Vidyamandir Classes Co-ordination Compounds

Co - ordination Compounds

BASICS Section - 1

I. Molecular or Addition Compounds

When a solution made by mixing two or more simple stable compounds in simple molecular (stochiometric)
proportions is allowed to evaporate, crystals of new substances may separate out. These substances are
termed as molecular or addition compounds. Some common examples are :

KCl + MgCl2 + 6H2O 

 KCl.MgCl2.6H2O
carnalite

Fe(CN)2 + 4 KCN   Fe(CN)2 . 4 KCN (or K4[Fe(CN)6] )

Potassium ferrocyanide
The molecular or addition compounds are of two types :
(a) Double Salts or Lattice Compounds :
(i) The addition compounds which are stable only in crystalline state and lose their identity in solution
form are called double salts.
(ii) When dissolved in water, these salts dissociate completely to give all the ions as are given by the
compounds from which these were formed.

K 2SO 4  Al2 SO 4 3  24 H 2O  K 2SO 4 . Al 2  SO 4 3 .24 H 2 O

Potash Alum

solution
 2K   aq   4SO 24   aq   2 Al3  aq 
(iii) The molar conductivity of such a solution would correspond to all the ions as given by the constituent
compounds.

(b) Co-ordination Complexes (or Compounds) :

(i) The addition compounds which do not lose identity even in solution form (i.e., they are stable in solid
as well as dissolved state) are called complex compounds.
(ii) In solution form, these compounds do not furnish all the ions which are given by the constituent
compounds.
solution
2 KCN + Ni (CN)2 
 K2[Ni(CN)4]   2K+ (aq) + [Ni(CN)4]2–

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(iii) The molar conductivity of such a solution would correspond to fewer ions as given by the constituent
compounds. In above example, the addition compound of KCN and Ni(CN)2 does not give Ni2+
and CN ions in aqueous solution and hence the molar conductivity of such a solution is because of
two K+ ions and one [Ni(CN)4]2– ion and not because of two K+ ions, one Ni2+ ions and four CN–
ions.
II. Co-ordination Compounds and Complex Ions :
Co-ordination compounds are the compounds in which the central metal atom is linked to a number of ligands
(ions or neutral molecules) by co-ordinate bonds i.e. by donation of lone pairs of electrons by these ligands to
the central metal atom.
If a such a compound carries positive or negative charge, it is called a complex ion, e.g. [Fe(CN)6]4,
[Cu(NH3)4]2+. Hence co-ordination compounds may also be defined as those compounds which contain
complex ions, e.g., K4[Fe(CN)6], [Cu(NH3)4]SO4, etc. In general, a complex ion is represented as [MLn]x
where M is the metal ion, L represents ligands, n is the co-ordination number of metal ion and x is the net
charge on the complex.
There are following four types of complexes :
(i) Cation as complex ion, (carrying a net positive charge) e.g., [Co(NH3)6]3+ in [Cr(NH3)6]Cl3.
(ii) Anion as complex ion, (carrying a net negative charge) e.g., [Fe(CN)6]3 in K3[Fe(CN)6].
(iii) Cation and anion both as complex ion. For e.g., [Pt(Py)4] [PtCl4].
(iv) Neutral complex (A complex carrying no net charge) e.g., [Ni(CO)4] etc.
The formation of a complex ion involve following two things :
(i) Ligands should have atleast one lone pair of electrons which can be donated to central metal atom or ion.
(ii) The central atom or ion should have vacant orbitals so as to accommodate the electrons donated by the
ligands.

TERMINOLOGY OF CO-ORDINATION COMPOUNDS : Section - 2

1. Centre of Coordination (Central atom/ion or Acceptor atom/ion) :

The cation or neutral atom to which one or more ligands neutral molecules or anions are attached or co-
ordinated is the centre of co-ordination.
The central, atom/ion must have empty orbitals as it acts as an acceptor and thus has to accommodate
electron pairs donated by the donor atom of the ligand. This explains why the transition metal having
empty d-orbitals, form co-ordination compounds very readily.
For example in the complexes [Ni(NH3)6]2+ and [FeCN)6]3–, Ni2+ and Fe3+ respectively are the central
ions.

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2. Ligands :
Any atom, ion or molecule which can donate alteast a pair of electrons to the central atom to form acoordinate
bond (or dative linkage) is called as ligand or coordinating group. Further in a ligand, the particular atom
which actually donates the electron pair is called the donor atom.
The ligands act as Lewis bases as they donate one or more electron pair to the central metal atoms or ions
which act as Lewis acids by accepting electrons.
Types of Ligands :
Ligands can be of following types depending on the denticity of the ligand i.e the number of donor atoms
present in a ligand. (Precisely, denticity of a ligand is the maximum number of donor atoms present in the
ligand which can be utilised to coordinate (or ligate) with the central atom simultaneously).
(i) Monodentate or unidentate Ligands : They have one donor atom, i.e. they supply only one electron
pair to the central atom. e.g. F–, Cl–, Br–, H2O, NH3, CO, SCN–, NO–, NH3, H2O etc.

(ii) Polydentate ligands or Multidentate ligands : These ligands coordinate using two or more donor
atoms. Structures of some bidentate or didentate, terdentate, tetradentate ligands have been shown below:
 Bidentate ligands :

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 Terdentate ligands :

 Hexadentate ligand :

Note :Polydentate ligands have flexible character. It is not necessary that all the donor atoms present in the polydentate
ligands should form co-ordinate bonds with central metal atom or ion. For example, ethylenediaminetetraacetate
ion (EDTA) which is hexadentate ligand can also function as pentadentate or tetradentate ligand with certain
metal ions. Sulphate ion (SO 24  ) , can act both as monodentate as well as bidentate as shown :

Ambidentate Ligands : There are certain ligands which have two or more donor atoms in forming complexes
only one donor atom is attached to metal ion. Such ligands are called ambidentate ligands or in other words
these are the ligands which can ligate through two different atoms present in it. Examples of such ligands are
the NO2–, CN–, SCN– ions. NO2– ion can coordinate to a central metal atom/ion either through nitrogen or
the oxygen atoms as depicted below :

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M  NO2– Nitro M  ONO– Nitrito

M  CN– Cyano M  NC– Isocyano
M  SCN– Thiocyanato M  NCS– Isothiocyanato

Chelation : When coordination of two or more donor atoms from a polydentate ligand to a single central
atom/ion takes place forming a closed or cyclic ring structure, it is called chelation and the ligand a chelating
ligand. The close ring compound thus formed is called chelate (or metal chelate).
Some Important Characteristic of Chelates :
(a) Chelating Effect : Chelating ligands form more stable complexes than the monodentate analogs. The complex
ion/compound have such ligands does not dissociate easily.
(b) Formation of Rings : Generally the chelate complexes with 5 or 6 membered rings are more stable. Out of
these, 5 membered rings are very stable when they involve saturated ligands, e.g., ethylenediamine, which
contains five membered stable ring structure. On the other hand 6-membered ring structures acquire
maximum stability when they involve unsaturated ligands containing conjugate double bonds.
(c) Steric Hindrance : Ligands with large groups form unstable rings than the ligands with smaller groups due to
steric hindrance.
(d) The complex compound having maximum number of rings formed with the ligands is most stable. For
example, a complex [M(en)3]3+ is less stable than a complex [M(EDTA)]– because in the former there
are 3 rings while in the latter has 5 rings.
(e) Entropy effect : The stability of the chelate complex is explained on the basis of entropy effect. To elaborate,
let us take an example of ethylene diamine ligand (en). When one end of ‘en’ is coordinated the probability
of coordination of the other end is high because this end is bound to stay close to the central atom/ion. This
shows that it is easier to form a chelate ring than forming coordinate bonds with two independent molecules.
Thermodynamically, the increased stability due to chelation can be attributed to an increase in the degree
of freedom of the system. A large change in entropy but only small heat of reaction generally accompany
the chelation process.
3. Co-ordination Number (C.N.) : The number of atoms (of the ligands) that are directly bound to the central
metal atom/ion by coordinate bonds is known as the co-ordination number of the central atom/ion. It is
actually the number of sigma bonds which the ligands form with the central metal atom/ion. Pie bonds, if
formed between the ligands and the central metal/ion, are not counted for this purpose.

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Co-ordination Number of Complexes

Complexes Ligands C.N.
[Ag(NH3)2]+ NH3 2
[HgI3]– I 3
[PtCl4]2–, [Ni(CO)4] Cl, CO 4
[Fe(CO)5], [Co(CN)5]3 CO, CN 5
[Co(NH3)6]3+, W(CO)6 NH3, CO 6
[Mo(CN)7]3– CN 7
[W(CN)8]4– CN 8
[Co(en)3]3+, [Fe(C2O4)3]3– en, C2O42– 6
[Co(H2O)2(NH3)4]3+ H2O and NH3 2+4=6

4. Co-ordination entity (sphere) :

The central metal atom/ion & the ligands that are directly attached to it, enclosed in a square bracket, are
collectively called as co-ordination sphere (or entity). The ionisable groups are written outside the bracket
and are called counter ions. The co-ordination sphere behaves as a single unit because the ligands
present in the co-ordination sphere are held tightly by the metal ion. Any ion present outside this sphere is
separated from the complex, when compound is dissolved in the water. Eg : In the following compounds
[Cr(NH3)6]Cl3, K4[Fe(CN)6], K2[PtCl4], [Ni(CO)4], K2[Ni(CN)6] the respective coordination entities
are : [Cr(NH3)6]3+ ; [Fe(CN)6]4– ; [PtCl4]2– ; [Ni(CO)4] ; [Ni(CN)4]2– ; and the counter ions are Cl–,
K+, K+, (no counter ion) and K+.
5. Co-ordination polyhedron :
The spatial arrangement of the ligand atoms which are directly attached to the central metal atom or ion,
in definite direction thereby giving a definite geometry to the complex ion or compound, is called coordination
polyhedron around the central atom or ion. The most common coordination polyhera are octahedral,
square planar and tetrahedral.

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6. Oxidation number of central atom :

It is is defined as the charge that the central metal ion would carry if all the ligands are removed alongwith
electron pairs. It is calculate as follows :
Example : K4[Fe (CN)6]
K4[Fe (CN)6]  4 K+ + [Fe (CN)6]4–
Charge on complex ion = – 4
Let charge on Fe = x,
Now charge on cynide ion (CN–) = –1
 x + 6  (–1) = –4
 x = +2
Hence oxidation no of Fe = +2 (or II)

Complexes Central metal ion Ligands Oxidation Number

[Co(NH3)6]3+ Co 6 NH3 III
[NiCl4]2 Ni 4 Cl II
[Co(CN)5F]3 Co 5 CN & 1 F III
[Ni(CN)4]2 Ni 4 CN II
[Ni(CO)4] Ni 4 CO 0
[Ni(H2O)6]2+ Ni 6 H2O II
[Fe(CN)6]4 Fe 6 CN II
[Cu(NH3)4]2+ Cu 4 NH3 II

7. Homoleptic and Hetroleptic Complexes :

Complexes in which central atom is coordinated with only one kind of ligands are called homoleptic
complexes, eg. [Co(NH3)6]3+. Complexes in which central atom is co-ordinated with more than one
kind of ligands are called hetroleptic complexes, eg. [Co(NH3)4 Cl2]+ .
8. Effect atomic Number (EAN rule and Sidgwick Theory) :
In order to explain the stability of co-ordination complexes Sidgwick proposed effective atomic number
(EAN) rule. He suggested that a metal ion will continue accepting electron pairs till the total number of
electrons in the metal ion (after gaining electrons from the donor atoms of the ligands) becomes equal to
that of the next higher noble gas. This total number of electrons is called the effective atomic number
(EAN) of the metal. This will become clear by taking the example of heaxamminecobalt(III) ion,
[Co(NH3)6]3+.
Aomic number of cobalt = 27.

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In the present complex, cobalt is present in the oxidation state of +3.

 Total no of electrons in Co3+ = 27 – 3 = 24.
Since each NH3 ligand donates two electrons to the cobalt ion,
Electrons donated by 6 NH3 ligands = 6  2 = 12.
EAN of Co3+ i.e. total no of electron present in Co3+ in complex = 24 + 12 = 36
(36 is the atomic number of Krypton (Kr), the next nearest noble gas)

In general,
EAN = (atomic number – oxidation state) + (C.N.  2)
or EAN = atomic no of the metal – no of electrons lost in ion formation + no of electrons gained from
ligands.

In the above example since the number 36 corresponds to the atomic number of krypton, according to
Sidgwick, the complex will be stable. Though EAN rule (which states that those complexes are stable
whose EAN is the same as the atomic number of the next noble gas) is applicable in many cases, there are
several examples in which EAN rule is not obeyed.

Illustration - 1 Apply the concept of EAN rule, on the complexes [Fe(CN)6]4– and [Fe(CN)6]3–. What
conclusion do you draw about the validity of the EAN rule from these two complexes ? (Atomic number
of Fe = 26)
SOLUTION :
(a) [Fe(CN)6]4– : Let O.S. of Fe in [Fe(CN)6]4– (b) [Fe(CN)6]3– : Let O.S. of Fe in [Fe(CN)6]3–
=x
=x
So, x + 6 (–1) = –4 x = +2
So, x + 6 (–1) = –3
Also, C.N. of Fe in [Fe(CN)6]4– = 6
So, x = +3
( CN– is a unidentate ligand)
Again, C.N. of Fe in [Fe(CN)6]3– = 6
So, EAN of Fe = (Z – O.S.) + 2 (C.N.) ( CN– is a unidentate ligand)
= (26 – 2) + 2 6 = 36 So, EAN of Fe = (26 – 3) + 2 6 = 35 
= Atomic number of Kr (next nearest inert gas). atomic number of Kr (36) (next nearest inert
So, in [Fe(CN)6]4–, EAN rule is valid. gas)
Thus EAN rule is not valid in [Fe(CN)6]3–.

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Illustration - 2 Predict the formulae of the carbonyl complexes of Fe (26) and Cr (24).
SOLUTION :
(a) Molecular formula of iron carbonyl [Fe(CO)n] (b) Molecular formula of chromium carbonyl
Calculation of the value of ‘n’ (C.N.) [Cr(CO)m]
Oxidation state of metal in carbonyls = 0 Again, O.S. of Cr in [Cr(CO)m] = 0
Again, according to EAN rule, EAN of Fe = 36 C.N. of Cr = m
(atomic number of Kr, next higher noble gas) Again, according to EAN rule, EAN of Cr = 36
But, EAN = (Z – O.S.) + 2 (C.N.) (atomic number of Kr, next higher noble gas)
 36 = (26 – 0) + 2 n But, EAN = (Z – O.S.) + 2 (C.N.)
So, n = 5 36 = (24 – 0) + 2 m
Thus, formula of iron carbonyl is [Fe(CO)5]. So, m = 6
So, formula of chromium carbonyl = [Cr(CO)6].

Illustration - 3 Calculate the EAN of the underlined atoms in the following complexes
3 2 2
(A)  AuCl2  (B)  Fe  C2O4  
 3
(C) Ca  EDTA  (D)  Ni  NH 3   en  ( Py ) 
 3 
SOLUTION :
(a) [AuCl2]– (Z for Au = 79) (c)  Ca  EDTA  
2
(Z for Ca = 20)
Let O.S. of Au be x.
Let O.S. of Ca be x.
So, x + 2 (–1) = –1 x = +1
So, x + 1 (–4) = –2
Again, C.N. of Au = 2
So, x = +2
( Cl– is a unidentate ligand)
Again, C.N. of Ca = 6
So, EAN = (Z – O.S.) + 2 (C.N.)
A4– is a hexabidentate ligand)
( EDTA
= (79 – 1) + (2 2) = 82.
So, EAN = (20 – 2) + (2 6) = 30.
3
(b)  Fe  C2O 4 3  (Z of Fe = 26) 2
  (d)  Ni  Py   en   NH3 3  (Z for Ni = 28)
 
Let O.S. of Fe be x. Let O.S. of Ni be x
So, x + 3 (–2) = –3 x + 0 + 0 + 3  0 = 2 (all are neutral ligands) ;
So, x = +3 So, x = +2
Again, C.N. of Fe = 6 ( Py and NH3, both are unidentate ligand
( C2O42  is a bidentate ligand) while (en) is a bidentate ligand)
So, EAN = (26 – 3) + (2 6) = 35. So, EAN = (28 – 2) + (2  6) = 26 + 12 = 38.

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Illustration - 4 1 mole of CoCl3.4NH3, on reaction with excess of AgNO3 gives one mole of a white
precipitate.
(a) What is the formula of complex ? (b) What is the C.N. of cobalt in this complex ?
SOLUTION :
Since the complex gives one mole of AgCl (a white precipitate) with AgNO3 solution, it indicates that out of
3 Cl– ions, only one is outside the co-ordination sphere, and the remaining Cl– ions, are inside the co-ordination
sphere.
 Two Cl– ions and all the four NH3 molecules are inside the co-ordination sphere.
(a) So, the formula of the complex is

 [CoCl2 (NH3 ) 4 ]  Cl 

[CoCl2 (NH 3 )4 ] Cl 
AgNO3
 AgCl  (white ppt.)
(b) Hence, the complex is [CoCl2(NH3)4]Cl
C.N. of Co in this complex = 6.

NOMENCLATURE OF CO-ORDINATION COMPOUNDS : Section - 3

Co-ordination compounds are formulated and named according to the system set up by Inorganic Nomenclature
Committee of the International Union of Pure and Applied Chemistry (IUPAC). The following rules are
observed while writing formulae and naming co-ordination compounds.
 Rules for Formula writing of Mono-Nuclear Co-ordination Compounds :
(i) Formula of the cation whether simple or complex is written first followed by that of the anion.
(ii) Sequence of symbols within the coordination formula
 The central atom is listed first.
 The ligands are then listed in alphabetical order based on the way the ligand is represented in the
formula.+++
The placement of the ligand in the list does not depend on the charge of the ligand.***
 If an abbreviation is used in a formula to represent a ligand the first letter of the abbreviation is used to
determine the position of the ligand in the alphabetical list.
 Wherever possible, the ligand formula should be written in such a way that the donor atom is closest
to the central atom to which it is attached.
 All the ligands are formuated without any space in between, also there should be no space between
the ligands the the central metal atom within the co-ordination sphere.

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Note :
+++ Following things should be kept in mind :
 A single letter symbol always precedes a two-letter symbol with the same initial letter, e.g. B
before Be ; O before OH, the group NH3 is treated as a single symbol and so is listed after Na.
 Where the entities to be arranged in a formula are polyatomic,
 The order of citation is decided by selecting the first symbol in the formula of a polyatomic
group.
For example, C5H5, SCN, NO2 and OH are ordered under C, S, N and O respectively.
 If the first symbols are the same, the symbol with the lesser right index is cited first,
e.g. NO2 precedes N2O2.
 If this still does not discriminate, the subsequent symbols are used alphabetically and numerically
to define the order, e.g. NH2 precedes NO2 which precedes NO3.
 To summarise and exemplify, the order of citation of some nitrogen-containing compounds is :
N3 , NH 2 , NH3 , NO 2 , NO3 , N 2O22  , N3

*** In order to simplify the rules and to resolve ambiguities that may arise when it is not clear whether a
ligand is charged or not, the charge on a ligand is no longer considered in determining ligand order in
the formulae of co-ordination compounds.
(iii) Use of enclosing marks : The formula for the entire co-ordination entity, whether charged or not, is
enclosed in square brackets. When ligands are polyatomic, their formulae are enclosed in parentheses.
Ligand abbreviations are also usually enclosed in parentheses
(iv) Ionic charges and oxidation numbers : If the formula of a charged co-ordination entity is to be written
without that of the counter-ion, the charge is indicated outside the square bracket as a right superscript,
with the number before the sign. The oxidation number of a central atom may be represented by a
Roman numeral, which should be placed as a right superscript on the element symbol.
Examples :
1. [PtCl6]2– 2. [Cr(OH2)6]3+
3. [CrIII(NCS)4(NH3)2]– 4. [CrIIICl3(OH2)3]
5. [Fe–II(CO)4]2–
Other Examples :
1. [Al(OH)(OH2)5]2+
2. [PtBrCl(NH3)(NO2)]–
3. [PtCl2(NH3)(py)]
4. [Co(en)F2(NH3)2]+, but [CoF2(NH2CH2CH2NH2)(NH3)2]+
5. [Co(NH3)5(N3)]2–

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 Rules for Naming of Mono-Nuclear Co-ordination Compounds :

(i) Order of naming ions : The positive ion (cation) is named first followed by the negative ion (anion) irrespective
of whether cation is complex or anion is complex. The complex part is written as one word e.g.,
[Co(NH3)6]Cl3, hexaamminecobalt(III) chloride.
(ii) Naming of ligands : Different types of ligands are named differently. (refer to the table)
(a) Negative ligands (organic or inorganic) : These type of ligands end in ‘-o’, e.g., CN (cyano), Cl
(chloro), NO2 (nitro), O2 (oxo). If the name of the anionic ligands ends in ide, ite or ate, the last
‘e’ is replaced by ‘O’ giving ido, ito or ato e.g. SO42 (sulphato), NH2 (amido), ONO (nitrito)
etc.
(b) Neutral ligands : These type of ligands have no special ending and are used as such except for NH3
(ammine), H2O (aqua), CO(carbonyl), CS (Thiocarbonyl) and NO (nitrosyl).
(c) Positive ligands : These type of ligands are used as such. These type of ligands generally end in ium,
e.g., NH2NH3+ (hydrazinium), NO+ (nitrosonium), NO2+ (nitronium) etc.
(d) Organic ligands : Organic free radicals are given their own names, e.g., CH3 (methyl), C2H5 (ethyl). For
organic neutral molecules, their names are used, e.g., P(C6H5)3-triphenylphosphine, C2H5N-pyridine (py)
etc.
Note : Enclosing marks “( )”are required for (a) neutral and cationic ligand names. (however, common ligands
such as aqua, ammine, carbonyl, nitrosyl, methyl, ethyl, etc., do not require enclosing marks, unless there is
ambiguity) ; (b) for inorganic anionic ligands containing numerical prefixes (such as triphosphato); (c) for any
compositional name (such as carbon disulfide) ; (d) for any substituted organic ligand (even if there is no
ambiguity in its use); (e) and wherever necessary to avoid ambiguity.

Denticity Name Ligand Charge Name of ligand in Donor

the complex Atom
Positive Ligands
Nitrosonium ion NO + +1 Nitrosonium N
Monodentate Nitronium ion NO 2 +1 Nitronium N

Hydrazinium ion NH 2 NH 3 +1 Hydrazinium N

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Neutral Ligands
Water H2O 0 Aqua/aquo O
Ammonia NH3 0 Ammine N
Carbon monoxide CO 0 Carbonyl C
Nitrgen Oxide NO 0 Nitrosyl N
Thiocarbonyl CS 0 Thiocarbonyl S
Thionitrosyl NS 0 Thionitrosyl N
Monodentate Pyridine (py) C5 H 5 N 0 Pyridine (py) N
Methyl amine CH3NH2 0 Methylamine N
Dinitrogen N2 0 Dinitrogen N
Dioxygen O2 0 Dioxygen O
Phosphine PH3 0 Phosphine P
O
Urea || 0 Urea O
H 2 N  C  NH 2

S
Thio-urea (tu) || 0 Thio-urea S
H 2 N  C  NH 2

Triphenylphosphine Ph3P 0 Triphenylphosphine P

Acetone CH3COCH3 0 Acetone O

Denticity Name Ligand Charge Name of ligand in Donor

the complex Atom
Bidentate Ethylenediamine (en) NH2(CH2)2NH2 0 Ethylenediamine (en) 2 N-atoms
(a bidentate ligand)
  C H
H 2 C  NH 2
| |
Tridentate Diethylene triamine  N
H 2C  N   CH 0 diethylenetriamine (dien) 3 N-atoms
2
H2 H2
  CH  NH
H 2 C  NH 
2 2 3
| triethylene-
Tetradentate Triethylene tetramine   CH  NH
 0 tetramine (trien) 4 N-atoms
H 2C  NH 2 2 3

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Negative Ligands
Hydride ion H –1 hydrido H
Monodentate Oxide ion O 2– –2 oxo O
Perioxide ion O 22  –2 peroxo O
Perhydroxide ion O2H –1 perhydroxo O
Hydroxide ion OH –1 hydroxo O
Fluoride ion F –1 fluoro (fluorido) F
Chloride ion Cl –1 chloro (chlorido) Fl
Bromide ion Br –1 bromo (bromido) Br
Iodide ion I –1 iodo (iodido) I
Acetate ion CH3COO – –1 acetato (acetatido) O
Cyanide ion CN  –1 cyano (cyanido) C

Isocyanide ion –1 Isocyano N

Sulphite ion SO 32  –2 sulphito O

Sulphide ion S2 –2 sulphido or thio S
Hydrogen-
sulphide ion HSO3 –1 hydrogensulphito O

Amide ion NH 2 –1 amido N

Imide ion NH2 –2 imido N

Nitrate ion NO 3 –1 nitrato N

Nitro ion NO 2 –1 nitro (nitrito-N) N

Nitrito ion ONO –1 nitrito (nitrito-O) O

Nitrido ion N3 –3 nitrido N

Azide ion N 3 –1 azido N

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(iii) Prefixes : Two kinds of numerical prefix are available for indicating the number of each type of ligand
within the name of the co-ordination entity.
(a) Prefixes di, tri, etc. are generally used for simple ligands. Enclosing marks around the ligand are not
required. e.g., if there are four NH3 molecules as ligands, we shall write tetraammine. Here note that
both ‘a’ i.e. last ‘a’ of tetra and first ‘a’ of ammine are to be retained.

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(b) Prefixes bis, tris, tetrakis, etc. are used with complex expressions (generally with those ligands which
include a numerical prefix in their names) and wherever required to avoid ambiguity. Enclosing marks
in the nested order must be placed around the multiplicand.
Elaboration : These prefixes are used for ligands containing di,tri etc in their names eg dipyridyl or
ethylenediamine, thus, their numbers are indicated by prefixed, bis-, tris-, tetrakis-, etc., for example
: [PtCl2(NH2CH2CH2NH2)2] (NO3)2 is named as dichlorobis (1, 2-ethanediamine) platinum (IV)
nitrate.
(iv) Preference order : All ligands whether negative, neutral or positive, are named in an alphabetical order.
The prefixes di, tri, etc. are not to be considered while determining this alphabetical order. The names of
the ligands are followed by the name of the central metal atom/ion. e.g. [PtCl(NH3)4(NO2)]SO4 is named
as tetraamminechloronitroplatinum (IV) sulphate.
(v) Naming of complex ion : Ligands are named first, followed by the metal atom. The ending of the name
of the metal depends upon the nature of the complex ion.
(a) If the complex ion is cation or the compound is non-ionic, the name of the central metal ion is written
as such followed by its oxidation state indicated by Roman numeral (such as II, III, IV) in the parenthesis
at the end of the name of the metal without any space in between the two. (0) is used for an oxidation
state of zero and a negative oxidation state is shown by a negative sign before the Roman numeral.
(b) If the complex ion is anion, the name of the central metal atom is made to end in “ate” followed by
the oxidation number in brackets without any space between them.
(c) While naming complex acid of transition metals, ending ‘ic’ is used, e.g. H4[Pt(CN)6] is named as
hexacyanoplatinic(II) acid.
Complex Ions
Example Negative complex Positive/neutral complex
Ni nickelate nickel
Pb plumbate lead
Sn stannate tin
Fe ferrate iron

(vi) Naming of the optical isomers : Dextro and Laevo rotatory optically active compounds are respectively
designated either by (+) and () or by d and  e.g. dextro rotating K3[Cr(C2O4)3] is named as
potassium (+)trioxalatochromate(III) or potassium dtrioxalatochromate(III).

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IUPAC Names (Some Examples)

Neutral Complexes :
[Co(NH3)3]Cl3 triamminecobalt(III) chloride
[Ni(CO)4] tetracarbonylnickel(0)
[Fe(CO)5] pentacarbonyliron(0)
[Pt(NH3)2]Cl2 diammineplatinum(II) chloride
[Co(NH3)3(NO2)3] triamminetrinitrocobalt(III)
[Cu(Gly)2] diglycinatocopper(II)
[Ni(DMG)2] bis(dimethylglyoximato)nickel(II)
[CuCl2{O=C(NH2)2}2] dichloridobis(urea)copper(II)

Complex Cations :
[Co(OH2)6]2+ hexaaquacobalt(II) ion
[Zn(NH3)4]2+ tetraamminezinc(II) ion
[Pt(en)2]2+ bis(ethylenediammine)platinum(II) ion
[Ni(en)3]3+ tris(ethylenediammine)nickel(III) ion
[PtCl2(NH3)2]Cl2 diamminedichloroplatinum(IV) chloride
[Cu(NH3)4(OH2)2 ]Cl2 tetraamminediaquacopper(II) chloride
[Co(NH3)5(ONO)]Cl2 pentaamminenitritocobalt(III) chloride
[CoCl(NH3)4(OH2)]Cl tetraammineaquachlorocobalt(II) chloride
[Ag(NH3)2]Cl diamminesilver(I) chloride
Complex anions
K[AgCl2] potassium dichloroargentate(I)
Ba[CuCl4] barium tetrachlorocuprate(II)
K3[Fe(CN)6] potassium hexacyanoferrate(III)
K4[Fe(CN)6] potassium hexacyanoferrate(II)
Cu2[Fe(CN)6] copper hexacyanoferrate(II)
[Au(CN)4]2 tetracyanoaurate(II) ion
[CoBr4]2 tetrabromocobaltate(II) ion
[HgI4]2 tetraiodomercurate(II) ion
[Ni(CN)4]2– tetracyanonickelate(II) ion
[Fe(C2O4)3]3 tri(oxalato)ferrate(III) ion
[Cr Cl2 (en)2]Cl2 dichlorobis(ethylenediammine)chromium(IV) chloride
K3[Cr(C2O4)3] potassium trioxalatochromate(III)

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Complexes containing cationic and anioic ions

[Cr(NH3)6][Co(CN)6] hexaamminechromium(III) hexacyanocobaltate(III)
[Pt(NH3)4][CuCl4] tetraammineplatinum(II) tetrachlorocuprate(II)
[Cr(NH3)6][Co(C2O4)3] hexaamminechromium(III) trioxalatocobaltate(III)
[Pt(py)4][PtCl4] tetrapyridineplatinum(II) tetrachloroplatinate(II)
[PtCl2(NH3)4] [PtCl4] tetraamminedichloroplatinum(II) tetrachloroplatinate(IV)

Note :1. The stable oxidation states of some of the transition metals of the three series are given below. These would
be helpful to find the oxidation states of the metal ions while naming complexes having cation and anion both
as complexes.
(i) First Transition Series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2, +3, +2, +3, +2, +3, +2, +3, +2, +3, +2, +3 +2, +3 +1, +2 +2
+4 +4, +5 +6 +4, +7

(ii) Second Transition Series

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 +4 +3, +5 +6 +4, +6, +3 +3 +2, +4 +1 +2
+7

(iii) Third Transition Series

La Hf Ta W Re Os Ir Pt Au Hg
+3 +4 +5 +6 +4, +6, +3, +4, +1, +3 +2, +4 +1, +3 +1, +2
+7 +6 +4

2. Naming of linkage isomers : Read the following eg carefully  [Co(NH3)5(NO2)]2+ has two isomeric
forms having red and yellow colours.
 The red colour isomer [CO(NH3)5(ONO)]2+ is named as :
pentaamminenitrito-O-cobalt(III) [or pentaamminenitritocobalt(III)] while ;
 The yellow isomer [Co(NH3)5(NO2)]2+, is named as
pentaamminenitrito-N-cobalt(III) [or pentaamminenitrocobalt(III)].
3. For some compounds common names are more popular than there IUPAC names eg. ferrocyanide rather
than hexacyanoferrate(II) for [Fe(CN)6]4 and ferricyanide rather than hexacyanoferrate(III) for [Fe(CN)6]3

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Vidyamandir Classes Co-ordination Compounds

Isomerism in Co-ordination Compounds

Isomers are compounds having same chemical formula but different arrangment of atoms. Because of different
arrangment of atoms, they differ in one or more physical or chemical property. This phenomenon is called as
isomerism.
The type of isomerism found in co-ordination compound is :
1. Structural isomerism : It is displayed by compounds that have different ligands within their co-ordination
sphere. It may be further sub-divided into different types as follows:
(A) Ionization isomerism : The co-ordination compounds exhibiting this type of isomerism give different
ions in solution. It occurs when the counter ion in a co-ordination compound is itself a potential ligand.

Eg.  PtCl 2  NH 3  4  Br2 , and  PtBr2  NH 3  4  Cl 2 etc.

(B) Solvent isomerism : This is a special type of ionisation isomerism which arises when solvent molecules
can form co-ordination bonds with the central atom/ion. In this, compounds having same composition
differ in the number of solvent molecules present as ligands (in the co-ordination sphere) and as free
solvent molecules of hydration (present outside the co-ordination sphere). This form of isomerism is
known as “hydrate isomerism” in case where water is involved as a solvent. For example, there are
three isomers of hexa-hydrates of chromic chloride with empirical formula CrCl3.6H2O.
[Cr(H2O)6]Cl3 : violet colour
[CrCl(H2O)5]Cl2.H2O : pale or bluish green colour
[CrCl2(H2O)4]Cl.2H2O : dark green colour
Apart from their distinctive colours, the three isomers can be identified by the addition of excess of
aqueous silver nitrate to their aqueous solutions, which precipitates silver chloride in the molar ratio of
3 : 2 : 1 respectively.

(C) Co-ordination isomerism : This type of isomerism is observed in the co-ordination compounds
having both cationic and anionic complex ions. The ligands are interchanged in both the cationic and
anionic ions to form isomers. For example :
(i) [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(ii) [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
(iii) [Cr(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Cr(NH3)2(SCN)4]

(D) Linkage isomerism : Co-ordination compounds having ambidentate ligands like NO 2 and SCN,
exhibit this type of isomerism. For example: [Co(NH3)5(NO2)]2+ has two isomeric forms having
red and yellow colours. The red colour isomer is [CO(NH3)5(ONO)]2+, while the yellow isomer is
[Co(NH3)5(NO2)]2+. In the first cation we have Co-(ONO) link, while in the second case, Co-
(NO2) link is there.

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2. Stereo-isomerism : This isomerism in coordination compounds is due to differences in arrangement of

ligands in space around a given metal atom or ion. It is of following two types :
(A) Geometrical isomerism
(i) Cis-trans isomerism : This type of isomerism occurs in complexes having square planar and
octahedral arrangement respectively. When similar groups are adjacent to each other, it is called
cis isomer, whereas when similar groups are opposite to each other, it is called trans isomer.
(a) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can have cis-
and trans-isomers.

(b) Complexes with general formula Ma2bc can have cis-and trans-isomers.

(c) Square planar complexes having unsymmetrical bidantate ligands can also show geometrical
isomerism.
For example [Pt(Gly)2] exhibit geometrical isomerism.

(d) Octahedral complexes : of type Ma4b2 and Ma3b3 exhibit geometrical isomerism.

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Note :  Complexes with general formula Mabcd can have three isomers isomers.

 Octahedral complexes of general formula, Mabcdef, can have fifteen isomers.

 The complexes of general formulae, Ma3b or Mab3, or Ma4 of square planar geometry do not show
isomerism.
 Geometrical isomerism does not occur in tetrahedral complexes, because the relative positions of the
ligands attached to the central metal atom or ion is same w.r.t. each other.
(ii) Facial and Meridionial isomerism : Another type of geometrical isomerism occurs in octahedral co-ordination
entities of the type [Ma3b3]like [Co(NH3)3(NO2)3]. If each trio of donor atoms occupy adjacent positions
at the corners of an octahedral face, we have the facial (fac) isomer. When the positions are around the
meridian of the octahedron, we get the meridional (mer) isomer shown in figure. Geometric isomer differ in
their physical characterstics, out of which, dipole moments and visible/UV spectra are important.

Note : [Ma 3b3 ] is more popularly classified using Facial & Meridional Isomerism as compared to cis-trans isomerism.
(B) Optical isomerism : The co-ordination compounds having same molecular formula but differing in their
abilities to rotate directions of the plane of polarized light are said to exhibit optical isomerism and such
molecules are called optical isomers (enantiomers or enantiomorphs).
(a) The optical isomers are pair of molecules which are non-super imposable mirror images of each
other.
(b) They possess the property of chirality. The essential requirement for a substance to be optically
active is that the substance should not have a plane of symmetry in its structure.
(c) Optical isomers of a compound have identical physical and chemical properties.
(d) The isomers which rotate the plane of polarized light to left direction are termed Leavo (-form).
While the isomers which rotate the plane of polarized light to right direction are termed Dextro (d-
form) .
 Optical isomers rarely occur in square planar complexes on account of the presence of axis of symmetry.
 Optical isomerism is expected in tetrahedral complexes of the type Mabcd but no optical isomer has been
isolated until now.

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 General formulae of optically active complexes :

(i) [M(AA)3]n , [M(AA)2a2]n , [M(AA)2ab]n , [M(AA)a2b2]n (where AA are symmetrical bidentate
ligands)
(ii) [Ma2b2c2]n, [Mabcdef]n , [M(AB)3]n (where AB are unsymmetrical ligands)

For Examples :
(A) [M(AA)3]n : eg. [Co(en)3]3+

(B) [M(AA)2a2]n [Co(en)2Cl2]+

Note : The trans form of [M(AA)2a2]n does not

show optical isomerism.

(C) [M(AA)2 ab]n [Co(en)2(NH3)Cl]2+

(D) [M(AA)a2b2]n eg . [CrCl2(en)(NH3)2]+.

(E) [Ma2b2c2] n eg : [Pt(py)2 (NH3)2 Cl2]2+

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 Vidyamandir Classes Co-ordination Compounds

(F) [Mabcdef] eg : [Pt(py)NH3NO2ClBrI]

(G) [M(AB)3] eg : [Cr(gly)3]

Illustration - 5 Write hydrate isomers of the following, and also discuss the conductance of the isomers.
(a) [Cr(H2O)6]Cl3 (b) [Cu(H2O)4]Cl2
SOLUTION :
(a) Hydratic isomers of [Cr(H2O)6]Cl3

Greater the number of ions, [Cr(H2O)5Cl]2+ + 2Cl– more is the conductance. Hence, decreasing order of
conductance is I > II > III > IV.
(b) Hydrate isomers of [Cu(H2O)4]Cl2

Hence, decreasing order of conductance is I > II > III.

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Illustration - 6 One mole of the complex has two isomers A and B. Each has one Co3+, five NH3, one Br–
and one SO42 stoichiometrically. A gives white precipitate with BaCl2 while B gives yellow precipitate with
AgNO3. What are A and B ? What is the type of isomerism shown by them ?
SOLUTION :
(a) Since A gives white precipitate of BaSO4 with BaCl2 solution, A is

 [Co(NH3 )5 Br]2   SO 42  

[Co(NH3 )5 Br] SO 4 
BaCl 2
 BaSO 4 
(A) (white ppt.)

(b) Since B gives a yellow precipitate of AgBr with AgNO3, B is :

AgNO3
 [Co(NH3 )5SO4 ]  Br  
[Co(NH3 )5SO4 ] Br   AgBr 
(B) (yellow ppt.)

Also, A and B are ionisation isomers.

Illustration - 7 (a)Write structures of all geometric isomers of square planar complexes.

(i) [Pd(NH3)2(Br)(I)] (ii) [Ni(en)Cl2]
(b) For which of the following complexes are optical isomers possible ? Explain your answers and draw
structures of enantiomers. (i) [Cr(NH3)4(C2O4)]+ (ii) [Cr(NH3)2(C2O4)2]–
(c) The compounds(s) that exhibit(s) geometrical isomerism is(are) :
(i) [ Pt (en)Cl2 ] (ii) [ Pt (en)2 ]Cl2 (iii) [ Pt (en) 2 Cl2 ]Cl2 (iv) [ Pt ( NH 3 )2 Cl2 ]
SOLUTION :
(a) (i) Geometrical isomers of [Pd(NH3)2(Br)(I)]

(ii) [Ni(en)Cl2] Only one isomer is possible as ethylene diamine (en) cannot span the trans position.

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Vidyamandir Classes Co-ordination Compounds

(b) Optical isomerism is possible in [Cr(NH3)2(C2O4)2]– (because it is of the type[M(AA)2a2]n ) but

[Cr(NH3)4(C2O4)]+ will not exhibit optical isomerism.
Note : General formulae of optically active complexes :
(i) [M(AA)3]n , [M(AA)2a2]n , [M(AA)2ab]n , [M(AA)a2b2]n (where AA are symmetrical
-bidentate ligands)
(ii) [Ma2b2c2]n, [Mabcdef] , [M(AB)3]n (where AB are unsymmetrical ligands)

The geometrical isomeris of [Cr(NH3)2(C2O4)]– are (one trans and three cis isomers) :
Now, only cis-isomers can exhibit optical isomerism because trans-isomers have two superimposable
mirror images.

Thus, [Cr(NH3)2 (C2O4)]– has two geometrical (one trans and one cis) isomers while two optical isomers.

(c) [Pt(en) 2 ]Cl2 can not show geometrical isomerism as all ligands attached to the central atom (Pt) are same
and [Pt(en) Cl2 ] does not show geometrical isomerism as discussed in Q.7(a) part (ii). Rest both
[Pt(en) Cl2 ]Cl2 and [Pt(NH 3 ) Cl2 ] are capable of showing geometrical isomerism as shown below :

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WERNER’S CO-ORDINATION THEORY Section - 4

Werner’s Co-ordination Theory

Alfred Werner was the first to formulate a theory to give a correct explaination for the characteristics of the
co-ordination compounds. The fundamental postulates of Werner’s theory are :
(i) Metals possess two types of valencies, namely, primary (principal) and secondary (auxillary) valency.
(ii) Primary valencies are those which a metal normally exhibits in the formation of its simple salts. Thus, in the
formation of PtCl4, CuSO4 and AgCl the primary valencies of Pt, Cu and Ag are 4, 2 and 1 respectively.
Primary valencies may be ionisable. They are non-directional and are only satisfied by negative ions.
(iii) Secondary valencies are those which a metal cation exercises towards a neutral molecule or negative
group in the formation of its co-ordination complexes. Secondary valencies are non-ionisable and are
satisfied by negative ions, neutral molecules (or even somtimes by some positive groups), having atleast
one lone pair of electrons (like H2O, NH3). In every case, the co-ordination number of the metal must be
fulfilled. In modern terminology, the primary valency corresponds to oxidation number and secondary
valency to the co-ordination number of the central metal.
(iv) The secondary valencies are always directed towards a fixed position in space about the central metal ion.
The number and arrangements of ligands in space determines the sterochemistry of a complex. For
example, in case of six secondary valencies the arrangement of secondary valencies is a regular octahedral
while in case of four secondary valencies arrangement might be either in a square planar or a tetrahedral
manner. Thus, this postulate predicates of existence of a variety of isomerisms in co-ordination compounds.
Remember that primary valencies are non-directional.
(v) To distinguish between the two types of valencies, Werner introduced square brakets [ ] to enclose atoms
making up the co-ordination complex and which are therefore not ionised. The portion enclosed in the
brackets is known as co-ordination sphere and the portion present outside the bracket as ionising sphere.
(vi) It is the directional nature of secondary valency due to which co-ordination compounds exhibits the
phenomenon of isomerism.
The important aspect of the structure of five different complexes of PtCl4 with ammonia prepared by
Werner are shown in table.

Co-ordination compounds of PtCl4 with NH3

Complex Modern formula Number of Cl– ions Total number of ions
formed
PtCl4.6 NH3 [Pt(NH3)6]Cl4 4 5
PtCl4.6 NH3 [PtCl(NH3)5]Cl3 3 4
PtCl4.6 NH3 [PtCl2(NH3)4]Cl2 2 3
PtCl4.6 NH3 [PtCl3(NH3)3]Cl 1 2
PtCl4.6 NH3 [PtCl4(NH3)2] 0 0 (non-electrolyte)

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 Vidyamandir Classes Co-ordination Compounds

In all these compounds, platinum exhibits a primary valency (oxidation number) of four and
secondary valency (co-ordination number) of six.
(vii) Primary valency in the complex, is represented by ‘. . . . . . . .’ and secondary valency by ‘________’.
(viii) In all cases, metal or metal ion should satisfy both primary and secondary valencies. Some negative
ions may satisfy primary as well as secondary valencies (dual nature). In the complexes, they are
____ ’.
represented as ‘ ........

Werner’s Representation of Complexes

Consider the case of CoCl3.xNH3 , where the maximum value of x = C.N. of Co(3+) (which is 6)
and the minimum value of x = C.N. - O.N. = 3
Various structures are summarised in Table.

 From table, it is clear that conductance of the complexes will be in the order D < C < B < A.
 They are represented as shown in the next page.

Note : Compund A & B have colours yellow and purple respectively but compound C (with empirical formula
[CoCl2(NH3)4]Cl ) is found to exist in two colours i.e green and violet showing that there must be two
isomers for empirical formula [CoCl2(NH3)4]Cl.

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Co-ordination Compounds Vidyamandir Classes

Werner was the first to describe the bonding features in co-ordination compounds. But his theory could not
answer basic questions like :
(i) Why only certain elements possess the remarkable property of forming co-ordination compounds ?
(ii) Why the bonds in co-ordination compounds have direction optical properties ?
(iii) Why co-ordination compounds have characteristic magnetic aqnd optical properties ?
Many approaches have been put forth to explain the nature of bonding in co-ordination compounds viz.
Valence Bond Theory (VBT). Cristal Field Theory (CFT). Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT). However we shall be restricting ourselves to VBT and CFT only.

BONDING IN CO-ORDINATION COMPOUNDS : VALENCE BOND THEORY Section - 5

The theory was developed by Pauling in 1931. The basic principles involved in this theory are :
(a) Orbital hybridization : The model utilizes the hybridisation of s, p and d valence orbitals of central
metal atom or ion (in which electron pairs donated by the ligands are accomodated) to account for
observed structures and magnetic properties.
(b) Bonding between ligand and the metal atom or ion : From the valence point of view, formation of
complex involves reaction between lewis bases (ligands) and lewis acids (metal atom/ion) with the
formation of co-ordinate covalent (or dative) bonds between them.
(c) Relation between the observed magnetic behaviour and the bond type : That is, the geometry of co-
ordination entity can be predicted if its magnetic behaviour is known.
The following are the main postulates of this theory :
(i) Metal-ligand bond arises by the donation of pairs of electrons by ligands to the empty hybridised
orbitals of central metal atom or ion. Remember it is basically overlap of atomic orbital of both the
entities
(ii) In order to accommodate these electrons, the metal ion must possess same number of vacant orbitals
of equal energy. These orbitals of metal atom (s,p or d) undergo hybridisation to give a set of hybrid
orbitals of equal energy and with definite directional properties. These vacant hybrid orbitals now
overlap with the ligands to form strong coordinate bonds.
(iii) The non-bonding electrons of the metal occupy the inner orbitals. They are grouped in accordance
with Hund’s rule. However, under the influence of some strong ligands, there may be some
rearrangement of inner electrons in the atomic orbitals (against Hund’s rule). During rearrangement
generally pairing takes place and consequently some orbitals are vacated and made available for
hybridisation.

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(iv) (For Octahedral complexes only) The d-orbitals involved in the hybridisation may be either (n  1) d-
orbitals or n d-orbitals***. The complexes formed in two ways are referred to as Inner orbitals
complex (or entity) or Outer orbital complex (entity). On the basis of spin they are also referred as
low spin and high spin complexes respectively.
(*** ‘n’ refers to the outermost principle shell of the central metal atom)

(v) If a complex contains unpaired electrons, it is paramagnetic in nature, whereas if it does not contain
unpaired electrons, it is diamagnetic in nature.
(vi) On the basis of value of magnetic moment, we can predict the number of unpaired electrons present
in the complex. If we know the number of unpaired electrons in the metal complex, then it is possible
to predict the geometry of complex species.
Magnetic Moment, s  n  n  2  B.M.
B.M. = Bohr Magneton, it is the unit of magnetic moment
s = spin only value
n = no. of unpaired electrons in the central metal atom/ion

(vii) Octahedral, square planar and tetrahedral complexes are formed as a result of d2sp3 (or sp3d2), dsp2
and sp3 hybridisation respectively.
For predicting the type of geometry (structure) of a complex species, the following guidelines
would be helpful :
(i) Electronic configuration of first transition series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2

(ii) For co-ordination number 4, the hybridizations possible are sp3 and dsp2, having tetrahedral and
square planar geometries respectively, while for co-ordination number 6, the hybridizations possible
are d2sp3 and sp3d2, having octahedral geometry in both the cases.
(iii) There are two types of ligands namely strong field and weak field ligands. A strong field ligand is
capable of forcing the electrons of the metal atom ion to pair up (if required). A weak field ligand is
incapable of making the electrons of the metal atom/ion to pair up.
(iv) Some ligands have been arranged below from the weakest to the strongest. This arrangement is called
as spectrochemical series. (As shown in the next page)

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I  Br   S2   SCN 2   Cl  F  NO3  OH  , urea  EtOH


weak
 C2O 4  OX   O  H 2O  NCS  EDTA  NH3
2 2
  
Border Line
< NH3 , pyridine < ethylene diammine (en) < dipyridyl (dipy)  phen  NO 2  CN   CO

Strong

Note :  This series has been determined experimentally and is not a postulate of VBT. However, we can use it to
predict the structure, electronic configuration, magnetic properties etc. of a co-ordination complex.
 Ligands given in the borderline criteria act both as strong and weak field ligands. By knowing the value of
magnetic moment, it may be suggested that whether they act as a strong and weak ligand in a particular
case.
 Generally NH3 behaves as a strong field ligand and H2O (or ligands nearby it in the series) as a weak field
ligand. The compound [Co(OX)3]3– , is one of the few rare examples where oxalate (OX) ligand acts as
a strong field ligand.
(vi) The common types of hybridisations are :

(A) Four coordinated complexes :

(A. 1) Tetrahedral Complexes

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Illustration - 8 Discuss the formation of [Ni(CO)4]0

SOLUTION : Oxidation state of Nickel in this complex is ‘0’. Its electronic configuration is [Ar] 3d8 4s2.

The CO ligand being a strong ligand will force the pairing of electrons in two half filled orbitalsand then the pair
of electrons from 4s will go to 3d orbital, and thus, the 4s orbital is vacated and can now accept an electron
pair.

Now, the empty 4s and 4p orbitals (i.e 4s, 4px ,4py and 4pz ) hybridize (or mix) to form four equivalent sp3
hybrid orbitals, each of which accepts an electron pair.

Now, each of the four sp3 hybrid orbitals accepts an electron pair from carbon monoxide ligands forming
Ni(CO)4.

Thus, the resulting complex has tetrahedral structure and diamagnetic due to absence of unpaired
electrons(magnetic moment = 0).

Illustration - 9 Discuss the formation of [CoCl4]2–

SOLUTION :
Oxidation state of Co in complex = +2 ; Outer electronic configuration of : Co atom = 3d74s2
 Co2+ = 3d7

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(i) Cl being weak ligand is unable to force (iv) Magnetism :

the pairing of electrons.  No. of unpaired electrons = 3
(ii) Hybridisation : sp3  Paramagnetic
(iii) Geometry : Tetrahedral  Magnetic moment
(s) = 3  3  2   15 = 3.87 B.M.

Illustration - 10 Discuss the formation [Zn(NH ) ]2+.

3 4

SOLUTION :
Oxidation state of Zn in complex = +2 ; Outer electronic configuration of : Zn atom = 3d104s2
Zn2+  3d10

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(i) Hybridisation  sp3 (iii) Magnetism :

(ii) Geometry  tetrahedral  No. of unpaired e = 0
 Diamagnetic
 Magnetic moment, s = 0 B.M.
(A.2) Square planar complexes :

Illustration - 11 Discuss the formation of [Pt(NH ) Cl ].

3 2 2

SOLUTION :
Oxidation state of Pt in complex = +2 ; Outer electronic configuration of : Pt atom  5d86s2
 Pt2+ ion  5d8

(i) NH3 being a strong ligand forces pairing of (iv) Magnetism

electrons of two half filled 5d-orbitals.
 No. of unpaired e = 0
(ii) Hydrisation : dsp2  Diamagnetic
(iii) Geometry : Square planar  Magnetic moment, s = 0

Illustration - 12 Disscuss the formation of [Cu(NH ) ]2+.

3 4

SOLUTION :
Oxidation state of Cu  +2 ; Outer electronic configuration of : Cu atom  3d104s1
 Cu2+ ion  3d9

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(i) Hybridisation  dsp2  No. of unpaired e– = 1

(ii) Geometry  Square planar  Paramagnetic
(iii) Magnetism  Magnetic moment,
s  11  2   3  1.732 B.M

Illustration - 13 Discuss the formation of (A) [Ni(CN)4]2– (B) [NiCl4]2–

SOLUTION :
(A) Formation of [Ni(CN)4]2– ;
Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom = 3d84s2
 Ni2+ ion = 3d8

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(i) CN– being a strong ligand, forces pairing of (iv) Magnetism

electron of two half filled 3d orbitals.  No. of unpaired e = 0
(ii) Hybrisation  dsp2  Diamagnetic
(iii) Geometry : Square planar
 Magnetic moment = 0 B.M

(B) Formation of [NiCl4]2–

Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom = 3d84s2
 Ni2+ ion = 3d8

(i) Cl being weak ligand is unable to force (iv) Magnetism

the pairing of electrons.  No. of unpaired e = 2
(ii) Hybridisation : sp3  Paramagnetic
(iii) Geometry : Tetrahedral  Magnetic moment

 2(2  2)  2.83B.M

Thus the c-oordination entities [Ni(CN)4]2– & [NiCl4]2– illustrate the useful rule originally called” the magnetic
criteria of bond type”, That is, the geometry of a co-ordinated entity can be predicted if its magnetic properties
are known. In above case this theory allows prediction of geometry of a four co-ordinated d8 complex : If the
complex is diamagnetic then its shape will be “Square Planar” and if it is paramagnetic then its shape will be
“Tetrahedral”.
Note : The above generalisation of VB theory is not accurate and is one of its draw backs.

(B) Six Co-ordinated Complexes

In an octahedral complex, two types of complexes occur i.e., inner orbital complex and outer orbital
complex. This distinction between inner and outer orbital complex is based purely on magnetic measurements.
In inner, orbital complex, (n – 1)d orbitals are used for hybridization whereas in outer orbital complex, nd
orbitals are used.

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Illustration - 14
Discuss the formation of [Cr(NH3)6]3+ .
SOLUTION :
Oxidation state of Cr = +3 ; Outer electronic configuration of : Cr atom = 3d5 4s1
 Cr3+ ion = 3d3

(i) Hybridisation : d2sp3 (v) Magnetism :

(ii) Geometry = Octahedral  No. of unpaired e = 3
(iii) Inner orbital complex  Paramagnetic
(iv) Spin paired (low spin complex)  Magnetic moment,
s  3  3  2   3.287 B.M

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Illustration - 15 Discuss the formation of Ferricyanide ion, [Fe(CN) ]3–.

6

SOLUTION :
Oxidation state of Fe = +3 ; Outer electronic of figuration of : Fe atom = 3d6 4s2
 Fe3+ ion = 3d5

(i) CN being strong ligand forces pairing (vi) Magnetism :No. of unpaired e = 1
of electrons of half field 3d-orbitals  Paramagnetic
(ii) Hybridisation : d2sp3,  Magnetic moment,
Geometry : Octahedral s  1.732 B.M
(iii) Inner orbital complex,
Spin paired (low spin complex)

Illustration - 16 Formation of [CoF ]3 :

6

SOLUTION :
Oxidation state of Co = +3 ; Outer electronic configuration of : Co atom  3d74s2
 Co3+ ion = 3d6

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(i) F being weak ligand is not able to force (vi) Magnetism :

pairing of electrons.  No. of unpaired e = 4
(ii) Hybridisation : sp3d2  Paramagnetic
(iii) Geometry = Octahedral  Magnetic moment,
(iv) Outer orbital complex s  4  4  2   4.90 B.M
(v) Spin free (high spin complex)

Illustration - 17 Formation of [Ni(NH ) ]2+

3 6

SOLUTION :
Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom  3d84s2
 Ni2+ ion = 3d8

(i) NH3 being weak ligand is not able to (vi) Magnetism :

force pairing of electrons.  No. of unpaired e = 2
(ii) Hybridisation : sp3d2  Paramagnetic
(iii) Geometry : Octahedral  Magnetic moment,
(iv) Outer orbital complex
s  2  2  2   2.83 B.M
(v) Spin free (high spin complex)

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Drawbacks of Valence Bond Theory :

(i) It can’t explain why some complexes of metal ion use inner orbitals (d2sp3, low spin complexes)
whereas some other make high spin complexes (sp3d2).
(ii) It can’t predict effectively whether a four co-ordinated complex is tetragonal or square planar e.g.,
[Cu(NH3)4]2+ is suggested to have sp3 configuration by V.B. Theory but X-rays study shows its geometry
as square planar, i.e. dsp2.
(iii) It doesn’t explain the variation of magnetic properties of complex with temperature.
(iv) It doesn’t explain or predict any distortion in symmetrical complexes.
(v) There is no quantitative interpretation of magnetic data.
(vi) It has nothing to say about the spectral properties of co-ordination compounds.
(vii) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of co-ordination
compounds.
(viii) It does not distinguish between strong and weak ligands.

CRYSTAL FIELD THEORY : Section - 6

Crystal field theory is now much more widely accepted than the valence bond theory. It assumes that the
attraction between the central metal and ligands in a complex is purely electrostatic. The transition metal which
forms the central atom in the complex is regarded as a positive ion of charge equal to the oxidation state. This
is surrounded by negative ligands or neutral molecules which have a lone pair of electrons. If the ligand is a
neutral molecule such as NH3, the negative end of the dipole in the molecule is directed towards the metal ion.
The electrons of the central metal are under repulsive force from those of the ligands. Thus, the outer most
electrons (which are generally present in the d orbitals) of central transition metal atom/ion occupy those d
orbitals which farthest away from the direction of approach of ligands.
In the crystal field theory, the following assumptions are made.
(i) Ligands are treated as point charges.
(ii) There is no interaction between metals orbitals and ligand orbitals.
(iii) The arrangement of the ligands around the central metal ion is such that the repulsion between these negative
points is minimum.
(v) Splitting of d-orbital energies : The five d-orbitals in an isolated gaseous metal atom/ion are degenerate i.e.
they have equal energy. If a spherically symmetric field of negative charges is placed around the metal, the
orbitals will remain degenerate, but all of them will be raised in energy as a result of repulsion between the
negative field and the electrons in the orbitals. If the field results from the influence of real ligands (either anions
or the negative ends of dipolar ligands such as NH3 or H2O), the symmetry of the field will be less than
spherical and the degeneracy of the d-orbitals will be removed. It is this splitting of d orbital energies and its
effects that form the basis of crystal field theory.

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Note : There are five d-orbitals namely, d xy , d yz , d zx , d x 2  y 2 , d z 2 which have been shown below :

It is better to divide the set of d orbitals in two groups :

(i) The orbit als in w hich lobes lie on t he axes ( d 2 2 , d 2 ) : referred to as " eg " orbitals in
x y z
Octahedral symmetry and " e " orbitals in Tetrahedral symmetry. (Also called as doubly degenerate
orbitals.)
(ii) The orbitals in which lobes lie in between the axes (d xy , d yz , d zy ) : referred to as " t2 g "
orbitals in Octahedral symmetry and " t2 " orbitals in Tetrahedral symmetry. (Also called triply
degenerate orbitals.)

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A. Crystal field splitting of d-orbitals in octahedral

complexes :
In an octahedral complex, the metal is at the centre of
the octahedron and the ligands approach it along the six
corners of the octahedral. The directions x, y, and z
point to three adjacent corners of the octahedron.
The lobes of the eg orbitals (d x 2  y 2 and d z 2 ) point

along the axes x, y and z. The lobes of the t2g orbitals

(d xy,d xz and d yz ) point in between the axes. It
follows that the approach of six ligands along the x, y, z,
 x,  y and  z direction will increase the energy of
the orbitals d and d (which point along the
x2  y 2 z2
axes) more than it increase the energy of the
d xy , d xz and d yz orbitals (which point between the
axes).
Thus, under the influence of an octahedral ligand field the d orbitals split into two groups of different energies
with " eg " orbitals having higher energy than the " eeg " orbitals. To understand this splitting more clearly
we can assume it to be a two step process as shown in fig.

In the first step, the ligands approach the central metal, producing a hypothetical spherical field which re-
pels all of the d-orbitals to the same extent. In the second, the ligands exert an octahedral field, which
splits the orbital degeneracy. In going from the first to the second step, average energy (the barycenter, or
“centre of gravity”) of the orbitals must remains constant and thus, the two eg orbitals to be the further

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repelled by 0.6 0 while the three t2g orbitals are stabilized to an extent of 0.4 0 as shown in figure.
This constancy of the barycenter of the d-orbitals holds for all complexes, regardless of geometry.
Significance of o : Consider a d1 co-ordination entity e.g., [Ti(H 2O) 6 ]3 formed in aqueous solutions

of Ti3+ (d1 ) ion, now the single d-electron occupies one of the lower energy t2g orbitals. Similarly in the

d 2 and d 3 co-ordination entities, the d-electrons will occupy the lower energy t2g orbitals in accordance

with the Hund’s rule. For d 4 ions, two possible patterns of electron distribution arise depending upon the
relative values of o and P where P represents the energy required for electron pairing in a single orbital
called the pairing energy.
(i) If o < P (weak field, high spin situation), the fourth electron enters one of the eg orbitals giving the
3
configuration t2g e1g (see fig). If now a fifth electron is added to a weak field co-ordination entity, the

configuration becomes t23g eg2 .

(ii) If o > P (strong field, low spin situation), pairing will occur in the t 2g level with e g level remaining

unoccupied giving configuration t 42g e0g . [Note : the pairing will occur (and consequently the e g level

will remain unoccupied) till the entities of d 6 ions.]

Note : Calculations show that co-ordination entities with four to seven d-electrons are more stable for strong field
as compared to weak field cases.

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B. Crystal field splitting of d-orbitals in Tetrahedral Complexes :

Consider eight ligands aligned on the corners of a cube
approaching a metal atom located in the center as shown
in figure.
In this (cubic) arrangement, however, the ligands do
not directly approach any of the metal d-orbitals, but
they come closer to the orbitals directed to the edges of
the cube (the d xy , d xz and d yz ) than to those directed
to the centers of the cube faces
(the d and the d ). Hence the t orbitals are
x2  y 2 z2 2
raised in energy while the e orbitals are stabilized
relative to the bary centre. Furthemore, since the centre-
of- gravity rule holds, the upper levels are raised by
0.4 o and the lower ones stabilized by 0.6 o from
the bary center, giving an energy level scheme that is
exactly the inverse of that for octahedral symmetry.

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If four ligands are removed from alternate corners of the cube in figure, the remaining ligands form a
tetrahedron about the metal.
The energy level scheme for tetrahedral symmetry shown in figure is qualitatively the same as that for cubic,
but the splitting (t ) is only half as large because there are half as many ligands. The two sets of degenerate
in this arrangement are labelled as t2 (d xy , d xz ,d yz ) and e (d x 2  y 2 , d z 2 ). The g subscripts which were
used for the octahedral and cubic field are no longer appropriate because the tetrahedron lacks a centre of
inversion.

4
Note : In tetrahedral complexes, mostly t  P ( t   o ) and hence they generally form high complexes
9
C. Crystal field splitting of d-orbitals is square planar complexes :
The square planar geometry may be considered to be derived from octahedral by removing the two ligands
which were approaching the central atom along the Z-axis (called tetragonal distortion). The splitting may
also be explained as : As the lobes of d x 2  y 2 point towards the ligands, this orbital has highest energy..

Though lobes d xy orbitals lie between the ligands but they are coplanar with them, hence this orbital is next
higher in energy. The lobes of d orbital point out of the plane of the complex but the torous around its
z2

centre lies in the plane, therefore d z 2 orbital is next higher in energy. The lobes of d xz and d yz orbitals
point out of the plane of the complex, hence they are least affected by the electrostatic field of the ligands,
and thus have lowest but equal energy. It must be kept in mind that the average energy of the orbitals
remains constant in this redistribution of energy as in previous cases. (the stronger the surrounding field, the

higher the d x 2 -y2 orbital will be raised, however the lower, occupied orbitals will drop in energy by a
corresponding amount)

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The square planar geometry is favoured by metal ions having a d8 configuration in the presence of a strong
field. This combination gives low spin complexes with the eight d-electron occupying the low-energy
d xy, d yz , d and d xy orbitals, while the high-energy orbital remains unoccupied.
z2

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Number of unpaired electrons in octahedral and tetrahedral complex.

[(W.F.) is the configuration for high spin and weak field complexes) (S.F) is the configuration for low spin
and strong field complexes)

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D. Factors affecting the magnitude of orbital splitting energy () :

The important factors are as follows :
(i) Oxidation state of the metal ion : The magnitude of o increases as the charge on the metal

ion increases. For example, for first row of transition metal ions, the values of o for M3+
complexes are roughly 50% larger than the values for M 2+ complexes.
(ii) Nature of the metal ion : In the d-block (transition) elements, within the same group, as we move
from 3d to 4d to 5d elements, the o increases and hence the tendency to form low spin complexes
increases. Thus the elements of the second and third transition series have greater tendency to form
low spin complexes than the first transition series. It is possible to arrange the metals according to a
spectrochemical series as well. The approximate order is

Mn2   Ni 2   Co2   Fe2   V 2   Fe3  Co3 

 Mn3  Mo3  Rh3  Ru 3  Pd 4   Ir 3  Pt 4 

4
(iii) Geometry of the co-ordination entity : As already stated, t   o i.e.  value for
9
tetrahedral complexes is nearly 50% of the  value for octahedral complexes.
(iv) Nature of the ligand : For the same metal ion, different ligands result in different amounts,
pertaining to their position in the spectro-chemical series. Strong field ligands cause higher splitting
compare to the weak field ligands. (Refer to the spectrochemical series)

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MISCELLANEOUS CONCEPTS Section - 7

A. Colour in Co-ordination Compounds :

Co-ordination compounds show a wide range of colour. When white light passes through a complex, some
part of it is absorbed and thus, the light which emerges is no longer white. The colour of the compound hence
observed, is complimentary to that of the wavelength which has been absorbed by the complex. Thus, colour
of a complex is not because of the light absorbed but is due to the light reflected (complementary colour). The
complementary colour is the colour generated from the wavelength left over; for example is green light is
absorbed by the complex, it appears red.
Table given the relationship of the different wavelength absorbed and the colour observed.

In co-ordination complexes energy difference () between two sets of d-orbitals is small. Radiations of
appropriate frequency absorbed from visible region can cause excitation of d-electrons from lower energy
orbital to higher energy orbitals. Remeining light is transmitted and the compound appears coloured. Consider
for example, the complex [Ti(H 2O)6 ]3+ , which is violet in colour. This is an octahedral complex where the

single electron ( Ti3+ is a 3d1 system) in the metal d orbital is in the t 2g level in the ground state of the
complex. The next higher state available for the electron is the empty eg level. If light corresponding to the

energy of yellow-green region is absorbed by the complex, it would excite the electron from t 2g level to the

eg level (t2 g 1eg0 

 t2 g 1e0g ) . Consequently, the complex appears violet in colour (Figure). The crystal
field theory thus, attributes the colour of the co-ordination compounds of d-d transition of the electron.

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If there are no d-electrons present or completely filled d-orbitals are present then there is no d-d transition
possible and complex appears colourless. For example, removal of water from [Ti( H 2O)6 ]Cl3 on heating
renders it colourless. Similarly, anhydrous CuSO 4 is white, but CuSO 4 .5 H 2O is blue in colour..

The influence of the ligand on the colour of a complex may illustrated by considering the [ Ni( H 2O )6 ]2  com-
plex, which forms when nickel(II) chloride is dissolved in water. If the didentate ligand, enthane-1, 2-
diamine(en) is progressively added in the molar ratios en : Ni, 1 : 1, 2 : 1, 3 : 1, the following series of
reactions and their associated colour changes occur :

[Ni(H 2O)6 ]2+ + en(aq)  [Ni(H 2O) 4 (en)]2+ (aq) + 2 H 2O

green pale blue

[Ni(H 2O)4 (en)]2+ (aq) + en(aq)  [Ni(H 2O) 2 (en) 2 ]2+ (aq) + 2 H 2O
blue/ purple

[Ni(H2O)2 (en)2 ]2+ (eq) + en(aq)  [Ni(en)3 ]2+ (aq) + 2 H 2O

violet
B. Stability of Co-ordination Compounds in Solutions :
A co-ordination compound is formed in solution by the stepwise addition of ligands to a metal ion. Thus,
formation of the complex, ML n may be supposed to take place by the consecutive n steps.

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K1, K 2 ............K n are called stepwise stability constants. In general, the values of successive stability
1
constants decrease regularly from K1 to K n .  n is called the overall stability constant (and  is called
n
as instability constant). The higher the overall stability constant value of the complex, the more stable it is.
Alternatively, values called instability constant explain the dissociation of the complex into metal ion and
ligands in the solution. e.g.,  n for [Co( NH 3 ) 6 ]3  is 5  1033.

C. Factors affecting the stability of a complex ion :

The stability of a complex ion depends upon the following factors.
(i) Higher the charge density on the central ion, the greater is the stability of its complexes, i.e., the
Charge
higher value of , the greater is the stability of its complexes. Electronegativity of the
Radius of ion
central ion influences the stability, the higher the electronegativity of the central ion, the greater is the
stability of its complex.
(ii) The stability of the divalent metal ions of the first transition series is in the following order :
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)
This order is called Irving Williams order.
(iii) The cyano and ammine complexes are far more stable than those formed by halide [Link] is due
to the fact that NH3 & CN  are strong Lewis bases.
(iv) Greater the basic strength of the ligand, greater is the stability of the complex.
(v) Chelating ligands form more stable complexes as compared to monodentate ligands.
(vi) If the ligand happens to be multidentate and cyclic without any steric effects, the stabilityofthe
complex is further increased. The effect is called macrocyclic effect.

D. Metal Carbonyls & Bonding in Metal Carbonyls

The homoleptic carbonyls (compounds containing carbonyl ligands only) are formed by most of the transition
metals. These carbonyls have simple, well defined structures. Tetracarbonylnickel (0) is tetrahedral,
pentacarbonyliron (0) is trigonalbipyramidal while hexacarbonyl chromium (0) is octahedral.

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The metal-carbon bond in metal carbonyls prossess both

s and p character. The M – C  bond is formed by
the donation of lone pair of electron on the carbonyl
carbon into a vacant orbital of the metal. The M – C
 bond is formed by the donation of a pair of electrons
from a filled d orbital of metal into the vacant antibonding
 * orbital of carbon monoxide. The metal to ligand
bonding creates a synergic effect which strengthens the
bond between CO and the metal (and hence decreases,
the bond order between C and O of CO and thereby
the bond length of C – O bond increases). The C – O
bond order will be in the order shown below :
Free CO > Metal carbonyl cation > Neutral metal carbonyl > Metal carbonyl anion.

Illustration - 18 Identify the complexes which are expected to be coloured. Explain :

(A) [Ti(NO3 )4 ] (B)  Cu(NCCH3 )4 + BF4

(C) [Cr ( NH 3 ) 6 ]3 3Cl  (D) K3[VF6 ]

SOLUTION :
(i) [Ti(NO3 )4 ]; Ti 4  : [ Ar ]3d 0 4 s 0 , No. of unpaired electrons = 0,  Colourless

(ii) [Cu ( NCCH 3 ) 4 ] BF4 ; Cu  :[ Ar ]3d 10 4s 0 , No. of unpaired electrons = 0,  Colourless

(iii) [Cr ( NH 3 ) 6 ]3 3Cl  ; Cr 3 : [ Ar ]3d 3 4 s 0 , No. of unpaired electrons = 3,  Colourless

(iv) K 3[VF6 ]; V 3 :[ Ar ]3d 2 4s 0 , No. of unpaired electrons = 2,  Colourless
Due to the presence of unpaired electrons in d-orbitals, two complexes i.e.,
[Cr ( NH 3 )6 ]3 3Cl  and K3[VF6 ] are coloured, others having all paired electrons arecolourless

Illustration - 19 Write down the IUPAC names of the following compounds :

(i) [Co(NH3 )5 ONO]Cl2 (ii) K3[Cr(CN)6 ] (iii) [Cr(NH3 )5 CO3 ]Cl

SOLUTION :
(i) Pentaamminenitritocobalt(III) chloride (ii) Potassium hexacyanochromate(III)
(iii) Pentaamminecarbonatochromium(III) chloride

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Illustration - 20 Write the IUPAC name of the compound [Cr(NH3 )5 (NCS)][ZnCl4 ]. Is this compound
coloured?
SOLUTION :
IUPAC name : Pentaammine isothiocyanatochromium (III) tetrachlorozincate (II). This compound is coloured
because Cr 3 has unpaired electrons in d-orbitals ( 3d3 configuration) which show colour through d-d
transition.

Illustration - 21 A, B, and C are three complexes of chromium (III) with the empiricial formula H O Cl Cr.
12 6 3
All the three complexes have water and chloride ion as ligands. Complex A does not react with concentrated
H 2 SO4 , whereas complexes B and C lose 6.75% and 13.5% of their original mass, respectively, on treatment
with concentrated H 2 SO4 . Identify A, B and C.
SOLUTION :
The compound A does not react with concentrated H 2SO 4 implying that all water molecules are co-

ordinated with Cr3+ ion. Hence, its structure would be [Cr(H 2O)6 ]Cl3 .
The compound B loses 6.75% of its original mass when treated with concentrated H 2SO 4 . This loss is

due to the removal of water molecules which is/are not directly co-ordinated to Cr3+ ion.
6.75
The mass of water removed per mole of the complex   molar mass of the complex
100
6.75
  266.5 g  17.98 g
100
This corresponds to one mole of water. Hence, the structure of the compound B will be
[CrCl(OH 2 )5 ]Cl2 .H 2O
The compound C loses 13.5 % of its mass when treated with concentrated H 2SO 4 which is twice of the
mass lost by the compound B. Hence, the structure of the compound C will be
[CrCl2 (OH 2 )4 Cl.2 H 2O.

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Illustration - 22 A metal complex having composition Cr ( NH ) Cl Br has been isolated in two forms (A)
3 4 2
and (B). The form (A) reacts with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammo-
nia, whereas (B) gives a pale yellow precipitate solution in concentrated ammonia. Write the formula of (A)
and (B) and state the hybridization of chromium in each. Calculate their magnetic moments (spin only value).
SOLUTION :
Compound (A) on treatment with AgNO3 gives white precipitate of AgCl, which is readily solution in

dil. aq. NH3 . Therefore it has at least one Cl ion in the ionization sphere furthermore chromium has co-
ordination number equal to 6. So its formula is [Cr(NH 3 )4 BrCl]Cl.
Compound (B) on treatment with AgNO3 gives pale yellow precipitate of AgBr soluble in conc NH3 .

Therefore it has Br  in the ionization sphere. So its formula is [Cr(NH 3 )4 Cl2 ]Br .

State of hybridization of chromium in both (A) and (B) is d 2sp3 .

Spin magnetic moment of (A) or (B), spin = n(n+ 2) = 3(3 + 2) = 15 = 3.87 BM

Illustration - 23 Write the IUPAC nomenclature of the given complex along with its hybridization and
structure.
K 2 [Cr ( NO )( NH 3 )(CN )4 ],   1.73 BM
SOLUTION :
The spin magnetic moment,  of the complex is 1.73 BM.   n(n  2)  1.73  n  1
It means that nucleus of the complex, chromium ion has one unpaired electron. Now, if NO is neutral then
Chromium under the influence of strong field ligand CN  would not have any unpaired electron, so the
ligand NO is unit positively charged and the IUPAC name of the compound is Potassium
amminetetracyanonitrosonium chromate(I)

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(a) Electronic configuration of Cr + : Cr + ion

(b) Electronic configuration of Cr + under the influence of strong field ligand CN 

So, Hybridization of the complex is d 2sp3 and its shape is Octahedral (as shown).

Illustration - 24 The 0.0001 molal solution of a complex AB10 has the freezing point of 0.0015C in
water. Assuming 100% dissociation of the complex, find the proper representation of the complex.

[ K f H 2O  1.86 Km1 ]

(A) [ AB8 ]B2 (B) [ AB3 ]B7 (C) [ AB7 ]B3 (D) [ AB5 ]B5
SOLUTION :
At 100% dissociation, van’t hoff factor, ‘i’ = n (no. of ions from the complex).

Now T f  i K f m

T f 0.0015
 in  8
Kfm 1.86  0.0001
Thus there should be 8 ions in solution
 The compound should be [AB3 ]B7 .

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My Chapter Notes

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 Vidyamandir Classes

Illustration - 1

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Vidyamandir Classes Basic Principle of Extraction

Basic Principle of Extraction

NEEDS FOR EXRACTION OF METALS Section - 1

We all use metals in our day to day life sometimes directly and sometimes indirectly. For example, Iron is
used making electromagnets, chains, etc. Steel is used in making machinery parts, household utensils. Silver
and gold are used in making jewellery. We can find numerous examples where we use metals. Since metals
do not occur in pure form in earth’s crusts, we need to extract metals from their ores or minerals.
Occurrence of Metals :
Metals occur in various forms. Some in native form, some in carbonate form and some in oxide form. Those
metals that are least reactive and have very little affinity for oxygen, moisture and other chemical reagents
occure in free or metallic or native state.
 Natural substances in which metals or their compounds occur in earth are called minerals.
 Those minerals form which metals can be extracted conveniently and proditably are known as ores.

llustration :
A certain metal M occurs in three compounds namely A, B, C. A has 15% of M, B has 66% of M and C has
71% of M. If we extract M from A, it costs Rs 35 per kg, if we extract it from B, it costs Rs 45 per kg and
if we extract from C, it costs Rs 1110 per kg.
Now both A, B, C are minerals as they contain M, but all cannot be called ores. Extraction of M from
mineral A would cost less but would result in a very less amount. Similarly, extraction from C would result in
large amount but it will also cost a large sum. Hence, B is the appropriate mineral from which M should be
extracted as it would give sufficient amount and would not even cost much. In that case, B is the ore of M.
for example : Bauxite (Al2O3 .2 H 2O) and Clay (Al2O3 .2SiO 2 .2 H 2O) both are minerals of Aluminium.
But still Bauxite is appropriate ore but not Clay since we can extract Aluminium more profitably and quan-
titatively from Bauxite.
Commercially Important Ores :
1. Native Ores :
These ores contain metals in the free state. They exist in free state because they are very unreactive.
Some of important metals are :
2. Sulphurised and Arsenical ores :
These ores consists of sulphides and arsenides in simple and complex forms of metals.

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Metal Name of the ore

Pb Galena PbS
Zn Zinc blende ZnS
Hg Cinnabar HgS
Ag Argentite or Silver glance Ag2S
Fe Iron pyrites FeS2
Cu Copper pyrites CuFeS2
Chalcocite or Copper glance Cu2S

3. Oxidised Ores
In these ores, metals are present as their oxides or oxy-salt as carbonates, nitrates, sulphates, phosphates,
silicates, etc.
Oxides : Haematite Fe 2O 3
Magnetite Fe3O4
Bauxite Al2O3.2H2O
Corundum Al2O3
Chromite FeO.Cr2O3
Tinstone (Cassiterite) SnO2
Pyrolusite MnO2

Carbonates : Magnesite MgCO3

Lime stone CaCO3
Dolomite CaCO3.MgCO3
Calamine ZnCO3
Malachite [Link](OH)2
Azurite Cu(OH)2.2CuCo3
Cerussite PbCO3
Siderite FeCO3

Nitrates : Chile saltpetre NaNO 3

Salt petre KNO 3

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Sulphates : Epsom salt MgSO4.7H2O

Gypsum CaSO4.2H2O
Glauber’salt Na2SO4.10H2O

Phosphates and Sillicates :

Fluor-apatite 3Ca3(PO4)2.CaF2
Felspar KAlSi3O8

4. Halide Ores :
Metallic halides are very few in nature. Chlorides are most common ores.
Common salt NaCl
Horn silver AgCl
Carnallite KCl.MgCl2.6H2O
Fluorspar CaF2
Cryolite Na3AlF6

Note : You Don’t need to cram all these compounds in one go. As you will read the chapter these com-
pounds will slowly set in your mind.

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METALLURGY Section - 2

The complete process of obtaining a pure metal from one of its ores is known metallurgy. The method to
extract a metal is generally not universal, as it depends upon a number of factors such as its chemical nature
and reactivity, nature of ore, nature of impurities and local conditions, etc. But still in general, metallurgy is
divided into following three steps.
I. Concentration of the Ore
II. Obtaining Crude Metal from Concentrated Ore
III. Refining of Crude Metal
Different methods are available for each of these stages. Choice of any method depends upon the nature
of metal and type of impurity present in the ore.
I. Concentration of the Ore :
Concentration of an deals with removal of unwanted impurities. Ores usually contain soil, sand, stones and
other useless silicates. These unwanted impurities are named gangue or matrix. For concentration, metal is
crushed and powdered and then it undergoes concentration. Concentration of ore involves physical as
well as chemical methods. It is also known as Dressing or Benefication of the ore.
(i) Hydraulic Washing (Gravity Separation)
Principle :
It is based on the difference in specific gravity of ore and gangue particles.
Working :
Powdered ore is agitated with running water which carries lighter particles like sand, clay away with
it.

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Type of Ore :
The oxides and carbonates type of ores are suitable for this method. For example : Tin’s ore Cassiterite
(SnO 2 ), Iron’s ore Haematite (Fe 2O3 ).

(ii) Magnetic Separation

Principle :
It is based on the magnetic and non-magnetic properties of ore and gangue.
Working :
A magnetic separator consists of a belt which moves on two rollers, one of the roller being a strong
magnet. Now, the powdered ore is dropped on the belt near the non-magnetic roller and as the ore
reaches the magnetic roller the magnetic particles get attracted and fall nearer to the roller while the
non-magnetic particles fall away from the rollers.

Type of Ore :
Separating Wolframite (Tungsten) ore from Cassiterite (Tin) ore, separating transition metal ores such
as Magnetite (Fe3O4 ), Pyrolusite (MnO2 ) and Chromite (FeO, Cr2O3 ) from unwanted gangue.
(iii) Froth Floatation
Principle :
Mineral particles are wetted by oils and the gangue particles are welled by water.
Working :
Collectors, frothing agents and froth stabilisers are added to the ore which mixed water. Collectors
enhance the non-wettability of mineral particles and froth stabilizers stabilize froth. Mineral particles
become wet by oils while gangue particles by water. Liquid mixture is agitated and air blown. Froth
is formed which carries off with it mineral particles. Light froth floats at the surface which is taken off
and from this froth mineral is recovered.

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Frothing agents : Pine Oil

Collectors : Fatty acids, Sodium Ethyl Xanthate
Froth Stabilizers : Cresols and Aniline
Depressants :
These are those chemicals that are used to prevent certain type of particles from forming the froth with
the bubbles. For example : NaCN (sodium cyanide) acts as a depressant in preveting ZnS from
forming the froth as it forms a layer of Na 2 Zn(CN)4 on surface of ZnS in concentration of zine
blende (ZnS). This is also known as selective frothing.
Type of Ore :
Sulphide ores eg: Galena (Pbs), Zinc blenda (ZnS), Cinnabar (HgS).
(iv) Chemical Separation (Leaching)
Principle :
It is based on the differences in the chemical properties of the ore and the gangue.
Working :
Ore is made soluble in a solvent and is then separated from the gangue. The solvent’s choice depends
upon the ore and gangue’s chemical properties.
Example :
1. In Bayer’s process, the impurities of iron and silicon are removed from the bauxite ore.
NaOH is added to the ore and as Al is amphoteric it dissolves forming sodium aluminate.
SiO2 being acidicoxide also dissolves as silicate ions. The insoluble iron impurities are re
moved by filtering. Next, CO 2 is bubbled through the solution lowering the pH. This enables
the precipitation of Al(OH)3 (sili-cate ions remain dissolved). The Al(OH)3 precipitated is
calcined (heated strongly) to give concentrated Al2O3 .

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 Na[Al(OH) 4 ] + SiO44 
Al2O3 + SiO2 + NaOH 

Na[Al(OH)4 ] + CO2 
 Na 2CO3 + Al(OH)3 ()


Al(OH)3(s)  Al2O3 + H 2 O()

2. Cyanide’s Process
Another example is the cyanide’s process for extraction of Au (from native form) and Ag (from
Ag 2S ore). The ore containing impurities is curshed and then treated with 0.1 – 0.2% soluton of
NaCN or KCN and aerated forming a soluble complex from complex which the metal is extracted
by the addition of Zn power in the solution.
For Au : 4 Au + 8 NaCN + 2 H 2O + O 2 
 4 Na[Au(CN)2 + 4 NaOH

2 Na[Au(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Au()

For Ag : Ag 2S + 4 NaCN  2 Na[Ag(CN)2 ] + Na 2S

2 Na[Ag(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Ag()

II. Obtaining Crude Metal :

This step involves reduction of concentrated ore. The concentrated ore i.e. Metal oxides, Metal sulphides,

Metal carbonates etc. are converted to metal in this step. M n+   M reduction occurs in this step.
Metal cabonates and Metal sulphides are difficult to reduce than metal oxides therefore they are first converted
to their oxides and then metal oxides is reduced to metal.
Conversion into Oxide Forms
Metallic ores are converted to metallic oxides by the two processes.
1. Calcination :
It involves heating of the ore below its fusion temperature in absence of air. It can remove moisture
from hydrated oxides or carbondioxide from carbonates. It is suitable for carbonate ores.


CuCO3 .Cu(OH)2 
 2CuO + CO2 + H 2O


ZnCO3 
 ZnO + CO2
Calcination makes the ore porous. The step is generally performed in a reverberatory furnace.

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2. Roasting :
It involves heating of the ore strongly in the presence of excess of air below its fusion temperature. It
is suitable for sulphide ores.

2 ZnS(s) + 3O2 (g) 
 2 ZnO(s) + 2SO2 (g)
Sometimes, a part of sulphide may act as a reducing agent as in case of extraction of lead.
PbO formed by roasting is reduced to lead by PbS.

2 PbS + 3O2 
 2 PbO+ 2SO2

PbS + 2 PbO 
 3Pb + SO2
Exception :
O
2  Cu S + Fe O + 3SO
2CuFeS2  2 2 3 2
1400° C

Note : Oxide ores are suitable for reduction. So, if we obtain ore in oxide form just after concentration as in case
of aluminium, then this ore is not required to undergo calcination and roasting as it already exists in oxide
form.

Reduction to Crude Metal

When the oxide form is obtained, then the metal has to be reduced. The choice of the reducing agent is
decided by the factors of energetics and economics.
Three main categories of reduction processes are :
(A) Chemical Reduction (B) Hydrometallurgy (C) Electrolytic Reduction
Now, we will discuss few important points of each category.

(A) Chemical Reduction Process

Carbon, Aluminium, Hydrogen and some other metals are used as reducing agents. These metals replace
less electropositive metals from their oxides.
(i) Reduction by carbon :
Carbon can be used to reduce a number of oxides and other compounds, and because of the low cost
and avilability of coke this methods is widely used. The disadvantages are that a high temperature is
needed, which is expensive and necessitates the use of a blast furance. Also, many metals combine
with caron, forming carbides, some examples are :
blast 1200C
Fe2 O3  C  Fe ; ZnO  C 
 Zn
furnance
electric electric
Ca 3 (PO4 )2  C 
P ; MgO  C  Mg
arc furnance

PbO  C 
 Pb

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(ii) Reduction by another metal :

If the temperature needed for carbon to reduce an oxide is too high for economic or practical purposes,
the reduction can be done by another highly electropositive metal such as Al, which liberates a large
amount of energy on oxidation to Al2O3. This is the bases of the thermite process : -

 9Mn  4Al2O3 ;
3Mn 3O4  8Al  B2O3  2Al 
 2B  Al2O3

Cr2O3  2Al 
 2Cr  Al2O3
Magnesium being more electropositive metal as compared to Al is used to reduce halides.
1000C
TiCl4  2Mg 
 Ti  2MgCl2

(iii) Reduction of oxides with hydrogen

This method is not widely used because many metals react with hydrogen at elevated temperatures,
forming hydrides.

Co3O4  4H 2 
 3Co  4H2O

2NH4 [MoO4 ]  7H 2 
 2Mo  8H2O  2NH 3
(iv) Self Reduction Process
The sulphide ore of less electropositive metals like lead, mercury, copper are heated in air as to
convert part of the ore into oxide or sulphate which then reacts with the remaining sulphide ore to
give the metal and SO2 gas.
No external reducing agent is used in this process.
Lead : 2 PbS  3O 2 
 2 PbO  2SO 2 (Extraction of lead from Galena, PbS)
2 PbO  PbS 
 3Pb  SO 2

Copper : 2 Cu 2S  3O 2 
 Cu 2O  2SO 2 (Extraction of copper from copper glance, Cu2S)
Cu 2S  2 Cu 2O 
 6 Cu  SO2

Mercury : 2HgS  3O 2 
 2 HgO  2SO 2 (Extraction of mercury from cinnabar, HgS)

2 HgO  HgS 
 3 Hg  SO 2

Another name for self reduction process is auto reduction process or air reduction process.
(B) Hydrometallurgy
This process is based on the principle that more electropositive metals can displace less electropositive
metals from their salt solution. The ore is treated with such chemical reagents which convert it into soluble
compound. By addition of more electropositive metals to the filtrate, the metal present in the ore can be
precipitated.

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Illustration :
Malachite ore is first calcined and the oxide obtained is dissolved in H2SO4. To the solution of CuSO4,
scrap iron is added which precipitates copper.

CuCO3 .Cu(OH) 2 
 2CuO  CO2  H 2O

CuO  H 2SO4 
 CuSO4  H 2O
(soluble)

CuSO4  Fe   FeSO4  Cu 
(soluble)
Similarly, silver can be obtained by cyanide process.
(C) Electrolytic Reduction
Oxide of highly electropositive metals like Na, K etc cannot be reduced with carbon at moderate temperature.
So, for their reduction, a very high temperature is required, at which they may combine with carbon to form
carbide. Thus, they are obtained by electrolysis of their oxides in fused or molten state.
Illustration :
Sodium is obtained by the electrolysis of fused mixture of NaCl and CaCl2 (Down’s Process) or by the
electrolysis of fused NaOH (Castner’s process).
 Na+ + Cl
NaCl (molten) 
Cathode : Na+ + le 
 Na
Anode : 2Cl 
 Cl2 + 2e

Similarly aluminium is obtained by the electrolysis of alumina mixed with cryolite.

(III) Refining of Crude Metal
The crude metal obtained is impure. The impure metal is subjected to some purifying processes
known as refining in order to remove the impurities. The processes used for refining depend upon the
nature of the metal and the nature of impurities.
(A) Distillation (B) Liquation (C) Pyrometallurgical Oxidation
(i) Cupellation (ii) Bessemerisation (iii) Poling
(D) Electrolytic Refining (E) Special Methods
(i) Mond’s Process (ii) Van Arkel Method (iii) Zone Refining

(A) Distillation
This process is used for those metals which are easily volatile such as: Zn, Hg, Cd. The impure metal is
heated in a furnace and its vapours are separately condensed in a receiver. The non-volatile impurities are
left behind in the furnace.

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(B) Liquation
This process is based on the difference in fusibility of metal and impurities. When the impurities are less
fusible than the metal, this process is employed. The impure metal is placed on the sloping hearth of the
furnace and gently heated. The metal melts and flows down leaving behind the impurities on the hearth. This
method is used to purify Bi, Sn, Pb and Hg.

(C) Bessemerisation (Pyrometallurgical oxidation)

The impure metal is heated in a furnace and a blast of compressed air is blown through the molten mass.
The impurities get oxidized. For example, the molten pig iron is taken in a Bessemer converter and compressed
air is passed which oxidizes the impurities.
2Mn + O2 
 2MnO ; Si + O2 
 SiO2
2C + O2 
 2CO ; MnO + SiO2 
 MnSiO3 (slag)

(D) Electrolytic Refining

It is different from electrolytic reduction. The impure metal is made anode and a thin sheet of pure metal is
made cathode.
As electrolysis proceeds, pure metal from anode is transferred to the cathode, whereas the impurities settle
down as anodic mud or anodic sludge. For examples Cu, Ag, Au, Pb, Zu, etc. are refined by this method.
(E) Special methods for Refining
(i) Mond’s Process
It is used mainly for refining of nickel. Impure Ni is treated with carbon monoxide at 330K  350K,
when volatile compounds Ni(CO)4 is formed.
The impurities are left behind and the volatile Ni(CO)4 is transferred into another container, where it is
heated more strongly at 450 K to give pure Ni. The CO gas produced is used again.

330  350 K 450K  470K

 Ni  CO 4  Ni  4CO
Ni  4 CO 
Im pure Volatile and (Pure)
highly toxic

(ii) Van Arkel Method

In this method, zirconium (or titanium) is heated in iodine vapour at about 870K to form volatile ZrI4.
The vapours of volatile ZrI4 are then decomposed electrically over tungsten filament to get pure metal,
and iodine is recovered.
870K 2075K
Zr  2 I2  ZrI 4 
 Zr  2 I2
(Im pure) (Vapours) (Pure)

As Van Arkel method and Mond’s process are quite related they are known as Vapour Phase
Refining.

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(iii) Zone Refining

This method is used for extracting ultra-pure metals. This method is based upon the principle that
when a molten solution of impure metal is allowed to cool, the pure metal crystallizes out, while the
impurities remain in the melt. A movable heater is fitted at one end of the rod of impure metal. The
heater is slowly moved across the rod. The metal melts at the point of heating and as the heater moves
on from one end of the rod to the other end, the pure metal crystallizes while the impurities pass into
the adjacent melted zone. This process is repeated number of times unless metal of desired purity is
obtained. The process is carried out in an inert atmosphere to prevent the oxidation of metal. For
example, Germanium, Silicon and Gallium for being used in semiconductors are purified by this method.

Important Terms
1. Flux
Flux is a substance which is added to remove non-fusible impurities by forming slag and decrease the
melting point of the melt during reduction. Flux can be of three types :
(a) Acidic flux - It is used to remove basic impurities. Examples of acidic flux include SiO2 (in
smelting of Cu) and borax.
(b) Basic Flux - It is added to remove acidic impurities. Examples include Fe2O3, CaCO3 (in
blast furnance) etc.
2. Furnance
A furnance is a structure built to produce high temperature. Examples of some farnaces are
reverberatory furnance, blast furnance and muffle furance.
3. Refractory materials
These are compounds / mixtures which can withstand very high temperature without melting and are
not affected by slags. They are used in the form of bricks for internal lining of furnaces.
Referectory materials may be of three types :
(a) Acid Refractories - SiO2, quartz.
(b) Basic Refractories - CaO(lime), magnesite, dolomite.(in blast furnance)
(c) Neutral Refractories - Graphite (used in Hall Heroult Process), Chromite, bone ash.

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IN - CHAPTER EXERCISE - A

1. List five ores which are smelted and give equations to show what occurs during smelting.
2. Name the process(es) used for concentration of tinstone.
3. Explain the role of collectors and froth stabilisers in Froth floation process.
4. Why is reduction by hydrogen not widely used.
5. Name three ores which undergo autoreduction give balanced equations.
6. Explain thermite process.

EXTRACTION OF IMPORTANT METALS Section - 3

GROUP 1
LITHIUM
Sources :
Lithium occurs mainly as silicate minerals like spodumene (LiAlSi2O6), Lepidolite.
SODIUM
Sources :
Sodium is the most abundant alkali metal. It is found in sea water, as rock salt (NaCl), Saltpetre (NaNO3),
Borax, Glauber’s salt (Na2SO4 . 10H2O), cryolite.
Extraction :
Sodium is obtained on large scale by two processes :
(A) Castner’s process :
In this process, electrolysis of fused NaOH is carried out at 330°C using iron as cathode and nickel
anode.

 Na   OH 
NaOH 

At Fe cathode: Na   e 
 Na

At Ni anode : 4OH   2H 2O  O2  4e

water formed at the anode gets partly evaporeted and is partly broken down to form H2 at cathode.
(B) Down’s process :
Sodium metal is manufactured mainly by this process. It involves the electrolysis of fused sodium
chloride (40%), calcium chloride (60%) and potassium fluoride using iron as cathode and graphite as
anode at about 600C.

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 Na+ + Cl
NaCl 
At Iron cathode Na   e 
 Na
At carbon anode 2Cl 
 Cl2  2e 

The electrolysis of pure NaCl presents the following difficulties :

 The fusion temperature of NaCl is high, i.e., 803C. At this temperature both sodium and chlorine are
corrosive.
 Sodium forms a metallic fog at this temperature.
To remove above difficulties, the fusion temperature is reduced to 600C by adding CaCl2 and KF.

POTASSIUM
Sources :
Potassium occurs mainly as deposits of KCl and carnallite (KCl . MgCl2 . 6H2O)

Extraction :
A cell similar to down’s cell can be used to obtain potassium by electrolysing fused KCl.

GROUP 2
MAGNESIUM

Sources : Magnesium salts occur in sea water. Entire mountain ranges (eg Dolomites in Italy) consist of the
mineral dolomite [MgCO3 . CaCO3] . It also occurs as magnesite (MgCO3) and carnallite.
Extraction :
(A) Dow’s sea water process :
Sea water contains MgCl2 . Water is treated with Ca(OH)2 which precipitates MgCl2 as Mg(OH)2.

MgCl2  Ca(OH)2 
 CaCl2  Mg(OH)2 
(in sea water)

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Vidyamandir Classes Basic Principle of Extraction

This is then converted back to MgCl2 .

 MgCl2   MgCl2 . 6H 2O   2H 2O
Mg(OH)2  2HCl 
dry HCl
MgCl2 . 6H2O  MgCl2 (anhydrous)
The obtained anhydrous MgCl2 is then electrolysed in fused state.
(B) From magnesite

MgCO3 
 MgO  CO2

MgO  C  Cl2 
 MgCl2  CO
(anhydrous)

MgCl2 is then electrolysed.

(C) Electrolysis of Fused Carnallite

Magnesium is prepared by electrolysis of fused MgCl2.

Anhydrous magnesium chloride is first prepared as in (A), (B) above

In order to lower fusion temperature of anhydrous MgCl2 and to increase the conductivity of electrolyte
NaCl or KCl (30%) is added. The electrolysis of MgCl2 is carried out at 700C. An air tight Iron vessel
serves as cathode. A carbon rod serves as anode and is enclosed by a porcelain tube. This arrangement
prevents the contact between magnesium and chlorine. Before starting the electrolysis, air above the electrolyte
is replaced by coal gas. This precaution is necessary because at about 700C magnesium reacts rapidly
with O2, N2 and CO2 present in air.

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 Mg2+ + 2 Cl
MgCl2 
At Fe cathode Mg2+ + 2e 
 Mg
At Carion anode 2 Cl 
 Cl2 + 2e

(D) In silico-thermic process / Pidgeon process :

Here calcined dolomite (CaO + MgO) is reduced by ferrosilicon at about 1200C in an electric
furnace working under reduced pressure (3mm) where pure magnesium distils over.

1200 C
CaO  2MgO  Si 
 2Mg  CaSiO3
3mm

CALCIUM
Sources :
It occurs in many common minerals like limestne, marble and chalk (CaCO3), dolomite, gypsum, Fluorspar
and also as coral.

Extraction by Electrolysis :
Calcium is obtained by electrolysis of a fused mass consisting six parts calcium chloride and one part
calcium fluoride at about 700C in an electrolytic cell made of graphite which acts as anode and a water
cooled cathode of iron which is suspended from the top in the fused mass. On passing current, calcium is
discharged at cathode. It gets solidified as cathode is water cooled.
 Ca 2   2Cl
CaCl2 
At graphite anode : 2Cl 
 Cl2  2e 
At Fe cathode : Ca 2   2e  
 Ca
Since metallic calcium is soluble in fused CaCl2 at electrolysis temperature, cathode is raised and Ca is
removed as soon as it is deposited.

Note : Na or K is obtained by electrolysis of fused NaOH or KOH respectively but calcium cannot be obtained in
the same manner as Ca(OH)2 decomposes into CaO (quick lime) which is difficult to fuse.

GROUP 3 - 7
 Ti is refined by Van Arkel - de-Boer method :

Note : TiO2 is very stable and can’t be reduced by C or CO as it forms carbides and hence is reduced by Na or
Mg.

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 Zirconium (Zr) is also refined by Van Arkel - de-Boer methods :

 Molybdenum and Tungsten are chemically reduced by H2

MoO3  H2 
 Mo  H2O ; WO3  H2 
 W  H 2O

GROUP 8
IRON
Sources :
Iron is the second most abundant metal and fourth most abundant element in the earth’s crust. It is extracted
from haematite (Fe2O3), magnetite (FeIIFe2IIIO4) and iron pyrites (FeS2) Famously called Fools Gold.

Extraction :

1. Crushing and Concentration :

The ore is crushed and washed with water (i.e., concentrated by levigating in a stream of water-
gravity separation or hydraulic washing) and then concentrated by electromagnetic process.

2. Roasting :
The concentrated ore is roasted in shallow kilns in the presence of excess of air. In roasting,
 Most of the moisture is removed.
 Impurities (like C, S, P, As and Sb) are removed in the form of their volatile oxides.
S + O2   SO
2
; 4As + 3O2   2AS O
2 3
; P + O2  P O
2 3
 Carbonates and sulphides are converted into oxides.
FeCO3   FeO + CO ; 4FeS + 11O 
2 2 2
 2Fe O + 8 SO
2 3 2
 Ferrous oxide is oxidised to ferric and thus avoids formation of slag with sand in further
processing.
4FeO + O2   2Fe O
2 3
(Otherwise FeO + SiO2   FeSiO )
3
 The entire mass becomes porous which makes reduction easy.
3. Smelting or Reduction :
The roasted ore (8 parts) mixed with coke (C), a reducing agent (4 parts) and limestone, a flux (1
part) is smelted (reduced) in a blast furnace lined with dolomite. Hot air blast is introduced near the
bottom of the furnace. Since the blast furnace has different temperature at different zones, different
reactions take place at different zones.
(a) Zone of Combustion : (1500°C -1600°C)
This zone is near the bottom of furnace and little above the tuyeres.
2C + O2 
 2CO + 58 Kcal
C + O2 
 CO + 97 Kcal
2
Both reactions are exothermic, a high temperature of about 1500C 1600C is attained.

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FeO  CO 
 Fe  CO2
CO 2  C 
 2CO
FeO  C 
 Fe  CO

(b) Zone of Fusion : (1200°C -1500°C)

It is just above the zone of combustion. Here the iron produced in upper zones melts and trickles
down in hearth while the slag being lighter floats over the molten iron and thus prevents oxidation of
Fe by blast of hot air. The molten metal and slag are removed from different outlets.
(c) Zone of Heat Absorption : (or middle zone) (800°C -1200°C)
In this middle part of furnace, rising CO2 (produced in the zone of combustion) is reduced to carbon
monoxide.
CO2 + C 
 2CO ; H = +39 kcal
The reaction being endothermic lowers the temperature of the zone. In addition to this, following
reactions also take place here.
(i) Limestone decomposes forming CaO which reacts with SiO2 forming slag.

CaCO3   CaO + CO2
CaO + SiO2 
 CaSiO3 (slag)
(ii) Any Fe3O4 which escapes reduction in the zone of reduction is reduced in this zone.
 3FeO + CO 
Fe3O4 + CO  2

(iii) Some impurities are reduced and get mixed up with Iron.
MnO + C   Mn + CO

SO2 + 2C 
 S + 2CO

SiO2 + 2C 
 Si + 2CO

P2O5 + 5C 
 2P + 5CO

Ca3(PO4)2 
 3CaO + P O
2 5

(d) Zone of Reduction : (300°C -700°C)

It is near the top of the furnace. Here the roasted ore is reduced by rising carbon monoxide CO. The
following reactions taking place in this zone are all reversible in nature.
300C  400C
3Fe2O3 + CO   2Fe3O4 (spongy iron) + CO2

680C  700C
Fe3O4 + CO   3FeO + CO2

FeO + CO 
 Fe + CO2

Fe3O 4 + 4 CO 
 3 Fe+ 4 CO 2

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 Iron obtained is impure. The product from blast furnace in called as Pig Iron. The net
productof blast furnace consists of Pig Iron, slag and fuel gases.
 The overall process for the extraction of Fe is thus :

3C  Fe 2O3 
 4Fe  3CO2

CaCO3  SiO2 
 CaSiO3  CO2

Cast Iron : The cast iron is specially made by igniting Pig iron with scrap iron and coke in a specially
designed furnace by blast of hot air. It contains 3% carbon in the form of graphite and carbide
and is extremely hard and brittle.

GROUP - 11
COPPER
Sources :
The most common ore is chalcopyrites CuFeS2. Other ores include Cu2S (Copper glance / chalocite),
basic copper carbonate CuCO3 . Cu(OH)2 (called malachite and is green) and cuprite Cu2O (is ruby red)

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Extraction :
It is a self reduction method. It can be achieved by two ways.
I. Pyrometallurgical II. Hyderometallurgical
(A) Pyrometallurgical Method :
1. Concentration of Ore : The ore is finely divided and concentrated by froth floatation method.
Here froth is made from pine oil and water by bubbling air into the mixture. Concentrated ore
adheres to the surface of froth leaving behind impurities.
2. Roasting : The concentrated ore is heated strongly in presence of air in a reverberatry furnace.
Sulphur, arsenic and antimony are removed in the form of their volatile oxides while the proper
ore is converted into a mixture of cuprous and ferrous sulphides. These sulphides are partially
oxidised to oxides.

S + O2 
 SO
2
2As2S3 + O2 
 2As O + 6SO
2 3 2

2Sb2S3 + O2 
 2SbO + 6SO
3 2

2CuFeS2 + O2 
 Cu S + 2FeS + SO
2 2

Minor Reaction : 2Cu2S + 3 O2 

 2Cu2O + 2SO2
2FeS + 3O2 
 2FeO + 2SO2

3. Smelting (Auto Reduction) : The roasted ore is mixed with sand (flux) and coke (fuel) and then heated
in water jacketed blast furnace called smelter. The oxidation of ferrous sulphide which started during roasting
now goes up a step further, ferrous oxide, formed reacts with sand to form ferrous silicates (slag). Here
some FeS reacts with Cu2O to form Cu2S again.

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FeO + SiO2 (sand) 

 FeSiO3 (Slag)
Cu2O + FeS   Cu2S + FeO
Slag, forming upper layer and molten mass consisting of Cu2S and little FeS, forming lower layer called
‘COPPER MATTE’ are removed from separate holes.
4. Bessemerisation : Molten matte is heated in Bessemer converter and blast of air mixed with sand is
blown through the molten mass. Here Iron (FeS) is completely removed as slag. A part of Cu2S is
oxidised to Cu2O and a part of Cu2S reduces Cu2O to metallic copper.
2Cu2S + 3O2 
 2Cu2O + 2SO2

2Cu2O + Cu2S 
 6Cu + SO2

The molten copper is poured off into sand moulds. As it cools, it gives up dissolved SO2 which forms
blister on the metal surface. The copper thus obtained is called as BLISTER COPPER (98% Cu).

5. Refining of Copper :
(a) Furnace or thermal Refining : Blister copper is melted in a reverberatory furnace provided with
silver lining and air is blown in where the impurities oxidise. Some of oxides escape and other form
a slag with silica.
The slag is removed.
(b) Poling : Molten Cu is stirred with poles of green wood to reduce Cu2O to Cu by CO and H2 from
green wood.
Cu2O + CO 
 2Cu + CO2
Cu2O + H2 
 2Cu + H2O

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(c) Electrorefining : The electrolyte bath contains an acidified solution of copper sulphate, impure copper
(blister copper) acts as anode while pure copper strip acts as cathode. The cathode grows in thickness
and pure Cu is scraped off.
Anode : Impure Cu
Electrolyte: 3.55% CuSO4 + 15% H2SO4 :  Cu2+ + 2e
Cu 
Cathode : Pure Cu
Temperature: 50C : Cu2+ + 2e 
 Cu (Pure)

Note : The impurities (Au, Ag, Pb ......) collect below the anode and is called anode mud.

(B) Hydrometallurgical Method :

Low grade ore is crushed and exposed to air and water when copper sulphide is oxidised to copper
sulphate. Some iron sulphate and sulphuric acid is also produced. This process takes one year.

(a) CuFeS2 + 4O2 

 CuSO4 + FeSO4

(b) 2Cu2S + 5O2 

 2CuSO4 + 2CuO
Cu glance

CuS + 2O2 
 CuSO4 (pale green liquid)

In NON-SULPHIDE ores, the crushed ore is leached with dilute H2SO4.

(c) [Link](OH)2 + 2H2SO4 
 2CuSO4 + CO2 + 3H2O
Malachite
The pale green liquor draining from the bottom to the heaps is collected in pans and treated with iron scraps
which precipitate out copper.
CuSO4 + Fe 
 FeSO4 + Cu
The precipitated copper is dried, melted and refined.

SILVER AND GOLD

Sources :
Silver is mainly found as sulphide ore Ag2S (argentite) Gold occurs mainly as grains of metal disseminated in
quartz veins.

Extraction :
Au, Ag are both first crushed and concentrated by froth floatation. Silver then directly undergoes leaching
while gold is leached after roasting.

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Leaching is done by Cyanide process.

1. Ag ore is leached with NaCN (or KCN) solution in presence of air when silver and its solt are
converted to soluble complex.
O
Ag 2S  4CN  

2
2[Ag(CN) 2 ]  S2 
Argento Cyanide
(so lub le)

O2(air) is pumped to force the reaction in forward direction.

4S2   5O2  2H2O 

 2SO42   2S   4OH 
Zinc dust is then added to precipitate Ag.

[ Ag(CN) 2 ]  Zn 
 Ag   [ Zn(CN) 4 ]2 
(pure)

2. The leaching process used for Au is called Mac Arthur Forest Cyanide Process :
Concentrated ore is taken in large vats made of cement or iron. It is then treated with dilute (0.5%)
solution of KCN in presence of air to form a soluble complex.

4 Au  8KCN  2H 2O  O 2 
 4 K[Au(CN) 2 ]  4KOH
(ore) Potassium Aurocyanide
(Soluble)

Note : If excess conc. KCN is used then

4Au  1 6CN   O2  2H 2O 
 4[ Au(CN)4 ]3  4OH 
(excess)

Zinc dust is then added :

2K[Au(CN)2 ]  Zn 
 K 2 [Zn(CN)4 ]  2Au 
(pure)

The obtained Gold (or Silver) still contains traces of impurities and thus electrolytic refining is performed.
The electrolyte used is AgNO3 + 10% HNO3(for silver) and AuCl3 + 10% HCl (for gold). Anode is the
impure metal while cathode is made of pure metal.
 Ag is also obtained from argnetiferrous lead (PbS . Ag2S) by Parke’s Process or Pattinson’s
Process :
 Ag, Au can also be extracted from anode mud formed during electrolytic refining of copper.
 Another method of extraction is amalgamation. Powdered ore is first converted to its amalgam and
then distilled to remove Hg in the form of vapour leaving behind pure metal.

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GROUP - 12
ZINC
Sources :
Zinc is found as Zinc Blende (ZnS), Colomine (ZnCO3) and zincite (ZnO)
Extration :
1. Concentration
The ore is concentrated first by gravity method and then by froth floatation process. If Fe2O3 is
present as an impurity, it is removed by magnetic separation.
2. Roasting
The concentrated ore is then roasted at 900C  1000C to convert ZnS and ZnSO4 to ZnO.
2ZnS + 3O2   2ZnO + 2SO2
ZnS + 2O2   ZnSO4
ZnSO4   2ZnO + 2SO2 + O2

Note : If calamine is used as the source, only calcination is required at high temperature.

ZnCO3 
 ZnO + CO2

3. Reduction by coke
The oxide, ZnO is reduced with coke at about 1500C to obtain metallic zinc which is distilled of and rapidly
cooled.
ZnO + C 
 Zn + CO

ZnO + CO 
 Zn + CO2

4. Electrolytic Refining
Zn thus produced contains impurities like Pb, Cd, and Fe. These impurities are removed by liquation. The
pure zinc is obtained by electrolysing the Zinc in presence of acidified ZnSO4 (ZnSO4 + dil H2SO4) as
electrolyte. Impure zinc is made the anode and pure zinc, the cathode.
Note : Zinc can also be extracted by electrolytic method. ZnS is first roasted at 700C to produce ZnO. Then, the
oxide ZnO is leached with H2SO4 to convert to sulphate (ZnSO4). After removing impurities by treating with
milk of lime, ZnSO4 is acidified and electrolysed to give pure zinc on cathode.

MERCURY
The most important ore is cinnabar (HgS) which is bright red coloured. The ore is first crushed and
concentrated by froth floatation method. It then undergoes Auto / self reduction

HgS  O2 
 HgO  SO 2

HgO  HgS   Hg  SO2

Refining is done by either liquation or distillation.

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GROUP - 13
ALUMINIUM :
Sources :
Aluminium is the most abundant metal and is commercially important. The most important ore of aluminium
is bauxite. This is a generic named for several minerals with formulae varying between Al2O3. H2O and
Al2O3 . 3H2O

Extraction (Electrolytic method from Bauxite) :

1. Purification of Bauxite
Bauxite contains mainly Iron oxide (Fe2O3) and silica as impurity. If iron oxide is the main impurity, it
is called red bauxite and if SiO2 is the main impurity, it is called white bauxite. It is difficult to remove
iron or silicon from aluminium, so the ore is purified before hand. It can be achieved by either of the
following processes.
(a) Bayer’s Process (for ores containing iron oxide as major impurity) :
Finely grounded ore is roasted at a low temperature to convert FeO to Fe2O3 and digested
with a concentrated solution of NaOH in an autoclave. Al2O3 (Amphoteric) dissolves forming
NaAlO2, while Fe2O3 (basic) remains undissolved. Fe2O3 is removed by filtration.

Al2O3.2H2O + 2NaOH 
 2NaAlO2 + 3H2O
The filtrate containing sodium aluminate is diluted, treated with a seed crystal of pure Al(OH)3
and then agitated, when pure Al(OH)3 is precipitated.

NaAlO2 + 2H2O 
 NaOH + Al(OH)3 
The precipitated Al(OH)3 is filtered, washed and ignited to give pure alumina, Al2O3.

2Al(OH)3   Al2O3(pure) + 3H2O

(b) Serpek’s Process (For ores containing silica, SiO2) :

The powdered ore is mixed with carbon and heated to 1800C in a current of nitrogen,
where aluminium nitride is formed. SiO2 is reduced to silicon, which volatilises away.
1800ºC
Al2O3 + 3C + N2 
 2AlN + 3CO

SiO2 + C 
 Si(volaties off) + 2CO
Aluminium nitride is hydrolysed by water to Al(OH)3 which on ignition gives pure alumina.

AlN + 2H2O 
 Al(OH)3 + NH3
1100C
2Al(OH)3  Al2O3(pure) + 3H2O

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Basic Principle of Extraction Vidyamandir Classes

(c) Hall’s Process [mainly for Red Bauxite] :

Crude bauxite reacts with Na2CO3 at 1000 C to give sodium aluminate and impurities Fe2O3 and
SiO2 form NaFeO2 and Na2SiO3 respectively.
 2NaAlO2 + CO2
Al2O3 + Na2CO3 
CO2 at a temperature of around 60C is passed into sodium aluminate solution producing Al(OH)3.
60C
2NaAlO2 + CO2 + 3H2O  2Al(OH)3  + Na2CO3

2Al(OH)3   Al2O3 (pure) + 3H2O
1100C

2. Electrolytic reduction of alumina (Hall - Heroult Process)

Aluminium can’t be isolated by electrolysis of aqueous solution of Al2O3, since aluminium is more
electropositive than hydrogen, so its electrolysis gives H2 at cathode.
Al2O3 is infusible (M.P. = 2050C), so it can’t be electrolysed. So pure alumina, dissolved in molten
Cryolite (Na3AlF6) containing some CaF2 or NaF is electrolysed at about 800C1000C. Cryolite
decreases melting point and increases conductivity while CaF2 and NaF are added only to increase
conductivity. The electrolysis is carried out in an iron cell lined with graphite (cathode). The anode is a
series of graphite rods.

 Al3+ + 3F
AlF3 
At cathode : Al3+ + 3e 
 Al

At the same time, Al2O3 dissociates into Al3+ and O2–.

Since ‘O’ is below F in the electronegativity series, O2 ions are selectively discharged at the anode as
oxygen.
 4 Al3+ + 6 O2
2 Al2O3 
At anode :  3 O2 + 12 e
6 O2 

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Vidyamandir Classes Basic Principle of Extraction

The oxygen liberated at anode combines with carbon of anode to form CO and CO2 so anode, which burn
away have to be replaced periodically. Molten Al collects at the bottom of cell (99% pure)
3. Electrolytic Refining
The cells layers contain three fused layers.
(a) The bottom anode layer of an alloy of Al, Cu, Si
(b) The middle layer of Cryolite and BaF2
(c) The top cathode layer of pure aluminium.
When a current is passed, Al3+ ions from the fused middle layer get discharged at the cathode, while an
equivalent amount of aluminium moves into the middle layer. Impurities (Cu etc) remain at the bottom.

GROUP - 14
TIN :
Sources :
It is mainly obtained from Cassiterite (SnO2) which contains Wolfromite (FeWO4 . MnWO4) as an impurity.
Extration :
1. Concentration of ore :
Ore is crushed to a fine powder and concentrated by gravity process. Ore is washed with the stream
of water to remove gangue and other silicon impurities. Tinstone and wolframite are left. Wolframite
is then removed by magnetic seperation.
2. Roasting :
The ore is roasted to remove volatile impurities.
S + O2   SO
2

2As2S3 + 9O2 
 2As O + 6SO
2 3 2

The roasted ore is washed with water to remove soluble impurities and dried. It contains 60 – 70% of
tin as SnO2 called Black Tin.

3. Smelting :
The ore is mixed with 1/5 th of its weight of powdered anthracite and a little limestone and heated in
reverberatory furnace. SnO2 is reduced to metallic state and silica is removed as slag.
SnO2 + 2C 
 Sn + 2CO

4. Refining :
It is refined by any of the following processes.
(a) Liquation : The crude tin is melted on the sloping hearth of a reverberatory furnace when tin
alone melts and flows out. The process is called sweating and the impure tin left is called
dross.

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Basic Principle of Extraction Vidyamandir Classes

(b) Electrolytic Refining : The electrolyte consists of hydrofluorosilicic acid (H2SiF6) containing
stannic sulphate (SnSO4) and H2SO4. A block of impure tin is anode and a thin strip of pure
tin the cathode.

LEAD
Sources :
Galena (PbS) is the principal ore.
Extraction :
(A) Self Reduction or Air reduction process :
This is used for samples of galena rich in lead. In this process roasting and smelting are done in same
furnace, but at different temperatures.
(i) Crushing and Concentration
The ore is crushed, finely powdered and concentrated by froth floating process. NaCN is
used as a depressant to prevent ZnS (if present) from coming out as froth. The concentrated
ore contains 50  60% of lead.
(ii) Roasting
The concentrated ore is roasted at a moderate temperature in a reverberatory furnace and in
a limited supply of air.
lim e
2PbS + 3O2 
 2PbO + 2SO2

PbS + 2O2 
 PbSO
4

(iii) Reduction (Smelting)

Air supply is cut off, fresh galena is added to roasted ore and the temperature is raised.
Galena reduces lead oxide and lead sulphate to metallic lead.

2PbO + PbS 
 3Pb + SO2

PbSO4 + PbS 
 2Pb + 2SO2
Molten lead is drawn from time to time and purified.

(B) Carbon Reduction Process :

This process is suitable when the ore contains more impurity (silica) and has low amount of lead. Here
roasting and smelting are done in different furnaces.
(i) Crushing and Concentration
This is done as in above process.

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Vidyamandir Classes Basic Principle of Extraction

(ii) Roasting
Concentrated ore is mixed with lime (CaO) and heated in presence of air when PbS is oxidised
mainly to PbO.
2PbS + 3O2 
 2PbO + 2SO2
Lime performs two important functions.
(a) Being more basic than PbO, lime preferentially reacts with SO2 (formed in the above
oxidation) to form calcium sulphite and thus favours the oxidation of galena in the
forward direction.
(b) It decomposes lead silicate (formed by reaction of PbSO4 with silica present as
impurity) to PbO which would otherwise have gone as slag.
PbS + 2O2   PbSO4
2PbSO4 + 2SiO2 
 2PbSiO3 + 2SO2 + O2
PbSiO3 + CaO 
 CaSiO3 + PbO

(iii) Smelting
The roasted mass is mixed with coke and lime (flux) and smelted in a blast furnace. Following
reactions occur.
PbO + C 
 Pb + CO
PbO + CO  Pb + CO2
CaO + SiO2  CaSiO3 (slag)

PbSiO3 + CaO  CaSiO3 + PbO

Little hematite is added to reduce any unchanged PbS to Pb.
2PbS + Fe2O3 + 3C 
 2Pb + 2FeS + 3CO

(iv) Refining
Impurities are Cu, As, Sb, Fe, Zn, Bi, Ag and sulphur. These are refined by either of flowing
processes :
(a) Oxidation or softening where impure metal is heated in current of air where Cu, Fe, Sn etc are
oxidised before lead.
(b) Desilverisation by Parke’s or Pattinson method to remove Ag.
(c) Electrorefining : Electrolysis of 1-15% Lead silica fluoride (PbSiF6) and 5-10%
(hydrofluorosilicic acid, H2SiF6) is carried out between pure lead sheets serving as cathode,
and crude impure lead as anode.

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 Basic Principle of Extraction Vidyamandir Classes

IN - CHAPTER EXERCISE - B

1. Cinnabar (HgS) and galena (PbS) on roasting often give their respective metals but zinc blende
(ZnS) does not.
Explain :
2. A metal is in combined sate as sulphide. Identify the steps (A), (B) and (C)


3. Why Zinc and not copper is used for the recovery of metallic silver from the complex  Ag  CN  2 
4. Describe the extraction of magnesium from sea water.

SOLUTIONS - IN - CHAPTER EXERCISE - A

1. Fe 2O3  C 
 Fe ; ZnO  C 
 Zn  CO 2  CO(gases)
(haematite) (zincite)

PbO  C   Pb ; MgO  C   Mg ; Ca 3 (PO4 ) 2  C  P

2. Tinstone is concentrated first by gravity seperation and then magnetic seperation is used to remove magnetic
impurities like wolframite.
3. Collectors enhance the non wettability of mineral particles and froth - stabilizers stabilize the froth.
4. Reduction by hydrogen is not widely used because many metals react at elevated temperartures, forming
hydrides. There is also a risk of explosion.
5. Galena (PbS), Chalcocite (Cu2S) and cinnabar (HgS).
6. In the thermite process, Al is used to reduce metal oxide to metal while it itself gets oxidised to Al2O3 which
produces a large amount of heat (1675 kJ/mol). This is utilised to join broken railway tracks.

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 Vidyamandir Classes Basic Principle of Extraction

SOLUTIONS - IN - CHAPTER EXERCISE - B

1. This is because HgS and PbS can undergoe self reduction while ZnS doesnot.
2. A = roasting, B = reduction, C = refining
4. Sea water contains MgCl2 which is precipitated as Mg(OH)2 (using Ca(OH)2). This is then converted back
to MgCl2(by HCl) and dried. MgCl2 is then electrolysed.

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 Vidyamandir Classes

My Chapter Notes

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 Vidyamandir Classes

Illustration - 1

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Vidyamandir Classes

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 Vidyamandir Classes

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 QUALITATIVE ANALYSIS

Theory Notes
QUALITATIVE ANALYSIS
Introduction :
You know that the qualitative analysis involves the detection of the anions and the cations
present in an inorganic mixture. Sometimes the knowledge of anions present in a mixture
provides important clues about the cations which may be present in a mixture and the scheme
of analysis to be followed. Therefore, it is desirable to first detect the presence of anions and
after that the cations. In this unit, we will discuss the scheme of detection of anions which will
be followed by the scheme of analysis of cations.

Classification of the Anions :

For the systematic identification of the anions present in any mixture, the anions are divided into
following three classes:
Anions of Class I :
The anions of Class I evolve gases or vapours on treatment with dil. HCl or dil. H 2SO4. These

.in
anions are carbonate, sulphite, sulphide, thiosulphate, nitrite .
Anions of Class II :
ps
The anions of Class II evolve gases or vapours on treatment with conc. HCl or conc. H 2SO4.
These anions are fluoride, chloride, bromide, iodide, nitrate and oxalate.
te

Anions of Class III :

yS

The anions of this class do not evolve any gas on treatment with acids. These are identified by
formation of precipitate on treatment with certain reagents. Sulphate, borate and phosphate
ions are the anions of Class III.
ud

Here we would like to emphasise the unlike scheme of classification of cations, the scheme of
classification of anions is not a rigid one since some of the anions belong to more than one of
St

the classes, e.g., acetate. Also, it is not always necessary to test for the presence of anions of
Class I before testing for the presence of anions of Class II or Class III in any mixture.

Preliminary Tests for the Anions

In this unit the tests for all these anions will be systematically discussed. We shall first discuss
the preliminary tests for detecting the presence of anions of Class I and Class II, which will be
followed by their confirmatory tests. As there are no preliminary tests for the anions of Class III
only their confirmatory tests will be discussed.
Preliminary Tests for the Anions of Class I :
Take about 0.2g of dry mixture in a test tube. Add 2 cm 3 of dilute hydrochloric or sulphuric
acid. If a gas is evolved, note its colour and odour and draw inference with the help of Table 1.
Heat the test tube if necessary. If no gas is evolved, anions of this class are absent in the

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 QUALITATIVE ANALYSIS

mixture.

Table 1: Preliminary Tests for the Anions of Class I

S. No. Observation Inference Explanation / Reaction

1. Colourlress, suffocating gas with smell SO32 may be present SO32–(aq) + 2H+(aq)  H2O(l) + SO2(g)
2
of burning sulphur; the gas turns Cr2 O7(aq) + 2H+(aq) + 3SO2(g)
3 2
acidified K2Cr2O7 paper green.  2Cr(aq)  3SO 4(aq)  H 2 O(l)
green

2. Colourless gas which turns KI starch S2– may be present S2–(aq) + 2H+(aq)  H2S(g)
paper blue. Pb 2+(aq) + H2S(g)
 PbS(s) + 2H+(aq)
Black

3. Light brown gas which turns KI starch NO 2 may be present 2NO 2(aq) + 2H+(aq)
paper blue.  H2O(l) + NO(g) + NO2(g)

.in
4. Colourless vapours with smell of CH3COO– may be present CH3COO–(aq) + H+(aq)
vinegar on warming the test tube  CH3COOH(g)
ps
When salts of the anions of Class I are treated with strong, non-oxidising acids, corresponding
te

acids are generated in the solution.

2 
SO3(aq)  2H (aq) 
 H 2SO3(aq)
yS

NO 2(aq)  H (aq)


 HNO 2(aq)
ud

2 
S(aq)  2H (aq) 
 H 2S(aq)

Out of these H2CO3, H2SO3 and HNO2 are thermally unstable and decompose into gaseous
St

products, whereas H2S and CH3COOH are evolved as vapours on warming:

H 2SO3(aq) 
 SO 2(g)  H 2 O(l)

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 QUALITATIVE ANALYSIS

2HNO 2(aq) 
 NO(g)  NO 2(g)  H 2 O(l)

Preliminary Tests for the Anions of Class II :

Take 0.2 to 0.3g of the mixture in a dry test tube and add 2-3 cm 3 of conc. sulphuric acid
drop-wise. Observe the reaction at room temperature and then warm the test tube gently. If no
gas or vapours are evolved, the anions of this class are absent. Draw interference inference
with the help of Table 2.
Table 2: Preliminary Tests for the Anions of Class I
S. No. Observation Inference Explanation / Reaction
1 Colourless, pungent smelling gas is
evolved, which gives white dense
fumes of NH4Cl when a glass rod
dipped in aqueous ammonia is
placed in the evolved gas. Cl– may be present Cl–(aq) + H+(aq)  HCl(g)
HCl(g) + NH3(g)  NH4Cl(g)

2 Reddish brown gas is evolved and

the solution in the test tube acquires
a yellow-red colour. Br– may be present Br–(aq) + 6H+(aq) + 3SO42–(aq)
 2HSO4–(aq) + Br2(g) + 2H2O(l)

3. Violet vapours of I 2 are evolved, which

turn the moist starch paper tubeblue.
.in
I–may be present 2I–(aq) + 6H+(aq) + 3SO42–(aq) 
ps
2HSO42–(aq) + SO2(g) + I2(g) + 2H2O(l)

4. Pungent smelling, brown fumes of NO 2 NO3– may be present NO–3(aq) + H+(aq)  HNO3(aq)
4HNO3(aq)  4NO2(g) + O2(g) + 2H2O(l)
te

are evolved. The evolution of NO 2

increases on heating the reaction Cu(s) + 4HNO3(aq) 
mixture with copper turnings. Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
yS

Preparation of Solution for Identification of the Anions

ud

The preliminary tests described in the preceding section do not always offer very conclusive
evidence for the presence of anions in a mixture. Therefore, further tests have to be performed
St

for confirmation of those anions which are indicated by the preliminary tests and for the detection
and confirmation of the anions of Class III which have no preliminary tests. These tests are
called confirmatory tests and are performed on the solution of anions which is prepared as
described below.
Preparation of Water Extract (W.E.):
All common acetates, nitrites, nitrates and thiosulphates are soluble in water. Confirmatory
tests for these anions can be performed with the water extract of the mixture. Water extract can
be prepared by boiling 1-2g of the mixture with 10-15 cm3 distilled water in a boiling tube for
a minute or two. Residue, if any, is filtered. The filtrate is called water extract (W.E.).
Preparation of Sodium Carbonate Extract (S.E.):
If the mixture is found to be partially or wholly insoluble in water, it is boiled with saturated
sodium carbonate solution. This treatment converts the anions present in mixture into soluble
sodium salts as a result of double decomposition e.g.,
BaSO 4(s)  Na 2 CO3(aq) 
H2O
 BaCO3(s)  Na 2SO 4(aq)
PbCl2(s)  Na 2 CO3(aq) 
H2O
 PbCO3(s)  2NaCl(aq)
For preparing sodium carbonate extract, take 0.5-1.0g of powdered mixture, 1.0-2.0g of
sodium carbonate and 5-10 cm3 of distilled water in a boiling tube or a 50 ml beaker. Heat with
stirring for 5-10 minutes. Cool the contents and filter. The filtrate is called sodium carbonate

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 QUALITATIVE ANALYSIS

extract (S.E.). This extract is used for confirming the presence of most anions except for
carbonate since sodium carbonate has been added during its preparation.
Confirmatory Tests for the Anions
After preparation of the water extract or the sodium carbonate extract, the following tests are
performed to confirm the presence of various anions in the mixture.
Tests for the Sulphide Ions
1. Take 1 ml of sodium carbonate extract in a test tube and add 1 – 2 ml of sodium nitroprusside
solution. A purple or violet colour confirms sulphide ions:
2 2 4
S(aq)  [Fe(CN)5 NO](aq) 
 [Fe(CN)5 NOS]aq
purple or violet colour

2. Take 1 – 2 ml of S.E. in a test tube, acidify it with acetic acid and boil to remove CO 2. Then
add 1 – 2 ml of lead acetate solution. Formation of black precipitate confirms sulphide ions:
2
S(aq)  Pb 2 
 PbS(s)

Tests for Sulphite Ions:

Take 2 – 3 ml of S.E. and add 2 – 3 cm3 of BaCl2 solution to it. A white precipitate may appear
due to the presence of SO32 , SO 42- or excess of CO32 ions present in the solution. Filter the
precipitate and divide into three parts.

.in
1. To the first part, add dil. HCl. Evolution of SO 2 gas which turns acidified dichromate paper
green confirms the presence of SO32 ions
ps
 2
BaSO3(s)  2H (aq)  5e 
 Ba (aa )  SO 2(g)  H 2 O (l)

2. To the second part, and add a few drops of KMnO4 solution and acidify with dil. H2SO4. If the
te

pink colour of KMnO4 is discharged, the presence of SO32 ions is confirmed.

yS


BaSO3(s)  H 2 O(l) 
 BaSO 4(s)  2H (aq)  2e]  5

MnO 4(aq)  8H (aq)


 5e  2
 Mn (aq)  4H 2 O(l) ]  2
ud

–––––––––––––––––––––––––––––––––––––––––––––––––
  2
St

5BaSO3(s)  2MnO 4(aq)  6H (aq) 

 5BaSO 4(s)  2Mn (aq)  3H 2 O(l)
3. To the third part, add I2 solution. If colour of iodine is discharged, SO32 is confirmed.
BaSO3(s)  I 2(aq)  H 2 O(l) 
 BaSO 4(s)  2HI(aq)

Tests for the Nitrite Ions

1. Take 5 drops of W.E. in a test tube. Dilute with 5 drops of distilled water. Add 5M acetic acid
until the solution is just a acidic. Cool the test tube in a cold water bath. Add 2-3 drops of
freshly prepared 0.2M FeSO4 solution to the cooled solution. Appearance of a brown colour
throughout the solution confirms the presence of nitrite ions.
NO 2(aq)  CH 3COOH (aq)  
 HNO 2(aq)  CH 3COO(aq)

3HNO 2(aq) 
 HNO3(aq)  H 2 O(l)  2NO(g)
2 2
[Fe(H 2 O)6 ](aq)  NO (g) 
[Fe(H 2 O)5 NO](aq)  H 2 O (l)
2. To 1 cm3 of W.E. add 5 drops of KI solution, 1 cm3 of starch solution and 1 cm3 of dil. H2SO4.
Appearance of a deep blue colour confirms the presence of nitrite ions.

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 QUALITATIVE ANALYSIS

2NO 2(aq)  4H (aq)

 
 2I(aq) 
 2NO (g)  I 2(aq)  2H 2 O (l)
I2(aq) + Starch  Blue coloured complex
3. Take 5 drops of W.E. in a test tube, acidify with 6 M acetic acid. Add a pinch of thiourea and
stir stirr well. Add 2 drops of FeCl 3 solution. A blood red colur confirms nitrite ions.
NO 2(aq)  H 2 NSCNH 2(s)  
 N 2(g)  CNS(aq)  2H 2 O(l)
 
Fe3(aq)  3CNS(aq) 
 Fe(SCN)3(aq)
(Blood red colour)

You should note that the nitrite ion is a moderately strong oxidizing agent in acidic medium. It
oxidizes S2 ,SO32 ,S2 O32 and I– ions to S, SO 2-4 , S and I2 respectively. Therefore, these anions
cannot be present if NO2– ions are present in the mixture.
2
S(aq)  NO 2(aq)  2H (aq)


 S(s)  NO(g)  H 2 O(l)
2
SO3(aq)  2NO 2(aq)  2H (aq)

 2
 SO 4(aq)  2NO(g)  H 2 O(l)
2  
S2 O3(aq)  2NO 2(aq)  2H (aq) 
 SO 4(aq)
2
 S(s)  2NO(g)  H 2 O(l)

2I(aq)  2NO 2(aq)  4H (aq)


 I 2(s)  2NO(g)  2H 2 O(l)

Test for the Nitrate Ions :

.in
Take 2 cm3 W.E. in a test tube. Add 4 cm3 concentrated sulphuric acid, mix two liquids thoroughly
and cool the mixture under a stream of cold water from the tap. Pour few cc of saturated
ps
solution of FeSO4 slowly down the side of the test tube so that it forms a separate layer on top
of the solution in the test tube. A brown ring will be formed at the zone of contact of the two
te

liquids.
  2 
 4H (aq)  3Fe(aq) 
 3Fe3(aq)  NO(g)  2H 2 O(l)
yS

NO3(aq)
2 2
[Fe(H 2 O)6 ](aq)  NO(g) 
[Fe(H 2O)5 NO](aq)  H 2O(l)
ud

This test for nitrate ion is based on its ability to oxidize Fe2+ to Fe3+ in acidic solution with the
product of NO gas. Since NO is more soluble in water at low temperature, in well cooled
St

solution it reacts with excess Fe2+ present in solution to form brown nitrosyliron (II) complex
ion, [Fe(H2O)NO]2+. Nitrite, bromide and iodide ions interfere in this test.

Test for the Chloride Ions

1. Acidify 2 – 3 cm3 of S.E. with dil. HNO3. Boil off CO2. Then add AgNO3 solution. Formation
of a curdy white precipitate, which is soluble in aqueous ammonia, confirms the presence of
chloride ions in the mixture.
Cl– (aq) + Ag+ (aq)  AgCl(s)
AgCl (s) + 2 NH3 (aq)  [Ag (NH3)2]+ (aq) + Cl– (aq)
2. Heat 0.5g of dry mixture with 0.5g of K 2Cr2O7 and 2 ml of conc. H2SO4 in a dry test tube, red
vapours of chromyl chloride will be evolved. Pass the vapours in dil. NaOH solution, a yellow
solution will be obtained. Acidify the solution with acetic acid and then add lead acetate solution.
Formation of a yellow precipitate of lead chromate, which is soluble in NaOH, confirms the
presence of chloride ions.
4NaCl(s)  K 2 Cr2 O7(s)  3H 2SO 4(l) 
 K 2SO 4(s)  2Na 2SO 4(s)  CrO 2 Cl2(g)  3H 2 O(l)
Chromyl chloride gas

CrO 2 Cl2(g)  4NaOH (aq) 

 Na 2 CrO 4(aq)  2NaCl(aq)  2H 2 O(l)

Page 5 of 29 [Link]
 QUALITATIVE ANALYSIS

Na 2 CrO 4(aq)  Pb(CH 3COO) 2(aq) 

 PbCrO 4(s)  2CH 3COONa (aq)
Due to the formation of chromyl chloride gas, this test is called chromyl chloride test. The test
fails if the mixture contains chlorides of Hg2+, Sn2+, Pb2+ or Ag+.
Test for the Bromide Ions
1. Acidify 2-3 ml of S.E. with dil. HNO3 and boil off CO2. Add AgNO3 solution. Formation of a
light yellow precipitate which is partially soluble in aqueous ammonia solution, confirms the
presence of bromide ions.
 
Br(aq)  Ag (aq) 
 AgBr(s)
Light yellow ppt.

2. Take 2 cm of S.E., acidify it with dil. HCl and boil off CO 2. Add 2 cm3 of carbon disulphide,
3

dichloromethane or carbon tetrachloride. Then add chlorine water drop-wise and shake. Bromide
ions are oxidized to bromine, which imparts an orange colour to the organic layer. This confirms
the presence of bromide ions in the mixture.
 
2Br(aq)  Cl2(aq) 
 2Cl(aq)  Br2(l)

Br2(l)  CS2(l) 
 Orange colour

Tests for the Iodide Ions

1. Acidify 2 – 3 cm3 of S.E., with dil. HNO3 and boil off CO2. Add AgNO3 solution. Formation of

.in
a pale yellow precipitate insoluble in aqueous ammonia confirms the presence of iodide ions in
the mixture.
ps
 
I(aq)  Ag (aq) 
 AgI(s)
Pale yellow ppt.
te

2. Take 2 cm of S.E. in a test tube. Acidify it with dil. HCl and boil off CO 2. Add 2 cm3 carbon
3

disulphide, dichloromethane or carbon tetrachloride. Then add chlorine water drop-wise and
yS

shake. Iodide ions are oxidized to iodine, which imparts a violet colour to the organic layer.
 
2I(aq)  Cl2(aq) 
 I 2(s)  2Cl(aq)
ud

CS2(l)  I 2(s) 
 Violet colour
The violet colour disappears on addition of excess of chlorine water. This confirms the presence
St

of iodide ions in the mixture.

I 2(s)  Cl2(aq) 
 2ICl (aq)
Iodine monochloride (colourless)

Test for the Sulphate Ions:

Take 1 – 2 cm3 of S.E., in a test tube. Acidifiy it with dil. HCl and boil off CO 2. Add BaCl2
solution. Appearance of a white precipitate, which is insoluble in conc. HCl and conc. HNO3,
confirms the presence of sulphate ions.
 2
SO 24(aq)  Ba (aq) 
 BaSO 4(s)

Test for Nitrate Ions in Presence of Nitrite Ions:

In presence of nitrite, nitrate cannot be tested either by heating with conc.H2SO4 or by the ring
test because both liberate NO2. Therefore, nitrite must be destroyed completely before testing
for the nitrate. Nitrite ions can be destroyed by any one of the following methods:
1. Add sulphamic acid, H2NSO3H, to the water extract containing NO 2 and NO3 ions. Acidify
the solution with dilute H2SO4. Nitrite will be decomposed and nitrogen gas will be evolved.
 
H 2 NSO3 H (aq)  NO 2(aq) 
 HNO 2(aq)  H 2 NSO3(aq)

Page 6 of 29 [Link]
 QUALITATIVE ANALYSIS

  2
H 2 NSO3(aq)  HNO 2(aq) 
 N 2(g)  H (aq)  SO 4(aq)  H 2 O(l)
2. Take 2 – 3 ml of water extract, add 1g solid NH 4Cl and boil till effervescence ceases.
NO 2(aq)  NH 4 Cl(aq)  
 N 2(g)  2H 2 O (l)  Cl(aq)
3. Take 2 – 3 ml of water extract, add urea and acidify with dil. H 2SO4. Boil the solution till
evolution of gases ceases.
 
NH 2 CONH 2(aq)  2NO 2(aq)  2H (aq) 
 2N 2(g)  CO 2(g)  3H 2 O(l)
Now divide the nitrite free solution thus obtained in two parts.
(a) Perform ring test with one part to confirm the presence of nitrate ions.
(b) Acidify the other part with dil. H2SO4. Add a little KI and 1 cm3 starch solution. Absence
of any blue colour indicates the complete removal of nitrite ions. Now add a piece of granulated
zinc to the solution. Appearance of a blue colour confirms the presence of nitrate ions.
 2
Zn (s)  2H (aq) 
 Zn (aq)  2H (g)
 
NO3(aq)  H 2(g) 
 NO 2(aq)  H 2 O(l)

2I(aq)  2NO 2(aq)  4H (aq)


 2NO(g)  I 2(s)  2H 2 O(l)

I 2(s)  Starch 
 Blue coloured complex

Tests for Nitrate Ions in Presence of Bromide and/or Iodide Ions

1. .in
Bromide and iodide interfere in the ring test of nitrate because of the colour of liberated bromine
ps
and iodine. In order to identify nitrate in presence of iodide and/or bromide, the interfering
halide should be expelled before performing the ring test. This can be done by boiling 2 – 3 cm3
te

of water extract or sodium carbonate extract with excess of chlorine water in a china dish, till
no more vapours of Br2 or I2 evolve.
yS

 
2Br(aq)  Cl2(aq) 
 2Cl(aq)  Br2(g)
 
2I(aq)  Cl2(aq) 
 2Cl(aq)  I 2(aq)
ud

Now perform the ring test on the halide free solution to identify the nitrate ion in the mixture.
2. Alternatively, take 2 – 3 cm 3 of water extract in a test tube. Acidify with dil.H 2SO4. Now add
St

1 cm3 of KI solution, 1 cm3 of starch solution and a few granules of zinc. Appearance of a blue
colour confirms the presence of nitrate ions in the mixture.
 2
Zn (s)  2H (aq) 
 Zn (aq)  H 2(g)
 
NO3(aq)  H 2(g) 
 NO 2(aq)  H 2 O(l)
  
2I(aq)  2NO 2(aq)  4H (aq) 
 2NO(g)  I 2(g)  2H 2 O(l)
I 2 + Starch 
 Blue coloured complex

Test for Chloride, Bromide and Iodide Ions in Presence of Each Other:
As you know that chloride, and iodide ions react with AgNO 3 solution to form a precipitate,
special tests are required to identify if more than one of them are present in the mixture. These
anions can be detected in presence of one another by any one of the following methods.
1. Acidify 2 – 3 cm 3 of S.E., with excess dil. H 2SO4 in a china dish. Add 0.5g of potassium
persulphate and heat gently. Add distilled water if necessary of to prevent dryness. Evolution of
violet vapours of I2 will confirm the presence of I– ions.
 2 2
2I(aq)  S2 O8(aq) 
 2SO 4(aq)  I 2(g)

Page 7 of 29 [Link]
 QUALITATIVE ANALYSIS

Boil till evolution of I2 ceases. If the solution after elimination of I2 is brown, it indicates the
presence of Br– ions. Continue boiling, brown vapours of Br2 will be evolved.
 2 2
2Br(aq)  S2 O8(aq) 
 2SO 4(aq)  Br2(g)
Add more K2S2O8 if required. Continue boiling till the residual solution becomes colourless.
Cool the solution, add dil. HNO 3 and AgNO3 solution. A curdy white precipitate soluble in
ammonia confirms the presence of Cl– ions in the mixture.
 
Cl(aq)  Ag (aq) 
 AgCl(s)
 
AgCl(s)  2NH 3(aq) 
[Ag(NH 3 ) 2 ](aq)  Cl(aq)
2. Acidify 2 – 3 cm3 of S.E. with dil. H2SO4 in a china dish. Boil off CO2. Add solid sodium nitrite
and boil. Evolution of violet vapours of I2 confirms the presence of iodide ions.
2NO 2(aq)  2I(aq)
 
 4H (aq) 
 2NO (g)  I 2(g)  2H 2 O(l)
Add distilled water if necessary to prevent dryness. Continue boiling till all iodine is expelled.
Cool the solution and divide into 2 parts.
To 1st part add 1 cm 3 CS2 (or CH2Cl2 or CCl4), 2 cm3 chlorine water and shake. Appearance
of an orange colour in organic layer confirms the presence of bromide ions.
 
2Br(aq)  Cl2(aq) 
 2Cl(aq)  Br2(l)

.in
CS2(l)  Br2(l) 
 Orange colour
If Br is present, boil the 2 nd part with 1 cm 3 of conc. HNO3 to expel Br2 gas. This treatment
–
ps
can be avoided if Br – ion is absent. Then add AgNO 3 solution. Formation of a curdy white
precipitate confirms the presence of Cl–  ions.
te

  
2Br(aq)  2NO3(aq)  4H (aq) 
 2NO 2(g)  Br2g)  2H 2 O(l)
 
 Ag (aq) 
 AgCl(s)
yS

Cl(aq)

TEST OF CATIONS
ud

Flame Test on Dry Samples

Bunsen Flame :
St

A Luminous Bunsen flame (air holes completely closed)m, about 5 cm long, is employed for
conducting blowpipe test. A reducing flame is produced by placing the nozzle of a mouth pipe
just outside the flame, and blowing gently, so as to cause the inner cone to play on the substance
under examination. An oxidizing flame is obtained by hold holding the nozzle of the blowpipe
about one third within the flame and blowing somewhat more vigorously in a direction parallel
with the burner top, the extreme, tip of the flame is allowed to play upon the substance.

Charcoal Cavity Test :

The test are carried out upon a clean charcoal block in which a small cavity has been made. aA
little of the substance is placed in the cavity and heated in the oxidizing flame, crystalline salts
break into smaller pieces: burning indicates the presence of an oxidizing agent (nitrate, chlorate
etc.). More frequently the powdered substance is mixed with twice its bulk of anhydrous
Na2CO3 or preferably with fusion mixture (an equimolar mixture of together Na 2CO3 and
K2CO3; this has a lower mp than Na2CO3) in a reducing flame. The initial reaction consists of
the formation of the carbonates of the cations present and the alkali salts of anions. The alkali
salts are largely adsorbed by the porous charcoal, and the carbonates are, for the most part,
decomposed into oxides and CO 2. The oxides of the metal may further decompose, or be
reduced to the metals, or they may remain unchanged. The final products of the reaction are,
therefore, either the metals alone, metals and their oxides, or oxides. The oxides of the noble

Page 8 of 29 [Link]
 QUALITATIVE ANALYSIS

metals (Ag and Au) are decomposed without the aid of the charcoal, to the metal, which is
often obtained as a globule and oxygen. tThe oxides of Pb, Cu, Bi, Sb, Sn, Fe, Ni and Co are
reduced either to a fused metallic globule (lead, bismuth, tin and antimony) or to a sintered
mass (copper) or to a glistening metallic fragments (iron, nickel and cobalt). The oxides of
cadmium, arsenic and zinc are readily reduced to the metal but these are so volatile that they
vapourise and are carried from the reducing to the oxidizing flame zone, where they are converted
into sparingly volatile oxides. The oxides thus formed are deposited as an incrustation round
the cavity of the charcoal block, zinc yields an incrustation which is yellow while not hot and
white when cold.
Incrustation of cadmium is brown and is moderately volatile, that of arsenic is white and is
accompanied by a garlic odour due to the volatilization of the arsenic. A characteristic incrustation
accompanies the globules of lead, bismuth and antimony.
The oxides of Al, Ca, Sr, Ba and Mg are not reduced by charcoal; they are infusible and glow
brightly when strongly heated. If the white residue or white incrustation left on a charcoal block
is treated with cobalt nitrate solution and again heated, a bright blue colour, which probably
consists of either a compound or a solid solution of cobalt (II) and aluminium oxide (Thenard’s
blue) indicates the presence of aluminium; a pale green colour, probably of similar composition
(Rinmann’s green), is indicative of zinc oxide; and pale zinc mass is formed when magnesium
oxide is present.

.in
Principle of Charcoal Cavity Test
ZnSO 4  Na 2 CO3 
 ZnCO3  Na 2SO 4
ps
(1:3)

ZnCO3 
 ZnO  CO 2
te

ZnO  C   Zn  CO
yS

Colour of bead, residue or incrustation will be used to diagnose the metal.

Colour of Bead Colour of Residue or Incrustation Inference
White bright bead which Incrustation does not form Ag+
ud

does not impart mark on

paper on rubbing
St

White brittle bead White Incrustation Sb 3+

Red bead Reddish brown incrustation Cu2+
Brittle bead Violet Red when hot and yellow Bi3+
incrustation when cold
White soft ball which mark
on paper Brown incrustation when hot and
yellow when cold Pb 2+
Bead does not from Yellow incrustation when hot while
white when cold Zn2+
–– Garlic smell like fumes As3+
–– Yellow incrustation on hot while on
cold dirty white incrustation Sn
–– Reddish brown incrustation Cd 2+

Page 9 of 29 [Link]
 QUALITATIVE ANALYSIS

–– Incrustation does not form but black

residue is left in the cavity Fe, CO, Ni, Mn
Cobalt Nitrate Bead Test:
This is also like charcoal cavity test. This test is performed in oxidizing flame rather than in
reducing flame.
The oxides of Al, Ca, Sr, Ba and Mg are not reduceding by charcoal; they are infusible and
glow brightly when strongly heated. If the white residue or white incrustation left on a charcoal
block is treated with a drop of cobalt nitrate solution and again heated, a bright blue colour,
which probably consists of either a compound or a solid solution of cobalt II and aluminium
oxide indicates the presence of aluminium. Other colours are listed in Table.
Principle
ZnSO 4  Na 2 CO3 
 ZnCO3  Na 2SO 4 Colour of Residue Inference
ZnCO3 
 ZnO  CO 2 Green Zn2+
2Co(NO3 ) 2 
 2CoO  4NO 2  O 2 Blue Al3+
Light Pink Mg2+
Bluish Pink PO 4 , AsO34 ,
silicates borates
CoO  ZnO 
 CoZnO 2
Cobalt zincate
.in
ps
(green residue)

1. Inner blue cone ADB continuing consisting C

Upper oxidizing zone
largely of unburnt gas.
te

2. A luminous tip at D (this is only visible

D Hottest portion of the flame ( 1 / 3 of L)
when the air holes are slightly closed).
yS

Upper reducing zone

Lower oxidizing zone
3. An outer mantle ACBD in which complete Lower reducing zone
combustion of gas occurs. A B
Lower temperature zone
ud

(Luminous flame is obtained when air holes

are completely closed)
St

(Non luminous flame is obtained when air

holes are completely opened)

Borax Bead Test :

A point wire is used for borax bead test. tThe free end of the point wire is coiled into small loop
through which ordinary match will barely pass. The loop is heated in Bunsen flame until it is red
hot and then quickly dipped into powdered borax Na2B4O710H2O. The adhering solid is held
in the hottest part of the flame, the salt swells up as it loses its water of crystallization and
shrinks upon the loop forming a colourless, transparent, glass like bead consisting of a mixture
of sodium metaborate and boric anhydride.
Na 2 B4 O7   2NaBO 2  B2 O3
the head is moistened and dipped into the finely powdered substance so that a minute amount
of it adheres to the bead. It is important to employ a minute amount of substance as otherwise
the bead will become dark and opaque in the subsequent heating. The head and adhering
substance are first heated in the lower reducing flame, allowed to cool and the colour is observed

Page 10 of 29 [Link]
 QUALITATIVE ANALYSIS

again.
Characteristic coloured beads are produced with salts of Cu, Fe, Cr, Mn, Co and Ni. Carry
out borax bead test with salts of these metals and compare results with those given below:
The coloured borax beads are due to the formation of colour borates; in those cases when
different coloured beads are obtained in the oxidizing and the reducing flames, borates
corresponding to varying stages of oxidation of the metal are produced. Thus, with the copper
salts in the oxidizing flame, one has.
Na 2 B4 O7 
 2NaBO 2  B2 O3
CuO  B2 O3 
 Cu(BO) 2
Copper(II)metaborate

The reaction , CuO  NaBO 2 

 NaCuBO3
Orthoborate

probably also occurs. In the reducing flame (i.e. in the presence of carbon), two reactions may
take place.
1. The coloured copper (II) is reducing to colourless copper (I) metaborate.
2Cu(BO 2 ) 2  2NaBO 2  C   2CuBO 2  Na 2 B4 O7  CO 
2. The copper (II) borate is reduced to metallic copper, that the bead appears red and opaque.
2Cu(BO 2 ) 2  4NaBO 2  2C   2Cu  2Na 2 B4O7  2CO 

.in
With iron salts Fe(BO2)2 and Fe(BO2)3 are formed in reducing and oxidizing flames respectively.
ps
Colours of Borax Beads

Oxidizing Flame Reducing Flame Metal

te

Hot Cold Hot Cold

yS

Green Blue Colourless Opaque Red Copper

brown
ud

Yellowish Yellow Green Green Iron

green
St

Yellow Green Green Green Chromium

Violet Amethyst Coloulrless Colourless Manganese
Blue Blue Blue Blue Cobalt
Violet Reddish Green Grey Nickel
Brown
Yellow Colourless Brown Brown Molybedenum
Rose Violet Rose Violet Red Violet Gold
Yellow Colourless Yellow Yellowish brown Tungeston
Yellow Pale Yellow Green Bottle green Uranium
Yellow Greenish Brownish Green Vanadium
Yellow

Page 11 of 29 [Link]
 QUALITATIVE ANALYSIS

Yellow Colourless Grey Pale violet Titanium

Orange Red Colourless Colourless Colourless Cerium
Group I : Radicals
Pb2+, Hg 22 , Ag+
Group Reagent – dil. HCl
Precipitates as – Chlorides
Since PbCl2 is not completely precipitated in group I as chloride because of its solubility in hot
water is 33.4g/litre of solvent. So Pb 2+ has been placed in both the groups.

Reactions of Pb 2+ ion
1. Dilute HCl: A white ppt. in cold solution of the acid is not too dilute.
Pb2+ + 2 Cl– PbCl2 
White
Soluble in hot water (33.4g/L at 100°C, 9.9 g/L at 20°C)
It is also soluble in conc. HCl or conc. KCl when the tetrachloroplumbate (II) ion is formed.
PbCl2  2Cl   [PbCl 4 ]2
If the ppt is washed and dil. NH3 is added, no visible change occurs (difference from Hg22+ or

.in
Ag+ ions), through a ppt. exchange reaction takes place and lead hydroxide is formed.
2. H2S (gas or saturated aqueous solution) in neutral or dilute acid medium, black ppt. of lead
ps
sulphide is obtained
Pb 2  H 2S  PbS  2H 
te

When H2S gas is introduced into a mixture which contains a ppt. of white lead chloride, the
latter is converted into lead sulphide (black) in a precipitate exchange reaction.
yS

PbCl2   H 2S   PbS  2H   2Cl

If the test is carried out in the presence of larger amounts of Cl– (KCl saturated), initially a red
ud

ppt. of lead sulphochloride is formed when introducing H2S.

2Pb 2  H 2S  2Cl 
 Pb 2SCl2  2H 
St

This, however, decomposes on dilution or on further addition of H 2S and a black ppt. of PbS
is formed.
Pb 2SCl2  
 PbS   PbCl2 
 2PbS  2Cl  2H 
PbSCl2  H 2S 

3. NH3 solution: White ppt of Pb(OH)2 is obtained

Pb 2  2NH 3  2H 2 O   Pb(OH) 2  2H 
Pb(OH)2 is insoluble in NH3 solution excess.
4. NaOH: White ppt. of Pb(OH)2
Pb 2  2OH    Pb(OH) 2 
The ppt. is dissolved in excess of NaOH, when tetrahydroxoplumbate (II) ions are formed.
Pb(OH) 2  2OH   [Pb(OH) 4 ]2
thus, lead hydroxide has an amphoteric character.

Page 12 of 29 [Link]
 QUALITATIVE ANALYSIS

5. H2SO4 (or soluble sulphate) white ppt. of PbSO 4 is obtained

Pb 2  SO 24 
 PbSO 4 
(white)

6. K2CrO4: Potassium chromate in neutral, acetic acid or ammonium solution yellow ppt of lead
chromate is obtained.
Pb 2  CrO 24 
 PbCrO 4  (yellow)

7. KI: yellow ppt of lead iodide is formed.

Pb 2  2I  
 PbI 2 
yellow ppt.

The ppt. is moderately soluble in boiling water to yield a colourless solution, from which it
separates as golden yellow plates on cooling.
An excess of a more conc.(6M) solution of the reagent dissolves the ppt. and tetraiodoplumbate
(II) ions are formed
PbI2  + 2 I– [PbI4]2–
The reaction is reversible, on cooling ppt. reappears.

Reactions of Hg 22+ ions

1. Dilute Hydrochloric acid or Soluble Chlorides: White precipitate of Hg 2Cl 2

.in
(calomel)_ is obtained.
Hg 22  2Cl 
 Hg Cl 
2 2
ps
(white)
Insoluble in dilute acids

Ammonia solution converts the ppt. into a mixture of mercury (II) amidochloride and mercury
te

metal, which are both insoluble.

yS

 Hg  Hg(NH 2 )Cl  NH 4  Cl 
Hg 2Cl 2  2NH 3 
Black White
ud

Shiny back
Mercury (II) chloride dissolves in aqua-regia, forming undissociated but soluble mercury (II)
St

chloride.
2. Hydrogen Sulphide (Gas or Saturated Aqueous Solution): In neutral or dilute
acid medium black precipitate, is obtained which is a mixture of Hg(II) sulphide and mercury
metal.
Hg 22  H 2S 
 Hg  HgS  2H 
Black Black

Sodium sulphide (colourless) dissolves the mercury (II) sulphide (but leaves mercury metal)
and a disulphomercurate (II) complex is formed.
HgS  S2  [HgS2 ]2
After removing the mercury metal by filtration black HgS can again be precipitated by
acidification with dilute mineral acid.
[HgS2 ]2  2H  
 HgS  H 2S 
Black

Sodium disulphate (yellow) dissolves both mercury and mercury (II) sulphide.
HgS   Hg  3SO 24   2[HgS2 ]2  S32
Aqua-regia dissolves the precipitate, yielding undissociated mercury (II) chloride and sulphur.

Page 13 of 29 [Link]
 QUALITATIVE ANALYSIS

12HCl  4HNO3  3Hg  

 6HgCl2  3S  4NO  8H 2 O
White

When heated with aqua-regia, sulphur is oxidized to H2SO4 and the solution becomes clear.
 SO 42  8H   6Cl  2NO 
S  6HCl  2HNO3 
3. Ammonia Solution:
Black ppt. which is a mixture of Hg metal and basic mercury (I) amidonitrate (white ppt.)
NH2
2Hg 22  NO3  4NH 3  H 2O 
 [Link]   2Hg  3NH 4
Black
NO3
white

This reaction can be used to differentiate between Hg 22 and Hg2+ ions.

4. Sodium Hydroxide: Black ppt. of mercury (I) oxide.

Hg 2  2OH  
 Hg 2 O H 2 O
Black
Insoluble in excess [Link]
soluble in dil. HNO3

.in
When boiling, the colour of the ppt. turns to grey, owing to disproportionation, when HgO and
Hg are formed.
ps
Hg 2O  
Boil
HgO   Hg
te

grey

5. Potassium Chromate: In hot solution a red crystalline ppt. of Hg 2CrO4 is obtained..

yS

Hg 22  CrO 24 

 Hg 2 CrO 4 
Red Crystalline (in put)
ud

If the test is carried out in cold, a brown amorphous ppt. with an undefined composition is
obtained, when heated the ppt. turns to red crystalline HgCrO 4.
St

Sodium hydroxide turns into black mercury (I) oxide.

Hg 2 CrO 4  2OH  
 Hg 2 O CrO 42  H 2 O
Red Black

6. KI Solution: Added slowly in cold solution, green ppt. of mercury (I) iodide.
Hg 2  2I  
 Hg 2 I 2 
Green

If excess of reagent is added disproportionation takes place, soluble tetraiodomercurate (II))ions

and a black ppt. of finely divided mercury being formed.
Hg 2 I 2  2I  
[HgI 4 ]2  Hg 
Green Black

Produces a mercury (II) cyanide solution and black ppt. of Hg metal. Is obtained.
Hg 22  2CN  
 Hg  [Hg(CN) 2 ]
Hg(I) ions to mercury metal (grayish black ppt)

Page 14 of 29 [Link]
 QUALITATIVE ANALYSIS

............................ Hg 22  Sn 2 
 2Hg   Sn 4
Greyish-Black

Hg (II) ions react in a similar way.

Reactions of Silver (I) Ions

1. Dilute Hydrochloric Acid (or Soluble Chlorides): White ppt. of AgCl is obtained.
Ag   Cl 
 AgCl 
White

With conc. HCl precipitation does not occur. After decanting from over the ppt., it can be
dissolved in conc. HCl, when dichloroargentate complex is formed.
AgCl  + Cl– [AgCl2]–
On dilution with H2O, the equilibrium shifts back to the left and the ppt. reappears.
Dilute NH3 solution dissolves the ppt., to form the diammine silver ion.
AgCl  + 2 NH3 [Ag(NH3)2]– + Cl–
Dilute HNO3 or HCl neutralizes the excess of NH 3, and the ppt. reappears because the
equilibrium is shifted back towards the left.
KCN dissolves the ppt. with formation of the dicyanoargentate complex.
AgCl  2CN   [Ag(CN) 2 ]  Cl 
Na2S2O3 dissolved the ppt. with the formation of a dithiosulphatoargentate complex.
AgCl  2S2 O32  [Ag(S2 O3 ) 2 ]3  Cl
.in
ps
Sunlight or ultraviolet light decomposes the AgCl precipitates, which turns to grayish or black
owing to the formation of the metal.
h
2AgCl    2Ag   Cl2 
te

2. H2S (Gas or Saturated aqueous Solution): Black ppt. of Ag2S is formed.

yS

2Ag   H 2S 
 Ag 2S  2H 
Black
ud

Hot conc.HNO3 decomposes the Ag2S, and sulphur remains in the form of a white ppt.
 3S  2NO  6Ag   6NO3  4H 2 O
3Ag 2S  8HNO3 
St

white

If the mixture is heated with conc. HNO3 for a considerable time, sulphur is oxidized to SO42–
and the precipitate disappears.
3. Ammonia Solution: Brown ppt. of Ag2O is obtained..
2Ag   2NH 3  H 2 O 
 Ag 2 O  2NH 4
Brown

The reaction reaches an equilibrium and therefore precipitation is incomplete at any stage (if
the NH4NO3 is present in the original solution or the solution is strongly acidic, no precipitation
occurs). The ppt dissolves in excess of NH3 solution, and diammine silver (I) complex is formed.
 2[Ag(NH 3 ) 2 ]  2OH 
Ag 2 O  4NH 3  H 2 O 

4. Sodium Hydroxide: Brown ppt. of AgO is obtained.

2Ag   2OH  
 Ag 2 O  H 2 O
Brown

A well washed suspension of the ppt. shows a slight alkaline reaction owing to the hydrolysis
reaction.
Ag2O + H2O 2 Ag(OH)2  2 Ag+ + 2 OH–
The ppt. is insoluble in excess of NaOH. The ppt. dissolves in NH 3 solution and in HNO3.
Ag2O  + H2O 2 Ag(OH)2  2 Ag+ + 2 OH–

Page 15 of 29 [Link]
 QUALITATIVE ANALYSIS

The ppt. is insoluble in excess of NaOH. The ppt. dissolves in NH 3 solution and in HNO3.
 2[Ag(NH 3 ) 2 ]  2OH 
Ag 2 O  4NH 3  H 2 O 
Ag 2 O  2H  
 2Ag   H 2 O
5. Potassium Iodide: Yellow ppt.. of AgI is obtained.
Ag   I    AgI 
The ppt. is insoluble in dil. or conc. NH3 solution, but dissolves readily in KCN and in Na2S2O3.
AgI  2CN  
[Ag(CN) 2 ]  I 
AgI  2S2 O32 
[Ag(S2 O3 ) 2 ]3  I 

6. Potassium Chromate: Red ppt. of Ag2CrO4 is obtained..

2Ag   CrO 24 
 Ag 2 CrO 4 
Red

The ppt. is soluble in diluted HNO3 acid and NH3 solution.

Ag2CrO4  + 2 H+ 2 Ag+ + Cr2O72– + H2O
Orange
 2[Ag(NH 3 ) 2 ]  CrO 42
Ag 2 CrO 4  4NH 3 

.in
7. Potassium Cyanide: When added drop wise to a neutral solution of AgNO 3; white ppt. of
AgCN is obtained.
ps
Ag   CN  
 AgCN 
White

When KCN is added in excess, ppt. dissolves owing to formation of dicyanoargentate (I) ion.
te

AgCN  CN  
[Ag(CN) 2 ]
yS

Second Group of Cations

ud

Group Reagent H2S in presence of dil. HCl

IIA Cu2+, Pb2+, Bi3+, Cd2+, Hg-2+
St

IIB As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+

Precipitates as Sulphides
Black PbS, CuS, HgS
Yellow CdS, As2S3, As2S5, SnS2
Orange Sb2S3, Sb2S5
Brown Bi2S3, SnS
Cations of IInd group are traditionally divided into two sub-groups the copper sub group and
are arsenic group. The basis of this division is the solubility of the precipitates in
ammoniumpolysulphide. White sulphides of the copper sub-groups are insoluble in this reagent,
those of the arsenic sub-group are soluble in this reagent with the formation of thiosalts.

II A Group :
The copper sub-group consists of Hg(II), Pb(II), Bi(III), Cu(II) and Cd(II). Although the bulk
of the lead ions are precipitated with dil. HCl together with other ions of the group –I, this
precipitation is rather incomplete owing to relatively high solubility of PbCl 2. In the course of
systematic analysis therefore, leads ions will still be present when the precipitation of the second

Page 16 of 29 [Link]
 QUALITATIVE ANALYSIS

group of the cations is the task.

The chlorides, nitrates and sulphates of the cations of the copper sub-group are quite soluble in
water. The sulphides,. Hydroxides and carbonates are insoluble. Some of the ions of copper
sub-group (Hg2+, Cu2+ and Cd2+) tend to form complexes (NH 3, RCOO–, etc.)
II B Group:
The arsenic sub-group consists of As 3+, As5+, Sb3+, Sb5+ and Sn4+ ions. These ions both acids
and bases. Thus As(III) oxide can be dissolved in HCl (6M) and As(III) cations are formed.
 2As3  6Cl   3H 2 O
As 2 O3  6HCl 
(Basic)

The same time As2O3 dissolves in NaOH (2M) forming arsenite anions.
As 2 O3  6OH    2AsO33  3H 2 O
The dissolution of sulphides in ammonium polysulphide can be regarded as the formation of
thiosalts from anhydrous thioacids. Thus the dissolution of As 2S3 (anhydrous thioacid) in
ammonium sulphide (anhydrous thiobase) yield the formation of ammonium and thioaresenite
ions (a thiosalt)
As2S3  + 3 S2–  2 As33–
All the sulphides of the arsenic sub-group dissolve in ammonia sulphide except tin (II) sulphide
(SnS); to dissolve latter, ammonium polysulphide is needed, which acts partly as an oxidizing
agent, thiostannate ions being formed:

.in
SnS  + S22–  SnS32–
Note that while tin is bivalent in the tin (II) sulphide ppt., it is tetravalent in the thiostannate ion.
ps
As3+, Sb3+ and Sn2+ ions can be oxidized to As5+, Sb5+ and Sn4+ ions respectively. On the other
hand, the latter three can be reduced by proper reducing agents. The oxidation reduction
potentials of the arsenic (V), arsenic (III) and Sb (V) – Sb(III) systems vary with pH, therefore
te

the oxidation or reduction of the relevant ions can be assisted by choosing an appropriate pH
of the reaction.
yS

Reactions of Mercury (II) Ions: (HgNO 3)

ud

1. Hydrogen Sulphide (Gas or Saturated Aqueous Solutions): In the presence of

dilute (1M) HCl, initially a white ppt of mercury (II) chlorosulphide forms, which reacts with
further amounts of H2S and finally a black ppt. of HgS is formed.
St

3Hg 2  2Cl 
 Hg 3S2 Cl2  4H 
White

 HgS  2H   2Cl 
Hg 3S2 Cl   H 2S 
Black

HgS is one of the least soluble precipitates known (K sp = 4 × 10–54).

HgS is insoluble in water, hot dilute HNO3, alkali hydroxides or coloulress ammonium sulphide.
Sodium sulphides (2M) dissolves the precipitate when the disulphomercurate (II) complex ion
is formed:
HgS  S2 
[HgS2 ]2
Black

Adding NH4Cl to the solution, HgS precipitates again aqua-regia dissolves the precipitate.
3HgS  6HCl  2HNO3   3HgCl2  3S  2NO  4H 2 O
HgCl2 is practically undissociated under these circumstances. Sulphur remains as a white ppt.,
which however dissolves readily if the solution is heated, to form H2SO4.
 SO 42  2H   2NO 
2HNO3  S  
White

2. Ammonia Solution: White precipitate with a mixed composition is obtained, essentially it

consists of HgO and mercuryoamidonitrate.

Page 17 of 29 [Link]
 QUALITATIVE ANALYSIS

2Hg 2  NO3  4NH 3  H 2 O 

 HgO  Hg(NH 2 )NO3  3NH 4
White

The salt like most of the mercury compounds, sublimes at atmospheric pressure.
3. Sodium Hydroxide: When added in small amounts, brownish-red precipitate with varying
composition is obtained; if added in stoichiometric amounts, the precipitate turns to yellow
when HgO is formed.
Hg 2  2OH  
 HgO  H 2O
Yellow
Insoluble in excess NaOH soluble in acids.

4. Potassium Iodide: When added slowly to the solution, red precipitate of HgI2 is obtained..
Hg 2  2I   HgI 2 (Re d)
The precipitate dissolves in excess reagent, when colourless tetraiodomercurate (II) ions are
formed
HgI 2  2I  
[HgI 4 ]2
Red

An alkaline solution of K 2[HgI4] serves as a selective and sensitive reagent for NH 4 ion
(Nessler’s Reagent).

.in
5. Potassium Cyanide: Does not cause any change in dilute solutions (difference from other
ions of the copper sub-group).
ps
6. Tin (II) Chloride: When added I in moderate amounts, white, silky precipitate of Hg 2Cl2
(calomel)
te

2Hg 2  Sn 2  2Cl   Hg 2 Cl2  Sn 4

yS

This reaction is widely used to remove the excess of Sn (II) ions, used for prior reduction, in
oxidation-reduction titrations.
If more reagent is added, mercury (I) chloride is further reduced and black precipitate of
ud

mercury is formed.
HgCl2  Sn 2 
 2Hg  Sn 4  2Cl
St

7. Cobalt (II) Thiocyanate Test: To the test solution add an equal volume of Co(SCN) 2
(about 10% freshly prepared), and stirr the wall of the vessel with a glass rod. A deep blue
crystalline precipitate of cobalt tetrathiocyanatomercurate (II) is formed.
Hg 2  Co 2  4SCN  
 Co[Hg(SCN) 4 ] 
Deep blue crystalline

Reactions of Copper (II) Ions

1. Hydrogen Sulphide (Gas or Saturated aqueous solution): Black precipitate of
CuS is formed.
Cu 2  H 2S   CuS  2H 
Ksp (CuS) = 10–44
The solution must be acidic (1M in HCl) in order to obtain a crystalline, easily filterable
precipitate. iIn the absence of acid, or in very slightly acid solutions a colloidal, brownish black
precipitate or colouration is obtained. By adding some acid and boiling, coagulation can be
achieved.
The precipitate is insoluble in boiling dilute (1M) H 2SO4 (distinction from Cd), in sodium
hyodrixide, Na2S and (NH4)2S. It is only very slightly soluble in polysulphides.

Page 18 of 29 [Link]
 QUALITATIVE ANALYSIS

Hot conc. HNO3 dissolves the CuS, leaving behind sulphur as a white precipitate.
 3Cu 2  6NO3  3S  2NO  4H 2O
3CuS  8HNO3 
White

When boiled for longer, sulphur is oxidized to H2SO4 and a clear solution is obtained.
S  2HNO3   SO 42  2NO  2H 
KCN dissolves the ppt., when colourless tetra cyano cuprate (I) ions and disulphide ions are
formed.
2CuS  8CN    2[Cu(CN) 4 ]3  S22
This is an oxidation and reduction reaction (cooper is reduced and sulphur is oxidized) coupled
with a formation of a complex.
When exposed to air, in the moist state, CuS tends to oxidize to CuSO 4.
CuS  2O 2   CuSO 4
and therefore becomes water soluble. A considerable amount of heat is liberated during this
process. A filter paper with CuS precipitate on it should never be thrown into a waste container,
with paper or other inflammable substances in it. Instead the precipitate should be washed a
way first with running water.
2. Ammonia Solution: When added slowly blue precipitate of basic copper sulphate is
formed.
2Cu 2  SO 24  2NH 3  2H 2 O 
.in
 Cu(OH) 2 CuSO 4  2NH 4
Blue
ps
Which is soluble in excess reagent, when a deep blue colouration is obtained owing to the
formation of tetrammine copper (II) complex ion.
te

 2[Cu(NH 3 ) 4 ]2  SO 42  2OH 

Cu(OH) 2  CuSO 4  8NH 3 
Blue
yS

If the solution contains NH 4 salt (or it was highly acidic larger amounts of NH3 were used up
for its neutralization) precipitation does not occur at all, but the blue colour appears right away.
ud

The reaction is characteristic for Cu 2+ ions in the absence of Nickel.

3. NaOH: In cold solution blue precipitate of Cu(OH) 2 is formed..
St

Cu 2  2OH  
 Cu(OH) 2 
Blue

The precipitate is insoluble in excess reagent. When heated, the precipitate is converted to
black CuO by dehydration.
Cu(OH) 2  
 CuO  H 2 O
Blue Black

In the presence of a solution of tartaric acid or of nitric acid, copper (II) hydroxide is not
precipitated by solutions of caustic alkalis but the solution is coloured, an intense blue . If the
alkaline solution is treated with certain reducing agents, such as hydroxyl amine, hydrazine,
glucose and acetaldehyde, yellow copper (I) hydroxide precipitated from the warm solution. It
is converted into red copper (I) oxide (Cu 2O) on boiling. The alkaline solution of Cu(II) salt
containing tartaric solution of Cu(II) salt containing tartaric acid is usually known as Fehling
solution; it contains the complex ion [Cu(C4H2O6)2]2–.
4. Potassium Iodide: Precipitates copper (I) iodide, which is white, but the solution is
intensely brown because of formation of triiodide ions.
2Cu 2  5I  
 2CuI   I3

Page 19 of 29 [Link]
 QUALITATIVE ANALYSIS

Adding an excess of Na2S2O3 to the solution triioide ions are reduced to colourless iodide ions
and the white colour of ppt. becomes visible. These reactions are used in quantitative analysis
for the iodometric determination of copper.
5. KCN: When added sparingly forms first a yellow precipitate of copper (II) cyanide.
Cu 2  2CN  
 Cu(CN) 2 
Yellow

The precipitate quickly decomposes into copper (II) cyanide and cyanogens (highly poisonous
gas) is liberated.
2Cu(CN) 2   2CuCN   (CN) 2 
Excess of KCN dissolves the precipitate and the colourless tetracyanocuprate (I) complex is
formed.
CuCN  3CN  
 [Cu(CN) 4 ]3
Colourless

tThe complex is so stable that H 2S cannot precipitate copper I sulphide from this solution
(distinction from Cd).
6. Potassium Thiocyanate (KSCN): Black precipitate of copper (II) thiocyanate is
obtained.
Cu 2  2SCN  
 Cu(SCN) 2 

.in
Colourless

The precipitate decomposes slowly to form white copper (I) thiocyanate and thocyanogen is
formedobtained.
ps
2Cu(SCN) 2  
 2CuSCN  (SCN) 2 
White
te

Thiocyanogen rapidly decomposes in aqueous solution.

yS

7. Potassium Ferrocyanide (K 4[Fe(CN) 6] ) : Chocolate brown colour precipitate of

Cu2[Fe(CN)6] is obtained.
Cu+2 + K4[Fe(CN)6]  Cu2[Fe(CN)6]
ud

Chocolate brown colour ppt.

St

Reactions of Bi 3+ Ions
1. With H 2S (Gas or saturated aqueous solution): Blackish brown precipitate of
Bi2S3 is obtained.
2Bi3  3H 2S 
 Bi 2S3  6H 
Black

Insoluble in cold. Dilute acid in (NH4)2S

Boiling conc. HCl dissolves the precipitate when H2S gas is evolved.
Bi 2S3  6HCl  2Bi3  6Cl  3H 2S 
Hot dil. HNO3 dissolves Bi2S3, leaving behind sulphur in the form of a white precipitate.
Bi 2S3  8H   2NO3 
 2Bi3  3S  2NO  4H 2O

2. With NH3 Solution: White basic salt of variable composition. The approximate chemical
reaction is

Page 20 of 29 [Link]
 QUALITATIVE ANALYSIS

Bi 2S3   NO3  2NH 3  2H 2 O 

 Bi(OH) 2 NO3   2NH 4
white

Bi(OH)2NO3 does not dissolve in excess NH3 (distinction from Cu and Cd)
3. With NaOH: White precipitate of Bi(OH) 3 is obtained.
Bi3  3OH  
 Bi(OH)3 
White

Slightly soluble in excess NaOH

Soluble in conc. HCl and insoluble in dilute HCl
Bi(OH)3  + 3 HCl  BiCl3 + H2O
BiCl3 + H2O  BiOCl 
white turbidity
When boiled precipitate loses water and turns yellowish white
Bi(OH)3  
 BiO  OH  H 2 O
Yellowish white

Both the hydrated and the dehydrated precipitate can be oxidised by 4-6 drops of conc. H 2O2
when yellowish brown bismuth ate ions are formed.
 BiO3  H   H 2 O
BiO  OH   H 2 O 2 

4. Potassium Iodide: When added drop-wise black precipitate of BiI 3 is obtained.

Bi3  3I  
 BiI3 
Black
.in
ps
The precipitate dissolves readily in excess reagent when orange coloured tetraiodobismuthate
ions are formed.
te

B i

3
+ I–
I [BiI4]–
When diluted with H2O, the above reaction is reversed and black precipitates of BiI3 reappear.
yS

5. KI: KI forms no precipitate (distinction from copper). Heating the precipitate with H 2O, BiI3
turns orange owing to the formation of bismuthyl iodide.
ud

 BiOI   2H   2I 
BiI3   H 2 O 
Orange
Bismuthyl iodide
St

6. Sodium Tetrahydroxostannate (II) (0.125M freshly prepared): In cold solution,

Bi3+ ions are reduced to Bismuth metal which separates in the form of a black precipitate. First
the sodium hydroxide present in the reagent reacts with Bi 3+ ions, Bi(OH)3 is then reduced by
tetrahydroxostannate (II) ions to form Bi metal and hexahydroxostannate is formed.
Bi3  3OH  
 Bi(OH)3 
Black

2Bi(OH)3  3[Sn(OH) 4 ]2 

 2Bi  3[Sn(OH)6 ]2

Reactions of Cadmium (II) Ions [Cd 2+]

1. Reaction with H 2S (Gas or saturated aqueous solution): Yellow precipitate of CdS is
obtained.
Cd2+ + H2S CdS  + 2 H+
Yellow

Page 21 of 29 [Link]
 QUALITATIVE ANALYSIS

The reaction is reversible, if the conc. of strong acid in the solution is above 0.5M, precipitation
is incomplete. Conc. acids dissolve the precipitate for the same reason. The ppt is insoluble in
KCN: this distinguishes Cd2+ ions from Cu2+.
2. Ammonia Solution: When added drop wise white precipitate of Cd(OH) 2 is formed.
Cd2+ + 2 NH3 + 2 H2O Cd(OH)2  + 2 NH4+
White
The precipitate dissolves in acid when the equilibrium shifts towards the left.
An excess of NH3 dissolves the precipitate, when tetraammine cadmiate (II) ions are formed.
 [Cd(NH 3 ) 4 ]2  2OH 
Cd(OH) 2  4NH 3 
White Colourless

3. NaOH : White precipitate of Cd(OH) 2

Cd 2  2OH  
 Cd(OH) 2 
White
insoluble in excess NaOH

White precipitate dissolves in dilute acids when equilibrium shifts in the backward direction.
4. KCN : White precipitate of Cd(CN) 2 is obtained when KCN is added slowly to Cd 2+ ions.
Cd 2  2CN  
 Cd(CN) 2 
white

.in
An excess of reagent (KCN) dissolves the precipitate with the formation of tetracyanocadmiate
ions.
ps
Cd(CN) 2  2CN   [Cd(CN) 4 ]2
The colourless complex is not very stable; when H 2S gas is introduced, CdS is precipitated
te

[Cd(CN) 4 ]2  H 2S 
 CdS  2H   4CN 
yellow
yS

(Difference from copper)

Reactions of Sn 2+ Ions
ud

1. H2S (Gas or Saturated Solution): Brown precipitate of SnS, from mildy acidic solutions.
The precipitate is soluble in conc. HCl. It is also soluble in yellow (NH4)2Sn (but not in colourless
St

(NH4)2S) to form a thiostannate treatment of the solution of ammonium thiostannate with an

acid yields a yellow precipitate of SnS2.
Sn 2  H 2S 
 SnS  2H 
SnS  S22 
 SnS32
SnS32  2H  
 SnS2   H 2S 

2. NaOH Solution: White precipitate of Sn(OH) 2, soluble in excess alkali.

Sn2+ + 2 OH– Sn(OH)2 
White
Sn(OH)2 + 2 OH –
[Sn(OH)4]2–
With NH3 solution, white Sn(OH)2 is precipitated which cannot be dissolved in excess NH3.
3. HgCl2 Solution: White precipitate of Hg2Cl2 and finally Hg metal (black)

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 QUALITATIVE ANALYSIS

HgCl2  Sn 2 
 Sn 4  Hg 2 Cl2 
White

Hg 2 Cl2  Sn 2 
 Sn 4  2Hg  2Cl
Black

Reactions of Sn Ions 4+

1. Hydrogen Sulphide: Yellow precipitate of Sn(IV) sulphide SnS 2 from dil. Acid solution.
The precipitate is soluble in conc. HCl in solution of alkali hydroxide and also in (NH 4)S and
(NH4)2Sn. Yellow SnS2 is precipitate upon acidification.
Sn 4  2H 2S 
 SnS2  4H 
SnS2  S2 
 SnS32
SnS2  2S22 
 SnS32  S32
SnS32  2H  
 SnS2   H 2S 

2 NaOH: NaOH solution  gelatinous precipitation precipitate (white) of Sn(OH) 4 soluble in

excess of the precipitant forming hexahydroxostannate (VI).
Sn 4  4OH  
 Sn(OH) 4 
Sn(OH)4  + 2 OH– [Sn(OH)6]2– 
3. With HgCl2: No precipitate (difference from Sn(II))
.in
ps
4. Metallic Iron: Reduces Sn 4+ ions to Sn2+
Sn 4  Fe 
 Fe 2  Sn 2
te

Third Group of Cations: Fe 2+, Fe3+, Al3+, Cr3+, Cr6+

yS

Group Reagent NH4OH in presence of NH4Cl

ud

Fe(OH)3 Red Brown

Al(OH)3 Gelatinous white
St

Cr(OH)3 Green (cotton like)

Reactions of Fe 3+ ions
1. NH3 Solution: Reddish brown, gelatinous precipitate of Fe(OH)3 insoluble in excess of the
reagent, but soluble in acids.
Fe3  2NH 3  3H 2 O 
 Fe(OH)3  3NH 4
(K sp 3.81038 )

Iron (III) hydroxide is converted during strong heating into Fe 2O3 the ignited oxide is soluble
with difficulty in dilute acids, but dissolves in vigorous boiling with conc. HCl.
2Fe(OH)3  
 Fe 2 O3  3H 2 O
Fe 2 O3  6H  
 2Fe3  3H 2 O
2. NaOH Solution: Reddish brown precipitate of Fe(OH) 3 in solute in excess of NaOH.
Fe3  3OH  
 Fe(OH)3 
Reddish brown

3. Hydrogen Sulphide: In acidic solution reduces Fe 3+ to Fe2+ and sulphur is formed as a

milky white precipitate.
2 Fe3+ + H2S  2 Fe+2 + 2 H+ + S 

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 QUALITATIVE ANALYSIS

White
If a neutral solution of FeCl3 is adds to a freshly prepared, saturated solution of H 2S, a bluish
colouration appear first, followed by the precipitation of sulphur. The blue colour is due to a
colloidal solution of sulphur of extremely small particle size.
4. Ammonium Sulphide: A black precipitate, consisting of Fe and sulphur is formed.
2Fe3  2S2  2FeS  S 
In HCl and black FeS precipitate dissolves and white colour of sulphur becomes visible.
FeS  2H    H 2S   Fe 2
From alkaline solution black iron (II) sulphide is obtained.
2Fe3  3S   Fe 2S3 
On acidification with HCl, Fe3+ ions are reduced to Fe2+ and sulphur is formed.
Fe2S3  4H    2Fe3  2H 2S  S 
The damp iron (II) sulphide precipitate, when exposed to air, is slowly oxidized to brown
Fe(OH)3.
4FeS  6H 2 O  3O 2 
 4Fe(OH)3  4S
Reddish brown

5. KCN: When added slowly, produces a reddish brown precipitate of Fe(CN) 3.

Fe3  3CN  
 Fe(CN)3 
Reddish brown
.in
ps
In excess, reagent dissolves giving a yellow solution, when hexacyanoferrate (III) ions are
formed.
Fe(CN)3  3CN  
[Fe(CN)6 ]3
te

6. K4[Fe(CN)6]: Solution intense blue precipitate of Fe(III) hexaycnoferrate (Prussian blue)

yS

4Fe3  3[Fe(CN)6 ]4 

 Fe 4 [Fe(CN)6 ]3 
Iron (III)hexcyanoferrate(II)
ud

(Prussian blue)

The precipitate is insoluble in dilute acids, but decomposes in conc. HCl. A large excess of the
reagent dissolves it partly or entirely, when an intense blue solution is obtained. NaOH turns
St

the precipitate red as Fe 2O3 and [Fe(CN)6]4– ions are formed.

Fe 4 [Fe(CN)6 ]3  12OH  
 4Fe(OH)3  3[Fe(CN)6 ]4
7. K3[Fe(CN)6]: A brown colouration is produced due to the formation of an undissociated complex,
Iron (III) hexacyanoferrate (III).
Fe3  [Fe(CN)6 ]3 
 Fe[Fe(CN)6 ]
Brown

Reactions of Al 3+ Ions
1. Ammonia Solution: White gelatinous precipitate of Al(OH)3, slightly soluble in excess of
reagent. The solubility is decreased in presence of NH4+ ions. A small proportion of the precipitate
passes into the solution as colloidal Al(OH)3 (Al(OH)3 solution), the solution is coagulated on
boiling the solution or upon the addition of soluble salts (e.g. NH4Cl) yielding a precipitate of
Al(OH)3, known as Al(OH)3 gel. The To ensure complete precipitation of NH 3 solution is
added in slight excess and the mixture is boiled until the liquid has a slight odour of NH3. When

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 QUALITATIVE ANALYSIS

freshly precipitated, it dissolves readily in strong acids and bases, but after boiling it becomes
sparingly soluble.
Al3  3NH3  3H 2 O 
 Al(OH)3  3NH 4
2. Sodium Hydroxide: White precipitate of Al(OH) 3 is obtained.
Al3  3OH  
 Al(OH)3 
White

The precipitate dissolves in excess NaOH forming tetrahydroxoaluminate (III) iron.

Al(OH)3  + OH– [Al(OH)4]–
The reaction is a reversible one, and any reagent which will reduce the OH – concentration
sufficiently should cause the reaction to proceed from sight to left with the consequently
precipitation of Al(OH)3. This may be effected by AlCl 3 or by adding the acid; in the latter
cause, a large excess of acid, in the latter case, a large excess of acid causes the precipitated
hydroxide to redissolve.
[Al(OH) 4 ]  NH 4 
 Al(OH)3   NH 3   H 2O
[Al(OH)4]– + H+ Al(OH)3  + H2O
Al(OH)3  + 3 H +
Al3+ + 3 H2O
The precipitation of Al(OH)3 by solutions of NaOH and NH3 does not take place in the presence
of tartaric acid, citric acid because of the formation of soluble complex salt.
3.
.in
Ammonium Sulphide Solution: A white precipitate Al(OH) 3 is obtained.
ps
2Al3  3S2  6H 2 O 
 2Al(OH)3  3H 2S 

4. Sodium Acetate Solution: No precipitate is obtained in cold, neutral solution, but on

te

boiling with excess reagent, a voluminous precipitate of basic aluminium acetate

yS

Al(OH)2(CH3COO) is formed
Al3  3CH 3COO   2H 2 O 
 Al(OH) 2 (CH 3COO)  2CH 3COOH
White
ud

Reactions of Cr 3+ Ions
1. Ammonia Solution: Green-grey or grey-blue gelatinous precipitate of Cr(OH) 3, slightly
St

soluble in excess of reagent in cold forming a violet or pink solution containing complex
hexamine chromium (III) ion; upon boiling the solution, Cr(OH) 3 is precipitated. Hence for
complete precipitation of chromium as the hydroxide, it is essential that the solution be boiling
and excess aqueous ammonia solution be avoided.
Cr 3  3NH 3  3H 2 O 
 Cr(OH)3  3NH 4
Cr(OH)3  6NH 3  [Cr(NH 3 )6 ]3  3OH 
In the presence of acetate ions and the absence of other trivalent metal ions, Cr(OH) 3 is not
precipitated. The precipitation of Cr(OH) 3 is also prevented by tartarates and citrates.
2. Sodium Hydroxide Solution: The green-grey ior grey blue precipitates of Cr(OH) 3 is
obtained..
Cr 3  3OH    Cr(OH)3 
The reaction is reversible; the addition of the acids, the precipitates readily,
tetrahydroxochromate (III) ions are formed
Cr(OH)3  + OH– [Cr(OH)4]–
Green
The solution is green. The reaction is reversible on (slight) acidification and also on boiling
Cr(OH)3 precipitates again.

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 QUALITATIVE ANALYSIS

On adding H2O2 to alkaline solution of [Cr(OH)4]–, a yellow solution is obtained, owing to the
oxidation of Cr3+ to CrO42-.
2[Cr(OH) 4 ]  2H 2 O 2  2OH  
 2CrO 42  8H 2 O
Yellow

3. Sodium Carbonate Solution: Precipitate of Cr(OH) 3 is obtained.

2Cr 3  3CO32  3H 2 O 
 2Cr(OH)3  3CO 2 

4. Chromate Test: Cr3+ ions can be oxidized to CrO 42– in several ways
(a) Adding an excess of NaOH to a Cr3+ salt followed by a few ml of 10% H 2O2. The
excess of H2O2 can be removed by boiling the solution for few minutes.
2[Cr(OH) 4 ]  3H 2 O 2  2OH  
 2CrO 42  8H 2 O
Yellow

(b) Oxidation can be carried out by Br2/H2O in alkaline solution (i.e. by OBr–).
2Cr 3  3OBr   10OH    2CrO 42  3Br   5H 2 O
(c) In acid solution Cr3+ ions can be oxidized by potassium (or ammonium) peroxodisulphate.
2Cr 3  3S2 O82  8H 2 O 
 2CrO 42  16H   6SO 42

Identification of CrO 42–:

.in
Having carried out the oxidation with one of the methods are described above, CrO42– ions can
be identified by anyone of the following methods.
BaCl2 Test: After acidifying the solution with CH 3COOH and adding BaCl 2, a yellow
ps
(a)
precipitate of BaCrO4 is formed.
Ba 2  CrO 24 
 BaCrO 4 
te

Yellow
yS

(b) Chromium Pentoxide (or Peroxide) Test :

On acidifying the solution with dil. H 2SO4 adding 2 to 3 ml of ether or amyl alcohol to the
ud

mixture and finally adding some H2O2, a blue coloration is formed . During the reaction CrO5 is
formed.
CrO 24  2H   2H 2 O 2 
 CrO5  3H 2 O
St

Blue colour

In aqueous solution blue colour fades spidlyspeedily,, because CrO 5 decomposes to Cr3+ and
oxygen.
4CrO5  12H  
 4Cr 3  7O 2  6H 2O

(c) Pb (OAc)2 Test : On acidification with acetic acid , followed by addition of lead acetate gives
PbCrO4 (yellow ppt.)
Pb+2 + CrO4–2  PbCrO4
(yellow ppt.)

Radicals of Group IV
Radicals Co2+, Ni2+, Zn2+, Mn2+
Group Reagent H2S in presence of NH 4OH and NH4Cl
Black CoS, NiS
Pink MnS
White ZnS

Group V of Cations

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 QUALITATIVE ANALYSIS

Radicals Ba2+, Sr2+, Ca2+

Group Reagent (NH4)2CO3 in presence of NH 4OH
Precipitates as Carbonates
White BaCO3, SrCO3, CaCO3
Reactions of Ba 2+ ions
1. Reactions with NH 3 Solution: No precipitate OF Ba(OH) 2 is obtained because of its
relatively high solubility. If the alkaline solution is exposed to the atmosphere some CO2 gas is
absorbed and a turbidity due to BaCO 3 is produced.
2. (NH4)2CO3 Solution: White precipitate of BaCO3, soluble in acetic acid and dilute mineral
acids
Ba 2  CO32 
 BaCO3 
White

The precipitate is slightly soluble in ammonium salts of strong acids.

3. (NH4)2C2O4 Solution: A white precipitate of Ba(C 2O4) is obtained slightly soluble in water
(0.09 g L–1) but readily dissolved by hot dilute acetic acid (distinction from Ca2+) and by mineral
acid.
Ba2+ + C2O42– Ba(COO)2 
4. Dilute Sulphuric Acid: Heavy, white, finely divided precipitate of BaSO4, practically insoluble

.in
in water (2.5 × 10 –3 g/L), almost insoluble in dilute acids and in (NH 4)2SO4 solution, but
appreciably soluble in boiling conc. H2SO4. By precipitation in boiling solution, or preferably in
ps
the presence of NH4OOCCH3, a more readily filterable form is obtained.
Ba 2  SO 24 
 BaSO 4 
te

BaSO 4  H 2SO 4  Ba 2  2HSO 4

yS

If BaSO4 is boiled with a conc. solution of Na2CO3 partial transformation into the less soluble
BaCO3 occurs in accordance with the equation.
BaSO4  + CO32– BaCO3  + SO42–
ud

Owing to the reversibly of the reaction, the transformation is incomplete. BaSO 4 precipitate
may also be dissolved in a hot 5% solution disodium ethylene diammine tetracetae (Na2EDTA]
St

in the presence of NH3.

5. Saturated CaSO4 Solution: Immediate white precipitate of BaSO4. A similar phenomenon
occurs if saturated SrSO4 is used.
This is because of the three alkaline earth metal sulphates, BaSO 4 is the least soluble. In the
solutions of saturated CaSO4 or SrSO4 the concentration of SO42– ion is high enough to cause
precipitation with larger amounts of Ba2+, because the product of ionic concentrations exceeds
the value of the solubility product.
SO42– + Ba2+ BaSO4 
6. K 2CrO 4 Solution: A yellow precipitate of BaCrO 4, practically insoluble in water
(3.2 mg L–1)
Ba 2  CrO 24 
 BaCrO 4 
Yellow

The precipitate is insoluble in dilute CH3COOH (distinction from Ca2+ and Sr2+ ions), but readily
soluble in mineral acids.
The addition of acid to K2CrO4 solution causes the yellow colour of the solution to change to
reddish orange, owing to the formation of dichromate.
2 CrO42– + 2 H+ Cr2O72– + H2O
The solubility products for SrCrO 4 and CaCrO4 are much larger than for BaCrO 4 and hence

Page 27 of 29 [Link]
 QUALITATIVE ANALYSIS

they require a larger CrO42– ion concentration to precipitate them. The addition of acetic acid
to the K2CrO4 solution lowers to the CrO 42– ion concentration sufficiently to prevent the
precipitation of SrCrO4 and CaCrO4 but it is maintained high enough to precipitate BaCrO 4.

Reactions of Ca 2+ Ions
1. Ammonia Solution: No precipitate as Ca(OH)2 is fairly soluble. With an aged precipitant
a turbidity may occur owing to the formation of CaCO 3.
2. (NH4)2CO3 Solution: White amorphours precipitate of CaCO 3 is obtained..
Ca 2  CO32   CaCO3 
On boiling the precipitate becomes crystalline. The precipitate is soluble in water which contains
excess carbonic acid (freshly prepared soda water) because of the formation of soluble
Ca(HCO3)2.
CaCO3  + H2O + CO2 Ca2+ + 2 HCO32–
On boiling, precipitate appears again, because CO 2 is removed during the process and the
reaction proceeds towards the left. Ba 2+ and Sr2+ ions reacts in a similar way.
The precipitate is soluble in acids, even in CH3COOH.
3. Dilute Sulphuric Acid: White precipitate of CaSO 4 is obtained.
Ca 2  SO 24 
 CaSO 4 
.in
The precipitate is appreciably soluble in water, i.e., more soluble than BaSO 4 and SrSO4. In
ps
the presence of C2H5OH solubility is much less.
CaSO4 + H2SO4 2 H+ + [Ca(SO4)2]2–
te

The same complex is formed if a precipitate is heated with a 10% of (NH 4)2SO4, leading to
partial dissolution.
yS

4. (NH4)2C2O4 Solution: White precipitate of CaC 2O4, immediately from concentrated and
slowly from dilute solution.
ud

Ca 2  C2 O 42 
 Ca(C2O 4 ) 
Precipitation is fascilitated by making the solution alkaline by NH3. The precipitate is practically
St

insoluble in H2O and CH3COH but readily soluble in mineral acids.

5. K2CrO4 Solution: No precipitate from dilute solution nor from conc. solution in the presence
of CH3COOH.
6. K4[Fe(CN)6] Solution: White precipitate of a mixed salt is obtained..
Ca 2  2K   [Fe(CN)6 ]4   K 2Ca[Fe(CN)6 ] 
In the presence of NH 4Cl the test is more sensitive. In this case potassium is replaced by
ammonium ions in the precipitate. The tests can be used to distinguish calcium from strontium,
barium and Mg2+ ions however interfere.

Reaction of Sr2+ (strontium) : Strontium sulphate is insoluble and precipitated by the addition of

Page 28 of 29 [Link]
 QUALITATIVE ANALYSIS

ammonium sulphate solution.

Sr (CH3COO)2 + (NH4)2 SO4  SrSO4 + 2 CH3COONH4
White ppt.

Sixth Group of Cations : Mg 2+, Na+, K+

Group Reagent No common group reagent
Reaction of Mg 2+ ions
1. Ammonium Solution: Partial precipitation of white gelatinous Mg(OH) 2.
Mg 2  2NH 3  2H 2 O   Mg(OH) 2  2NH 4
The precipitate is very sparingly soluble in water (1.2 × 10–2g/L) but readily soluble in ammonium
salts.
2. NaOH Solution: White precipitate of Mg(OH) 2, insoluble in excess NaOH, but readily
soluble in NH4+ salts.
Mg 2  2OH  
 Mg(OH) 2 

3. (NH4)2CO3 Solution: In the absence of NH4+ salts, a white precipitate of basic magnesium
carbonate is obtained..
5Mg 2  6CO32  7H 2 O 
.in
 4MgCO3  Mg(OH) 2  5H 2O  2HCO3
In the presence of NH4+ salts, no precipitation occurs, because the equilibrium is shifted to left
ps
NH4+ + CO32– NH3 + HCO3–
te

4. Na2CO3 Solution: White voluminous precipitate of basic carbonate as above is formed,

insoluble in bases but readily soluble in acids and in solutions of NH4+ ions.
yS

5. Na2HPO4 Solution: White crystalline precipitate of Mg(OH) 4PO46H2O in the presence of

NH4Cl (to prevent precipitation of Mg(OH) 2) and NH3 solution).
ud

Mg 2  NH3  HPO 42   MgNH 4 PO 4 

The precipitate is sparingly soluble in water, soluble in CH 3COOH and in mineral acids. The
St

precipitate separates slowly from dilute solutions because of its tendency, to form supersaturated
solutions, this may usually be overcome by cooling and by rubbing the test tube or beaker
beneath the surface of the liquid with a glass rod.
A white flocculants precipitate of MgHPO4 is produced in neutral solutions.
Mg 2  HPO 42 
 MgHPO 4 

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