic peroxides form salts by direct union with acidic oxides:
Na2O2 + S02 = Na2SO4

Pb02 + S02 = PbSO4

(11) Acidic Peroxides: The acidic peroxides generally produce typical

acids in presence of water by loss of oxygen. Cr0 4, S207, C1207, Sn0 3, C1202,
C102, U04 etc. are examples of acidic peroxides.

Reactions :
(i) With water the acidic peroxides react to form normal acids with the
evolution of oxygen :

2 S207 + 4 H20 = 4H2SO4 + 01

2 CrO4 + 2H20 = 2H2Cr04 + 02

(ii) With sulphuric acid oxygen is evolved:

2 Cr0 4 + 3H 2SO4 ) Cr2(SO4)3 + 3 H20 + 02
(iii) Acidic peroxides form salts with alkali oxides with the evolution of
oxygen:

Cr04- + Na 20 Na2Cr04 + 02
S2Q7+ Na2O Na2SO4 + 02

(111) Neutral Peroxides : As the name implies, it is neutral and has

neither basic nor acidic characteristics. A well-known example is H202-

Classification of Peroxides Based Upon Structures

The classification of peroxides on a structural ground depends upon the

oxidation state of the elements combining with oxygen. It has been assumed that
the oxygen atom or atoms over and above those required to form the normal
oxide may either be doubly linked to the metal atom or singly linked to both the
metal and oxygen atom.
 OXIDES AND HYDROXIDES 223

(i)The peroxides having the excess oxygen atom or atoms doubly linked to

metal atom arc known as "polyoxides".

0 = Pb = 0 0 = Mn = 0

(ii)Ile peroxides having the excess oxygen atom or atoms singly linked to

the metal and oxygen, forming a chain or ring are "normal peroxides". These

contain oxygen in –1 oxidation state.

0
11 0
O_ S=O
N af-- 0
/ 0
Na— 0
I

0--- S=O
11 < 0
0
(Na202) (BaO,)
(S207)

The direct oxygen-oxygen bonds in normal peroxides usually break down at

high temperatures. Mostly clecLropositive metals form peroxides having 02-2

ion which contains no unpaired electrons.

(iii)Oxides of alkali metals, such as K, Rb and Cs, contain oxygen With

oxidation number –^ and are called superoxides. These have the general formula
2

MO2 ( K0 2, Rb02 CsO2). These are ionic solids having M' cation and 02,
anion. These arc coloured solids having magnetic properties and contain unpaired
exists
electrons. It is to be noted that superoxide ion, 02, only in the solid

state but gives 0 2 and H202 in water:

2KO2 + 2H 2 0 = 02 + H 202 + 2KOH

Polyoxides, peroxides and superoxides can be distinguished from one another

by the actions of water or dilute acids upon them.

(i) Peroxides have group —0---0— and hence yield 11202 as a characteristic

product with water or dilute acid :

 224 INTRODUCflON TO MODERN INIORGANICCHEMISIRY

Na — ^ HCI i i ()

— 0 -4 1 + 2 NaCI
Na HCI H---O

B 0-4 + BaO
H/ H---O
0

Superoxidcs produce H 2 0 2 and also 0 2 gas With water:

2 Rb0 2 + 2H 2 0 = 0 2 + H 2 0 + 2RbOH

(iii)Polyoxides are not attacked by dilute acids and not at all by water. but
with strong HCI or H 2 SO 4 produce chlorine and oxygen respectively

2 0--Mn=O + 2H 2 SO 4 2 MnSO4 + 2H 2 0 + 02
2 O=Mn=O + 8HCI 2 MnCl2 + 2 C12 + 4H20
(iv) Both peroxides and superoxides also produce chlorine or oxygen when
acted upon by strong HCI or H 2 SO 4 but by a different mechanism

B302 + H 2SO4 BaSO4 + H202

2H 2 0 2 2H 2 0 + 02
Ba0 2 + 2HCI BaCl 2 +H202
H202 H20 + 0
2 HCI + 0 H20 + C12

The distinguishing reactions of polyoxides, peroxides and superoxidcs arc

given in Table 8-1.
Table 8-1. Distinction between Peroxides, Polyoxides and
Superoxides.
Reagerus Peroxides Superoxides Polyoxides Normal
oxide
o2-2 o2-2 0-2
()2-1
1. WateT HA HA + 02 No reaction OH-
2. Dil. Acids H2()2 H2()2 + 02 No reaction
3. Conc. HCI C12 C12 + 02 C12
4. Conc. H,S()^ 011 ('L
 OXU)F,S XND I IYDRO)GDES 225

B. Classification of Oxides on the Basis or Bonding Systems

There are three classes of oxides on the basis of the nature of chemical
bonds.

0) Ionic Oxides (ii) Covalent Oxides (iii) Intermediate Oxides

e.g. U20 e.g. S02 e.g, Fe203

BaO CO2 ZnO
MgO CO BcO
CaO Cl207

The ionic oxides are generally formed by the alkali and alkaline earth mcials.

The covalent oxides are mostly formed by the the non-metals.

II

The transition metals and many other heavy metals form oxides containing
bonds which are conveniently regarded as being intermediate between ionic and
covalent bonds.

The ionic oxides when soluble in water give bases due to dissociation into
ions. Whereas the covalent oxides of the non-metals are usually acidic,
dissolving in water to produce solutions of acids. These oxides arc, thercfore,
known as acid anhydrides. The ionic oxides function as basic anhydrides. Many
of the intermediate oxides do not react appreciably with water and some of them
show characteristic of both acids and bases generally known as amphoteric.

Elements having large positive oxidation number tend to form covalcr I

oxides. Thus, CO2, S03, Sb2O5, C1207 are some of the, covalent oxidcs.
If an element forms more than one oxides the covalent oxide will be that having
the element in the highest oxidation state. Thus, AS205 having +5 arsenic is
more covalent (more acidic) than AS203 containing +3 arsenic. S03 having S in
+6 state is more acidic than S02 having S in +4 state. Similarly, Cr03 is acidic,
Cf203 amphoteric and CrO distinctly basic. Covalency is also favoured by the
small size of the positive ion. Hence, BeO is almost covalent oxide as compared
to the strongly basic BaO containing large barium ion.

—15
226 WIRODUCMON TOMODERN NORGANICCHEMISIRY

HYDROXIDES

Hydroxides are compounds of oxides with water. Thus, the following

examples illustrate the formhtion of hydroxides of an element by the
combination of its oxides with water :
OH
H
MO I M or M(OH)2
OH
\ OH

OH
H
M 20 + OHI M2Z\ or 2 MOH

OH

The stability and definiteness of the hydroxides depend upon the reversibility
of the above reactions. Definite and stable hydroxides are formed by those
elements which are most clectropositive and most clearonegative. These can be
isolated in the free state and have great stability when heated.

The hydroxides or hydroxy compounds are important class of compounds

containing hydrogen, oxygen and at least one other element. They can often be
made by the reaction of water with an oxide. Thus, when calcium oxide, CaO, is
treated with a limited amount of water, the product is solid calcium hydroxide,
Ca (OH)2:

OH

CaO + 0 H Ca
H OH

Solutions of sodium hydroxide, NaOH, and calcium hydroxide are alkaline,

but not all hydroxy compounds are alkaline and also not all of them are soluble
in water. Some of the hydroxides, such as water, HOH, ethyl alcohol, C21-150H,
are neutral and again a large number of them such as sulphuric acid, S02(OM2,
phosphoric acid, PO(OH) 3 and boric acid, B(OH) 3 , are acidic. It has become
customary to use the term hydroxide to hydroxy compounds which give basic
 OMDES AND HYDROXIDES 227

solutions or contain the hydroxly group as OH - ion. The ionic oxides which
react with water generally produce bases whereas the covalent oxides give acids.

In general, if the hydroxyl group exists in a compound as the OH- ion, the
compound is called a hydroxide. The hydroxides may be classified into various
groups. Ile main groups of hydroxides are
1. Basic Hydroxides.
11. Amphoteric Hydroxides.
Ill. Acidic Hydroxides.
IV. Neutral Hydroxides.

I. Basic Hydroxides

Basic hydroxides are generally formed by metallic elements and the degree of
electropositive character of the metal determines the basic proper-Lies and also the
solubility of the basic hydroxides. Thus the alkali rDetal hydroxides are strongly
basic and highly soluble in water and give high concentration of OH - ions in
solution. The alkaline earth metal hydroxides are less basic and less soluble in
water as compared to the alkali metal hydroxides. The heavy metal hydroxides
which are mostly insoluble in water are regarded as basic because they have the
ability to react with acids to form salts and water. The relationship of the
properties with the charge and size of the metal ions will be discussed latter.
Thus, according to the properties, the basic hydroxides may be subdivided into
three troups -.—
(a) alkali metal hydroxides.
(b) Alkaline earth metal hydroxides.
(c) Heavy metal hydroxides.

The mode of formation of these three groups of basic hydroxides also

illustrates the difference in their properties.
(a) Alkali metal hydroxides : (i) When an alkali metal comes in
contact with water, there is a violent reaction, in course of which the alkali
metal hydroxide is formed with evolution of hydrogen from water. The hydrogen
bums in air with a flame indicating as if the alkali metal is burning in water.
iolent ,
2M+2HOH ' 2MOH+H2
reaction
228 DMODUMON TO MODMN WORGAINTICCIIENUSTRY

(ii)When an alkali metal salt solution in water is elecLrolysed, the alkali

metal is Berated at the cathode and reacts with water forming the hydroxides.

(iii)
The alkali metal oxides are freely soluble in waterjo form alkali metal
hydroxides in solution.

(iv)The alkali metal hydroxides are not convened to their oxides on strong

heating,

(b) The alkaline earth metal hydroxides : (i) The reaction between
water and the alkaline earth metal is not as violent as in the case of the alkali
metals. As expected, the reactivity with water increases in the group with
increasing atomic number. Lithium, an alkali metal, in this respect resembles
magnesium as already explained in connection with the diagonal relationship in
the Periodic Table.

OH
slow I
M+2HOH + H2
reaction
OH

(ii) The alkaline earth metal hydroxides are also formed by precipitation
from their salt solutions by adding alkali hydroxides. Thus,

MgC12 + 2 NaOH = Mg(OH) 2 + 2 NaCl

(6i) The alkaline earth metal hydroxides are also formed by direct reaction of
their oxides with water. thus,

CaO + H 20 = Ca(OH)2

(iv) Unlike alkali metal hydroxides, the alkaline earth metal hydroxides are
converted to their oxides on strong heating by loss of water. Thus,

Ca(OH) 2 -^-H-
'O' CaO

ti 7o ,
Ba(OH)2 BaO

(c) The heavy metal hydroxides : (i) The hydroxides of copper,

nickel, iron cobalt etc. are included in this sub-group. The formations of these
hydroxides do not take place with the direct reaction of the heavy metal, or their
oxides with water. These hydroxides are best prepared by the addition of a soluble
 OXID M
- AND I riDROMDES 229

alkali hydroxide to the heavy metal salt solutions in water. The heavy metal
hydroxides are precipitated in the form of insoluble product
FCC13 + 3 NH40H = Fe(OH) 3 + 3 N1140

CUSO4 + 2 NaOH = Cu(OH) 2 + Na2SO4

(ii) Since the heavy metal hydroxides are generally insoluble in water, their
basic character is revealed by their dissolution in acids indicating neutralization
reaction forming salts and water. Thus,
Fc(OH) 3 + 3 HCI = FeC13 + 3 H20

(iii) The heavy metal hydroxides are easily converted to their oxides by
heating when water is lost. Thus,

Ni(OH)2 –H20 - NiO

It may be mentioned here that the results of the dehydration of a heavy metal
hydroxide may produce intermediate products which may be described as
oxyhydroxides. Some of these oxyhydroxidcs are formed during the direct
reaction and no heating is required. However, on strong heating these
oxyhydroxides also give the metallic oxides. Thus,
Partial
FeO.OH
Fe(OH)2 dehydration'
— air heating
Fe(OH)2 oxidation--' FcO.OH -4 Fe203

Water vapour
Fe --* FeO.OH
or normal rusting Lepidocrocite

Similarly, MnO.OH, AIO.OH etc. are formed by partial dehydration of the

normal hydroxides.
11. Amphoteric Hydroxides

In conformity with the definition of amphoteric oxides, the amphoteric

hydroxides may be dcf-ined in a similar fashion since the latter are derived from
the former. It is not possible to classify all hydroxides sharply as either basic or
acidic. The hydroxides of those elements situated in the cenLre of the Periodic
Table are amphoteric.
230 MRODUC`nON TDMODERN INORGANIC CHEMISTRY

Amphoteric hydroxides are those which are able to neutralize both acids and
bases and hence possess both acidic and basic characters.

For instance, Be(OH)2, AI ( OH )3, Zn(OH)2, Pb(OH) 2 etc. are amphoteric

hydroxides and act both as acids or bases and hence are soluble in either strongly
basic or strongly acidic solutions.

The acidic hydroxides generally give H I ions in solution and basic

hydroxides produce OH- ions as the case may be. Thus in the case of Zn(OH)2,

we have,

Zn(OH)2 ) Zn *2 + 2 OH- (basic)

Zn(OH)2) Zn0272 + 2H+ (acidic)

Hence, such hydroxides are soluble in acids, as in HCI and also in alkali, e.g.
NaOH:

Zn(OH)2 + 2HCI = ZnC12 + 21-120

Zn(01-r)2 + 2NaOH = Na 2ZnO 2 + 2H20

A more precise equation showing the amphoteric behaviour of AI(OH)3 may be
given as follows :—

AI ( OH)3 (H20), + OH - ^'^_ Al (H20)2 (OH)4- + H 2 0 -- (1)

AI(OH)3 (H20)3 + H 30+ Al (H,0)4 (OH)2+ + H 2 0 -- (2)

In equation (1), a proton is transferred from AI(OM3 (H20)3 to OH-. In

equation (2), a proton is transferred from H 30+ to Al (OH)3 (H20)3-

Similarly, for other amphoteric hydroxides the replacement of the

surrounding groups of the metal as shown in the case of Al may be used to show
the amphoteric character.

III. Acidic Hydroxides (Hydroxy Acids)

Both the metals and non-metals can form acidic hydroxides and definition
follows the same pattern as that of the acidic oxides. But the acidic hydroxides of
the non-metals are more important since they behave as strong acids.
 OMDES AND HYDROXIDES 231

It— f
I
The acidic hydroxides are those which react with base to neutralize it
roducing salt and water:
P
OH OH ?H

V2S OP—OH 02N—OH —OH

UH ()H VrI
(H2SO,) (113PO4) (RNO'3) (H3BO3)
the
From above examples, we ^an derive a definition for the basicity of an
acid.

Basicity of an acid is the number of OH groups combined with an element

and capable of producing H I ions. The basicity of the acids have been given in
Table 8-2.

Table 8.2. Basicity or some acids.

Acid Hydroxideform Basicity

H2SO4 S02(OH)2 2

H3PO4 PO(OH)3 3

HNO3 NO2(OH) 1

H3BO3 B(OH)3 3

SO(OH)2 2

HC103 C102(OH)
RMnO4 MnO3(OH)
H3ASO4 AsO(OH)3 3

H3AS03 As(OH)3 3

H3PO3 POH(OH)2 2

H3PO2 R)H2(OH) 1

CH3COOH CH3CO(OH) 1
232 LN-FRODUCnON TO MODFRN D40RG&NIC CHEMISTRY

Thus the acidic hydroxides contain one or more OH groups which are
capable of producing H I ions by rupture of the 0—H bond. The hydroxy acids
are classified as ortho, meta- and pyro- acids on the basis of the OH groups and
their elimination during condensation reaction.
Ortho-acids : Theoretically the fully hydroxylated compounds from the
valence considerations are generally known as onho-acids. Thus,

OH OH

13-014 HO—Si—OH
I I

OH OH
Orthoboric acid OTthosilicic acid

But in many cases the theoretical hydroxylated compounds are not formed or
do not exist. The formula for the true orthocompounds may be written but these
refer to only hypothetical compounds. Thus, ortho-phosphoric acid should be
formed by the hydroxylation Of P205 where all the 5 oxygen is replaced by OH :

P20 5 - P2(OH)jo or P(OH)5

Hypothetical ortho -phosphoric acid

But P(OH) 5 does not exist. Hence the compounds which contain the maximum
number of OH groups in actual practice are generally referred to as ortho-acids.
For instance,

OH 0

0 ! P--OH 0 =S--OH

UH
Ortho -phosphoric acid Ortho-sulphuric acid

Meta-acids : The meta-acids result from the ortho-acids. When water

molecule is eliminated from one molecule of the ortho—compound, the product
obtained is called a meta-acid. Thus,

-1410
OP(OH 3) 02P(OH) or HP03
Or tho -phosphoric acid Meta-phosphoric acid
 OXIDES AND HYDROXIDES 233

—H20,
B(OH)3 OB(OH) or HB02
Orthoboric acid MeLaboric acid

—H20
Si(OH), OSi(OH)2 or H2SiO3
Orthosilicic acid Metasilicic acid

The meta-acids may also be derived from the hypothetical hydroxylated ortho-
acids. Some of these compounds may give a series of meta-acids which may or
may not exist. Thus fully hydroxylated orlho-acid of the compounds C1207 may
be formulated as given below. Thus, by elimination of one molecule of
H20
successively, gives rise to Ist-, 2nd-and 3rd meta-chloric acids.

CROH)7 —H20
00(01­1^
Hypothetical orthochloric acid I st meta-

I
H 20
03CROH) 02C'1(OH)3
3rd meta - (Perchloric acid) 2nd meta-

Pyro-acids : Pyro-acids are formed when two or more molecules of the

true ortho-or any intermediate form or meta-acids combine together with the
elimination of water molecule. The pyro-acids are formed by condensation
reaction and the compounds formed are also known as condensed products. Thus,
two molecules of orthophosphoric acid may combine by elimination of I
molecule of H 20 to forp pyrophosphoric acid.

— I
OP(OH) 3 + OP(OH)3 H20 ---> 03 P2(OH), or H4P207
OTthophosphofic acid (two molecules) Pyrophosphoric acid

—5H20
4 B(OH)3 05B4(OH)2
4 molecules of Il 3 B0 3 or H2B407
Pyroboric acid H213407
234 INTRODUCTION TO MODERN INORGANIC CHEMISIRY

0 0

1­10 — S — H S— OH
ill 11
0 0

_H'0

0 0
11 11
S— 0 — S — OH
11 11
0 0
pyrosulphuric acid or H2S2()7

IV. Neutral Hydroxides

These hydroxides do not ordinarily show acidic or basic behaviour, and
neither form H + or OH- ions, although both the groups may be present in the
molecular structures. The organic hydroxy compounds, Such as alcohols like
CH 3 0H , CAM etc. have OH group which does not give H + or OH- ions and
hence are neutral. Similarly, water. HOH, is neutral.
Acidic and Basic Character or Hydroxides
It may generally be concluded that an OH group presentin an acid, ionizes
to form a HI ion. But an OH group present in a metal hydroxide produces an
OH- ion. This necessarily implies that a hydroxy compound or hydroxide having
the general formula MOH, behaves as an acid or as a base or as neutral according
to the nature of the bonding in OH group. If the OH bond is ruptured or under-
goes a cleavage in such a manner as to produce H I ion, the compound is an acid;
and if the cleavage occurs to give OH - ion, the compound is a base. A hydroxy
compound MOH may undergo cleavage as in 0) or (11).

M H M H
 OMDES AND IffDRO)CDES 235

Thus in (1) the rupture takes place so that the electron pair is retained by the
oxygen atom and the ions M* and OH- are formed. This cleavage gives a base.
In (11), the electron pair is retained by the oxygen atom together with the element
M, forming an MO- ion and H+ 'ion. This cleavage gives an acid. If the bond is
such that no cleavage of the above type occurs, the hydroxide will behave as a
neutral substance. If M has very low eicctronegativity, the electrons are shifted
towards oxygen and away from M. Thus NaOH gives Na+ and OH- ions

Na H Na+ + o. H- base

But if M is a highly eleuronegative non-metal, such as Cl, the electrons are

pulled towards the Cl, away from H. Withdrawal of electron from H to 0 and
finafly the increase of electron density towards M, will leave H to be ionized as
H+ ion and MO group as negative MO- ion. Such substances act as acid.

H2SO4 having the electronic structure shown below behaves as an acid

Ihecause of the shifting of electron density away from H atoms for the same
reason :

—2

:0.
t. 2H+
:0: S 0 H

0: 0:
.........................
H

The general equation of the dissociation of a hydroxide may thus be represented

by the following equations :

M(OH) ) M+ + (OH)- base

M(OH) ) MO- + H+ acid

236 INTRODUCTION TO MODEMN INORGANIC CHEMISTRY

or generally,
M(Ojj),;^=^ M+n + n(OH)- and M(01­1)n;Z=-^^ MOn^ + nH + The two ways

in which hydroxides may react with H20 are as follows :

H H+
M__O__ :H +0 /M-0 - + H—O 1 acid
\H H

H
H_,
M— : O—H + 0 /,O—M + OR - base
H H

if M-0 bond is almost covalent, then O—H bond in the hydroxide is broken
giving H + (H30+) ion and hence acidic. If M-0 bond is ionic, water tends to

attack M, displacing the OH - ion and giving basic reaction with the formation of
hydrated ion [M—H201+- It may also be mentioned that those cations that
become attached to the oxygen of H 20, break the O—H bond releasing H + ion
and are thus acidic. The anions that attack the H Of H20, dislodge the OH - ion
and are basic. Thus Hg'2, CU,2 are acidic; C2-2, NH 2 - and S-2 are basic. These
reactions are known as "hydrolysis" to which reference has already been made
earlier.

The hydroxyl compounds of metals, which have various oxidation states,

become less basic and more acidic as the oxidation state is increased. For
instance, the hydroxides of manganese exhibit marked difference in acid-base
behaviour as shown in Table 8.3.

Table 8.3. Acid-base character of hydroxides and oxidation

states of Mn.

Compound Hydroxide formulation Oxidation state Character

Mn(OH)2 Mn(OH)2 Mn(+2) moderately basic

Mn(OH)3 Mn(OH)3 Mn(+3) Weakly basic
H 2MnO3 Mn0(OH), Mn(+4) Weakly acidic
H 2Mn04 Mn02(OH)2 Mn(+6) Definitely acidic
RMn04 Mn03(OH) Mn(+ 7) Strongly acidic
 OXDES AND HYDROXIDES 237

Manganese in its +2 state behaves as a typical metal giving the basic

hydroxide Mn(OH) 2 . But in permanganic acid Mn has oxidation state +7 and
shows a non-metallic character analogous to chlorine In HC10 4 . This may be
viewed from the positions of both Mn and CI in the Periodic Table since both
occupy group VII, although Mn is a transition element. The high charge of Mn
(+7) strongly attracts electrons. The 0—H bonds in H20 become very weak and
protons are split off to leave the oxygen associated with Mn. Thus HMn04
behaves as a strong acid in water.

Questions and Problems

I . What are the difterent classes of oxides ? Discuss their properties and reactions.

Why is Mg(OH) 2 formed when magnesium reacts with water whereas MgO is
2. .
produced when it bums in steam?
3. Arrange the following oxides in the order of increasing acidity:—

As203 , B203, BaO, BcO, FcO, N2 05 , P204, P203, C1207-

4. Write an equation showing that H 20 2 is an acid.

5. Distinguish between dioxides and peroxides in terms of electronic structures.

6. How will you classify peroxides on the basis of their reactions and on the basis
of their structures? Illustrate your answer with examples.
7. What are peroxides, superoxides and polyoxides? How will you distinguish
them from one another?
8. What is meant by the basicity of an acid? Give examples.

9. Define with examples ortho, meta- and pyro-acids. Discuss the modes of
formation of meLa-acid and PYTO-acid from ortho-acids.
10. Discuss the amphoteric character of hydroxides.
11. What is the relationship between the oxidation states and the acidic and basic
character of metal hydroxides?

12. How will you classify the oxides in terms of bonding systems? Give examples.
13. Predict the product in the following reactions:^

(a)A few drops of hot water are added to solid sodium peroxide.

(b) Sodium peroxide is dissolved in excess cold water.

(c)Potassium superoxide and manganese dioxide are added to dilute H2SO4.

(d)S03 is added to H202.

(e)S03 gas is passed over CaO.

238 INTRODUCT71ON TO MODERN INORGANIC CHEMISTRY

14. Explain peroxides with examples.

15. Describe the preparation. properties and uses of sulphur trioxide, nitrogen
tetroxide.
16. HOW
is OTthophosphoric acid converted to other phosphoric acids?

17. Write the acidic and basic characters of oxides.

18. Write a note on modem views of acids and bases.
19. Explain why H 20 is neutral, HOCI is acidic and NaOH is alkaline.
20. What are amphoteric oxides?
21, Classify the following as acidic, basic, amphoteric or neutral oxides
S02, C,203- P401& BcO, CO2
22. Comment on the acidic and basic character of the following oxides
MnO, MnO2, Mn203, Mn2O7, Mn304
23. Non-metal oxides create air pollution problems. Explain the reasons.
24. How would you distinguish between peroxides and Super oxides ? Give examples
of their reactions.
 CHAPTER 9

ACIDS AND BASES

The acids and bases are among the most important classes of compounds and
these two classes of substances are, in effect, opposite to each other and yet
interrelated through neutralization reactions forming salts which, therefore,
become closely related to acids and bases. It may be mentioned that the terms
acids and bases have been defined in many ways according to various concepts. In
this chapter a brief review of some of the elementary concepts regarding acids and
bases are given.

1. The Arrhenius Concept

Accordinj to Arrhenius concept an acid is a hydrogen-containing substance
which yields H+ ion (i.e., H30+, hydronium ion) when dissolved in water.
Base is a substance which contains CH groups and produces OH - ion when
dissolved in water.
Arrhenius concept is based upon ionic dissociation of compound in water.
Thus HCI is an acid because it produces H 30+ ion in water but CH 4 is not an
acid. Similarly, NaOH is a base because it yields OH - ion in water but C2HSOH
is not a base. CH 4 does not yield H+ ion in water, so also C 2 H S OH does not
give OH- ion in water:
HCI + H20 H30+ + Cl-
NaOH + H20 Na+ + OH-
The strengths of acids and bases according to the Arrhenius concept are
defined in terms of the concentrations of H+ ion and OH- ion respectively that
are present in aqueous solution.
The process of neutralization is, therefore, considered to be the combination
of H' ions and OH - ions to form neutral water:
H++ OH­) H20
 I

240 INTRODUC11ON TO MODERN INORGANIC C1 IEMISTRY

The above definitions for acids, bases and acid-base reactions have been
extended to apply to more general cases by several new concepts.

2. The Protonic or Briinsted Concept

According to Brbnsted concept, also known as Br6nsted-Lowry concept, the

following definitions for acids and bases have been adopted as a modification of
the Affhenius concept.

An acid is a substance that can give up protons to another species.

A base is a substance that can accept protons,

Stated more simply, an acid is a proton donor, while a base is a proton

acceptor.

It can be seen that the Br6nsted concept does not specify a solvent. Acids
and bases are related by the general equation :

IfB H' + B-
acid proton base

Generally, it may be written as

Acid -'
- Base + Proton

For instance, when ammonia in dissolved in water, the reaction

H20 + NH 3 _
^ NH4* + OH-

takes place. Here H 2 0 gives up the proton and is an acid and

NH3 accepts the
proton and is, therefore, a base. Similarly, the reverse reaction indicates NH 4 + as

an acid and OH - as a base. Thus in the above reaction, two acids and two bases

are involved at equilibrium conditions. The acid-base pair associated with the
loss or gain of proton is caHed a Conjugate Pair. Thus, NH4+ is the conjugate
acid of the base NH 3 and H20 is the conjugate acid of base Off - and vice versa.

The general equation for the equilibrium reaction may be written as

Acid, + Base2 '_ Acid 2 + Base,

Thus, in order that an acid acts as a proton donor, a proton acceptor must be
present to receive it. The ions which remain after protons have been donated
from the acid molecule are the Conjugate bases of the respective acid. Similarly,
 ACIDS AND BASES 241

the species formed when a proton is added to a base is the Conjugate acid of that
base.

H+

HC1 + H 2 0 ---) H 3 0+ + Cl_

acid base acid base

H+

/ \1
Also, H30+ + Cl - --4 HO + H20
acid base acid base

Some of the acid-base systems according to the Br6nsted concept are given
below:

Acid, B-2 Acid, Base,

HO + NH3 Nf­14' + cl-

NH4' + OH- H20 + NH,

H 30+ + OH- H20 + H2O

H20 + NH3 N1­14+ + OH-

HSO 4- + OH- H20 + SO4-2

Thus, Cl-, SO4 -2, OH- are conjugate bases of HCI, HSO4- and H20
respectively. H 20 , HSO4- and HO are conjugate acids of the bases OH-, SO4 ;j2
and Cl- respectively.

Tbus, the following species may be regarded as acids

Molecular species HCI, H 2SO4, CH3COOH, HCN, H2S, HP etc.

Anionic species HSO4-, HCO,-, HIPO4-, Hpo^-2, HS - etc.

Cationic species H30*, NH4*, Al(H20)6+3 etc.

—16
^
42 )y^' LN-TRODUCI-IONTOMODI-JLN'INORGX'NICCIIE.\41SIRY

The following species are regarded as bases

etc
Molecular species H20, NH3, CH3NH2 -

Anionic species OH—, HS — , S—', HCO3—, HSO4—, Cl — etc.

Cationic species Fc(H20)50H*2, Cu(H20)30H' etc.

From the above examples of acids and bases, it is seen that certain species

are classed as both acids and bases depending upon the manner they behave in a

given reaction.

A"Whiprotic species : A species that acts both as a proton donor and proton
acceptor is said to be amphiprotic.

Thus, H 20 is amphiprotic. It loses proton to a base, such as NH 3, or

accepts a proton from an acid, such as HCI :

H20 + NH 3NH,' + OH-

acid base

H20 + HCI 1130+ + CI_

base acid

Hence neutralization reactions according to Br6nsted concept ar- acid-base

reactions between the conjugate acid and conjugate base of an amphiptotic
solvent.

The proton -containing negative ions are amphiprotic;

HS- + OH- S-2 + H20

acid base

HS - + H30' H29 + H20

base acid

The conjugate base and acid relationship may be shown as:

 ACIDS AND BASES 243

-H+ 014 - Conjugate base of water

/I-1
H20
\.
+H+ H 30+ Conjugate acid of water

'n CO3-2 Conjugate base of

HCO3_
HCO3-

+H+ H2CO3 Conjugate acid of HCO3-

Amphoteric hydroxides react with both acids and bases because they are
generally arnphiprotic :

[AI(H20)3 (OH)31 + OH- ) [A'(H20)2(Oli)41— + H20

acid base

[Al(H20^(OH)3] + H 30+ ) (AI(H20)4(OH)21+ + H20

base acid

According to Br6nsted concept a solution of NaCl in H20 is neutral, since

Na + and Cl - do not exhibit any tendency to gain proton in H20 which is the
solvent and in which NaCl is not hydrolysed. But aqueous solutions of AIC13,
ZnC1 2 and FeC13 etc. show acidic reactions because the cations are hydrated and
hydrolysed. Thus, A1+3 ion is hydrated [AI(H20)61 +3 and hydrolyscd as indicated
above. [AI(H20)6] +3 is an acid and donates a proton to H 20, which acts as a
base. The enhanced proton releasing tendency of A1 +3 ion is due to the co-
ordination of H20 to A1 +3 in which the electrons are shifted towards the positi-

H
JU+3
0
H

vely charged A1 +3 , thereby weakening the O—H bond. H* ion is thus released
easily. Generally, small ions with high positive charge become hydrated in
aqueous solution and act as Br6nsted Acids. Na + , K + etc. which are of large size
and small charge do not show this character.

Polyprotic acid : Acids containing one proton which can be donated is

monoprotic acid. Those acids containing more than one donatable proton are
known as polyprotic acids. Thus HCl, HNO3, HCN etc. are monoproLic, whereas
H 3PO4. H2SO4. H 3 AsO4 are polyprofic.
244 MRODUC11ON TO MODMN NORGANIC CI IEMSIRY

Non-aqueous system : Non-aqueous solutions also lose or gain proton

and fit into the Br6nsted concept of acids and bases. Thus when water is
dissolved in liquid ammonia:

H 20 + NH3 N114+ + 01-F

acid base

When perchloric acid is dissolved in concentrated H 2SO4 , acid-base reaction

occurs

HC104 + H,SO4 H3SO4' + C'0_4

acid base

When concentrated H 2SO4 is dissolved in glacial acetic acid, we have again

acid-base reaction :

H2SO4 + CH3COOH HSO4- + CH,COOH,+

acid base

3. The Lewis Concept

G. N. Lewis has proposed a more generalized theory in which acids and
bases have been defined on the basis of electronic structures.

An acid is a substance (molecules or ions) which can accept a pair of

electrons.

A base is a substance (molecules or ions) which can donate a pair-of

electrons.

An acid-base reac6on, therefore, consists of the donation of a pair of

electrons from a base to an acid with the formation of a coordinate bond between
the two.
H H

HI + : N—H H—N_H] + coordination

I I
H H

H + + * ^ H- ^ H20 coordination

A + : B * ^^ A : B coordinated bond
acid base
From the electronic configurafions, different types of Lewis acids may be
distinguished.
 ACIDS AND BASFS 245

(i) Compounds having less than a full octet of electrons, e.g., BF 3 and

S03:
F 0
F 0:*^: 0 H+
F

F + B F . B. F

base acid

0]
?
+2
Ca+2 0: S
Ca 6:-2 + tO
0 0
base
acid

(ii)
Positive ions are often considered as acids :

Ag+ + 2 * NH 3[Ag (:NH3)J+

acid base
CO+3 + 6NH
3 ICO (:NH3)61 +3
acid base
(iii) Metal atoms, such as Ni, function as an acid in the formation of
nickel carbonyl:

Ni+4 * CO ) Ni(CO)4

(iv)Compounds having double ormultiple bonds (except C=C double

bond). rnese have acidic sites :

O=C=O + :b7. H )O=C=o

I .. I

(acid) (base) H

0 = C/^)—
'OH
246 U-;'MODUCnON TO MODERN INORGANICaIFMISTRY

S02+0-2 [000],
S

(v) Compounds having the central atom capable of expanding its valence
shcll are Lewis acids:

SIC14 + 2CI - [SnC^J-2

SiF4 + 2F- [SiF61_2

PC1 5 + Cl— IPCI61—

Since Lewis acids draw electron towards it, they are known as "electrophilic

(electron loving) reagents.

Lewis bases can also be grouped as follows

(i) Molecules containing an atom with two or less number of unshared

electron-pairs. Thus the number of unshared electron-pairs in Nc, HF, H20,
NH 3, PC13 etc. determines the properties and the reactions.

A torn or Electronic No. ofpaired Reaction Exarriple

molecule structure electrons
(Ione pairs)

Ne 4 Non-basic X

VeTy weakly HF +: SO.3

HF H., F 3 basic = HF1 S03

H20 H--^ * 2 basic H20: H"

H
I

NH3 H—N Stro;gly H,NS BF,

I basi ;
H
 ACIDS AND BASFS 247

CI Cl
Cl: + 0 C, : P : 0
CI
base acid

Base strength decreases in the series :

CH 3 N > H 3 N > F 3 N— Electron with charge capacity different.
Acid strength decreases in the series
BBr3 > BC1 3 > BF 3 — because of greater resonance stabilization.

(ii) Negative ions are Lew is bases:

+ H30+ HCl + H20

acid
H 0 + H30+ H20 + H2O
base acid

(iii) Compounds containing C=C double bonds also act as Lewis bases. High
solubility of AgC104 in benzene is considered as an acid-basc reaction on the
basis of Lewis concept. Interactions of —C=C— with BF3, AlBr3 etc. also
represcnt-acid-base reactions. Ag + ion with hydrocarbon gives "n-complex".
Interactions of AIC13 and BF3 With —C = C— also result in the formation of
11
n-complexes".

I I +
—C— C
Ag++ - I
—C— Ag
I
acid base

AlCl 3 + Cl— [AIC141—

acid base
248 INIRODUCTION TO MODFRN INORGANIC CHEMSIRY

Lewis bases supply electron pair to a nucleus and are "nucleophilic (nucleus
loving) reagents".

4. The Lux-Flood Concept

Protonic concept of Bronsted cannot be applied to systems having no proton

particularly in the case of oxide systems. According to Lux-Flood concept, the
definitions of acids and bases are as follows :—

Base Any substance which gives up oxide ion (0-2).

Acid Any substance which gains or takes up oxide ions.

Hence,

base acid + no-2

Th i s view is particularly applicable to reaction at high temperature.

CaO is a base because i t g i ves Up 0-2 ions:

CaO ^^ Ca+2 + 0-2

base acid
SO4-2 is a base because it gives up 0-2ions:
SO4-2 — So, + 0-2

CaO Ca+2
+ S03 A_) • SO4 -2
base acid acid base
• Sio -2
CaSO4 + Si02 ­4 Ca*2 3 + S03
base acid acid base acid

S03 and Ca*2 are acids because they take up oxide ions as shown by the
above equation :
A __4
S03 + ZnO ZnSO4
acid base
A
Na2O + ZnO -4 2Nal + ZnO2-2
base acid

Strength of acids is determined by the magnitude of the equilibrium constant,

 ACIDS AND BASES 249

K [Acid] X [0-21
[bawl

According to this concept, the strength of the following acids are given in the
increasing order:
p04-3 > B02-
> SiO3-2 > TiO3-2

5. The Usanovich Concept

This concept gives a comprehensive definition of acids and bases comprising

all aspects of their reactions.

An acid in defined as any substance which-

(i) neutralizes a base,
(ii) gives up cations,
(iii)combines with anions or electrons.
Similarly, a base is defined as any substance which-
(i) neutralizes an acid,
(ii) gives up anions or electrons,
(iii)combines with cations.

The following examples in a tabular form explain the various aspects of the

Usanovich concept :—

Acid Base Saft Jusfification

S0 3 Na2O Na2SO, Na2O gives 0-2

S03 combines wiLh 0-2

Fe(CN)2 KCN K4Fe(CN)6 KCN gives CN-
Fe(CN)2 combines with CN-
Sb2S 3 S-2
M)2S M)2SbS4 (NH4)2S gives
S-2
Sb2S3 gains
C12 Na NaCl Na loses an elecLron
Cl gains an clectron
HC1 141^3 Nli^Cl HCI gives H'

NH3 combines with H+

NH4 Oir NH3 + H20 NH'4 gives H+

- OH- combines with H+

 250 LNIRODUCTION TO MODIIZN IINORGANIC CIIEWSTRY

of
The Strengths Acids

From the point of view of ionization theory, the strengths of acids (or
bases) depend on the extent to which they dissociate into ions.

As mentioned in chapter 8, a molecule represented by MOH dissociate

giving an OH— or H * ions depending on the charge and size and electronegativity
of M. A large ion with a small positive charge has less attraction for the electron
of the OH— ion than does a small ion with a positive charge.

Thus alkali metal hydroxides, MOH, form strong bases and their strength
increases as the size of the alkali metal ion increases. The comparative strengths
of the various bases are qualitatively given in Table 9. 1.

Table 9.1. Strengths of bases on the basis of ion size and

charge or the metals.

Base Size of the metal ion Charge of Qualitative

A I metal ion strengths

UOH 0.60 +I Weak base

NaOli 0.95 +1 Strong base
KOH 1.33 +1 Very strong base
CsOH 1.69 +1 Strongest base
Mg(OH)2 0.65 +2 Weaker base
AI(OH)3 0.50 +3 Weaker base

The strength of an acid is a measure of tendency of its conjugate base to pan

away with the proton to another base. A strong acid having a great tendency to
donate proton is a conjuate to weak base with small tendency to accept proton.
Hence stronger the acid the weaker is the conjugate base and stronger the base the
weaker is the conjugate acid. Thus, strong HCI has a weak conjugate base Cl-.
The polyprodc acids, such as H3PO4, undergo stepwise ionization reactions. The
strength in this case can be measured by ionization constants K. Thus the
smaller the value of ionization constant K, the less is the degree of ionization
and hence less strong the acid. This applies to other polyprotic acids and provides
an approximate measure of the relative strengths of acidity due to ionization. The
neutral molecule more readily gives up the proton than does the negatively
 ACIDS AND BASES 251

charged anion. The strength of an acid depends mainly upon the value of the first
ionization constant.
H3PO4 W1 + HPO 4- ' Ki = 0.75 x 10,2
H 2 PO4_ 1 H+1 + F[Po4-2
K2 = 0.62 x 10-7
BPO4-2H+' + PO4-1 I X 10-13
K3 =
[H+] [H2PO4-']
Where K, = and so on for K2 and K3.
[H3PO41
Thus the smaller the value of ionization constant K, the less is the degree of
ionization aO hence less strong the acid.
Comparing the electronic structure of some acids and the first ionization
constants it is found that the oxidation number of the central atom determines
the strengths of the acids. Thus, H2SO4 is a stronger acid than
H2SO3 or H3PO4
because the oxidation number of S in H2SO4 is +6 and in 14 2 SO 3 it is +4 and
that of P in H3PO4 is +5. Thus,
+6 +5 +4
H 2 SO4 H3PO4 F12SO3

S with oxidation number +6 in H 2 SO4 obviously exerts a greater pull on all

the electron pairs of 0 atoms than does S in H2SO3:

R14 2+1
H:O: S H :0: S:O

The comparative strengths of some well-known hydroxy acids (oxyacids) on

the basis of the oxidation numbers of the acid-forming elements arc given by the
sequence:
7 6 5 4 3
HC104 > H2SO4 > HNO 3 > H 2SO 3 > H3AsO3 > HCIO

Both the charge and the size of the central element determine the strengths of
the acids in the above compounds. For instance,
252 INTRODUCnON T IO MODERN INORGANIC CHEMISIRY

4 4
H2SO3 > H2SCO3

because of the smaller size of S than Se although the oxidation number is the
same in both cases.

Ionic Potential : The ratio between the charge and the radius of an ion is
called ionic potential. If Z is the charge, r the radius of an ion, then the ionic
potential ^o is expressed as,
Z
41– r

It has been shown that values of y also determine the acidic or basic character
of a compound or an ion. Thus,
(p > 3.2 — acidic
9 < 2.3 — basic
2.3. < 4 (p <3.2 — amphoteric

The strengths of acids may be correlated to the number of oxygen and

hydrogen atoms in the molecule in two ways :—

(1)The greater the difference between the number of oxygen and number of
hydrogen atoms, the stronger the acid.

(2)The greater the number of non-hydrogenated oxygen atoms per molecule,

the greater is the strength of acid.

These two points have been illustrated in the Table 9.2 regarding oxyacid of
the general formula
H^MOY

where x and y are the numbers of hydrogen and oxygen atoms in the molecule
respectively.

In the cases of acids which do not contain the oxygen atoms, the
determination of strengths is based mainly on the ionic sizes or interatomic
distance or electronegativity of H and the non-metallic element forming the acid
molecule. Thus, the following two series have been arranged in decreasing
acidity :
 ACU)S AND BASES 253
HF > H20 > NH3
HI > HBr > HCI > HF
H2Te > H2SC > H2S > H20
The decreasing electronegativity in the order F > 0 > N gives rise to
the
decreasing strengths of dids. But decreasing atomic sizes of halogens and
those in the chalcoiens series produce acids of decreasing strengths. In the
halogen acids, the bond distances H—X increase from 1.0 A for HF to 1.7 AO in
M and also the bond energy decreases. HI, therefore, is a stronger acid since it
gives up proton relatively easily. The charge of the anion also influences base
strengths. For instance, the base strength of the monoatomic anions increases
in the series N-3 > 0-2 > p-, i.e., NH 3 is a stronger base than H20 which is a
stronger base than HF.
In the case of oxyacids the factors influencing the acid strengths are : (i)
electronegativity, (ii) number of oxygen atoms and (iii) the oxidation states of
the element forming the hydroxy compounds. These are shown in Table 9.2.
Superacids : When strong acids are dissolved in very acidic solvents, the
solutions are highly effective protonating agents. Such solutions are known as
superacids. Fluorosulphonic acid and hydrogen fluoride act as good systems for
the formation of superacids :
SbF 5 + HF SbF;-6 + H,F+
SbF5 + HS03F FS03SbF 5 + H2S03F+
Alkanes are easily protonated by superacids:
CH3
I
CH3—C—CH 3 + superacid
I
CH3

CH3
I

I Ck13
CH3 —
CH4 (CH3)3C' + CH4
254 INTRODUCTION TO MODERN INORGANIC CHEMISMY

Table 9.2. Relative strengths of oxyacids of the general formula

HxMOy.
Structural No. of No. of No. of first Strengths
fornuila H 0 non- ionization ofacid
atoms atoms hydro- constant (Remarks)
x y )^--x genated (K)
atoms
0
. I

H00 CI(OH) 1 1 0 0 9.6xlO-' very weak

+3
GO(OH) 1 2 1 1 ,X,0-2 weak
HC102
+5
H00, 002(01-1) 1 3 2 2 —10 strong
+7
HC10, C103(014) I 4 3 3 —10 very strong
.1
HBrO Br(OH) 2X I U-2
I 1 0 0 weak
+1
M0 I(OH) 1 1 0 0 1XIO-11 very weak
+3
H 3BO3 B(OH)3 3 3 0 0 5x107'0 very weak
+3
H3 A,(^ As(OH)3 3 3 0 0 WO-lo very weak
.5
5X,g-3
HASO4 AsO(OH)3 3 4 1 1 weak
+4
H 4SiO4 Si(OH)4 4 4 0 0 1XIO-10 very weak
+3
HNO2 NO(OH) 1 2 1 1 4.5x10-4 weak
+5
NO,(01-1) 1 3 2 2 _103 strong
HNO3
+4
1.7x10-3 weak
H2SO^ SO(OH)2 2 3 1 I
-6
_103
H2SO4 S02(OH)2 2 4 2 2 strong
+5
H3PO4 PO(OH)3 3 4 1 1 7.5 x 10-3 weak
+7
HM04 MnO3(OH) I 4 3 3 —10 very
strong
 AMS AND BASM 255

Acids & base as catalysts :

H2SO4
1. CH'COOH + C2HSOH Ca CH 3 COOC 2 H 5 + 1120-
talyst -_')

AIC13
2. Cjl^ + CH 3 0 C6HSCH3 + HCL

3. RX + H20 ag. KOH -4 ROH + HX.

Catalyst

Hard & Soft Acids and Bases (HSAB)

The classification is based on cleuronegativity values and size and is

actually a form of Ltwis acid-base concept.

Hard acids : These are metals having low clectronegativity values usually
0.7 to 1.6. Exception is H + ion which is also a hard acid on the basis of very
3 +4
small size. Similarly ions such as B* , C are hard acids because of very small
size and high charge.

Ilard Bases : Donor atoms of very high electronegativity values such as

oxygen and flourine. The oxoanions such as SO4 -2, -3
CO 3 ', PO4 etc. are
included in this group.

Soft Acids : Metals having high cleuronegativities (1.9 — 2.5) and also
having large size and low charge are soft acids. Ag', Aul. pt*2, Hg*2, pb+2 etc.

are soft acids.

Soft Bases : Group of ligands containing non-mctal clectronegative

elements such as C, P, As, Br, I and H_ ion (having electronegativity values
2.1 - 2.96 are included in soft acids.

The equilibrium of the reaction between Hard and Soft acids and bases
generally follow the equation:

HA: SB + SA: HB ^^ HA: HA + SA: SB

Applications of HSAB principle:

1. Qualitative analysis scheme for metal cafions.

2. Oxidation reduction reactions.

3. Geochemical classification of elements and their occurrence in nature as

minerals.
256 NMODUC1710N TO MODIRN INORGANIC CHEMISTRY

4. Toxicology of the elements and medicinal chemistry.

5. Clinical application and chclation therapy.

QUESTIONS AND PROBLEMS

I . Write a brief note on Br6nsted concept of acids and bases.
2. Write a note on modem views about acids and bases.
3. Write a short note on Lewis concept of acids and bases.
4. Write a note on Lewis and Br6nsted concepts of acids and bases.
5. What is the relationship of charge and size of the acid-forming elements with the
strength of the acid?
6. Arrange the following acids in terms of increasing strength
1-1 3 1303, H,SiO,, HNO 2, RNO3, H 2S01, RMn01-
7. What is the basis of the strength of acids in halogen acids?
8. How will you determine the strength of acids in terms of the oxidation number of
the acid-forming elements?
9. What are amphiprotic substances ? Illustrate with suitable examples.
10. Define the terms "acid" and "has e" according to the Arrhenius concept and the
protonic concept.
11. Write equations for Lh(: reaction of the following acids with water
HCI, HNO 3, HC104 and NH4'- What is the role played by water in these acid-base
reactions?
12. Classify the following substances aLs acids and bases giving reasons:—
—2 , Na,
BF,, NH 3 , NH, + , Ag+, S03, CaO, KCN, OH – , SO4 C12, H*.
13. What are the conjugate acids and bases? What are the conjugate bases of the
following acids?
H 2CO3, H 2 0, HC104, HCN
14. Give a brief account of modem views regarding acids and bases.
15. Write a note on acids and bases.
16. Write a note on modem views on acids and bases.
17. What are hard and soft acids and bases? Mention about the applications of hard
and soft acids and bases concept.