d - block Elements

Introduction:
The elements belonging to group 3 to 12 are called d-block elements or transition elements.
These are present between s-block and P-block elements.
The properties of these elements are intermediate between the properties of s-block and p-
block elements. That means the d-block elements represent change or transition in properties
from most electropositive s-block elements to least electropositive p-block elements. Therefore
these elements are called transition elements.
These elements contain partially filled d-orbitals and hence they are called as d-block elements.
A Transition Element is defined as that which contains at least one unpaired d-electron in its
atom or ions with common oxidation state.
Zinc, Cadmium, Mercury have completely filled d-orbitals in the atomic state as well as in their
common oxidation states. Therefore they are not regarded as transition metals. However, being
the end members of the 3d, 4d and 5d transition series, respectively, their chemistry is studied
along with the chemistry of the transition metals.
The general electronic configuration of d-block elements is (n-1) d1-10ns1-2.
The d-block comprises of 3d, 4d, 5d and 6d series of elements.
First transition series or 3d series [Sc (21) to Zn (30)]
This is also called as 3d series which corresponds the filling of 3d orbital. It starts from scandium
whose atomic number is 21 and includes 10 elements till zinc whose atomic number is 30.
Second transition series or 4d series [Y (39) to Cd (48)]
This is also called as 4d series which corresponds the filling of 4d orbital. It starts from yttrium
whose atomic number is 39 and includes 10 elements till cadmium whose atomic number is 48.
Third transition series or 5d series [La (57) to Hg (80)]
This is also called as 5d series which corresponds the filling of 5d orbitals. This series consists of
elements from Lanthanum, La (Z = 57) to Mercury, Hg (Z = 80) except 14 elements of lanthanoid
series from Cerium, Ce (Z = 58) to Lutetium, Lu (Z = 71).
Fourth transition series or 6d series [Ac (89) to Cn (112)]
This is also called as 6d series which corresponds the filling of 6d orbitals. This series consists of
elements from Actinium, Ac (Z = 89) to Copernicium, Cn (112) except 14 elements of actinoid series
from thorium, Th (Z = 90) to lawrencium, Lr (Z = 103)

1
General trends in properties of first row of transition metals:

Electronic configuration of the elements of first transition series:

Element Atomic number Electronic configuration:

Scandium 21 1s2 2s2 2p6 3s2 3p6 4s2 3d1

Titanium 22 1s2 2s2 2p6 3s2 3p6 4s2 3d2

Vanadium 23 1s2 2s2 2p6 3s2 3p6 4s2 3d3

Chromium 24 1s2 2s2 2p6 3s2 3p6 4s1 3d5

Manganese 25 1s2 2s2 2p6 3s2 3p6 4s2 3d5

Iron 26 1s2 2s2 2p6 3s2 3p6 4s2 3d6

Cobalt 27 1s2 2s2 2p6 3s2 3p6 4s2 3d7

Nickel 28 1s2 2s2 2p6 3s2 3p6 4s2 3d8

Copper 29 1s2 2s2 2p6 3s2 3p6 4s1 3d10

Zinc 30 1s2 2s2 2p6 3s2 3p6 4s2 3d10

Chromium and copper exhibit anomalous electronic configurations.
Electronic configuration of chromium (Z = 24) is 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Electronic configuration of copper (Z = 29) is 1s2 2s2 2p6 3s2 3p6 4s1 3d10
The actual configurations of these elements are explained on the basis of stability concept of
half-filled or completely-filled (n-1) d-orbitals. The (n-1) d-subshell is more stable when it has
5 or 10 electrons, which means that each d-orbital is either half-filled or completely filled.

Metallic character:
All the transition elements are metals. They exhibit most of the properties of metals.
They possess metallic luster, high density, high melting and boiling points, malleability,
ductility, high tensile strength, hardness etc.
Most of the transition elements of the first row form metallic bonds due to the presence
of incomplete outermost energy level. The strength of the metallic bond depends upon
the number of unpaired d-electrons. As the number increases the strength also
increases. Due to the absence of unpaired electrons 'Zn' is not a hard metal.
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 Ionization energy:
The ionization energies of first row elements gradually increases with increase in atomic
number. The ionization energy of Zn is very high than all the other metals which is due to its
fully filled d-orbital. The third ionization energy of Mn and Zn is very high than the others.
Ionic radii:
In the first row transition elements the ionic radii decrease with increase in atomic
number. The value of ionic radii also depends on the oxidation state of metals. As the
oxidation state increases the ionic radius decreases and as the oxidation state decreases
the ionic radius increases.
Oxidation states:
d – block elements shows more than one oxidation states due to involvement of both ns
and (n – 1)d electrons in the compound formation.
The lower oxidation state is generally shown when only ns−electrons participate in
bonding and higher oxidation states are exhibited when both ns and (n-1) d−electrons
take part in bonding. (Generally lower oxidation state is equal to the number of ns–electrons
and the maximum oxidation state is equal to the sum of the outer s – electrons and unpaired d –
electrons.)
The maximum oxidation state in first series is +7 exhibited by manganese. In second and
third transition series, the maximum oxidation sate is +8 exhibited by Ruthenium and
osmium in their oxides.
In a given series of d – block elements the oxidation state increases up to nearly middle
element and then decreases. The most common oxidation state of first transition
elements (3d - series) is +2.
Variable oxidation states of 3d series

I series Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d 4s23d1 4s23d2 4s23d3 4s13d5 4s23d5 4s23d6 4s23d7 4s23d8 4s13d10 4s23d10
+1

+3 +2 +2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3

+4 +4 (+4) +4 (+4) (+4) +4

+5 (+5) (+5) (+5)

+6 +6 (+6)

+7

3
 The relative stability of various oxidation states of a given element can be explained on
the basis of stability of d0, d5, d10 configurations. For example, Ti+4 (3d0 4s0) is more
stable than Ti+3 (3d1 4s0), Mn+2 (3d5 4s0) is more stable than Mn+3 (3d4 4s0); Fe+3 (3d5 4s0)
is more stable than Fe+2 ((3d6 4s0), etc.

Colour:

Transition metal ions are generally coloured due to the presence of unpaired d – electrons.
Which absorb light from the visible region and thus move to higher energy level.
The colour of transition metal ions is due to excitation of electrons from d – orbitals of
lower energy to the d – orbitals of higher energy. The energy required for d-d electron
excitations available in visible range. Therefore, transition metal ions absorb certain
radiation from the visible region and exhibit the complementary colour.
The transition metal ions with completely filled d-orbitals are colourless. For example
Zn+2, Cd+2 and Hg+2 ions are colourless. Since they have completely filled d orbitals in
Zn+2 (3d10), Cd+2 (4d10) and Hg+2 (5d10) ions.
The transition metal ions which have completely empty d-orbitals such as Sc3+ (3d0 4s0),
Ti 4+ (3d0 4s0), etc., are also colourless.
The energy required to excite a d-electron of transition metal ion is small. Hydrated
copper (+2) ion i.e. [Cu(H2O)6]+2 absorbs red colour from the visible light appears blue,
the complementary colour of red. Thus [Cu(H2O)6]+2 appear blue.

Example:

Ion Colour
Cu+2 Blue
Fe+2 Pale green
Fe+3 Yellow
Cr+3 Green
Mn+2 Pink
Zn+2 Colourless

Cu+2 ions are coloured and are paramagnetic:

Electronic configuration of Cu+2 ion = 1s2 2s2 2p6 3s2 3p6 3d9
Cu+2 ion contains one unpaired d – electron. So it is coloured and paramagnetic.

4
Magnetic properties:
Those substances which are weakly attracted by the magnetic field are called
paramagnetic substances. This magnetic character arises due to the presence of
unpaired electrons. Most of the transition elements and their ions contain unpaired d -
electrons. So they are paramagnetic substances.
Example: Ti+3, Cu+2, Sc+2 have unpaired electrons
Those substances which are repelled by the magnetic field are called diamagnetic
substances. This magnetic character arises due to the presence of paired electrons.
Transition metal ions which contain paired electrons are diamagnetic substances.
Example: Ti+4, Cu+, Zn+2 have all the electrons completely paired.
Those substances which are strongly attracted by the magnetic field are ferromagnetic
substances. These also contain unpaired electrons. Iron, cobalt and nickel are
ferromagnetic substances.
Paramagnetism arises from the presence of unpaired of electrons. The magnetic
moment is determined by the number of unpaired electrons and is calculated by using
spin-only formula. i.e.,
Where ‘n’ is the number of unpaired electrons and ‘μ’ is the magnetic moment in units of
Bohr magneton (BM). A single unpaired electron has a magnetic moment of 1.73 (BM).
The magnetic moment increases with the increasing number of unpaired electrons.
Greater the number of unpaired electrons in a substance, the greater is its magnetic
moment and larger shall be its paramagnetic nature.

Catalytic property:
Many d – block elements and their compounds act as catalysts in various chemical
reactions. This property may be either due to their variable valency which enables them
to form unstable intermediate compounds or due to providing suitable reaction surfaces
for the reactants to be adsorbed

Some catalysts used in the industries.

Process Catalyst
Hydrogenation of oils Ni
Synthesis of ammonia by Haber’s process Fe
Synthesis of nitric acid by Ostwald’s process Pt
Synthesis of Sulphuric acid by contact process (for the V2O5
oxidation of SO2 into SO3)
In the decomposition of KClO3 for preparation of oxygen MnO2

5
Complex formation:
d – block metal ions have a great tendency to form complexes due to their small sizes,
high nuclear charges and due to the presence of vacant d – orbitals.
The bonds involved in the formation of complexes are co-ordinate bonds. So complexes
are called co-ordinate compounds. In complexes the groups which donate the electron
pairs are called ligands and the metal ions which accept the electron pairs are called
central metal ions.
The central metal ions and the ligands are represented in a square bracket and other
ions are represented outside the bracket. The square bracket part is a complex ion and
it involves as a single unit in chemical reactions.
Example:
1. K3 [Fe (CN)6] Potassium ferricyanide.
2. [Cr (NH3)6]Cl3 Hexamminechromium (III) chloride.
In a series the stability of complexes increases with an increase in the atomic
number of the elements and in a particular oxidation state with decrease in the size
of its atoms. When the d – block metal atom exhibits more than one oxidation state,
the highest valent ion forms more stable complex.

Review questions:
Example set:
1. Transition elements are ______ block elements.
a. s
b. p
c. d
d. f
Solution: c)

2. The first transition element in the 3d series is:

a. scandium
b. chromium
c. nickel
d. copper
Solution: a)
3. The property, which is not characteristic of transition metals, is:
a. Variable oxidation states
b. Tendency to form complexes
c. Formation of colored compounds
d. Electro negative behaviour
Solution: d)

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Alloy formation
Alloys are homogeneous solid solutions in which the atoms of one metal are
randomly distributed among the atoms of the other metal.
Alloys are generally formed by the atoms that have metallic radii within about 15%
of each other.
Because of similar radii and other characteristics of transition elements, alloys are
readily formed by these metals. The alloys thus formed are hard, have high melting
points and are more resistant to corrosion than parent metals.
For example, the most common alloys are ferrous alloys: Chromium, vanadium,
tungsten, molybdenum and manganese are used for the production of a variety of
steels and stainless steel.
Alloys of transition metals with non-transition metals such as brass (copper-zinc)
and bronze (copper-tin) are also industrially important alloys.
 Co-ordination Compounds

Module 1: Introduction, ligands, co-ordination number, IUPAC nomenclature

Double salts or lattice compounds:

The addition compounds which are stable in solid state only but are broken down into
individual constituents when dissolved in water are called double salts or lattice compounds.
Their solutions have the same properties as the mixture of individual components.
For example, when Mohr’s salt, FeSO4.(NH4)2SO4.6H2O, is dissolved in water, it exhibits the
properties of FeSO4 and (NH4)2SO4, i.e., they produce Fe2+, 𝑁𝐻4+ , and 𝑆𝑂42− ions in the solution.
Thus, each ion has its identity in the double salt.

Carnallite: KCl.MgCl2.6H2O;
Potash alum: K2SO4. Al2(SO4)3.24H2O etc. are the examples of double salts.

Co-ordination or complex compounds:

The addition compounds in which some of the constituent ions or molecules lose their identity
and when dissolved in water they do not break up completely into individual ions, are called co-
ordination compounds or complex compounds.
The properties of their solutions are different from those of their constituents. When crystals of
CuSO4.4NH3 are dissolved in water there is hardly any evidence for the presence of Cu 2+ ions or
ammonia molecules. A new ion [Cu(NH3)4]2+ is furnished in which ammonia molecules are
directly linked with the metal ion.
Similarly, the aqueous solution of Fe(CN)2.4KCN does not give tests of Fe2+ and CN- ions but
gives the test for a new ion [Fe(CN)6]4-. The ions [Cu(NH3)4]2+ and [Fe(CN)6]4- are called complex
ions.

(Thus, a co-ordination or complex compound may be defined as a molecular compound that

results from the combination of two or more simple stable molecular compounds and retains
its identity in the solid as well as in dissolved state.)
Definition of the terms used in coordinate compounds:

1. Central atom/ion or centre of coordination:

The atom/ion to which one or more neutral molecules or anions are attached is called the
central metal atom/ion.
Since, the central ion acts as an acceptor and thus, has to accommodate electron pairs
donated by the donor atom of ligand, it must have empty orbitals. These central atoms/ions
are also referred to as Lewis acids.
(This explains why the transition metals, having empty d – orbitals form coordination
compounds very readily.)
For example, in the complexes [Ni(NH3)6]2+ and [Fe(CN)6]3-, Ni2+ and Fe3+ ions respectively are
the central metal ions.
2. Ligands:
The neutral molecules; anions or cations which are directly linked with central metal atom or
ion by donating electron pairs in a complex compound are called ligands.
The ligands are attached to the central metal ion or atom through coordinate bonds or dative
linkages. Free ligands have at least one electron pair that is not engaged in bonding. Some
examples are:

The ligand acts as a donor as it donates one or more electron pairs to the central metal atom or
ion which acts as an acceptor. The ligands are thus Lewis bases and central metal ions are Lewis
acids. The formation of complex ion involves following two things.
a. Ligands should have lone pair or pairs of electros which can be donated to the central metal
ion or atom.
b. The central atom or ion should have vacant orbitals of nearly equivalent energy to
accommodate the electrons donated by ligands. This condition is easily fulfilled by atoms or
ions of transition metals.
Types of ligands:
Ligands can be of following types depending on the number of donor atoms present in them.

i. Mono or unidentate ligands: Ligands which are linked to a central atom/ion through only
one donor atom are called as mono dentate ligands. i.e., they supply only one electron pair
to central metal atom or ion.
F-, Cl-, Br-, H2O, NH3, CN-,𝑁𝑂2− , OH-, CO etc. are examples of monodentate ligands.
ii. Bidentate ligands: Ligands which are having two donor atoms and are capable of forming
two coordinate bonds with the same central atom are called bidentate ligands.
Some examples are: Ethylenediamine (en), Oxalate (C2O4-2 ), Carbonate (CO32-).

iii. Tridentate ligands: The ligands having three donor atoms and are capable of forming three
coordinate bonds are called tridentate ligands.
Ex: Diethylenetriamine (dien), 2,2’,2-Tripyridine (terpy).

iv. Tetradentate ligands: The ligands having four donor atoms are called tetradentate ligands.
Ex: Triethylenetetramine (trien)
v. Pentadentate ligands: The ligands having five donor atoms are called pentadentate ligands.
Ex: Ehylenediaminetriacetate
vi. Hexadentate ligands: The ligands having six donor atoms are called hexadentate ligands.
Ex: Ehylenediaminetetraacetate (EDTA)
(Ligands having more than two donor atoms are also called as polydentate ligands).

Chelating ligands:
A bidentate or a polydentate ligand is known as a chelating ligand if, on coordination, it
results in the formation of a closed or cyclic ring structure. The complexes, thus formed are
called chelates. The word chelate has been derived from the Greek word chelate meaning
claw. The complex formed by Cu2+ ion with ethylenediamine is an example of a chelate.

The following are the characteristics of chelates:

 a. Chelating ligands form more stable complexes than monodentate ligands. This is called
chelating effect, all types of polydentate ligands can act as chelating ligands.
b. The chelates containing 5 or 6 membered rings including metal atom are comparatively
more stable. Chelating ligands which do not contain unsaturated groups (double bonds),
in general, form five membered stable complexes while chelating ligands having
unsaturated groups (double bonds) form six membered stable complexes.
c. Ligands with larger groups form more unstable rings than with smaller groups due to
steric hindrance.
Ambidentate ligand: A unidentate ligand containing two possible donar atoms, can thereby
coordinate through either of donar atoms. Such a ligand is called ambidentate ligand.
Ex: NO2- (M←NO2 M←ONO)
-
CN (M←CN M←NC)
SCN- (M←SCN M←NCS)
3. Co-ordination number:

The total number of atoms of the ligands that are directly attached to the central metal atom or
ion by coordinate bonds in a complex compound is known as the coordination number of the
metal atom or ion. Thus, the coordination numbers of silver and copper ions in the complexes
[Ag(NH3)2]+ and [Cu(H2O)4]2+ are 2 and 4 respectively.

4. Co-ordination sphere:

The central metal atom or ion and the ligands directly attached to it are collectively called as
the coordination sphere. Coordination sphere is written inside square bracket, as for example
[Co(NH3)6]3+.
Remember that the central metal atom and the ligands inside the square bracket behave as a
single entity. Any ion present outside the sphere will be separated from the complex when the
compound dissolved in water.
Thus, the various terms used in a coordination compound can be illustrated as below:
5. Oxidation number:

It is a number (numerical value) which represents the electric charge on the central metal atom
of a complex ion. For example, the oxidation number of Fe, Co and Ni in [Fe(CN6)]4-, [Co(NH3)6]3+
and Ni(CO)4 is +2, +3 and 0 respectively.

Complex ion:

A complex (coordinate) ion is an electrically charged or a neutral species formed by the

combination of a central cation with more than one ligand species.
The charge carried by a complex ion is the algebraic sum of charges carried by the central ion
and the ligands coordinated to it. Charges of some complex compounds are given below:

S.No Complex compound (ion) Charge on complex ion

(i) [Cu(NH3)4]2+ (+2) of Cu + (0) of NH3
 Net charge = +2
(ii) [Fe(CN)6]4- (+2) of Fe + (-6) of 6 CN
 Net charge = -4
(iii) (Co(NH3)5Cl]2+ (+3) of Co + (0) of NH3 + (-1) of Cl
 Net charge = +2
(iv) [Co(NH3)3Cl3] (+3) of Co + (0) of NH3 + (-3) of Cl
 Net charge = 0

Nomenclature of Co-ordination compounds (IUPAC system):

The following rules are adopted for naming all types of coordination compounds:
1. If a coordination compound is ionic, the name of cation is given first whether or not it is the
complex ion followed by the name of the anion just like naming a simple salt. The names of
cation and anion are separated by a space.
2. Within a complex ion, the ligands are named first followed by the metal ion

Naming of the ligands:

a. Anionic ligands ending with – ide are named by replacing – ide with suffix – o or replacing –
e by – o.
Anion Symbol Name as ligand
Chloride Cl- Chlorido
Bromide Br - Bromido
Cyanide CN- Cyano
Oxide O2- Oxo
2−
Peroxide 𝑂2 Peroxo
Hydroxide OH - Hydroxo
 Sulphide S2- Sulphido
Amide 𝑁𝐻2− Amido
Nitride N3- Nitrido
Phosphide P3- Phosphido

Ligand whose names end in – ite or – ate become – ito or – ato, i.e., by replacing the ending
– e with – o.
Anion symbol Name of the ligand
2−
Carbonate 𝐶𝑂3 Carbonato
2−
Oxalate 𝐶2 𝑂4 Oxalato
2−
Sulphate 𝑆𝑂4 Sulphato
−
Nitrate 𝑁𝑂3 Nitrato
2−
Sulphite 𝑆𝑂3 Sulphito
Acetate CH3COO - Acetato
Nitrite ONO - (bonded through oxygen) Nitrito – O
𝑁𝑂2− (bonded through nitrogen) Nitrito – N or Nitro

b. Neutral ligands are called with the same names as their neutral molecules or with their
special names, e.g.,
H2O Aquo (Aqua) NH3 Ammine
CO Carbonyl; NO Nitrosyl;
CS Thiocarbonyl; NS Thionitrosyl
c. Positively charged ligands have suffix – ium.
NH2 - 𝑁𝐻3+ Hydrazinium; 𝑁𝑂2+ Nitronium
d. If the number of a particular ligand is more than one in the complex ion, the number is
indicated by using Greek prefixes such as di, tri, tetra, penta, hexa etc. However, when the
name of the ligand includes a number, e.g., dipyridyl, ethylenediamine, then bis, tris,
tetrakis are used in place of di, tri, and tetra etc.
e. When more than one ligand is present, they are named in alphabetical order without
separation by hyphen.
3. The oxidation state of the central metal is shown by Roman numerical in bracket
immediately following its name.
4. Complex positive ions and neutral coordination compounds have no special ending.
5. Complex negative ions always end in the suffix – ate. In most of the cases, the suffix – ate is
fixed to names of the metals.
Name of components present in coordination sphere are written continuously without a
gap, e.g.,
K3[Fe(CN)5NO] potassium pentacyanonitrosylferrate (II)
 Some names of the metals in the anionic complexes are given below.

Element Metal as named in ionic complex

Cobalt Cobaltate
Nickel Nickelate
Chromium Chromate
Iron Ferrate
Copper Cuprate
Silver Argentate
Lead Plumbate

6. The name of the neutral coordination compound is given in one word only as the name of
Ni(CO)4 is tetracarbonylnickel (0). The following examples will make the rules more clear.
Coordination compounds containing complex cations:
[Pt(NH3)6]Cl4 Hexaammineplatinum(IV) chloride
[Co(NH3)4(H2O)Cl]Cl2 Tetraammineaquochloridocobalt(III) chloride
[Fe(H2O)4(C2O4)]2SO4 Tetraaquooxalatoiron(III) sulphate
[Ag(NH3)2]Cl Diamminesilver(I) chloride
Coordination compounds containing complex anions:
K4[Fe(CN)6] Potassium hexacyanoferrate(II)
K3[Fe(CN)6] Potassium hexacyanoferrate(III)
Na[Ag(CN)2] Sodium dicyanoargentate(I)
Na3[Co(NO2)6] Sodium hexanitrocobaltate(III)
K3[Fe(CN)5NO] Potassium pentacyanonitrosylferrate(II)
Non-ionic coordination compounds:
Fe(CO)5 Pentacarbonyliron (0)
[Co(NO2)3(NH3)3] Triamminetrinitrocobalt (III)
Coordination compounds containing complex cations and anions:

[Cr(NH3)6][Co(CN)6] Hexaamminechromium (III), hexacyanocobaltate (III)

[Pt(NH3)4][CuCl4] Tetraammineplatinum (II), tetrachloroidocuprate (II)

Writing the formula of a coordination compound from its IUPAC name:
Following rules are followed in writing the formula of a coordination compound:
1. Formula of the cation whether simple or complex is written first followed by that of an anion.
2. The coordination sphere is written in square brackets
3. The following sequence of symbols within the coordination sphere is followed:
i. Metal atom
ii. Anionic ligands
iii. Neutral ligands
iv. Cationic ligands
a. If there are number of ligands of same type (anionic, neutral or cationic), they are listed
alphabetically according to first alphabet of their names. For example if 𝑁𝑂3− , 𝑆𝑂4− , OH-,
Br- etc., are present, they are written as Br-, 𝑁𝑂3− , OH- and 𝑆𝑂42− .
When two ligands have same donor atom, the ligands with fewer such atoms is cited
first followed by the ligand having more atoms. For example, 𝑆𝑂42− , precedes 𝑆2 𝑂32− .
When the numbers of defining atoms are same, subsequent symbol decides the
sequence. For example, 𝑁𝐻2− precedes NO2 because H comes before O.
4. Polyatomic ligands are enclosed in parentheses but all ligands are formulated without any
space in between
5. The number of cations or anions to be written in the formula is calculated on the basis of
total negative charge on the anion, as the complex as a whole is electrically neutral.
6. Sometimes abbreviations for certain ligands are used in parentheses instead of their
structural formulae. For example,
(en) ethylenediamine (ethane – 1, 2 – diamine)
(dien) diethylenetriamine
(trien) triethylenetetraamine
(edta or EDTA) ethane – 1, 2 – diamine tetraacetato
(dmg) dimethylglyoximato
Few examples are given here to explain the above rules.
Example 1:
Trichlorotriamminecobalt(III)
The metal complex is a neutral substance. The name of the central metal is written first. Its
oxidation state, then the ligands and their numbers are written.
Therefore the formula is written as [CoIII(NH3)3(Cl3)]
Example 2:
Tetramminecopper(II) hydroxide. The complex is a cationic complex. The formula of the cation
is written in the same order as in neutral complex. i.e. the central metal, its oxidation state;
ligands and their numbers.
Therefore [CuII(NH3)4]+2
The name of the anion only is given and not its number. Therefore hydroxide. The number is
inferred from the oxidation state of the complex species.
Therefore complete formula is [Cu(NH3)4](OH)2
Example 3:
Potassium tetrachloropalatinate(II)
The complex is an anionic complex
The cation is potassium. From the oxidation state of the complex anion, the number of cations is 2.
The anion, obtained by applying the above procedure, is [Pt II(Cl4)]-2
Therefore complete formula is K2[PtCl4]
 Co-ordination Compounds
Module 2: Theories of Co-ordination compounds

To explain the formation of complex compounds many theories have been suggested. The most
successful of the earliest theories is Werner’s theory. It is based on certain assumptions which
are listed here.
Werner’s Theory of Co-ordination compounds:
Postulates
1. A complex has always a central metal atom. This may be an ion or a neutral atom.
2. A metal ion in a complex compounds shows two types of valencies, namely primary and
secondary valencies.
3. Primary valency (Ionisable valency) corresponds to the oxidation state of metal atom or
ion. Secondary valency (Non-ionisable valency) corresponds to the co-ordination
number of the central metal.
4. Every metal has a fixed number of secondary valencies or co-ordination number in each
of its oxidation states.
5. The co-ordination number of the metal is the number of donor atoms of ligands, which
forms the number of coordinate covalent bonds with the central metal atom or ion, in a
complex compound.
In majority of the commonly found complex compounds, the co-ordination numbers
observed as 2 or 4 or 6.
i) Co(III) and Pt(IV) have 6 co-ordination number
Ex: [Co(NH3)6]Cl3 ; K2[Pt(Cl)6]
ii) Cu(II), Pt(II), Zn(II) have 4 Co-ordination number
Ex: [Cu(NH3)4]2+ ; [Cu(OH)4]2- ; [Pt(NH3)4]+2 ; [Zn(CN)4]-2 ; [ZnCl4]-2
iii) Ag(I) has 2 Co-ordination number
Ex: [Ag(NH3)2]+ ; [Ag(CN)2]-
6. The secondary valencies of the central metal may be satisfied by negative ions (Cl–, Br–,
CN– etc..) or by neutral molecules (H2O, NH3 etc), or by positive ions (NH2-NH3+, NO+
etc). This valency is non-ionisable. The donar atoms of the ligands are directly
attached to the metal atom and its attachment to the metal ion is shown by thick lines.
In some complex compounds both primary and secondary valencies may be satisfied by
negative ions.
Ex: [Co(NH3)4Cl2]Cl
7. The primary valency can be satisfied by negative ions. Its attachment to the metal ion
will be shown by dotted lines.
8. The ligands are directed in space around the central atom symmetrically in such a way
that the complex has a definite structure.
 Ex: i) If the complex has 2 ligands, it gives linear structure.
[Ag(NH3)2]+; [H3N – Ag – NH3]+
ii) If the complex has 4 ligands (or if the coordination number is 4), the geometry of the
complex may be either a tetrahedral or a square planar.
Ex:

iii) If the complex has 6 ligands, the geometry of the complex is octahedral.
Ex: [Co(NH3)6]+3

9. The charge of complex ion is equal to the sum of charges of metal and ligands.
Ex 1 : K4[Fe(CN)6]
Oxidation state of Fe is +2
Oxidation state of CN– is –1
Charge of complex ion [2+6(-1)] = – 4
i.e., [Fe(CN)6]4–

Ex 2 : [Co(NH3)6]+3 [Cl–]3
Oxidation state of Co is +3
Oxidation state of NH3 is 0
Charge of complex ion (+3) + 6(0) = +3
i.e., [Co(NH3)6]3+

Advantages of Werner’s theory:

a) Werner’s theory can explain the isomerism in complex compounds.
Ex: [Co(NH3)4(NO2)2]+ give two isomers
 b) We can distinguish the following complex compounds of same molecular formula
[Co(NH3)5SO4]Br [Co(NH3)5Br]SO4
(I) (II)
[Co(NH3)5SO4]Br gives yellow precipitate with AgNO3.
[Co(NH3)5Br]SO4 gives white precipitate wit BaCl2 solution.

Defects in Werner’s theory:

Inspite of the capacity to explain the formation of complex compounds, Werner’s theory is
having many defects. Some of the important drawbacks are enumerated here.
1. Werner’s theory does not correlate electronic configuration of the central metal with the
formation of the complex compounds. Now it is known that the central metal try to acquire
the next inert gas structure through coordinate bond formation. Hence complexes are
formed.
2. The postulates of Werner do not offer any explanation to the colour of the complex
compounds. It is appropriate at this juncture, to know how the d – d transition takes place
and result in the colour to the complex.
3. Werner’s theory is incapable of explaining the magnetic behavior. The magnetic property
depends on the number of unpaired electrons present in the metal ion. Werner’s theory is
not related to electronic configuration and so this property could not be explained.
Sidgwick Theory of Co-ordination compounds:
Sidgwick suggested that the bond between the ligands and the metal ion is co-ordinate
covalent or semipolar bond. He says that the ligands donate the electron pair to metal ion
forming a coordinate covalent bond. Here ligand (L) is donor and metal ion (M) is acceptor.
It is denoted by “L  M”
According to Sidgwick’s concept, the structure of the complex ion [Co(NH3)6]3+ is represented as
 Here, each NH3 donates a lone pair of electrons to cobalt (III) ion. The donation is represented
by an arrow. In the process the central atom acquires the same or nearest number of electrons
as that of its nearest inert gas. This number is known as EAN. The principle is referred
commonly as EAN rule.

Effective atomic number (EAN):

“The total number of electrons the central metal ion possesses including the electrons those
gained from ligands in the bonding, is called Effective Atomic Number (EAN)”
In many complexes it is equal to the atomic number of the nearest inert gas.
EAN value of metal can be calculated as follows using the relation.
EAN = {(Atomic number of metal) – (Oxidation state of metal) + [2×number of donor atoms
of ligands]}
Many complexes obey EAN rule

At. no. No. of e’s At. No.

Complex Central No. of e’s EAN of the metal
S.No of the lost = Ox. of next
compound metal gained (y) = (z-x+y)
metal State(x) inert gas

1. [Co(NH3)6]Cl3 Co 27 3 12 (27-3+12)=36 36(Kr)

2. K4[Fe(CN)6] Fe 26 2 12 (26-2+12)=36 36(Kr)
3. [Pd(NH3)6]+4 Pd 46 4 12 (46-4+12)=54 54(Xe)
4. [PtCl6]–2 Pt 78 4 12 (78-4+12)=86 86(Rn)

Some complexes do not obey EAN rule

Ex: 1) [Fe(CN)6]3– (26-3+12) = 35
2) [Ni(CN4)]2– (28-2+8) = 34
Valence Bond Theory:
This theory was developed by Pauling. This can explain the kind of bonding, shape and magnetic
properties of complex compounds. Main points are…
1. The central metal atom or ion makes available the necessary number of vacant orbitals
to equal to its co-ordination number. These vacant orbitals are hybridized together to
form hybrid orbitals that are equivalent in energy and symmetry.
2. The ligands must have at least one lone pair of electrons.
3. The vacant hybrid orbitals of metal atom/ion overlap with the ligand orbitals containing
lone pair of electrons to form coordinate covalent bonds.
4. The non-bonding electrons of the metal occupy the inner d-orbital which do not involve
in the hybridization. Sometimes under the influence of some strong ligands the electrons
undergo rearrangement against the Hund’s max multiplicity rule.
5. If a complex contains unpaired electrons, it is paramagnetic in nature; if it does not
contain unpaired electrons it is diamagnetic in nature.
6. The central metal atom may utilize the d-orbitals of either the penultimate shell or the
valence shell resulting in the inner d-orbital complexes or outer d-orbital complexes
respectively.
7. The number of unpaired electrons in complex may indicate the geometry of the complex.
8. From the number of unpaired electrons in the complex the extent of paramagnetism
can be calculated.
 Geometry (shape) and magnetic nature of some complexes (application of Valence bond Theory)

Configuration No. of
Ox. Hybridi Geometry
Complex Unpaired Magnetic nature
state zation shape
electrons
[NiCl4]2– : ::: +2 sp3 Tetrahedral 2 Paramagnetic

sp3

[Ni(CN)4]2– : : : : +2 dsp2 Square 0 Diamagnetic

planar
dsp2

[Fe(CN)6]4– :: : ::: +2 d2sp3 Octahedral 0 Diamagnetic

d2sp3

[Co(H2O)6]+2 : ::: :: +2 sp3d2 Octahedral 3 Paramagnetic

sp3 d2
Examples of inner orbital complexes and outer orbital complexes:
Ex 1: Formation of [Fe(CN)6]4– :
In this complex, the oxidation state of Fe is ‘+2’
Valence shell electronic configuration of Fe (Z=26): 3d6 4S2
Valence shell electronic configuration of Fe2+ion: 3d6 4S0

As the cyanide ion (CN−) is strong ligand, the unpaired electrons in the 3d orbitals are forced to
pair up.

Since there are six ligands around the central metal ion (coordination number is 6) the most
feasible hybridisation is d2sp3. Hence Fe2+ undergoes d2sp3 hybridization to form six d2sp3
hybrid orbitals.

Each of the hybrid orbital accepts a pair of electrons from cyanide ion forming six Fe—CN
coordinate bonds. (Six pairs of electrons from six CN− ions occupy the six hybrid orbitals.)

Hence, the geometry of the complex is octahedral and the complex is diamagnetic because of
absence of unpaired electrons.
In the formation of this complex, since the inner ‘d’ orbitals (3d) are used in hybridisation, this
complex is called inner orbital complex.

 Example for another inner orbital complex is [Co(NH3)6]3+

Outer orbital complex:

Ex-1: Formation of [CoF6]3–:

In this complex, the oxidation state of Co is ‘+3’
Valence shell electronic configuration of Co (Z=27): 3d7 4S2
Valence shell electronic configuration of Co3+ion: 3d6 4S0

The fluoride ion (F−) is a weak ligand and pairing of electrons does not occur.
Since there are six ligands around the central metal ion (coordination number is 6) the most
feasible hybridisation is sp3d2. Hence, Co3+ undergoes sp3d2 hybridization to form six sp3d2
hybrid orbitals.

Each of the hybrid orbital accepts a pair of electrons from fluoride ion forming six Co—F
coordinate bonds. (Six pairs of electrons from six F− ions occupy the six hybrid orbitals)

Hence, the geometry of the complex is octahedral and the complex is paramagnetic because of
presence of four unpaired electrons.
In the formation of this complex, since the outer ‘d’ orbitals (4d) are used in hybridisation, this
complex is called outer orbital complex.

Drawbacks of Valence Bond Theory:

1. It is a qualitative approach describing bonding in co-ordination compounds.
2. The theory fails to explain the finer aspects of the magnetic properties of co-ordination
compounds.
3. This theory does not provide an answer to the origin of characteristic colours of complex
ions.
4. It does not explain why [Co(NH3)6]+3 is an inner orbital complex and
[CoF6]-3 is an outer orbital complex.
Valence Bond Theory:
This theory was developed by Pauling. This can explain the kind of bonding, shape and magnetic properties
of complex compounds. Main points are…
1. The central metal atom or ion makes available the necessary number of vacant orbitals to equal to its
co-ordination number. These vacant orbitals are hybridized together to form hybrid orbitals that are
equivalent in energy and symmetry.
Number of orbitals and Types of hybridisation
Coordination number Type of hybridisation Geometry
2 sp Linear
sp 3 Tetrahedral
4
dsp 2 Square planar
sp3d2 Octahedral
6 2
d sp 3 Octahedral

2. The ligands must have at least one pair of electrons. The vacant hybrid orbitals of metal atom/ion
overlap with the ligand orbitals containing pair of electrons to form metal ligand coordinate bond.
3. The non-bonding electrons of metal occupy the inner d-orbital which do not involve in the hybridization.
Sometimes under the influence of strong ligands the electrons undergo rearrangement against the
Hund’s max multiplicity rule.
4. If a complex contains unpaired electrons, it is paramagnetic in nature; if it does not contain unpaired
electrons it is diamagnetic in nature. Complexes having unpaired electrons are coloured.
5. The central metal atom may utilize either inner d-orbitals (n-1) or outer d-orbitals (nd) for the
hybridisation. The complexes thus formed are referred to as inner orbital or low spin and outer orbital
or high spin complexes respectively.
6. It is usually possible to predict the geometry of a complex from the knowledge of its magnetic behavior.
7. From the number of unpaired electrons in the complex the extent of paramagnetism can be calculated.
 Co-ordination Compounds
Module 3: Isomerism
Isomers are the compounds that are having same molecular formula but different
structural or spatial arrangement of atoms and differ in their physical and
chemical properties.
Isomerism in co-ordination compounds may be divided into two types
a. Structural isomerism
b. Stereo isomerism
a. Structural isomerism:
The isomers differ in the arrangement of ligands within the complex are called
structural isomers and the phenomenon is called structural isomerism.
(The isomers that differ in the bonding of ligands to the central metal atoms are called
structural isomers and the phenomenon is called structural isomerism.)
1. Ionization isomerism:
This type of isomerism arises when co-ordination compounds give different ions
in solution.
(This isomerism arises when the counter in a complex salt is itself a potential ligand and can
displace a ligand which can then become the counter ion.)
Example: i) [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl
ii) [Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2
2. Hydrate isomerism:
Isomers differing in the number of water molecules attached to the metal ion as
ligands in co-ordination sphere.
(This type of isomerism arises when different number of water molecules are present inside
and outside the co-ordination sphere.)
Example: [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
Violet Green
3. Linkage isomerism:
Isomers of this type have different kinds of linkages of a ligand to the central mental ion.
(This type of isomerism occurs in complex compounds which contain ambidentate ligands such
as NO2-, CN-, and SCN-)
Example: [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5ONO]Cl2
4. Co-ordination isomerism:
This isomerism is caused by the interchange of ligands between the two complex ions.
(This type of isomerism is observed in co-ordination compounds having both cationic and
anionic complex ions. The ligands are interchanged between the cationic and anionic complex
ions to form isomers.)
Example: [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
5. Ligand isomerism:
Some ligands, capable of exhibiting isomerism, can give different isomeric complexes.
Example: [Pt(NH2CH2CH2CH2NH2)2]2+ and [Pt(NH2CHCH2NH2)2]2+

CH3
6. Polymerization isomerism:
Compounds having the same empirical formula but different molecular weights.
Example: [Pt(NH3)2Cl] and [Pt(NH3)4][PtCl4]

Stereo isomerism in complex compounds:

Complex compounds having same molecular composition and structure but differ
in the spatial arrangement of the ligands are called stereo isomers. This
phenomenon is called stereoisomerism.
It is of two types.
a. Geometrical isomerism
b. Optical isomerism
Geometrical isomerism in co-ordination number 6 compounds:
The arrangement of six ligands in a complex around the central metal ion is
possible in two different ways. Those are regular hexagon and regular octahedron.
If the complex Ma4b2 (where M = central metal atom; a,b = ligands) has hexagonal
structure it can give three isomers corresponding to (1, 2), (1, 3) and (1, 4)
positions of a and b, while octahedral arrangement can give only two isomers.
X – ray analysis confirmed that co-ordination number 6 complexes exhibit
octahedral arrangement by giving two isomers of Ma4b2 type. Hence co-
ordination number 6 complexes have octahedral structure.
Geometrical isomerism arises in coordination complexes due to different possible
geometric arrangements of the ligands.
If two similar ligands are arranged adjacent to each other it is called as cis isomer.
If the ligands are arranged opposite to each other it is called as trans isomer.
1. No isomerism is possible in [Ma6] or [Ma5b] type of complexes.
Example: [Co(NH3)6]3+; [Co(NH3)5Cl]2+
2. [Ma4b2] and [Ma4bc] type of complexes can give two isomers. Those are cis
and trans – isomers.
Example: [Co(NH3)4Cl2]+ gives cis and trans isomers.

3. [Ma3b3] type of complexes also can exhibit geometrical isomerism and gives
two isomers. Those are facial (fac) and meridional (mer) isomers.
Example: [Co(NH3)3Cl3] gives facial (fac) and meridional (mer) isomers.
4. [M(aa)2b2] (where aa = bidentate ligand) type of complexes having two
bidentate ligands, can exhibit geometrical isomerism.
Example: [Co(en)2Cl2]+ gives cis and trans isomers.

Optical isomerism in co-ordination number 6 compounds:

[Coordination compounds which possess chirality exhibits optical isomerism.
Coordination compounds having same molecular formula but differ in their
abilities to rotate the directions of the plane of polarized light are said to exhibit
optical isomerism and these molecules are called as optical isomers.
The isomer which rotates the plane of polarized light to right direction is termed
as dextro rotatory (d-form or ‘+’ form) while the isomer which rotates the plane
of polarized light to left direction is termed as laevo rotatory (l- form or ‘–‘ form).
The pair of two optically active isomers which are non-superimposable mirror
images of each other are called Enantiomers.]
1. The cis isomer of [M(aa)2b2] type complexes has no plane of symmetry. So it
can give two optical isomers (d and l)

2. Complexes of [M(aa)3] type having three bidentate ligands are also

unsymmetrical and shows optical isomerism.
 Example: [Pt(en)3]4+ gives optical isomers.

Stereo isomerism in co-ordination numbers 4 compounds:

Complex compounds with co-ordination number 4 give either tetrahedral or
square planar structure.
1. No isomers are possible for [Ma4], [Ma3b] type of complexes (either square
planar or tetrahedral)
Example: Ni(CO)4, [Cu(NH3)4]2+
2. Square planar complexes of formula [Ma2b2] and [Ma2bc] can show
geometrical isomerism. Metals like Pt (II), Pd (II), Ni (II), Cu (II) give square
planar structure having dsp2 hybridization.
Example: [Pt(NH3)2(CN)2] and [Pt(NH3)2Cl2] gives cis, trans isomers

The geometrical isomers of [Ma2bc] type: Example: [Pt(NH3)2Cl NO2] are

3. Square planar complexes of the type [Mabcd] also show geometrical isomerism
and gives three geometrical isomers.
Example: [Pt(NH3)(Py)ClBr] gives three isomers.

 Some complex compounds of Cu, Zn, Ni, Pt can give tetrahedral structure.
These metals undergo sp3 hybridisation.
[Mabcd] type of tetrahedral complexes show optical isomerism.

Applications of complex compounds:

I. Applications in qualitative analysis:
a. Separation of AgCl from Hg2Cl2:
In the Ist group silver ions precipitated as white ppt of AgCl. It is soluble in
ammonia due to the formation of [Ag(NH3)2]Cl
On the other hand, white ppt of Hg2Cl2 turns black on treatment with ammonia.
b. Separation of Cu and Cd:
Cadmium is separated from a mixture of copper and cadmium ions by adding
KCN. Copper ion forms a stable complex with KCN in the solution where as
cadmium complex being unstable, decomposes to give Cd+2 ions. These ions give
yellow precipitate with H2S
c. Test for Fe+2 (ferrous ion) and Fe+3 (ferric ion):
Ferrous salt solution gives deep blue colored precipitate with potassium
ferricyanide. These tests indicate the presence of ferrous ion.
Ferric salt with potassium ferrocyanide. This indicates the presence of ferric ion.
d. Test for K+ and 𝑵𝑯+
𝟒 ion:

Potassium salt solution gives yellow precipitate with sodium cobaltinitrite. The
test indicates the presence of potassium ion.

Nessler’s reagent is used for identification of ammonium ion. It gives chocolate

brown precipitate.

e. Test for nickel ions:

Nickel salts react with dimethyl glyoxime in presence of ammonium hydroxide to
give red precipitate of nickel dimethyl glyoxime

f. The complex “Ferroin” is used as indicator in some redox titrations.

[Fe(phenanthroline)3]2+

II. Applications in quantitative analysis:

a. Estimation of several cations like Mg+2, Zn+2, Cu+2, Ni+2 using EDTA as titrant in
presence of suitable indicator.
Example: Erio chrome black – T
b. Dimethyl glyoxime is used for estimation of nickel.
Example: 8-hydroxyquinoline is used for estimation of zinc.
c. Hardness of water can be calculated by EDTA complexes with Ca+2; Mg+2.
 Surface Chemistry
Module – 1
Surface chemistry is the study of the processes that occur at the interface of two
bulk phases. The bulk phases can be of the type solid – gas, solid – liquid, liquid –
gas and liquid – liquid. There is no interface between gases because of their
complete miscibility. The bulk phase can be solutions or pure compounds.
Absorption
In absorption, the substance penetrates through the surface into the bulk of the
solid or liquid and distributed uniformly throughout the bulk of the solid or liquid.
(or)
In the process of absorption molecules of one phase interpenetrate uniformly
among those of another phase to form a solution with the second phase.
Example: sponge in H2O
Adsorption:
There are several examples, which reveal that the surface of a solid has the tendency
to attract and retain the molecules of the phase with which it comes into contact.
These molecules remain only at the surface and do not go deeper into the bulk.
“The accumulation of molecular species at the surface rather than in the bulk of a
solid or liquid is termed adsorption.”
Example: Inert gases on charcoal etc..
The molecular species or substance, which concentrates or accumulates at the
surface, is termed adsorbate and the material on the surface of which the
adsorption takes place is called adsorbent. (Ex: In the adsorption of H2 gas on
platinum or nickel, H2 gas is adsorbate and Pt or Ni is adsorbent)
Adsorption is essentially a surface phenomenon. Solids, particularly in finely
divided state, have large surface area and therefore acts as good adsorbents.
Charcoal, silica gel, alumina gel, clay, colloids, metals in finely divided state, etc.
acts as good adsorbents.
Examples of adsorption:
a. If a gas like O2, H2, CO, Cl2, NH3 or SO2 is taken in a closed vessel containing
powdered charcoal, it is observed that the pressure of the gas in the enclosed
vessel decreases. This is because these gas molecules are adsorbed on the
surface of the charcoal.
b. To the solution of an organic dye, say methylene blue, when animal charcoal is
added and the solution is well shaken and filtered, it is observed that the filtrate
is colourless. This is because these molecules of the dye from the solution are
adsorbed on the surface of the charcoal.
c. Aqueous solution of raw sugar (Molasses), when passed over beds of animal
charcoal, becomes colourless as the colouring substances are adsorbed by the
charcoal.
d. The moist air becomes dry in the presence of silica gel because the water
molecules present in air get adsorbed on the surface of the silica gel.
It is clear from the above examples that solid surfaces can hold the gas or liquid
molecules by virtue of adsorption.
Desorption: The process of removing an adsorbed substance from a surface on
which it is adsorbed is called desorption. i.e. it is the reverse process of adsorption.
Sorption: Sorption is a process in which both absorption and adsorption takes place
simultaneously.
Eg: Dyes get adsorbed as well as absorbed in the cotton fibers, i.e., sorption
Distinction between Adsorption and Absorption
In adsorption, the substance accumulates on the surface and does not penetrate
through the surface into the bulk of the adsorbent. In absorption, the substance is
uniformly distributed throughout the bulk of the solid.
For example, when a chalk stick is dipped in ink, the surface retains the colour of
the ink due to adsorption of coloured molecules in the ink while the solvent of the
ink goes deep into the stick due to absorption. On breaking the chalk stick, it is
found to be white inside.
Water vapors are absorbed by anhydrous calcium chloride but adsorbed by silica gel.
In the same manner, ammonia is absorbed by water and is adsorbed by charcoal.
In other words, in adsorption the concentration of the adsorbate increases only at
the surface of the adsorbent, while in absorption the concentration is uniformly
distributed throughout the bulk of the solid.
Types of adsorption: Adsorption can be classified into two categories as described
below,
1. Depending upon the concentration:
In adsorption the concentration of one substance is different at the surface of the
other substance as compared to adjoining bulk or interior phase.
a. Positive adsorption: If the concentration of an adsorbate is more on the surface
as compared to its concentration in the bulk phase then it is called positive
adsorption.
Example: H2 on activated carbon, CH4 on activated carbon, when a concentrated
solution of KCl is shaken with animal charcoal, it shows positive adsorption.
b. Negative adsorption: If the concentration of the adsorbate is less on the surface
than its concentration in the bulk then it is called negative adsorption.
Example: When a dilute solution of KCl is shaken with animal charcoal, it shows
negative adsorption.

2. Depending upon the nature of force existing between adsorbate molecule and
adsorbent:
a. Physical adsorption: If the forces of attraction existing between adsorbate and
adsorbent are van der Waals forces, the adsorption is called physical adsorption.
This type of adsorption is also known as physisorption or van der Waals adsorption.
It can be easily reversed by heating or decreasing the pressure.
b. Chemical adsorption: If the forces of attraction existing between adsorbate
particles and adsorbent are of a chemical nature. i.e. are almost of the same
strength as chemical bonds, the adsorption is called chemical adsorption. This type
of adsorption is called as chemisorption or Langmuir adsorption. This type of
adsorption cannot be easily reversed.
Comparison between physisorption and chemisorptions:

Physisorption Chemisorption
(van der Waals adsorption) (Langmuir adsorption)
It is not specific in nature It is highly specific in nature.
Enthalpy of adsorption is low (usually Enthalpy of adsorption is high (usually
in range of 20 – 40 kJ/mol) in the range of 50 – 400 kJ/mol)
Forces of attraction are van der Waals Forces of attraction are chemical
forces. bonds.
It is readily reversible It is irreversible
It usually takes place at low It takes place at high temperature. It
temperatures and decreases with increases with the increase of
increasing temperature. temperature.
It depends on the nature of gas. Easily It is also depends on the nature of gas.
liquefiable gases are adsorbed readily. Gases which can react with the
adsorbent show chemisorption.
It results into multimolecular layers on It results into monomolecular layer
the adsorbent surface. only on the adsorbent surface.
No appreciable activation energy is High activation energy is sometimes
required. required.
In case of gaseous adsorbates decrease In case of gaseous adsorbates decrease
of pressure on the surface causes of pressure on the surface does not
desorption. cause desorption.
 Module – 2
Factors affecting adsorption
Adsorption of gases on solids depends on the following factors:
a. Nature of the gas (adsorbate)
b. Nature of the solid (adsorbent)
c. Surface area of the solid
d. Pressure of the gas
e. Temperature
a. Nature of the adsorbate:
Since physical adsorption is non – specific, every gas (i.e. adsorbate) gets adsorbed
on the surface of any solid. How much of the gas will get adsorbed depends on the
nature of the gas. Under any given condition of temperature and pressure, the easily
liquefiable gases such as NH3, HCl and SO2 are adsorbed more than the gases like H2,
N2 and CO. The ease with which a gas can be liquefied is determined by its critical
temperature, Tc. Tc is the temperature above which a gas cannot be liquefied, and
however high the applied pressure may be. This implies that gases with high critical
temperature values can be easily liquefied as compared to gases with low critical
temperature values. The table given below illustrates the correlation between the
extent of adsorption of gases on charcoal with their ease of liquefaction.
Volume of gases at N.T.P adsorbed by 1g charcoal at 288 K
Gas H2 N2 CO CH4 CO2 HCl NH3 SO2
Volume adsorbed (cc) 4.7 8.0 9.3 16.2 48 72 181 380
Critical temp. (K) 33 126 134 190 304 324 406 430

Since chemisorption is specific in nature, a gas is chemisorbed only when it forms

chemical bonds with the adsorbent. A gas which is physisorbed at a certain
temperature can be chemisorbed when the temperature is increased dramatically.
For e.g., at 83 K nitrogen (N2) is physisorbed on iron surface as N2 molecules. At
room temperature there is no physisorption of N2 on iron surface. However, at
773K nitrogen is chemisorbed on iron surface as nitrogen atoms.
b. Nature of the adsorbent:
The nature of the adsorbent has profound effect on the process of adsorption.
Solids with porous structure are potentially good adsorbents. Among them,
activated carbon is the most common adsorbent for gases which are easily
liquefied. Activated carbon is used in gas masks to adsorb poisonous gases such as
methane (CH4).
(Activated carbon is prepared from a variety of raw materials including wood, lignite,
coal, bone, nut shells and petroleum residues. The new material is activated in an
atmosphere of CO2, CO, O2 water vapor air or other selected gases at a temperature
between 573 K and 1273 K. This is often followed by quenching in air or water.
Adsorption on activated carbon is associated with the presence of small and uniform
pores. The surface area of activated carbon is approximately 1000 m2/g.)
Apart from activated carbon, silica gel, aluminium oxide and clay are used as
adsorbents. It is common knowledge that small satchets containing silica gel are
used in electronic equipments such as camera to keep the lenses dry. As mentioned
earlier, silica gel is used to adsorb water vapor, which is always present in the humid
weather conditions.
c. Surface area of the solid adsorbent:
The extent of adsorption depends directly upon the surface area of the adsorbent, i.e.
larger the surface area of the adsorbent, greater is the extent of adsorption.
Surface area of a powdered solid adsorbent depends upon its particle size. Smaller
the particle size, greater is its surface area.
d. Pressure of the gas - Adsorption Isotherms:
The extent of adsorption of a gas on a solid generally increases with pressure. The
extent of adsorption is given by x/m, (the ratio of the mass (x) of the adsorbate and
the mass (m) of the adsorbent) when a dynamic equilibrium has been attained. The
plot drawn between extent of adsorption of the gas and pressure, at constant
temperature, is called as the adsorption isotherm. The two most common
adsorption isotherms namely, Freundlich isotherm and Langmuir isotherm will be
discussed.
Freundlich Adsorption Isotherm:
Freundlich, in 1909, gave an empirical relationship between the quantity of gas
adsorbed by unit mass of solid adsorbent and pressure at a particular temperature.
The relationship can be expressed by the following equation
x/m = k.p 1/n (n > 1) ... (1)
Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure P,
k and n are constants which depend on the nature of the adsorbent and the gas at a
particular temperature.
The relationship is generally represented in the form of a curve where mass of the
gas adsorbed per gram of the adsorbent is plotted against pressure.
These curves indicate that at a fixed pressure, there is a decrease in physical
adsorption with increase in temperature. These curves always seem to approach
saturation at high pressure. At equilibrium pressure, Ps, x/m reaches its maximum
value, that is, no further adsorption takes place even if the pressure is increased.

Fig. 1: Adsorption isotherm Fig. 2: Freundlich isotherm

Taking the logarithms on both sides of the equation (1)

𝒙 𝟏
𝒍𝒐𝒈 ( ) = 𝒍𝒐𝒈 𝑲 + 𝐥𝐨𝐠 𝑷 … … (𝟐)
𝒎 𝒏

If the plot of log (x/m) versus log P yields a straight line, it implies that the
adsorption process confirms to Freundlich isotherm.
 𝟏
From the intercept, the parameter K is obtained, while the slope is equal to ( ).
𝒏
𝟏
The Factor can have values between 0 and 1 (probable range 0.1 to 0.5).
𝒏
𝟏 𝒙
When = 0, = constant, the adsorption is independent of pressure.
𝒏 𝒎
𝟏 𝒙 𝒙
When = 1, = k p, i.e. ∝ p, the adsorption varies directly with pressure.
𝒏 𝒎 𝒎

Both the conditions are supported by experimental results. The experimental results
always seem to approach saturation values at high pressure. This factor cannot be
explained by Freundlich Adsorption Isotherm. Thus it fails at high pressure.
Langmuir Isotherm:
Langmuir adsorption isotherm is based on the following assumptions.
a. Adsorption proceeds to form only monolayers on the surface of the adsorbent.
b. All the sites available on the adsorbent surface are equivalent and the surface is
perfectly uniform, that is flat.
c. The ability of a gas molecule to get adsorbed at a particular site is independent
of the occupation of neighboring sites. This implies that there is no interaction
between adjacent adsorbed molecules.
d. A dynamic equilibrium exists between the adsorbed molecules and the free gas
molecules.
Initially, since the surface is completely free of any gas molecules, every molecule
of the gas that strikes the surface of solid may get adsorbed. After some time, only
those gas molecules may get adsorbed which strike the part of the surface that is
not already covered. This means, that initially the rate of adsorption is high and
then decreases as less surface is available for adsorption. The adsorbed gas
molecules escape from the surface of the adsorbent.
A dynamic equilibrium exists between the adsorbed molecules and the free gas
molecules. It implies that the adsorbed molecules also undergo desorption,
probably due to thermal agitation. When the rate of adsorption equals the rate of
desorption, dynamic equilibrium is established.
If θ is the fraction of surface area of adsorbent covered with gas molecules, at any
instant, then (1- θ) is the fraction of the surface of the solid which is vacant.
From kinetic theory of gases, it is known that the rate at which gas molecules collide
per unit area of a surface is directly proportional to the pressure of the gas.
The rate of adsorption depends on both the pressure of the gas and fraction of
surface available for adsorption. Hence,
Rate of adsorption = Ka (1 – θ) P …..(1)
The rate of desorption is directly proportional to the fraction of the surface covered
with gas molecules.
i.e. Rate of desorption = Kd (θ) …..(2)
At equilibrium, the rate of adsorption is equal to the rate of desorption i.e.,
Ka (1 – θ) P = Kd (θ) …….. (3)
(1− 𝜃) 𝐾𝑑
= …………… (4)
𝜃 𝐾𝑎 𝑃

1 𝐾𝑑
Or ( − 1) = , 𝑇ℎ𝑒𝑛
𝜃 𝐾𝑎 𝑃
𝐾𝑎 𝑃
𝑜𝑟, 𝜃 =
𝐾𝑑 +𝐾𝑎 𝑃
𝐾𝑃
𝑜𝑟, 𝜃 = … … (5)
1+𝐾𝑃
𝐾𝑎
Where 𝐾 = = constant
𝐾𝑑

Now, the extent of adsorption (x/m) is proportional to the fraction of surface

covered. Therefore,
𝑥 𝑘𝐾𝑃
= 𝑘𝜃 = … . . (6) where ‘k’ is a constant of proportionality.
𝑚 1+𝐾𝑃
𝑥 𝛼𝑃
𝑜𝑟, = … . . (7) (𝑤ℎ𝑒𝑟𝑒 𝛼 = 𝑘𝐾)
𝑚 1+𝐾𝑃

This is the equation which describes the Langmuir adsorption isotherm. Here ‘α’
and K are the Langmuir parameters and are characteristic of a particular system at
a particular temperature.
Freundlich and Langmuir adsorption isotherms are also applicable to adsorption
processes in solutions. In place of equilibrium pressures, equilibrium concentrations
of the adsorbates are used and the isotherms are expressed in the forms,
1
𝑥
= 𝐾𝑐 𝑛 (𝑛 > 1)(𝐹𝑟𝑒𝑢𝑛𝑑𝑙𝑖𝑐ℎ 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚)
𝑚

𝑥 𝛼𝑐
= (𝐿𝑎𝑛𝑔𝑚𝑢𝑖𝑟 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚)
𝑚 1+𝐾𝑐

Where 'c' is the concentration of the solute in solution.

e. Effect of temperatures on adsorption:

Generally physisorption takes place at low temperatures while chemisorptions takes

place at high temperatures. At 463 K, N2 gas undergoes physisorption on iron metal.
But at 723 K iron nitride compound is formed due to chemisorption. So, as the
temperature rises, physisorption may change in to chemisorptions or desorption may
also take place (as in the case of inert gases on activated charcoal).
𝑥
The amount of gas adsorbed by unit mass of adsorbent (i.e, ) changes with
𝑚
temperature. The process of adsorption is exothermic in nature. Hence according to
Le Chatelier principle, the extent of adsorption decreases with a rise in temperature.
This is very true in the case of physical adsorption. But in case of chemical adsorption
𝑥
the effect of temperature is complex. The amount of ( value) increases first with
𝑚
increase in temperature, reaches a maximum and then decreases on further rising
𝑥
the temperature. The change in the amount of adsorption ( ) with temperature for
𝑚
physical and for chemical adsorptions are shown in the figures given below. These
𝑥
graphs that show the variation of with temperature are known as “adsorption
𝑚
isobars”. (graphs drawn at constant pressure).
The adsorption isobars are used to distinguish physical adsorption from chemical
adsorption. As can be seen from the above graphs, their shapes are different and
hence physisorption and chemisorptions processes can be distinguished.
Application of adsorption:
The phenomenon of adsorption finds a number of applications. Important
applications are given as follows.
(i) Production of high vacuum: The traces of air still remaining in the vessel evacuated
by a vacuum pump to give a very high vacuum can be adsorbed by charcoal.
(ii) Gas masks: Gas mask (a device which consists of activated charcoal or mixture of
adsorbents) is usually used by coal miners to adsorb poisonous gases during
breathing.
(iii) Control of humidity (Dehumidification): Silica and aluminium gels are used as
adsorbents for removing moisture and controlling humidity of air in rooms.
(iv) Removal of colouring matter from solutions: Animal charcoal removes colours
of solutions by adsorbing coloured impurities. Animal charcoal is used as
decolouriser in the manufacture of cane sugar.
(v) Heterogeneous catalysis: Mostly heterogeneous catalytic reactions proceed
through the adsorption of gaseous reactants on solid catalyst. For example,
a. Finely powdered nickel is used for the hydrogenation of oils.
b. Finely divided vanadium pentoxide (V2O5) is used in the contact process for
the manufacture of sulphuric acid.
(vi) Separation of inert gases: Due to the difference in degree of adsorption of gases by
charcoal, a mixture of noble gases can be separated by adsorption on coconut
charcoal at different low temperatures.
(vii) In curing diseases: A number of drugs are used to kill germs by getting
adsorbed on grems.
(viii) Froth floatation process: A low grade sulphide ore is concentrated by
separating it from silica and other earthy matter by this method using pine oil
and frothing agent.
(ix) Adsorption indicators: Surfaces of certain precipitates such as silver halides
have the property of adsorbing some dyes like eosin, fluorescein, etc. and
thereby producing a characteristic colour at the end point in volumetric analysis.
(x) In dyeing: Many dyes get adsorbed on the cloth either directly or by the use
of mordants.
(xi) Chromatographic analysis: Chromatographic analysis based on the
phenomenon of adsorption finds a number of applications in analytical and
industrial fields.
(xii) Softening of hard water:
a. The hard water is made to pass through a column packed with zeolite
(sodium aluminium silicate)
b. Ca++, Mg++ ions which are responsible for hardness, get adsorbed on
zeolite, exchanging sodium ions.

c. The exhausted zeolite is regenerated with 10% of sodium chloride solution.

(xiii) De – Ionisation of water:

a. Water can be de-ionised by removing all dissolved salts with the help of
cation and anion-exchanger resins.
b. Cation-exchanger is an organic synthetic resin such as polystyrene-
containing a macroanion (R—SO–3 etc) which has adsorbed H+ ions.
c. A resin containing a basic group (R3Na+ etc.) Which has adsorbed OH– ions
acts as anion exchanger.
 The Colloidal State
Introduction:
The foundation of colloidal chemistry was laid down by an English scientist, Thomas
Graham, in 1861. The credit for the various advances in this field goes to eminent
scientists like Tyndall, Hardy, Zsigmondy, N.R. Dhar, S.S. Bhatnagar and others.
Thomas Graham classified the soluble substances into two categories depending upon
the rate of diffusion through animal and vegetable membranes or parchment paper.
a. Crystalloids: They have higher rate of diffusion and diffuse though the
membrane or parchment paper.
Examples: All strong acids, bases and salts and organic compounds such as sugar,
urea etc.
b. Colloids (Greek word, kolla, meaning glue-like): They have slower rate of diffusion
and cannot diffuse through the membrane or parchment paper.
Examples: Starch, gelatin, gum, silicic acid and hemoglobin etc.
The above classification was discarded i.e., the terms colloid does not apply to a
particular class of substances but is a state of matter like solid, liquid and gas. Any
substance can be brought into colloidal state. The colloidal state depends on the particle
size. It is regarded as intermediate state between true solution and suspension.
A colloidal solution is a heterogeneous system in which one substance is dispersed
(dispersed phase) as large particles in another substance (dispersion medium).
Features of the three types of solutions
Property Suspension Colloidal solution True solution
Nature Heterogeneous Heterogeneous Homogeneous
Particle size > 1000 nm 1 nm – 1000 nm < 1 nm
Separation by
(i) Ordinary filtration Possible Not possible Not possible
(ii) Ultra- filtration Possible Possible Not possible
 Settling of particles Settle under Settle only on Do not settle
gravity centrifugation
Appearance Opaque Generally transparent Transparent
Diffusion of particles Does not diffuse Diffuses slowly Diffuses rapidly

Phases of colloids and their classification:

Phases of colloids: We know that a colloidal solution is of heterogeneous nature.
It consists of two phases which are as follows
Internal phase or Dispersed phase (Discontinuous phase): It is the component
present in small proportion and is just like a solute in a solution. For example in the
colloidal solution of silver in water, silver acts as a dispersed phase.
External phase or Dispersion medium (continuous phase): It is generally
component present in excess and is just like a solvent in a solution. For example, in
the colloidal solution of silver in water. Water act as a dispersion medium.
Classification of colloids: The colloids are classified on the basis of the following
criteria
a. Classification based on the physical state of the dispersed phase and
dispersion medium: Depending upon the physical state of dispersed phase and
dispersion medium whether these are solids, liquids or gases, eight types of
colloidal systems are possible.
 Different types of colloidal systems:
Dispersed Dispersion
Colloidal System Examples
phase Medium
Liquid Gas Aerosol of liquids Fog, clouds, mist, fine
insecticide sprays
Solid Gas Aerosol of solids Smoke, volcanic dust, haze
Gas Liquid Foam or froth Soap lather, Lemonade froth,
foam, whipped cream, soda
water
Liquid Liquid Emulsions Milk, emulsified oils, medicines
Solid Liquid Sols Most paints, starch in water,
proteins, gold sol, arsenic
sulphide sol, ink, cell fluids
Gas Solid Solid foam Pumice stone, styrene rubber,
foam rubber
Liquid Solid Gels Cheese, butter, boot polish,
jelly, curd
Solid Solid Solid sols (coloured Ruby glass, some gem stones
glass) and alloys

b. Classification based on Nature of interaction between dispersed phase and

dispersion medium: Depending upon the nature of interactions between dispersed
phase and the dispersion medium, the colloidal solutions can be classified into two
types as (i) Lyophilic and (ii) Lyophobic sols.
(If water is the dispersed medium the terms used are hydrophilic and hydrophobic)
i. Lyophilic colloids (solvent loving or water loving): The colloidal solutions in
which the particles of the dispersed phase have a great affinity for the dispersion
medium, are called lyophilic colloids. Examples: Starch, gelatin, glue and agar
sols in water
 ii. Lyophobic colloids (solvent hating or water hating): “The colloidal solutions
in which there is no affinity between particles of the dispersed phase and the
dispersion medium are called lyophobic colloids.” Examples: Gold sol, silver
sol, arsenic sulfide sol in water
Distinction between lyophilic and lyophobic sols:
Property Lyophilic sols Lyophobic sols
Can easily prepared by shaking Cannot be easily prepared.
Ease of preparation or worming the substance with Special methods are
solvent required for preparation
Surface tension Generally lower than that of Same as that of the
the medium dispersed medium
Viscosity Much higher than that of the Same as that of the medium
medium
Reversibility Reversible Irreversible
Stability More stable Less stable
Visibility Particles can’t be detected Particles can be detected
even under ultramicroscope under ultramicroscope.
Migration in the Particles may migrate in either Particles migrate either
electric field direction or do not migrate in towards cathode or anode
an electric field because do not in an electric field because
carry any charge. they carry charge.
Action of Addition of smaller quantity of Coagulation takes place
electrolyte electrolyte has little effect even by the addition of small
quantity of electrolyte.
Hydration Extensive hydration takes place No hydration
Examples Gum, gelatin, starch, proteins, Metals like Ag and Au,
rubber etc. hydroxides like Al(OH)3,
Fe(OH)3, metal sulphides
like AS2S3 etc.
c. Classification based on types of particle of dispersed phase: Depending upon the
type of the particles of the dispersed phase, the colloids also can be classified.
i. Multimolecular colloids: In these, a large number of atoms or small
molecules of the dispersed phase (having diameter less than 1nm) aggregate
together to form species having the size in the colloidal range (diameter >
1nm). The species thus formed are called multimolecular colloids.
For example, gold sol and Sulphur sol etc. A gold sol contains gold particles
of various sizes having many atoms. Sulphur sol consists of particles
containing thousand or more of S8 sulphur molecules. In these colloids, the
particles are held together by van der Waal's forces. They are usually
lyophobic in nature.
ii. Macromolecular colloids: Macromolecules in suitable solvents form
solutions in which the sizes of the macromolecules are in the colloidal range.
Such systems are called macromolecular colloids. These macromolecules
forming the dispersed phase are generally polymers having very high
molecular masses. These colloids are quite stable and resemble true
solutions in many respects.
Examples of naturally occurring macromolecules are starch, cellulose,
proteins, enzymes, gelatin etc. The man-made macromolecules are
polythene, nylon, polystyrene, synthetic rubber etc. They are usually
lyophilic in nature.
iii. Associated colloids:
Certain substances behave as strong electrolytes at low concentrations, but
at higher concentrations these substances exhibit colloidal characteristics
due to the formation of aggregated particles. These aggregated particles are
called micelles. These are also called as associated colloids.
The formation of micelles takes place only above a particular temperature called
Kraft Temperature (Tk) and above a particular concentration called the Critical
micelle concentration (CMC). On dilution, these colloids revert back to individual
 ions. Surface active agents such as soaps and synthetic detergents form
associated colloids in water. For soaps, the CMC is about 10 - 4 to 10 - 3 mol L-1.
Micelles have both a lyophilic and lyophobic parts. Micelles may consist of
more than 100 molecules.

Mechanism of Micelle Formation:

Micelles are formed by specific molecules which have lyophilic as well as lyophobic
ends. Ordinary soap which contains sodium stearate (C17H35COONa) forms micelle
in water. When dissolved in water, it dissociates into C17H35COO- and Na+ ions. The
stearate ion (C17H35COO-) consists of two parts, a long hydrocarbon chain which is
hydrophobic (because it is nonpolar) and a polar carboxyl group (COO-) which is
hydrophilic.

When the concentration of sodium stearate is below its CMC, then it behaves as a
normal electrolyte and ionizes to give Na+ and C17H35COO- ions. As the
concentration exceeds the CMC, the hydrophobic end starts receding away from
the solvent and approach each other. However, the polar COO- part interacts with
water. This leads to the formation of a cluster having the dimensions of a colloid
particles. In each cluster a large number of stearate groups clump together in a
spherical manner such that the hydrocarbon parts interact with one another and
the COO- groups remains projected in water to the surface.
 Aggregation of RCOO- ions to form a micelle

Properties of Colloidal Sols:

Heterogeneous nature:
Colloidal solutions are biphasic (heterogeneous) in nature. It consists of the
dispersed phase and the dispersion medium. In the colloidal solution, each particle
is contained within its own surface boundary and therefore has a separate
existence from the dispersion medium.
Colligative properties:
Colloidal particles being bigger aggregates, the number of particles in a colloidal
solution is comparatively less as compared to those in a true solution. Hence, the
values of colligative properties (osmotic pressure, lowering in vapour pressure,
depression in freezing point and elevation in boiling point) are of small order as
compared to values shown by true solutions at same concentrations.
Optical properties:
Although a colloidal solution appears to be homogenous because the dispersed
particles are too small to be seen, it can be distinguished from a true solution by its
ability to scatter light.
The scattering of light by colloidal particles when light beam is passed through
colloidal solution is called the Tyndall effect. This effect was first observed by
Tyndall in 1869. If a strong beam of light is passed through a colloidal sol placed in
a dark room, the path of the beam got illuminated due to the scattering of light by
colloidal particles. The illuminated path of the beam is called Tyndall cone. True
solutions don’t exhibit Tyndall effect therefore we cannot see the path of the light.
In this way Tyndall effect is used to distinguish between a colloidal solution and a
true solution.

Demonstration of Tyndall effect

Mechanical Properties:
Brownian movement:
Brownian movement was first discovered by Robert Brown, a botanist, in 1827. He
observed that pollen grains in water do not remain at rest but move about
continuously and randomly. This continuous random movement (Brownian
motion) was observed in colloidal solutions when the colloidal solutions are viewed
under a powerful ultra-microscope, this is known as Brownian movement.
Brownian motion in colloidal sols arises due to the impact of the molecules of the
dispersion medium with the colloidal particles. It has been postulated that the
impact of the molecules of dispersion medium on the colloidal particles are
unequal. This leads to the zig-zag (random) motion of the colloidal particles.
This motion is independent of the nature of the colloid but depends on the size of
the particles and viscosity of the solution. Smaller the size and lesser the viscosity,
the faster is the motion
 Zig-zag or Brownian motion

This random movement decreases as the size of the particles increases because the
effect of the impacts average out. When the size of the dispersed particles
increases beyond the colloidal range, Brownian motion stops, i.e., no Brownian
movement is observed.
The significance of Brownian movement is that
a. It provides a direct demonstration of ceaseless motion of molecules as postulated
by kinetic theory.
b. It counters the force of gravity acting on colloidal particles and hence helps in
providing stability to colloidal sols by not allowing the particles to settle down.
Electrical Properties:
Electrophoresis:
The colloidal particles are electrically charged and they carry a charge, that is, either
the colloids are negatively charged or positively charged. The dispersion medium
has an equal and opposite charge making the system neutral as a whole.
Since the colloids carry charge, they repel each other and do not combine to form
bigger aggregates. This is the reason why a sol is stable.
The existence of charge on the colloidal particles is inferred from the observation
that the colloidal particles move either towards the cathode or anode when the
colloidal sol is placed in an electric field. This phenomenon of movement of
colloidal particles towards the oppositely charged electrodes in the presence of an
electric field is called electrophoresis.
Electrophoresis is carried out by placing the colloidal solution in a U tube which is
fitted with platinum electrodes.
 Apparatus for electrophoresis

When electric current is passed, the charged colloidal particles move towards the
oppositely charged electrode. A colloidal sol of As2S3, which is negatively charged
will move towards the anode when placed in an electric field.

Emulsion:

“The colloidal systems in which one liquid are dispersed in another liquid is called
emulsions the two liquids otherwise being mutually immiscible.”
(or)
“Emulsions are the colloidal solutions in which both the dispersed phase and the
dispersion medium are liquids.”
A good example of an emulsion is milk in which fat globules are dispersed in water.
The size of the emulsified globules is generally of the order of 10–6 m. Emulsions
resemble lyophobic sols in some properties.
Types of Emulsion: Depending upon the nature of the dispersed phase, the
emulsions are classified as;
a. Oil-in-water emulsions (O/W): The emulsion in which oil is present as the
dispersed phase and water as the dispersion medium (continuous phase) is
called an oil-in-water emulsion. Ex: Milk
b. Water-in-oil emulsion (W/O): The emulsion in which water acts the dispersed
phase and the oil acts as the dispersion medium is called a water-in-oil emulsion.
These emulsions are also termed oil emulsions. Ex: Butter and cold cream
Cleansing action of soaps
We know that a micelle consists of a hydrophobic hydrocarbon part - like central core.
The cleansing action of soap is due to the fact that soap molecules form a micelle
around the oil droplet in such a way that hydrophobic part of the stearate ions is in
the oil droplet and hydrophilic part projects out of the grease droplet like the bristles.
Since the polar groups can interact with water, the oil droplet surrounded by
stearate ions is now pulled into water and is removed from the dirty surface.
Thus soap helps in emulsification and washing away of oils and fats. The negatively
charged sheath around the globules prevents them from coming together and
forming aggregates.