CHM 221: Inorganic Chemistry I

2nd Semester 2022/2023

Lecture Note

Content
 General properties of transition elements
 Concepts of acids and bases: Arrhenius, Bronsted-Lowry , Lewis concepts

General Properties of Transition Elements

Introduction
In the extended form of the periodic table, the elements have been grouped into four
blocks namely s, p, d and f-blocks. The d-block elements are also known as
transition elements, and they are present between s-block and p-block elements
They are named transition elements because their properties are intermediate
between the properties of s-block and p-block elements i.e. d-block elements
represent a transition in properties from electropositive s-block elements to least
electropositive p-block elements. The transition elements either have partially filled
d-orbital (or f-orbital) thus, their outermost-shells are incomplete.
Forty elements belong to d-block with the fourth, fifth, sixth and seventh periods
consisting of ten elements each. There are four complete rows (called series) of ten
elements each i.e., first transition to fourth transition series. Each series starts with a
member of group three (IIIB) and ends with a member of group twelve (IIB) as shown
below.

The d-block elements include the most common metal used in construction and
manufacturing (iron), metals that are valued for their beauty (gold, silver and
platinum), metals used in coins (nickel, copper) and metals used in modern
technology (titanium). Copper, silver, gold and iron were known and used in early

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civilization. Certain d-block elements are also important in living organisms. In this
course we shall focus on the d-block elements, specifically elements of the first
transition series.
Electronic Configuration of Transition elements
In the d-block transition elements, the last differentiating electron is accommodated
on penultimate d-orbitals, i.e., d-orbitals are successively filled. The first transition
series consist of ten elements i.e., from Scandium (Z=21) to Zinc (Z=30). These are
also called 1st row transition elements. Their electronic configurations are given in
table below:

Table 1.0 Electronic Configuration of 1st Row Transition Elements (Z = atomic

number)

Some general trends in the electronic configuration of 1st row transition elements
include the following:
(i) The 4s orbitals are conventionally denoted as the outermost orbitals even
though in the atoms of these elements the 3d and 4s orbitals have similar
energies. This is because radial probability studies have shown that their
4s electrons are positioned furthermost from the nucleus. Thus, their
neutral atoms lose a 4s electron first before 3d electrons.
(ii) Along the 1st row transition series, the 3d shell is gradually filled up except
for chromium (3d54s1) and copper (3d104s1) which have configurations that
are different than expected. This deviation is explained on the basis of
stability concept of half-filled or completely filled d-orbitals. The d-subshell
is more stable when 5 or 10 electrons are present, i.e., every d-orbital is
either singly occupied or doubly occupied.

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 (iii) Copper is included amongst the transition elements even though its outer
electronic configuration is 3d104s1. This is because it has the 3d9
configuration in its commonly occurring +2 oxidation state. i.e Cu2+ ions.
(iv) Zinc is not commonly considered a transition element since in both the
element and its compound, the 3d electron shell remains fully filled. It
therefore does not show some of the characteristic properties of transition
elements. However, zinc metals showing similarities in some of chemical
properties with transition metals are also included in this block. These are
considered as end members of the transition series in order to maintain a
rational classification of elements.
(v) Scandium is included amongst the transition elements only by definition.
So far, only the +3-oxidation state of Sc has been established. Its
compounds therefore do not show the general characteristics of transition
elements.

General Characteristics of Transition Elements

The members belonging to a given transition series do not differ so much from one
another. These elements show horizontal and vertical relationships or they show
similarities in a period as well as in group. The general trends of some of the
important properties are discussed below.

1. Metallic Character
All transition elements are metals. Thus they are characterized by their unique
metallic properties, which distinguish them from other elements. Their physical and
chemical properties contribute to their metallic nature. They exhibit most of the
properties of metals. They possess metallic lustre, high density, high melting and
boiling points, malleability, ductility, high tensile strength, hardness and brittleness.
They are also good conductors of heat and electricity.
These properties reveal that both metallic and covalent bonding are present in the
atoms of this element. The metallic bonding is due to possession of one or two
electrons in the outermost energy shell and relatively low ionisation energies. Copper
shows exceptionally high thermal and electrical conductivity because of the
existence of metallic bonds.
Their high malleability and ductility means they can be easily hammered into thin
sheets (malleability) and drawn into wires (ductility). This property of copper is
essential for its use in various industrial applications, such as metalworking and
wiring. Copper is also highly ductile, meaning it can be drawn into thin wires or
filaments without breaking which makes it used in the construction of brass
instruments like trumpets and trombones. Its ductility allows manufacturers to shape
and form intricate components of these instruments.
Their brittleness is associated with covalent bonding, while their hardness is due to
the presence of strong metallic bonding among their atoms. This is formed from
overlap between the singly filled orbitals of different atoms of the elements. The
greater the number of unpaired electrons, the greater the number of metallic bonds
and, therefore the greater the hardness of the metals. Cr for example has maximum

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number of unpaired electrons and is a very hard metal. Zn is softer in nature since it
does not have any unpaired d-orbital electron.

2. Atomic/Ionic Radii
The atomic radii of the elements of the 1st row transition elements decrease with
increase in atomic number but this decrease becomes small after midway. Thus, the
atomic radius gradually decreases from scandium to chromium but from chromium to
copper, it is nearly the same. As shown below

Table 1.1 Atomic radii (pm) of 1st row transition elements

The decrease in atomic radii in the 1st transition series, in the beginning, is due to an
increase in nuclear charge from member to member which tends to pull the ns
electrons inward, i.e., it tends to reduce the size. At the same time, the addition of
extra electrons to d-orbitals also provides the screening effect. As the number of d
electrons increases, the screening effect increases. Thus, there are operating two
effects namely screening effect and nuclear charge effect which oppose each other.
In the midway onwards of the series both these effects become nearly equal and
thus, there is no change in atomic radii (i.e. for Mn and Fe)
The values of atomic radii at the end of the series are bit higher. This is due to
electron-electron repulsions d-orbital electrons. These repulsions become
predominant at the end of the series and thus size increases. It is evident from the
high atomic radii value of zinc.
The ionic radii follow the same trend as the atomic radii. For the same oxidation
state, the ionic radii generally decrease as the atomic number increases.

The ionic radii also decrease with increase of charge on the ion.

.
3. Melting and Boiling Points.
The transition metals have very high melting and boiling points. In each series, the
melting points of these metals rise to a maximum value and then decrease with
increase in atomic number. However, manganese has abnormally low melting points.
The melting points of most of the first transition series elements except Zn above
900ºC.The high melting and boiling points of transition metals are attributed to the
stronger forces that bind their atom together. The presence of one or more unpaired
d-electrons contributes to higher interatomic forces on account of covalent bonding
and therefore, to high melting points. However, this concept does not explain why
manganese having five unpaired d electrons possesses lower melting point than that

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of vanadium or cobalt which have only three unpaired d electrons. The complex
structure is responsible for this abnormal behaviour. When no unpaired electrons are
present, the melting points is low as in the case of Zn.

4. Ionisation energies
There is a gradual but irregular increase in the ionisation energy values as we move
from left to right along the first transition series elements. The increase in nuclear
charge as we move across the row would attract the outermost electrons with
greater force and hence the ionisation energies are expected to increase at each
step. However, since the differentiating electron is added to the 3d orbitals, it
screens the 4s electrons thereby decreasing the attraction between the nucleus and
the 4s electrons. This screening effect decreases the magnitude of the nuclear
charge and consequently, the ionisation energies increase but quite slowly along the
first row. The value of zinc is appreciably higher due to additional stability associated
with completely filled 3d-level in zinc. The first ionisation potential values are
tabulated below in kJ mol-1.

5. Variable oxidation states

The transition elements with the exception of a few show a large number of oxidation
state. The various oxidation states are related to the electronic configuration of their
atoms. Variable oxidation states of the first row transition elements is due to the
involvement of d-orbital and s-orbital electrons in bonding as the energies of both
subshells are nearly equal. The lower oxidation state is generally shown when s-
orbital electrons participate in bonding, while higher oxidation states are exhibited
when d-orbital and s-orbital electron take part in bonding. For example, Fe could lose
its two 4s electron to form Fe2+ ion or lose its 4s electrons and one 3d electron to
form Fe3+ ions. Thereby existing in the +2 and +3 oxidation states. Amongst the 1st
row transition elements, manganese has the widest range of oxidation states (from -
1 to +7).
The oxidation states of first row transition elements are tabulated below. The
oxidation states within the brackets are not stable.

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Trends in Oxidation States of 1st Row Transition Metals
The following trends can be observed amongst the 1st row transition metals:
(i) Generally, within the transition series, the highest oxidation state increases
with increase of atomic number, reaching to a maximum in the middle and then
starts decreasing. For example, in the first transition series manganese shows the
maximum oxidation state of +7.
(ii) In general, the minimum oxidation state sown by a transition metal is equal to
the number of ns-electrons. Except scandium, (which has +3 oxidation state), there
is a common occurrence of +2 oxidation state where the 4s electrons have been
formally lost. For chromium and copper, the lowest oxidation state is +1. This is due
to their electronic configurations, Cr(3d54s1) and Cu(3d104s2). Thus, it is evident that
after scandium d-orbitals are more stable than 4s-orbital, i.e., the energy associated
with 3d-subshell is less than that of
4s-subshell.
(iii) In the first five elements of the first transition series, the maximum oxidation
state is equal to the sum of the 4s and 3d-electrons. For example, maximum
oxidation state for titanium is +4 for vanadium +5. For the remaining five elements
the maximum oxidation state is not related to their electronic configurations. The
common oxidation states for the elements from Fe to Ni are +2 or +3. The oxidation
state higher than +3 is rarely shown.
(iv) Some of the transition metals form compounds in zero oxidation state. The
common examples are Ni(CO)4 and Fe(CO)5 in which nickel and iron are in
zerovalent state.
(v) In +2 and +3 oxidation states, the bonds formed are mostly ionic. On the other
hand, in higher oxidation states, the bonds formed are essentially covalent. Higher
states are usually attained with elements of high electronegativity such as fluorine
and oxygen. For example, in ions such as MnO4- the bond formed is covalent.

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(vi) The relative stability of various oxidation states of a given element can be
explained on the basis of stability of d0, d5 and d10 configurations. For example, Ti4+
(3d04s0) is more stable than Ti3+(3d34s0). Mn2+ is also more stable than Mn3+.

6. Tendency to form Coloured Complex Ions

A substance appears coloured because it absorbs light at-specific wavelengths in
the visible part of the electromagnetic spectrum and transmits or reflects the rest of
the wavelengths. Each wavelength of visible light represents a different colour, while
white light is a combination of all colours. Most of the compounds of transition metals
are coloured in the solid or in solution states. The colour of transition metal ions
arises from the excitation of electrons from the d-orbitals of lower energy to the d-
orbitals of higher energy. The energy required for d--d electron excitations is
available in the visible range. It is for this reason that transition metal ions have the
property to absorb certain radiations from the visible region and exhibit the
complementary colour.
The transition metal ions which have completely filled d-orbitals such as Zn2+ ions
are colourless as the excitation of electron or electrons is not possible within d-
orbitals. The transition metal ions which have completely empty d-orbitals such as
Sc3+ are also colourless. The colours and outer electronic configurations of important
ions of the elements of first transition series are tabulated below:
Table 1.2: colours and magnetic moments of ions of the first transition series

7. Magnetic properties
Majority of substances show magnetic nature. These are either paramagnetic or
diamagnetic. A paramagnetic substance is one which is weakly attracted into a
magnetic field and a diamagnetic substance is one which is repelled by a magnetic
field. The paramagnetic behaviour arises due to the presence of one or more singly
occupied atomic orbitals, while diamagnetic behaviour is due to presence of paired
electrons in the atomic orbitals.

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Most of the compounds of transition elements are paramagnetic in nature as
unpaired electrons in d-subshell are present. The magnetic character is expressed in
terms of magnetic moment. Paramagnetic behaviour increases as the number of
unpaired electrons increases from 1 to 5. After d 5 configuration, there is decrease in
magnetic moment as the number of unpaired electrons decreases.
In the case of iron, cobalt and nickel the unpaired electron spins are much more
pronounced. As a result, these elements are much more paramagnetic than the rest
of the elements. These elements are termed ferromagnetic and can be magnetised.
The magnetic character is expressed in terms of magnetic moment.

8. Tendency to form Complexes

1st row transition metals have a marked ability to form complex compounds. This
ability is on account of following three reasons:
(i) Small size (ii) high nuclear charge (iii) a number of vacant orbitals of equivalent
energy where the electrons donated by ligands can be accommodated.
Ligands are species with lone pair of electrons which they can readily donate. These
species can be neutral molecules such as NH3, H2O, NO, etc., or ions such as Cl-
CN-, etc. The number of attachments with ligands is referred to as the coordination
number of metal ion and it mis usually four or six. The compounds containing
complex ions are termed as coordination compounds. [Cu(NH3)4Cl2] and Ni(CO)4 are
some examples of coordination compounds.

9. Catalytic properties
Most transition metals and their compounds act as catalyst. Their catalytic activity
can be attributed to a number of reasons.
Firstly, their ability to exhibit variable oxidation states. Catalysis on the surface
involves formation of bonds between reactant molecules and the surface of the
catalyst atoms. Since transition metals can use both their 4s and 3d electrons for
bond formation, this has the effect of increasing the concentration of the reactant at
the catalyst surface and weakening the bonds in the reactant molecule. This results
in lowering of activation energy and subsequently speeding up of the rate of reaction.

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Secondly, adsorption of Reactants. Transition metals can adsorb reactant molecules
onto their surfaces. This adsorption weakens chemical bonds within the reactants,
facilitating the breaking and formation of new bonds during the reaction. The ability
to adsorb reactants is crucial for many catalytic reactions.
Thirdly, Surface Area: Many transition metal catalysts are finely divided or have high
surface areas, which provides a large area for reactant molecules to come into
contact with the catalyst. This increased surface area enhances the efficiency of
catalysis.
Some common examples are (i) Pt - used as a catalyst in the manufacture of H2S04.
(ii) Fe - used as a catalyst in the manufacture of NH3 by Haber process (iii) Ni.- used
as a catalyst in the hydrogenation of oils. (iv) Pt, palladium (Pd), and rhodium (Rh),
are commonly used in catalytic converters to facilitate the conversion of harmful
exhaust gases into less harmful substances. By using these transition metal
catalysts, the catalytic converter helps to reduce harmful emissions from the
vehicle's exhaust, making it a critical component for environmental protection and
compliance with emissions standards.

10. Alloy Formation

Transition metals form a large number of alloys. Since d-block elements are quite
similar in atomic size, the atoms of one metal can substitute the atoms of other metal
in its crystal lattice. Thus, on cooling a mixture solution of two or more transition
metals, smooth solid alloys are formed. Alloys containing mercury as one of the
constituent elements are called amalgams. The purpose of making alloys is to
develop some useful properties which are absent in the constituent elements. For
example: stainless steel is a corrosion-resistant alloy of iron, chromium and in some
cases, nickel and other metals.

11. Formation of Interstitial Compounds

Small non-metallic atoms such as H, B, C, N, etc., are able to occupy interstitial
spaces of the lattices of the d-block elements to form combinations which are termed
interstitial compounds. These are non-stoichiometric in nature and do not follow the
common rules of valency. The bonds present are neither typically ionic nor covalent.
The formulae do not correspond to any normal oxidation state of the metal. Some of
the characteristics of interstitial compounds are:
(i) The interstitial compounds have similar chemical properties as the parent metals
but differ appreciably in their physical properties such as density, conductivity,
(ii) As a result of filling up of the interstitial spaces, the metals become rigid and hard.
Steel is quite hard as it is interstitial compound of Fe and C.
(iii) Interstitial compounds possess high melting points which are higher than those of
pure metals.

Some Important Compounds of Transition metals

The transition metals combine with a number of non-metals such as oxygen,
nitrogen, carbon, halogens, sulphur and phosphorus, etc., to form useful binary
compounds. General trends in oxides, halides and sulphides are discussed below.

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(a) Oxides: The elements of first transition series form a number of oxides having
general formulae MO, M2O3, M3O4. The oxides are generally formed when the
metals are strongly heated at high temperature in the atmosphere of oxygen. These
oxides exhibit acidic, basic and amphoteric behaviour. The oxides in lower oxidation
states are basic in nature, the oxides in intermediate oxidation states are amphoteric
while the oxides of higher oxidation states are acidic in nature. The important and
common oxides of the elements of first transition series include TiO, V 2O3 etc.
(b) Halides: Transition metals combine with halogens at high temperatures to form
compounds called halides. On account of high activation energies of these reactions,
high temperature is usually needed to start the reaction, but once the reaction starts,
the heat of reaction is sufficient to maintain the continuity of the reaction (Reactions
are exothermic in nature). Metals in higher oxidation states only form fluorides as it is
the most electronegative and reactive element.
(c) Sulphides: Sulphides of transition metals can be formed either by direct
combination of the metals with sulphur or by action of H2S or Na2S on the salts of
these metals. Sulphides of transition metals are coloured usually black and are
insoluble in water.

Concepts of Acids and Bases

Introduction
The concept of an acid, and a base are ancient ones that modern chemical science
has adopted and refined. The term acid originates from the Latin word acidus,
meaning sour, while the term alkali is an Arabic word for the ashes that comes from
burning certain plants. Thus, Acids and bases were first recognised as specific
classes of compounds because of the distinctive properties exhibited by their
aqueous solutions.
Acids and bases are foundational concepts in the field of chemistry, playing a pivotal
role in understanding chemical reactions, solution properties, and the behaviour of
substances in various environments. The study of acids and bases has a rich history,
with several prominent theories developed over time to elucidate their nature and
interactions. In this lecture, we will delve into three key acid-base theories: the
Arrhenius theory, the Brønsted-Lowry theory, and the Lewis theory, each providing a
distinct perspective on the fundamental properties of acids and bases..
Arrhenius Concept of Acids and Bases
This concept was presented in 1887 by the Swedish Chemist Svante Arrhenius.
According to this concept all substances which give H+ ions when
dissolved in water are called acids while those which ionise in water to furnish OH -
ions are called bases. i.e.

Thus, according to this concept, substances like HCl, H2SO4, HNO3, CH3COOH etc.
are acids since they give H+ ions, when dissolved in water.

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While substances like NaOH, NH4OH, KOH, Ca(OH)2 etc. are bases, since they give
OH- ions in water.

Acid-base neutralisation reactions taking place in water

The reaction between an acid and a base is termed neutralisation, i.e., neutralisation
involves the reaction between H+ and OH- ions to form water.

However, according to the Arrhenius concept, free H+ ions do not exist in water.
They combine with solvent molecules, i.e., hydrated to form hydronium or
hydroxinium (H3O+) ions. For example, the ionisation of HCl acids in aqueous
solutions should be represented as:

Thus, the formation of salt(NaCl) and H20 from neutralisation reaction between HCl
and NaOH can be represented below:

Basicity or Protoclty of an Acid

The basicity or protocity of an acid is the number of hydrogen ions which can be
furnished by one molecule of the acid upon dissociation. An acid liberating 1, 2 or 3
H+ ions are respectively known as monobasic, dibasic and tribasic (monoprotic,
diprotic and triprotic). Polyprotic or polybasic acids are acids that possess more than
one dissociable hydrogen ion eg., H2SO4 and H3PO4. Their dissociation usually
takes place in steps.

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It should be noted that basicity of an acid is not necessarily the number of hydrogen
atoms present in one molecule of the acid but the number of hydrogen ions furnished
by one molecule.
Acidity or Hydroxicity of a Base
Similarly, the acidity or hydroxicity of a ,base is the number of hydroxyl ions
produced from one molecule of the base on dissociation. A base liberating 1, 2 or 3
OH- ions are respectively known as monoacidic or monohydroxic, diacidic or
dihydroxic, triacidic or trihydroxic. Sodium hydroxide (NaOH), ammonium hydroxide
(NH4OH), potassium hydroxide (KOH) are monoacidic or monohydroxic bases while
calcium hydroxide [Ca(OHh] barium hydroxide
[Ba(OH] are diacidic or dihydroxic bases.
Strength of Acids and Bases
The strength of an acid or a base in Arrhenius concept is based on the extent of
ionisation or the equilibrium constant.
The equilibrium constant, Ka for the acid, HX, is :

The equilibrium constant, Kb for the acid, BOH, is :

The acids which are highly ionised in aqueous solutions, i.e., giving large number of
hydrogen ions are known as strong acids. The value of Ka for strong acids is higher
than 0.1. HCIO4, HNO3, H2SO4, HCl, etc., are very strong acids. The value of Ka is
very small for weak acids such as CH3COOH, H3PO3, H2CO3, H3BO3, etc. For
example, Ka value of CH3COOH is 1.8 x l0-5 at 25ºC. In other words, in the case of
weak acid, the ionisation is only slight and the major part remains as undissociated
molecules.
The bases which are highly dissociated in aqueous solution to produce large number
of OH- ions are called strong alkalies. The value of Kb for strong alkalies is higher
than 0.1. NaOH, KOH, Ba(OH)2, etc., are strong bases. The value of Kb is low for
weak bases such as NH4OH, Al(OH)3, Fe(OH)3, etc.

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Applications (or advantages) of Arrhenius concept
The Arrhenius concepts has aided the understanding of the following:
(i) Acidic character of aqueous solutions of non-metallic oxides e.g, CO2, SO2, SO3.
etc. This is because these oxides can give off H+ ions in water. E.g.

(ii) Basic character of aqueous solutions of metallic oxides e.g., CaO, Na 2O etc. and
compounds like NH3, N2H4. This is because these oxides can give of OH- ions in
water.

(iii) Acid-base neutralization reaction taking place in water.

(iv) The catalytic properties of acids in many reactions can be explained by saying
the H+ ions are available from the acids.
Limitations of Arrhenius concept
(i) It is applicable only to aqueous solutions. For the acidic or basic properties, the
presence of water is necessary. Dry HCl for example, cannot act as an acid.
(ii) According to the concept, acid-base neutralisation reactions take place only in
water and hence cannot explain such reactions occurring in other solvents or in the
gas phase. E.g., the formation of NH4Cl (s) by the combination of NH3 (g) and HCl(g)
cannot be explained by the Arrhenius concept.
(iii) The concept does not explain acidic or basic properties of acids and bases in
non-aqueous solvents like liquid NH3 or SO2

Bronsted-Lowry Concept of Acids and Bases

The ·concept was proposed independently by Bronsted and Lowry in 1923.
According to this concept acids are the species capable of donating the proton in a
reaction while bases are the species capable of accepting the proton in a reaction,
i.e., acids are proton donors (protogenic) and bases are proton acceptors
(protophilic). AN illustrative example is shown by HCl. When HCl looses one proton
(H+) to give Cl- ion, it can be regarded as a Bronsted-Lowry acid. i.e.

Similarly, since Cl- ion can accept a proton to form HCl, Cl ion act as a Bronsted-
Lowry base. i.e.

On combining the two equations above, we arrive at an equation which shows that
HCl is a Bronsted Lowry acid and Cl- ion is a Bronsted-Lowry base.

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Bronsted Lowry acids which can lose one proton are called monoprotic acids while
those that lose two or more protons are called polyprotonic acids. Similarly, Bronsted
Lowry bases that accept one proton are called monoprotonic bases while those that
accept two or more protons are called polyprotonic bases. Some examples are
shown below.

Thus, all Arrhenius acids are also Bronsted Lowry acids, but all Arrhenius bases ae
not Bronsted Lowry bases. This is shown by the behaviour of HCl in the following
two reactions:

HCl behaves as an Arrhenius acid in equation 1 by forming H3O + ion when dissolved
in water. On the other hand, equation 2 shows HCl losing a proton which combines
with NH3 to form NH4+ ion, hence HCl acts as a Bronsted Lowry acids
Conjugate acid-base pairs
When an acid loses a proton, the residual part of it tends to regain a proton.
Therefore, it behaves as a base. For example in the reaction between HCl(aq) and
NH3(aq) as shown below,

HCl loses a proton and gives Cl- ion.Hence,HCl acts as an acid and Cl- ion is its
base. i.e.

Thus, the HCl (acid)-Cl- (base) pair is called conjugate acid-base pair. (Conjugate
meaning “related”). Similarly, the proton lost by HCl is accepted by the NH 3 molecule
to form NH4+ ion. i.e.

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Thus, the NH4+ (acid) – NH3 (base) pair is also called conjugate acid-base pair.
If in the above reaction, the acid, HCl is labelled acid and its conjugate base, Cl - as
base1. NH3 is labelled as baseII and its conjugate acid, NH4+ as acidII . The reaction
can thus be written as :

Any acid-base reaction involves two conjugate pairs, i.e., when acid reacts with a
base, another acid and base is formed. Thus, every acid has its conjugate base and
every base has its conjugate acid. Some more examples are given below:

On the bases of proton interaction, molecules or ions can either lose or gain a
proton. In some instances, they can also lose as well as gain a proton.
An important example is the behaviour of H2) in the following acid- base reactions:

In reaction (i) H20 molecule loses a proton and hence acts as an acid. In reaction (ii)
H2O gains a proton and hence behaves as a base. Thus, H2O can be said to behave
as an acid as well as a base.
Based on proton interaction, solvents can be classified into four types :
(i) Protophilic solvents: Solvents which have the tendency to accept protons, e.g.,
water, alcohol, liquid ammonia, etc.
(ii) . Protogenic solvents: Solvents which have the tendency to donate protons,
e.g., water, liquid hydrogen chloride, glacial acetic acid, liquid hydrofluoric acid, etc.
(iii) Amphiprotic solvents : Solvents which have both thetendencies to accept or
donate pro.tons, e.g., water, liquid ammonia, alcohol, etc.
(iv) Aprotic solvents: Solvents which neither donate nor accept protons, e.g.,
benzene, carbon tetrachloride, carbon disulphide, etc.
Relative strength of Bronsted-Lowry acids and Bronsted-Lowry Bases
Relative strength of Bronsted-Lowry acids and Bronsted-Lowry bases can be
determined by treating these substances with water. When an acid reacts with H20,
the water acts as a base and when a base reacts with water, water acts as an acid.
Therefore, the strength of an acid depends on its ability to transfer its proton to H 20
(which acts as a Bronsted base) to form its conjugate base. For example, when a
monoprotonic acid such as HCl reacts with H20, it transfers its proton to the H2O to

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from H3O+. Since HCl is a strong acid, it is nearly completely ionised in water. The
reaction can thus be depicted as follows:

The longer arrow shows that the reaction proceeds almost towards the right. The two
acids viz HCl and H2O are competing for donating a proton to the base, but since the
equilibrium of this reaction lies towards the right, HCl donates the proton more
strongly than does H3O+. ion. Thus we can say HCl is a strong acid and H3O+. is a
weak acid.
Similarly, H2O and Cl- are competing to gain a proton. Since the reaction proceeds
towards the right, H2O molecules gains the proton more strongly than does Cl- ion.
Therefore, H2O is a strong base and Cl- is a weak base.
In summary, the strength of a Brønsted acid is measured by its acidity constant, and
the strength of a Brønsted base is measured by its basicity constant; the stronger the
base, the weaker is its conjugate acid.

Limitations of Bronsted-Lowry Concept

(1) A substance is termed as an acid or base if it reacts with some other substance,
i.e., if it donates proton to other substance, it is an acid and if it accepts proton from
other substance, it is a base.
(2) There are number of acid-base reactions in which no proton transfer takes place,
e.g.,

Thus, the protonic definition cannot be used to explain the reactions occurring in
non-protonic solvents such as COCI2, SO2, N2O4, etc.

Lewis Concept of Acids and Bases

A more general and fundamental concept of acid-base behaviour was proposed by
G.N. Lewis in 1923 (the same year in which Bronsted concept was introduced).
However, the concept became influential only in 1930 onwards. According to this
concept, a base is a substance which can furnish a pair of electrons to form a
coordinate bond whereas an acid is a substance which can accept a pair of
electrons. A Lewis acid is a substance that acts as an electron acceptor or
electrophile while a Lewis base is a substance that acts as an electron donor or
nucleophile.
A simple example of an acid-base is the reaction between a proton and a hydroxyl
ion.

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According to Lewis concept, the following types of species can act as
Lewis acids:
(i) Molecules in which the central atom has incomplete octet: Lewis acids are
electron deficient molecules such as BF3, AICl3, etc.

(ii) Molecules in which the central atom has empty d·orbitals: The central atom of the
halides such as SiX4, TiC4, SnCl4, PX3, PF5, SF4, etc., have vacant d-orbitals. These
can, therefore, accept an electron pair and act as Lewis acids.

(ii) Simple cations: All cations are expected to act as Lewis acids since they are
electron deficient in nature. However, cations such as Na+, K+, Ca2+, etc., (inert gas
configuration) have a very little tendency to accept electrons, while the cations like
H+, Ag+, Fe3+, Cu2+, etc., have greater tendency to accept electrons and, therefore,
act as Lewis acids.

(iii) Molecules having a multiple bond between atoms of dissimilar electronegativity:

Typical examples of molecules belonging to this class of Lewis acids are CO 2, SO2
and SO3. Under the influence of attacking Lewis base, one n-electron pair will be
shifted towards the more negative atom.

(iv) Elements with an electron sextet: Oxygen and sulphur atoms contain six
electrons in their valency shell and can accept a lone pair of electrons and act as
Lewis acids.
The following species can act as Lewis bases :
(i) Neutral species having. at least one lone pair of electrons: For example,
ammonia, amines, alcohols, etc., act as Lewis bases as they contain a pair of
electrons.

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(ii) Negatively charged species or simple anions: For example, chloride, cyanide,
hydroxide ions, etc., act as Lewis bases.

(iii) Multiple bonded compounds: The compounds which form coordination

compounds with transition metals such as CO, NO, ethylene, acetylene, etc., can act
as Lewis bases.

It may be noted that all Bronsted bases are also Lewis bases but all Lewis acids are
not Bronsted acids.
Limitations of Lewis Concept
(i) Lewis theory fails to explain the relative strength of acids and bases as different
types of reactions are involved.
(ii) Conventional protonic acids such as HCI, H2SO4 do not form coordinate bonds
with bases, hence they are not covered under Lewis concept.
(iii) All acid-base reactions are fast. However, the formation of coordinate bond is
very slow in certain cases.

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