Chapter 7-9
Chapter 7-9
Chapter 7-9
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.
2Mg + 02 = 2MgO
2CO + 02 = 2CO2
heat
SnC1 2 + C12 SnC14
Cu + S h"_ CuS
190 D41RODUCnON TO MODERN INORGANIC C1 IEMISTRY
(c)Removal of hydrogen :
oxidized to sulphur:
-1-12, S
H2S
Chlorine is evolved when HCl is heated with Mn02. Here HCI is oxidized
to chlorine :
-H2_4
2HCI C12
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.
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
(c)Removal of oxygen :
CUO -:^' Cu
CuO + H2 = Cu + H20
FeC13 FcCl2
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)
Naturally, when the reaction takes place in the reverse manner i. e.,to the
left, this indicates reduction. Hence the following definition :
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.
Na +e cathode — Nal
anode, 1)
20 - - e '
Cl
k - 12
0MAT1ON-RIDUCTIO N REAC11ON'S
195
reduction reactions do not occur spontaneously but take place only if electrical
energy is supplied.
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.
electric current by the same mechanism of electron transfer from Zn to H' ions
or Cu *2 ion respectively.
Whe n the electrons in the outermost energy level (or valence electrons) are
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
(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,
H, S 0,
2(+1) + x + 4(-2) = 0
2 + x - 8 = 0
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
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
numbers during the reaction and indicate the electrons gained and lost by them.
necessary.
Rule 4. Use H 2 0 molecules in order to form higher oxygen containing
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
Cl^ + 2e 2CI-
Fe+3 + 2CI-
Fe+ 2Cl2- -e
Since the loss and gain of electrons during the process must be equ ', the second
C12 + 2e 2CI-
2Ee3 + 6CI-
By adding 2Fg.Cl2 + C12
or 2FcCl,
2FeC12 + C12
'Me equation is obtained in the completed and balanced form.
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
reaction underlining the symbols of those elements which undergo change in the
reactions :
Br2 + 2e 213r
.1 +6
The loss and gain of electrons must be equal. Hence the upper haff-reaction
be
is to multiplied by 4 :
11 2_a-2 - 8e + (2)
411 20 H2SO4 + 811+
+2+12-14 +3 +1
K2Cr2O7 +6e 2Cr + 2K + 7 0-2 (1)
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,
6 Kl— 6e = 31 2 + 6K+I
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
+1 7 -8
K Mn 0 4+ 5e Mn+2 + K +I + 4 0-2 (1)
+1_2
H 2S — 2e 2H+ + SO (2)
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
-2
80 + 161-1 1= 81-120
species which will obviously depend upon the acid used. Generally, the acid used
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,
iodide !-.
202 LVIRODUCHONIMMODERN LNORGANIC CHEMISIRY
'4
Na§2()3 Na2 10406
+8 to 4 x 21 = + 10
2
and 12 + 2e = 21-
Reactions
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
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
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:
KMn0
+7 4 + 5e Mn+2
gi4_
1_014 — 2e ) 262
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.
Zn + Cu* 2 = Zn,2 + CU
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.
%.:/
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
we can measure the potential difference of the cell as a whole. Each half-cell
the
has equilibrium reaction :
Zn 4z^^ Zn +2 + 2e
higher electron density than the Pt of hydrogen electrode. Hence the greater
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
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
negative electrode (cathode) because its electron density is higher than that 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 :
Cell reaction— Zn + 2H + —^ Zn +2 + H2
OXLDAIION-REDUCMON REACTIONS 209
-C
Zn I Zn-2 (I M) I I H- (I M) H 2 (Pt) I atm
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
to form H + ions than does Cu. Consequently, electrons flow from the H-
electrode to the Cu-clecLrode. The electrode processes are :
Cathodic reduction Cu *2 + 2c Cu
The zero potential of H-electrode is above this figure of 0.34. Hence the
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
Elements Electrode
Reduced Elecoutie O)a&zed
f— reaction form potential
(volts)
Silver Ag Ag + +e -0-80
MencuTy Hg +2 +2e -0-85
H9
Bromine
213r- Br2 + 2e - 1-06
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.
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
explosive violence and metals with low positive potential liberate hydrogen at a
reasonable speed. The displacement reactions are generally applicable and any
There are two types of cells which make use of oxidation-reduction reactions
1. The Primary Cells : These are irreversible cells. The electrodes and
electrolytes cannot be restored to their original states once they have been
potential. The "dry cell" is a primary cell and reactions are irreversible.
2. The Secondary Cells : In these cells the chemicals used and 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.
Mn02 oxidizes H2, otherwise it will collect and stop the reaction :
11
OXIDATION - RE DUCTION RFACTIONS 213
H2 + Mn0 2 + 2H + = Mn *2 + 2H20
When the battery produces current, the following reaction takes place.
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.
PbO2 + 4H+ + So -2
4
+ 2e discharge
— PbSO4 + 21-120
charge
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) 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
(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
(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.
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
CO2 + H 20 = H2CO3
B203 + 31-1 20 = 21-131303
) 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.
(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
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
(h) Peroxides : These are oxides which contain more oxygen combined
to an element than what is necessary for its highest oxides according to the
Peroxides have been classified into the following groups on the basis of
their reactions :—
(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 :
addition to bases :
(iv) The basic peroxides form salts by direct union with acidic oxides:
Na2O2 + S02 = Na2SO4
Reactions :
(i) With water the acidic peroxides react to form normal acids with the
evolution of oxygen :
Cr04- + Na 20 Na2Cr04 + 02
S2Q7+ Na2O Na2SO4 + 02
(i)The peroxides having the excess oxygen atom or atoms doubly linked to
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
0
11 0
O_ S=O
N af-- 0
/ 0
Na— 0
I
0--- S=O
11 < 0
0
(Na202) (BaO,)
(S207)
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
(i) Peroxides have group —0---0— and hence yield 11202 as a characteristic
Na — ^ HCI i i ()
— 0 -4 1 + 2 NaCI
Na HCI H---O
B 0-4 + BaO
H/ H---O
0
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
There are three classes of oxides on the basis of the nature of chemical
bonds.
The ionic oxides are generally formed by the alkali and alkaline earth mcials.
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.
—15
226 WIRODUCMON TOMODERN NORGANICCHEMISIRY
HYDROXIDES
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.
OH
CaO + 0 H Ca
H OH
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.
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,
(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
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
(iii) The heavy metal hydroxides are easily converted to their oxides by
heating when water is lost. Thus,
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
Amphoteric hydroxides are those which are able to neutralize both acids and
bases and hence possess both acidic and basic characters.
hydroxides and act both as acids or bases and hence are soluble in either strongly
basic or strongly acidic solutions.
we have,
Hence, such hydroxides are soluble in acids, as in HCI and also in alkali, e.g.
NaOH:
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
UH ()H VrI
(H2SO,) (113PO4) (RNO'3) (H3BO3)
the
From above examples, we ^an derive a definition for the basicity of an
acid.
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 :
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
-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-
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
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
—2
:0.
t. 2H+
:0: S 0 H
0: 0:
.........................
H
or generally,
M(Ojj),;^=^ M+n + n(OH)- and M(011)n;Z=-^^ MOn^ + nH + The two ways
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.
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:—
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.
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.
The above definitions for acids, bases and acid-base reactions have been
extended to apply to more general cases by several new concepts.
following definitions for acids and bases have been adopted as a modification of
the Affhenius concept.
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
Acid -'
- Base + Proton
H20 + NH 3 _
^ NH4* + OH-
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.
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+
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:
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.
etc
Molecular species H20, NH3, CH3NH2 -
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.
Amphoteric hydroxides react with both acids and bases because they are
generally arnphiprotic :
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.
and fit into the Br6nsted concept of acids and bases. Thus when water is
dissolved in liquid ammonia:
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 :
Ni+4 * CO ) Ni(CO)4
(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:
Since Lewis acids draw electron towards it, they are known as "electrophilic
Ne 4 Non-basic X
H
I
CI Cl
Cl: + 0 C, : P : 0
CI
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
Lewis bases supply electron pair to a nucleus and are "nucleophilic (nucleus
loving) reagents".
Hence,
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
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
The following examples in a tabular form explain the various aspects of the
Usanovich concept :—
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.
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.
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
R14 2+1
H:O: S H :0: S:O
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
(1)The greater the difference between the number of oxygen and number of
hydrogen atoms, the stronger the 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
H2SO4
1. CH'COOH + C2HSOH Ca CH 3 COOC 2 H 5 + 1120-
talyst -_')
AIC13
2. Cjl^ + CH 3 0 C6HSCH3 + HCL
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.
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.
The equilibrium of the reaction between Hard and Soft acids and bases
generally follow the equation: