E0289

Based on the Board's New Textbook
Salient features :
1. A complete book for understanding the syllabus of Chemistry XII.
2. Chapter Outline, Important Terms, Units, Laws, Formulae, Properties and Reactions given at
the beginning of each chapter.
3. Model answers to all the textual questions as well as additional questions for understanding
basic and advanced concepts given in the Textbook.
4. Answers to inquisitive and brain stimulating questions under the titles ‘Can you tell ?’,
‘Just think’, ‘Use your brain power’, etc. are given in each chapter.
5. Includes important questions from NCERT book for reference.
6. Includes well-formulated ample number of Multiple Choice Questions (MCQs).
7. Simple and lucid language.
8. Neat fully-labelled, authentic and easily-reproducible diagrams.
9. Very useful book to understand the subject well and to prepare thoroughly for HSC Board
Examination as well as other competitive examinations like NEET, JEE MAIN, MHT-CET, etc.
By
NAVNEET
New Edition : 2020
E0289
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Published by : Navneet Education Limited, Dantali, Gujarat. 2001

CTP
Printed by : Navneet Education Limited, Dantali, Gujarat. (30-6-2020)
2
PREFACE
It gives us great pleasure to present you this first edition of Navneet Chemistry Digest (Part II) for
Standard XII. This book is prepared according to the Maharashtra Board’s New Textbook and latest
question pattern.
We understand that the Higher Secondary Examination is very crucial in a student’s career. As in the
past, this Navneet Digest will help you to triumph.
Each chapter of the Digest begins with important Terms, Units, Laws, Formulae, Properties, Reactions,
etc. for instant revision. This book includes all the questions given in the Board’s Textbook as well as
important questions from NCERT book and also many additional questions with their model answers
so as to cover every concepts given in the Textbook.
Besides these, all the other questions or informations given in various boxes in the textbook such as
'Can you tell?', ‘Do you know?’, 'Use your brain power', 'Observe and discuss', etc. are also included.
Ample number of Multiple Choice Questions (MCQs) have been given to enable the students to prepare
for any type of competitive examination, such as NEET, JEE MAIN, MHT-CET, etc.
Neat, accurate and easily reproducible diagrams are given in each chapter.
In short, this Chemistry Digest contains a lucid and clear explanation of the subject matter in simple
language.
We hope this Digest will help the students to master the subject. Besides it will also help them to secure
excellent marks in the examination and pave the way for realising their dreams of a bright and fruitful
career.
We have taken utmost care to see that this Digest proves to be very useful to the students as well as
the teachers. Suggestions for improvement of the Digest are most welcome and will be gratefully
acknowledged and appreciated.
—The Publishers
3
CONTENTS
Page No.
9. Coordination Compounds . . . 155
10. Halogen Derivatives . . . 150
11. Alcohols, Phenols and Ethers . . . 116
12. Aldehydes, Ketones and Carboxylic Acids . . . 189
13. Amines . . . 277
14. Biomolecules . . . 339
15. Introduction to Polymer Chemistry . . . 383

16. Green Chemistry and Nanochemistry . . . 418
Chapter Nos. 1 to 8 are included in Chemistry Digest: Part 1, published separately.
4
9 COORDINATION COMPOUNDS
COORDINATION COMPOUNDS
CHAPTER OUTLINE
Page No.
.... Important Terms … 6
.... Exercises
9.1 Introduction … 7
9.2 Types of ligands … 7
9.2.1 Monodentate ligands … 7
9.2.2 Polydentate ligands … 7
9.2.3 Ambidentate ligand … 7
9.3 Terms used in coordination chemistry … 9
9.3.1 Coordination sphere … 9
9.3.2 Charge number of complex ion and oxidation state of metal ion … 9
9.3.3 Coordination number (C.N.) of central metal ion … 9
9.3.4 Double salt and coordination complex … 9
9.3.5 Werner theory of coordination complexes … 9
9.4 Classification of complexes … 13
9.4.1 Classification on the basis of types of ligands … 13
9.4.2 Classification on the basis of charge on the complex … 13
9.5 IUPAC nomenclature of coordination compounds … 15
9.6 Effective Atomic Number (EAN) Rule … 17
9.7 Isomerism in coordination compounds … 19
9.7.1 Stereoisomers … 19
9.7.2 Structural isomers (Constitutional isomers) … 19
9.8 Stability of the coordination compounds … 30
9.8.1 Factors which govern stability of the complex … 30
9.9 Theories of bonding in complexes … 31
9.9.1 Valence Bond Theory (VBT) … 31
9.9.2 Octahedral complexes … 33
9.9.3 Tetrahedral complexes … 33
9.9.4 Square planar complex … 33
9.9.5 Limitations of VBT … 33
9.9.6 Crystal Field Theory (CFT) … 38
9.9.7 Factors affecting Crystal Field splitting parameter ( ) … 38

9.9.8 Colour of the octahedral complexes … 38
9.9.9 Splitting of d-orbitals in tetrahedral and octahedral complexes … 38
9.10 Applications of coordination compounds … 46
.... Multiple Choice Questions … 47
9. COORDINATION COMPOUNDS 5
1. Coordination compound : It consists of a central metal atom or ion surrounded by atoms, molecules or
anions called ligands bonded by coordinate bonds, e.g. cisplatin, Pt (NH ) Cl , [Cu(NH ) ]SO .

2. According to Werner’s theory, metal atom or ion in the complex has primary valence (outer sphere) and
secondary valence (inner sphere).
3. Coordination number (C.N.) : The number of ligand donor atoms directly bonded to the central metal atom
or ion by coordination bonds or number of electron pairs involved in the coordinate bonds is coordination
number (C.N.).
; (i) Monodentate ligands (Cl\, OH\, NH , H O, etc.)

; (ii) Bidentate (en, C O\ etc.)

4. Ligands : IIIII; (iii) Tridentate (dien)
; (iv) Tetradentate (trien)
; (v) Hexadentate (EDTA)
5. Classification of complexes on the basis of types of ligands :
(1) Homoleptic complexes Ni(CO) , [Co(NH ) ]Cl

(2) Heterleptic complexes [Co(NH ) Cl H O]Cl

6. Classification of complexes on the basis of charge :
(1) Cationic sphere complexes, [Zn(NH ) ]>, [Co(NH ) Cl]>

(2) Anionic sphere complexes, [Ni(CN) ]\, [Fe(CN) ]\

(3) Neutral sphere complexes, [Pt(NH ) Cl ], [Ni(CO) ]

7. Effective atomic number : EAN:Z9X;Y
8. Isomerism in complexes : (1) Stereoisomerism : (i) Geometrical isomerism
(ii) Optical isomerism
(2) Structural isomerism : (i) Ionisation isomerism
(ii) Linkage isomerism
(iii) Coordination isomerism
(iv) Solvate isomerism
; (i) Valence bond theory (VBT)
; (ii) Crystal field theory (CFT)
9. Bonding in complexes : IIIIIII
; (iii) Ligand field theory (LFT)
; (iv) Molecular orbital theory (MOT)
10. Valence bond theory (VBT) : A central metal atom or ion undergoes hybridisation like sp, dsp, dsp, etc.
forming hybridised orbitals to accommodate the lone pairs of electrons from the ligands.
11. (1) Inner complex : (n91) d orbitals of metal are used
(2) Outer complex : nd orbitals of metal are used.
12. Crystal field theory (CFT) :
Degenerate d-orbitals : dxy , dyz , dzx , d(x9y) and dz
6 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

13. Crystal field splitting :
(1) For octahedral complex :
(2) For tetrahedral complex :
14. Factors affecting stability of the complex : (1) Charge to size ratio of the metal ion
(2) Nature of ligands
; (1) In biology
; (2) In medicines
15. Applications of the coordination compounds : ––
; (3) To estimate hardness of water
; (4) In electroplating
(★ ) Indicates question from the textbook.
Units
9.1 Introduction
9.2 Types of ligands
9.2.1 Monodentate ligands
9.2.2 Polydentate ligands
9.2.3 Ambidentate ligand
Q. 1. What are double salts ? (1 mark)

Ans. Double salts are crystalline molecular or addition compounds containing more than one salt in simple molecular
proportions soluble in water and in solution they ionise and exhibit all the properties of the constituent ions.
For example, K SO · Al (SO ) ·24H O

K SO · Al (SO ) · 24H O(aq) IIIIIJ 2K>(aq) ;2Al>
(aq) ;4SO4(aq) ;24H O(l)
29
■
Q. 2. Define coordination compound. (1 mark)

Ans. Coordination compound : It consists of a central metal ion or atom surrounded by atoms, molecules or anions
called ligands by coordinate bonds, e.g. cisplatin Pt(NH ) Cl , [Cu(NH ) ]SO . ■

Q. 3. Define Lewis bases and Lewis acids with respect to a coordination compound. (2 marks)
Ans. Lewis bases : In a coordination compound the ligands being electron pair donors they are Lewis bases.
Lewis acids : The central metal atom or ion being electron acceptor behaves as a Lewis acid.
For example, in the coordination compound, [Cu(NH ) ]>, NH is a Lewis base and Cu> is a Lewis acid. ■

Q. 4. Write the formula of anticancer drug cisplatin. (1 mark)
Ans. Cisplatin : or Pt(NH ) Cl .

■
★ Q. 5. Name the Lewis acids and bases in the complex [Pt Cl (NH ) ]. (1 mark)

Ans. Lewis acid : Pt2;
Lewis bases : Cl\ and NH ■

★ Q. 6. What are ligands ? What are their types ? Give one example of each type. (4 marks)
Ans. Ligands : The neutral molecules or negatively charged anions (or rarely positive ions) which are bonded by
coordinate bonds to the central metal atom or metal ion in a coordination compound are called ligands or donor
groups. For example in [Cu(CN) ]\, four CN\ ions are ligands coordinated to central metal ion Cu>.

Ligands can be classified on the basis of number of electron donor atoms in the ligand i.e. denticity.
(1) Monodentate or unidentate ligand : A ligand molecule or an ion which has only one donor atom with a lone pair
of electrons forming only one coordinate bond with metal atom or ion in the complex is called monodentate or
unidentate ligand. For example NH , Cl\, OH\, H O, etc.

(2) Polydentate or multidentate ligand : A ligand molecule or an ion which has two or more donor atoms with the
lone pairs of electrons forming two or more coordinate bonds with the central metal atom or ion in the complex is
called polydentate or multidentate ligand. For example, ethylene diamine, H N–(CH ) –NH .

According to the number of donor atoms they are classified as follows :
(i) Bidentate ligand : This ligand has two donor atoms in the molecule or ion. For example, ethylenediamine,
H N–(CH ) –NH .

(ii) Tridentate ligand : This ligand molecule has three donor atoms or three sites of attachment.
.. .. ..
E.g. Diethelene triamine, H N –CH –CH – NH –CH –CH – NH . This has three N donor atoms.

(iii) Tetradentate (or quadridentate) ligand : This ligand molecule
has four donor atoms.
Eg. Triethylene tetraamine which has four N donor atoms.
(iv) Hexdentate ligand : This ligand molecule has six donor atoms. E.g. Ethylenediamine tetracetato.
(3) Ambidentate ligand : A ligand molecule or an ion which has two or more donor atoms, however in the formation
of a complex, only one donor atom is attached to the metal atom or an ion is called ambidentate ligand. For
example, NO\ which has two donor atoms N and O forming a coordinate bond, M < ONO (nitrito) or M < NO

(nitro).

(4) Bridging ligand : A monodentate ligand having more than one lone pairs of electrons, hence can attach to two or
more metal atoms or ions and hence acts as a bridge between different metal atoms is called bridging ligand.
For example : OH\, F\, SO\ , etc. ■

★ Q. 7. What are bidentate ligands ? Give one example. (1 mark)
Ans. For answer, refer to Q. 6 (2) (i). ■
Use your brain power !

(Textbook page 192)
Q. Draw Lewis structures of the following ligands and identify the donor atom in them :
NH , H O.

Ans.
Ligand Lewis dot structure Donor atom
NH N

H O O

Units
9.3 Terms used in coordination chemistry
9.3.1 Coordination sphere
9.3.2 Charge number of complex ion and oxidation state of metal ion
9.3.3 Coordination number (C.N.) of central metal ion
9.3.4 Double salt and coordination complex
9.3.5 Werner theory of coordination complexes
Q. 8. Define coordination sphere. Give example. (2 marks)

Ans. Coordination sphere : A coordination entity consisting of a central metal atom or ion and the coordinating
groups like neutral molecules or anions (ligands) written inside a square bracket is together called coordination
sphere. This is a discrete structural unit. The ionisable groups (generally ions) called counter ions are written
outside the bracket.
For example, in the coordination compound K [Fe(CN) ], the coordination sphere is [Fe(CN) ]\ while K>

represents counter ion. ■
Try this …
(Textbook page 193)
Q. Can you write ionisation of [Ni (NH ) ] Cl ?

Ans. [Ni (NH ) ] Cl IIIIIJ [Ni (NH ) ]2; ;2Cl 9

Q. Identify coordination sphere and counter ions.
Ans. Coordination sphere : [Ni (NH ) ]>

Counter ions : Cl\
Q. 9. Define and explain charge number of a complex ion. (2 marks)
Ans. Charge number of a complex ion : The net charge carried by a complex ion or a coordination entity is called
its charge number.
Explanation :
(i) Charge number is equal to the algebraic sum of the charges carried by central metal atom or ion and all the ligands
attached to it.
(ii) E.g. consider anionic complex, [Fe(CN) ]\.

Charge number of [Fe(CN) ]\:Charge on Fe> ions;6;charge on CN\:(;2);6(91):94

Hence charge number of [Fe(CN) ]\ is 94. ■

Q. 10. Explain the oxidation state of a metal in a complex. (2 marks)
Ans.
(i) The oxidation state of a metal atom or ion in the complex is the apparent charge carried by it in the complex.
(ii) It depends upon the atomic number and electronic configuration of the metal atom or ion.
(iii) The coordination number, the formula and geometry of a complex depend upon the oxidation state of the metal
atom or ion. ■
Q. 11. What is the charge on a monodentate ligand X in the complex, [NiX ]\ ? (2 marks)

Ans. The charge number of the complex ion is 92. Nickel being divalent, its oxidation state is ;2. If the charge on
monodentate ligand X is y, then
Charge number:charge on Ni>;charge on 6X
92: ;2;4;y
y: 91
Hence the charge on ligand X is 91. ■
Q. 12. Calculate the oxidation state of a metal in the following complexes :

(a) [Fe(NH ) ](NO ) (b) Ni(CO) . (2 marks each)

Ans.
(a) [Fe(NH ) ](NO ) & [Fe(NH ) ]> ; 3NO\

NH is a neutral ligand, and the charge number of complex ion is ;3.

If the oxidation state of Fe is x then,
;3:x;6(0)
x: ;3
The oxidation state of Fe is ;3.
(b) Ni(CO) is a neutral complex and CO is a neutral ligand. If the oxidation state of Ni is x, then

zero:x;5;(zero)
x:zero.
The oxidation state of Ni is zero.
■
Can you tell ?

(Textbook page 193)
Q. A complex is made of Co (III) and consists of four NH molecules and two Cl\ ions as ligands. What is the

charge number and formula of complex ion ?
Ans. The complex ion has formula, [Co(NH ) Cl ]>.

The charge number is ;1.

Q. 13. Define and explain the term coordination number (C.N.) of a metal in the complex. (2 marks)
Ans. Coordination number or legancy (C.N.) : The number of (monodentate) ligands which are directly bonded by
coordinate bonds to central metal atom or ion in a coordination compound is called coordination number (C.N.) of
the metal atom or ion.
Explanation :
(i) The coordination number (C.N.) is a characteristic property of the metal and its electronic configuration.
(ii) C.N. takes the values from 2 to 10, of which 4 and 6 are very common.
(iii) The light transition metals show C.N. 4 and 6 while the heavier transition metals show C.N. 8.
(iv) The geometry and shape of a complex compound depends upon C.N. of the metal.
■
Q. 14. Mention primary valence, secondary valence and coordination number in the following complexes :
(a) [Cu(NH ) ]Cl (b) [Co(NH ) Cl ] (c) K [Fe(CN) ] (d) [CoF ]\

(e) [Pt(NH ) Cl ] (f) [Pt(NH ) (Py) Cl ] (g) Cr(CO) (h) [Ni(CN) ]\ (2 marks each)

Ans.
Primary valence /
Complex Secondary valence Coordination number
Valency of metal
(a) [Cu(NH ) ]Cl 2 4 4

(b) [Co(NH ) Cl ] 3 6 6

(c) K [Fe(CN) ] 2 6 6

(d) [CoF ]\ 3 6 6

(e) [Pt(NH ) Cl ] 2 4 4

(f) [Pt(NH ) (Py) Cl ] 2 6 6

(g) Cr(CO) 0 6 6

(h) [Ni(CN) ]\ 2 4 4

■

(Textbook page 193)
Q. Coordination number used in coordination of compounds is somewhat different than that used in solid
state. Explain.
Ans.
● In a coordination compound the coordination number is the number of donor atoms of ligands directly attached
to metal atom or ion.
● In a solid state, the number of closest constituent atoms or ions in contact with a particular atom in the crystal
lattice is called coordination number.
● In a coordination compound, coordination number depends upon nature of metal atom or ion, and its electronic
configuration.
● In a solid state, the coordination number depends upon the crystalline structure of the unit cell.
★ Q. 15. What is the coordination number and oxidation state of metal ion in the complex [Pt (NH ) Cl ]\ ?

Ans. Coordination number:6
Oxidation state of Pt:;4. ■
Can you tell ?

(Textbook page 194)
Q. What is the coordination number of (a) Co in [CoCl (en) ]>, (b) Ir in [Ir(C O ) Cl ]> and (c) Pt in

[Pt(NO ) (NH ) ] ?

Ans. (a) Coordination number of Co in [CoCl (en) ]>:6

(b) Coordination number of Ir in [Ir (C O ) Cl ]>:6

(c) Coordination number of Pt in [Pt (NO ) (NH ) ]:4

★ Q. 16. What is the difference between a double salt and a complex ? Give an example. (2 marks) OR
Illustrate with example, the difference between a double salt and a coordination compound (complex).
(2 marks)
Ans. Double salt Coordination compound (complex)
(1) Double salts exist only in the solid state and (1) Coordination compounds exist in the solid state as
dissociate into their constituent ions in the aqueous well as in the aqueous or non-aqueous solutions.
solutions.
(2) Double salts lose their identity in the solution. (2) They do not lose their identity completely.
(3) The properties of double salts are same as those of (3) The properties of coordination compounds are
their constituents. different from their constituents.
(4) Metal ions in the double salts show their normal (4) Metal ions in the coordination compounds show
valence. two valences namely primary valence and second-
ary valence satisfied by anions or neutral molecules
called ligands.
(5) For example in K SO . K SO . Al (SO ) . 24H O. (5) In K [Fe(CN) ], ions K> and [Fe(CN) ]\ ions

The ions K>, Al> and SO\ show their properties. show their properties.

■
Remember …
(Textbook page 194)
When a complex is dissolved and a solution is formed, it does not dissociate into simple metal ions. When
[Co(NH ) ]Cl , is dissolved in water it does not give the test for Co> or NH . However, on reacting with AgNO

a curdy white precipitate of AgCl corresponding to 3 moles is observed.

Q. 17. What are the postulates of Werner theory ? (4 marks)
Ans. The following are the postulates of Werner theory :
Postulate (1) Unlike metal salts, the metal in a complex possesses two types of valencies : primary (ionizable)
valency and secondary (nonionizable) valency.
Postulate (2) The ionizable sphere consists of entities which satisfy the primary valency of the metal. Primary
valencies are generally satisfied by anions.
Postulate (3) The secondary coordination sphere consists of entities which satisfy the secondary valencies and are
nonionizable.
The secondary valencies for a metal ion are fixed and satisfied by either anions or neutral ligands. Number of
secondary valencies is equal to the coordination number.
Postulate (4) The secondary valencies have a fixed spatial arrangement around the metal ion. Two spheres of
attraction in the complex [Co(NH ) ]Cl are shown.

Question 9.1 : (Textbook page 194)

Q. One mole of a purple coloured complex of CoCl and NH on treatment with excess AgNO produces two

moles AgCl. Write the formula of the complex if the coordination number of Co is 6.
Ans. : One mole of the complex gives 2 moles of AgCl. It indicates that two Cl\ ions react with Ag> ions. The
complex has two ionisable Cl\ ions. The formula of the complex is then [Co(NH ) Cl]Cl .

Can you tell ?
(Textbook page 194)
Q. One mole of a green coloured complex of CoCl and NH on treatment with excess of AgNO produces 1

mole of AgCl. What is the formula of the complex? (Given : C.N. of Co is 6)
Ans. : Since 1 mol of complex gives 1 mol of AgCl, it indicates the complex on dissociation gives 1 mol Cl\.
Hence complex has one mol ionisable Cl\ ions. Since C.N. of Co is 6, the formula of the complex is
[Co(NH ) Cl ]Cl.

Units
9.4 Classification of complexes
9.4.1 Classification on the basis of types of ligands
9.4.2 Classification on the basis of charge on the complex
Q. 18. Define the following terms. (2 marks)

(1) Homoleptic complexes : Consider [Co (NH ) ]>. Here only one type of ligands surrounds the Co> ion. The

complexes in which metal ion is bound to only one type of ligands are homoleptic.
(2) Heteroleptic complexes : Look at the complex [Co (NH ) Cl ]>. There are two types of ligands, NH and Cl

attached to Co > ion. Such complexes in which metal ion is surrounded by more than one type of ligands are

heteroleptic. ■
(Textbook page 195)
Q. Classify the complexes as homoleptic and heteroleptic : (a) [Co (NH ) Cl]SO , (b) [Co (ONO)(NH ) ]Cl ,

(c) [CoCl (NH )(en) ]> and (d) [Cu (C O ) ]\.

Ans. Homoleptic Complexes : (d) [Cu (C O ) ]\

Heteroleptic Complexes : (a) [Co (NH ) Cl]SO

(b) [Co (ONO)(NH ) ]Cl , (c) [CoCl (NH )(en) ]>

★ Q. 19. What are cationic, anionic and neutral complexes ? Give one example of each. (3 marks)
Ans.
(1) Cationic sphere complexes : A positively charged coordination sphere or a coordination compound having a
positively charged coordination sphere is called cationic sphere complex.
For example : [Zn(NH ) ]> and [Co(NH ) Cl]SO are cationic complexes. The latter has coordination sphere

[Co(NH ) Cl]>, the anion SO \ makes it electrically neutral.

(2) Anionic sphere complexes : A negatively charged coordination sphere or a coordination compound having
negatively charged coordination sphere is called anionic sphere complex. For example, [Ni(CN) ]\ and

K [Fe(CN) ] have anionic coordination sphere; [Fe(CN) ]\ and three K> ions make the latter electrically

neutral.
(3) Neutral sphere complexes : A neutral coordination complex does not possess cationic or anionic sphere.
[Pt(NH ) Cl ] or [Ni(CO) ] are neither cation nor anion but are neutral sphere complexes. ■

(Textbook page 195)
Q. Classify the complexes as cationic, anionic or neutral : Na [Fe(CN) ], Co(NH ) Cl ,

Cr(H O) (C O ) \, PtCl (en) and Cr(CO) .

Ans. Cationic complexes : [Co(NH ) ]Cl

Anionic complexes : Na [Fe(CN) ], [Cr(H O) (C O ) ]\

Neutral complexes : Cr(CO) , Pt Cl (en)

★ Q. 20. Is the complex [CoF ] cationic or anionic if the oxidation state of cobalt is ;3 ? (1 mark)

Ans. In the complex, Co carries ;3 charge while 6F\ carry 96 charge. Hence the net charge on the complex is 93.
Therefore it is an anionic complex. ■
★ Q. 21. Classify following complexes as homoleptic and heteroleptic complex :

(a) [Cu(NH ) ]SO ; (b) [Cu(en) (H O)Cl]> (c) [Fe(H O) (NCS)]> (d) Tetraaminezinc(II) nitrate.

( 12 mark each)
Ans. Homoleptic complex :
(a) [Cu(NH ) ]SO (d) Tetraaminezinc(II) nitrate : [Zn(NH ) ](NO )

Heteroleptic Complex :
(b) [Cu(en) (H O)Cl]> (c) [Fe(H O) (NCS)]> ■


Unit
9.5 IUPAC nomenclature of coordination compounds
Q. 22. Summarise the rules of IUPAC nomenclature of coordination compounds. (3 marks)

Ans. Following rules are followed for naming coordination compounds recommended by IUPAC :
(1) In case of a complex ion or a neutral molecule, name the ligand first and then the metal.
(2) The names of anionic ligands are obtained by changing the ending -ide to -o and -ate to -ato.
(3) The name of a complex is one single word. There must not be any space between different ligand names as well as
between ligand name and the name of the metal.
(4) After the name of the metal, write its oxidation state in Roman number which appears in parentheses without any
space between metal name and parentheses.
(5) If complex has more than one ligand of the same type, the number is indicated with prefixes, di-, tri-, tetra-, penta-,
hexa- and so on.
(6) For the complex having more than one type of ligands, they are written in an alphabetical order. Suppose two
ligands with prefixes are tetraaqua and dichloro. While naming in alphabetical order, tetraaqua is written first and
then dichloro.
(7) If the ligand itself contains numerical prefix in its name, then display number by prefixes bis for 2, tris for 3, tetrakis
for 4 and so forth. Put the ligand name in parentheses. For example, (ethylenediamine) or (en) would appear as

tris (ethylenediamine) or tris(ethane-1, 2-diamine).
(8) The metal in cationic or neutral complex is specified by its usual name while in the anionic complex the name of
metal ends with ‘ate’. ■
Try this ...

(Textbook page 197)
Q. Write the representation of the following :
(i) Tricarbonatocobaltate(III) ion. Ans. (i) [Co(CO ) ]\

(ii) Sodium hexacyanoferrate(III). (ii) Na [Fe(CN) ]

(iii) Potassium hexacyanoferrate(II). (iii) K [Fe(CN) ]

(iv) Aquachlorobis(ethylenediamine)cobalt(III). (iv) Co(en) (H O)(Cl)

(v) Tetraaquadichlorochromium(III) chloride. (v) [Cr(H O) Cl ]Cl

(vi) Diamminedichloroplatinum(II). (vi) Pt(NH ) Cl

★ Q. 23. Write the formula for tetraamineplatinum(II) chloride. (1 mark)
Ans. Formula of tetraamineplatinum(II) chloride : [Pt(NH ) ]Cl

Table 9.1 : IUPAC names of anionic and neutral ligands
Anionic ligand IUPAC name Anionic ligand IUPAC name
Br\, Bromide Bromo CO \, Carbonate Carbonato

Cl\, Chloride Chloro OH\, Hydroxide Hydroxo
F\, Fluoride Fluoro C O \, Oxalate Oxalato

I\ Iodide Iodo NO \, Nitrite Nitro (For N-bonded ligand)

CN\, Cyanide Cyano ONO\, Nitrite Nitrito (For O-bonded ligand)
SO \, Sulphate Sulphato SCN\, Thiocyanate Thiocyanato (For ligand

donor atom S)
NO \, Nitro Nitrato NCS\, Thiocyanate Isothiocyanato (For ligand

donor atom N)
Neutral ligand IUPAC name Neutral ligand IUPAC names
NH , Ammonia Ammine (Note the spelling) H O, water Aqua

CO, Carbon monoxide Cabonyl en, Ethylene diamine Ethylenediamine
Table 9.2 : IUPAC names of anionic complexes
Metal Name Metal Name Metal Name
Al Aluminate Fe Ferrate Zn Zincate

Cr Chromate Pb Plumbate Ag Argentate
Cu Cuprate Mn Manganate Sn Stannate
Co Cobaltate Mo Molybdate
Au(Gold) Aurate Ni Nickelate
Table 9.3 : IUPAC names of some complexes
Complex IUPAC name
(i) Anionic complexes :

(a) [Ni(CN) ]\ Tetracyanonickelate(II) ion

(b) [Co(C O ) ]\ Trioxalatocobaltate(III) ion

(c) [Fe(CN) ]\ Hexacyanoferrate(II) ion

(ii) Compounds containing complex anions and metal cations :
(a) Na [Co(NO ) ] Sodium hexanitrocobaltate(III)

(b) K [Al(C O ) ] Potassium trioxalatoaluminate(III)

(c) Na [AIF ] Sodium hexafluoroaluminate(III)


Complex IUPAC name
(iii) Cationic complexes :
(a) [Cu(NH ) ]> Tetraamminecopper(II) ion

(b) [Fe(H O) (NCS)]> Pentaaquaisothiocyanatoiron(III) ion

(c) [Pt(en) (SCN) ]> Bis(ethylenediamine)dithiocyanatoplatinum(IV)

(iv) Compounds containing complex cation and anion :
(a) [PtBr (NH ) ]Br Tetraamminedibromoplatinum(IV) bromide,

(b) [Co(NH ) CO ]Cl Pentaamminecarbonatocobalt(III) chloride,

(c) [Co(H O)(NH ) ]I Pentaammineaquacobalt(III) iodide

(v) Neutral complexes :
(a) Co(NO ) (NH ) Triamminetrinitrocobalt(III)

(b) Fe(CO) Pentacarbonyliron(0)

(c) Rh(NH ) (SCN) Triamminetrithiocyanatorhodium(III)

★ Q. 24. Write formula of the following complexes :

(a) Potassium amminetrichloroplatinate(II)
(b) Dicyanoaurate(I) ion. (2 marks)
Ans. (a) Potassium amminetrichloroplatinate(II) (b) Dicyanoaurate (I) ion
K[Pt(NH )Cl ] [Au(CN) ]\ ■

Unit
9.6 Effective Atomic Number (EAN) Rule
Q. 25. State effective atomic number (EAN). (1 mark) OR

State and explain effective atomic number (EAN). How is it calculated ? (2 marks)
Ans. Effective atomic number (EAN) : It is the total number of electrons present around the central metal atom or ion
and calculated as the sum of electrons of metal atom or ion and the number of electrons donated by ligands.
It is calculated by the formula : EAN:Z9X;Y
where, Z:Atomic number of metal atom
X:Number of electrons lost by a metal atom forming a metal ion
Y:Total number of electrons donated by all ligands in the complex.
Generally the value of EAN is equal to the atomic number of the nearest inert element.
Explanation : Consider a complex ion [Co(NH ) ]>

Oxidation state of cobalt is ;3 hence X:3.
There are six ligands, hence Y:2;6:12
Atomic number of cobalt, Z:27
EAN:Z9X;Y:2793;12:36.
■
Try this …
(Textbook page 197)
Q. Find out the EAN of (a) [Zn(NH ) ]>

(b) [Fe(CN) ]\

Ans. (a) For the complex ion, [Zn(NH ) ]> :
(b) For the complex ion, [Fe(CN) ]\ :
Atomic number of Zn:Z:30
For Fe, Z:26 (Atomic number)
Charge on metal ion: ;2
X:2 (Due to ;2 charge on Fe)
Number of electrons lost by Zn atom:X:2
Y:12 (Due to 6 CN\ ligands)
Total number of electrons donated by 4NH
EAN:Z9X;Y
ligands:Y:2;4:8
:2692;12
EAN:Z9X;Y
:36
:3092;8
:36
(Note : This is atomic number of the nearest
inert element Kr.)


(Textbook page 197)
Q. Do the following complexes follow the EAN rule (a) Cr(CO) , (b) Ni(CO) , (c) Mn(CO) ,

(d) Fe(CO) ?

Ans. (a) Cr(CO) : EAN:Z9X;Y (b) Ni(CO) : EAN:Z9X;Y

:2490;8 :2890;8
:32 :36
(c) Mn(CO) : EAN:Z9X;Y (d) Fe(CO) : EAN:Z9X;Y

:2590;10 :2690;10
:35 :36
Conclusion : (a) Cr(CO) and (c) Mn(CO) do not follow EAN Rule.

Q. 26. Find effective atomic number (EAN) in the following complexes :

(1) [Ni(CO) ] (2) [Fe(CN) ]\ (3) [Co(NH ) ]> (4) [Zn(NH ) ]> (5) [Pt(NH ) ]> (2 marks each)

Atomic number Number of Number of
Ans. Complex Metal of metal electrons lost electrons from EAN:Z9X;Y
by metal ligands
Z X Y
(1) [Ni(CO) ] Ni 28 0 4;2:8 2890;8:36 (Kr)

(2) [Fe(CN) ]\ Fe 26 2 6;2:12 2692;12:36 (Kr)

(3) [Co(NH ) ]> Co 27 3 6;2:12 2793;12:36 (Kr)

(4) [Zn(NH ) ]> Zn 30 2 4;2:8 3092;8:36 (Kr)

(5) [Pt(NH ) ]> Pt 78 4 6;2:12 7894;12:86 (Rn)

■

Q. 27. What is effective atomic number (EAN) in the following complexes ?
(1) [Fe(CN) ]\ (2) [Cu(NH ) ]> (3) [Pt(NH ) ]>. (2 marks each)

by metal ligands
Z X Y
(1) [Fe(CN) ]\ Fe 26 3 6;2:12 2693;12:35

(2) [Cu(NH ) ]> Cu 29 2 4;2:8 2992;8:35

(3) [Pt(NH ) ]> Pt 78 2 4;2:8 7892;8:84

■
Q. 28. Calculate EAN in the following complexes :

(1) [Cr(H O) (NH ) (en)]Cl ; (2) [Ni(en) ]SO ; (3) Na [Cr(C O ) ]. (2 marks each)

by metal ligands
Z X Y

2H O:4

(1) [Cr(H O) (NH ) (en)]Cl Cr 24 3 2NH :4 12 2493;12:33

en:4
(2) [Ni(en) ]SO Ni 28 2 2en:8 2892;8:34

(3) Na [Cr(C O ) ] Cr 24 3 3C O \ :12 2493;12:33

■
Units
9.7 Isomerism in coordination compounds
9.7.1 Stereoisomers
9.7.2 Structural isomers
Q. 29. Define in coordination compounds : (1) Isomerism (2) Isomers. (2 marks)

Ans.
(1) Isomerism : It is the phenomenon in coordination compounds having same molecular formula but different
physical and chemical properties due to different arrangements of the ligands around the central metal atom or ion
in the space.
(2) Isomers : The isomers are the coordination compounds having same molecular formula but different physical and
chemical properties due to the difference in arrangements of the ligands in the space. ■
Q. 30. Mention the types of isomerisms in coordination compounds. (2 marks)

Ans. There are two principal types of isomerisms in coordination compounds as follows :
(A) Stereoisomerism (B) Structural isomerism (OR Constitutional isomerism)
(A) Stereoisomerism is further classified as :
(i) Geometrical isomerism
(ii) Optical isomerism
(B) Structural isomerism is further classified as :
(i) Ionisation isomerism
(ii) Linkage isomerism
(iii) Coordination isomerism
(iv) Solvate (or hydrate) isomerism ■
Q. 31. Why does stereoisomerism arise in the coordination compounds ? (2 marks)

Ans. In the coordination compounds (complexes) the ligands are linked to the central metal atom or ion by coordinate
bonds which are directional in nature and hence give rise to the phenomenon of stereoisomerism.
In this isomerism, the different stereoisomers have different arrangements of ligands (atoms, molecules or ions) in
space around the central metal atom or ion. Hence they have different physical and chemical properties and give
rise to the phenomenon of stereoisomerism. ■
Q. 32. Define, in coordination compounds : (1) Stereoisomerism (2) Stereoisomers. (1 mark each)
Ans.
(1) Stereoisomerism : The phenomenon of isomerism in the coordination compounds arising due to different spatial
positions of the ligands in the space around the central metal atom or ion is called stereoisomerism.
(2) Stereoisomers : The coordination compounds having same molecular formula but different stereoisomerism
due to different spatial arrangements of the ligand groups in the space around the central metal atom or ion are
called stereoisomers. ■
Q. 33. Define : (1) Geometrical isomerism and (2) Geometrical isomers. (1 mark each)
Ans.
(1) Geometrical isomerism : The phenomenon of isomerism in the heteroleptic coordination compounds with the
same molecular formula but different spatial arrangement of the ligands in the space around the central metal atom
or ion is called geometrical isomerism.
(2) Geometrical isomers : The heteroleptic coordination compounds having same molecular formula but different
geometrical isomerism due to different spatial arrangements of the ligands in the space around the central metal
atom or ion are called geometrical isomers. ■
Q. 34. Define cis and trans isomers in the coordination compounds. (2 marks)
Ans.
(1) Cis-isomer : A heteroleptic coordination compound in which two similar
ligands are arranged adjacent to each other is called cis-isomer. For
example,
Cis-Diamminedichloroplatinum(II)
(2) Trans-isomer : A heteroleptic coordination compound in which two

similar ligands are arranged diagonally opposite to each other is called
trans-isomer. For example,
Trans-Diamminedichloroplatinum(II)
■

Q. 35. Write structures for geometrical isomers of Diamminebromochloroplatinum(II). (1 mark)
Ans.
Cis-Diamminebromochloroplatinum(II) Trans-Diamminebromochloroplatinum(II) ■
Q. 36. Explain the geometrical isomerism of the octahedral complex of the type [MA B ] with suitable example.

(2 marks)
Ans.
(1) Consider an octahedral complex of a metal M with coordination number six and monodentate ligands a and b
having formula [MA B ].

(2) Cis-isomer is obtained when both the B ligands occupy adjacent (1, 2) positions.
(3) Trans-isomer is obtained when the ligands B occupy the opposite (1, 6) positions.
(4) For example, consider a complex [Co(NH ) Cl ]>. The structures of cis and trans isomers are

(a)
(b)
Fig. 9.1 (a) and (b) : Cis and trans-isomers of [CoCl (NH ) ]> ■

Try this ...
(Textbook page 199)
● Draw structures of cis and trans isomers of [Fe(NH ) (CN) ] 9

Q. 37. Explain the geometrical isomerism of the octahedral complex of the type [M(AA) B ]n< with a suitable

example. (3 marks)
Ans.
(1) Consider an octahedral complex of metal M with coordination number six and a bidentate ligand AA and
monodentate ligand B having molecular formula [M(AA) B ]n< .

(2) Bidentate ligand AA has two identical coordinating atoms.
(3) Cis-isomer is obtained when two bidentate AA ligands as well as two ‘B’ ligands are at adjacent positions.
(4) Trans-isomer is obtained when two AA ligands and two B ligands are at opposite positions.
(5) For example, consider a complex [Co(en) Cl ]>.

(a)
(b)
Fig. 9.2 (a) and (b) : cis and trans-isomers of [CoCl (en) ]> ■

Q. 38. Explain the geometrical isomerism of the octahedral complex of the type [MA BC] with suitable example.

(3 marks)
Ans.
(1) Consider an octahedral complex of metal M with coordination number six and monodentate ligands A, B
and C.
(2) Cis-isomer is obtained when both the ligands B and C occupy adjacent (1, 2) positions.
(3) Trans-isomer is obtained when the ligands B and C occupy opposite positions.
(4) For example, consider a complex [Pt(NH ) BrCl] of the type [MA BC].


(a)
(b)
Q. 39. Define : (1) Optical isomerism (2) Optical isomers. (1 mark each)
Ans.
(1) Optical isomerism : The phenomenon of isomerism in which different coordination compounds having same
molecular formula have different optical activity is called optical isomerism.
(2) Optical isomers : Different coordination compounds having same molecular formula but different optical activity
are called optical isomers. ■
Q. 40. Explain : (1) Plane polarised light (2) Optical activity. (1 mark each)
Ans.
(1) Plane polarised light : A monochromatic light having vibrations only in one plane is called a plane polarised
light. This light is obtained by passing monochromatic light through NICOL prism.
(2) Optical activity : A phenomenon of rotating a plane of a plane polarised light by an optically active substance is
called optical activity. This substance is said to be optically active. ■
Q. 41. Explain : (1) Dextrorotatory substance (2) Laevorotatory substance. (1 mark each)
Ans.
(1) Dextrorotatory substance : An optically active substance which rotates the plane of a plane polarised light to
right hand side is called dextrorotatory or d isomer denoted by d.
(2) Laevorotatory substance : An optically active substance which rotates the plane of a plane polarised light to the
left hand side is called laevorotatory or l isomer and denoted by l. ■
Q. 42. What are the conditions for the optical isomerism in coordination compounds ? (2 marks)
Ans.
(1) Optical isomerism is exhibited by those coordination compounds which possess chirality.
(2) There should not be the presence of element of symmetry which makes the complex optically inactive.
(3) The mirror images of the complex molecule or ion must be non-superimposable with the molecule or ion. ■
Q. 43. What are enantiomers ? (1 mark)
Ans. Enantiomers : The two forms of the optical active complex molecule which are mirror images of each other
are called enantiomers.
There are two forms of enantiomers, d form and l form. ■
Remember ...
(Textbook page 199)
Our hands are non superimposable mirror images. When you hold your left hand up to a mirror the image
looks like right hand.
Q. 44. Draw diagrams for the optical isomers of a complex, [Co(en) ]>. (2 marks)

Ans. The complex [Co(en) ]> has two optical isomers.

Fig. 9.3 : Optically active forms of [Co(en) ]> ■

Q. 45. Explain the optical isomerism in the octahedral complex with two symmetrical bidentate chelating
ligands. (2 marks)
n<
Ans. The octahedral complexes of the type [M(AA) Q ] , in which two symmetrical bidentate chelating ligands

like AA and two monodentate ligands like a are coordinated to the central metal atom or ion exhibit optical
isomerism and two optical isomers d and l can be resolved. For example, [Pt Cl (en) ].

The cis-form is unsymmetrical and optically active while trans-form is symmetrical and hence optically inactive.
The optical isomers of cis-form (d and l ) of this complex along with trans-form are shown below,
Fig 9.4 : Optically active (cis) and optically inactive (trans) forms of the complex [CoCl (en) ]> ■


Try this...
(Textbook page 199)
(1) Draw enantiomers of [Cr(OX) ]\ where OX:C O \ :

(2) Draw (A) enantiomers and (B) cis and trans isomers of [Cr(H O) (OX) ]\ :

(A) Enantiomers :
(B) Cis and trans isomers :
Q. 46. When are optical isomers called chiral ? (1 mark)
Ans. When the mirror images of optical isomers of the complex are nonsuperimposable they are said to be chiral.
For example, [Co(en) (NH ) ]>. ■

★ Q. 47. Predict whether the [Cr(en) (H O) ]> complex is chiral. Write structure of its enantiomers.

(2 marks)
Ans. (i) Complex is chiral.
(ii) The following are its enantiomers
★ Q. 48. Draw isomers in each of the following :

(a) [Pt(NH ) ClNO ]

(b) [Ru(NH ) Cl ]

(c) [Cr(en )Br ]> (1 mark each)

Ans.
(a) [Pt(NH ) ClNO ]

Geometric isomers :
(b) [Ru(NH ) Cl ]

Geometric isomers :

(c) [Cr(en )Br ]>

Optical isomers :
Geometric isomers :
★ Q. 49. Draw geometric isomers and enantiomers of the following complexes.

(a) [Pt(en) ]> (b) [Pt(en) ClBr]> (2 marks)

Ans. The complex [Pt(en) ]> has two optical isomers.

Optical isomers of [Pt(en) ClBr]>

Q. 50. Define and explain ionisation isomerism. (2 marks)

Ans. Ionisation isomerism : The phenomenon of isomerism in the metal complexes in which there is an exchange of
ions between coordination (or inner) sphere and outer sphere is known as ionisation isomerism.
Explanation : (i) Ionisation isomers have same molecular formula but different arrangement of ions in the inner
sphere and outer sphere in the complex. (ii) Hence on ionisation, these ionisation isomers produce different ions
in the solution. This ionisation isomerism is also called ion-ion exchange isomerism.
Examples : (A) [Co(NH ) Cl ] Br and (B) [Co(NH ) ClBr] Cl

Ionisation :
(A) [Co(NH ) Cl ] Br & [Co(NH ) Cl ]> ; Br\

(B) [Co(NH ) ClBr]Cl & [Co(NH ) ClBr]>;Cl\

In the isomers (A) and (B), there is an exchange of ions namely Br\ and Cl\.
■
★ Q. 51. What are ionisation isomers ? Give an example. (2 marks)

Ans. Ionisation isomers : The coordination compounds having same molecular composition but differ in the
compositions of coordination (or inner) sphere and outer sphere and produce different ions on ionisation in the
solution are called ionisation isomers. For example, Pentaamminesulphatocobalt (III) bromide [Co(NH ) SO ] Br,

Pentaamminebromocobalt(III) sulphate [Co(NH ) Br] SO . ■

Q. 52. Define : (1) Linkage isomerism (2) Linkage isomers. OR
What is linkage isomerism ? Explain with an example. (2 marks)
Ans.
(1) Linkage isomerism : The phenomenon of isomerism in which the coordination compounds have same metal
atom or ion and same ligand but bonded through different donor atoms or linkages is known as linkage isomerism.
(2) Linkage isomers : The coordination compounds having same metal atom or ion and ligand but bonded through
different donor atoms or linkages are called linkage isomers.
For example : Nitro complex [Co(NH ) NO ]Cl and nitrito complex [Co(NH ) ONO] Cl

(Yellow) (Red) ■
Q. 53. Explain linkage isomers with NO 2\ group as a ligand. (2 marks)

Ans.
(1) Nitro group (–NO\) is an ambidentate ligand. NO\ group may link to central metal atom, through N or O.

(2) The two linkage isomers are, [Cl : ; Ag < : NO ]\ and [Cl : ; Ag < O–NO]\

Choloronitroargentate(I) ion Chloronitritoargentate(I) ion
■

Q. 54. Write linkage isomers of a complex having constituents Co>, 5NH and NO 2\ . (2 marks)

Ans.
(i) NO \ is an ambidentate ligand which can be linked through N or O.

(ii) The linkage isomers are as follows :
(a) [Co(NH ) (NO )]> Pentaamminenitrocobalt(III) ion

(b) [Co(NH ) (ONO)]> Pentaamminenitritocobalt(III) ion
■
Can you tell ?

(Textbook page 200)
Q. Can you write IUPAC names of isomers (I) [Co(NH ) SO ]Br and (II) [Co(NH ) Br]SO ?

Ans.
Coordination compound IUPAC name
(I) [Co(NH ) SO ]Br Pentaamminesulphatocobalt(III) bromide

(II) [Co(NH ) Br]SO Pentaamminebromocobalt(III) sulphate

Can you tell ?

(Textbook page 199)
Q. Write linkage isomers of [Fe(H O) SCN]>. Write their IUPAC names.

Ans.
Linkage isomers IUPAC name
(a) [Fe(H O) SCN]> Pentaaquathiocyanatoiron(II)

(b) [Fe(H O) NCS]> Pentaaquaisothiocyanatoiron(II)

Q. 55. Define : (1) Coordination isomerism (2) Coordination isomers. (1 mark each)
Ans.
(1) Coordination isomerism : The phenomenon of isomerism in the ionic coordination compounds having the same
molecular formula but different complex ions involving the interchange of ligands between cationic and anionic
spheres of different metal ions is called coordination isomerism.
(2) Coordination isomers : The ionic coordination compounds having same molecular formula but different complex
ions due to interchange of ligands between cationic and anionic spheres of different metal ions are called
coordination isomers.
For example, (I) [Co(NH ) ]>[Cr(CN) ]\ and (II) [Cr(NH ) ]>[Co(CN) ]\

(cationic) (anionic) (cationic) (anionic) ■
Q. 56. Give three examples of coordination isomers. (1 mark each)

Ans.
(1) [Cu(NH ) ][PtCl ] and [Pt(NH ) ][CuCl ]

(2) [Cr(NH ) ][Cr(CN) ] and [Cr(NH ) (CN) ][Cr(NH ) (CN) ]

(3) [Cr(NH ) ][Cr(SCN) ] and [Cr(NH ) (SCN) ][Cr(SCN) (NH ) ] ■

Q. 57. Define Solvate or Hydrate isomerism. (1 mark)
Ans. Solvate or Hydrate isomerism : The phenomenon of isomerism in the coordination compounds arising due to
the exchange of solvent or H O molecules inside the coordination sphere and outer sphere of the complex is known

as solvate or hydrate isomerism. ■
Q. 58. Define solvate or hydrate isomers. OR
What are hydrate isomers ? Explain with examples. (2 marks)
Ans. Solvate or Hydrate isomers : The coordination compounds having the same molecular formula but differ in the
number of solvent or H O molecules inside the coordination sphere and outer sphere of the complexes are called

solvate or hydrate isomers.
For example : [Cr(H O) ] Cl ; [Cr(H O) Cl]Cl · H O; and [Cr(H O) Cl ] Cl·2H O. ■

Q. 59. A coordination compound has formula CoCl · 6H O. Write the hydrate isomers of the complex.

(2 marks)
Ans. The possible hydrate isomers of the coordination compounds having molecular formula CoCl · 6H O are

as follows :
(1) [Co(H O) ]Cl ; (2) [Co(H O) Cl] Cl ·H O

(3) [Co(H O) Cl ] Cl· 2H O (4) [Co(H O) Cl ] · 3H O. ■

★ Q. 60. Consider the complexes [Cu(NH ) ] [PtCl ] and [Pt(NH ) ] [CuCl ]. What type of isomerism these two

complexes exhibit ?
Ans. Since in these two given complexes, there is an exchange of ligands between cationic and anionic constituents, they
exhibit coordination isomerism. ■
Units
9.8 Stability of the coordination compounds
9.8.1 Factors which govern stability of the complex
★ Q. 61. How can stability of the coordination compounds be explained in terms of equilibrium constants ?
(2 marks)
Ans. Stability of the coordination compounds : The stability of coordination compounds can be explained on the
basis of their stability constants. The stability of coordination compounds depends on metal-ligand interactions. In
the complex, metal serves as electron-pair acceptor (Lewis acid) while the ligand as Lewis base (since it is electron
donor). The metal-ligand interaction can be realized as the Lewis acid-Lewis base interaction. Stronger the
interaction greater is stability of the complex.
Consider the equilibrium for the metal-ligand interaction :
M a;
;nLx\ & [MLn]a>(9nx)
where a, x, [a;(9nx)] denote the charge on the metal, ligand and the complex, respectively. Now, the
equilibrium constant K is given by
[MLn][a;(9nx)]
K:
[Ma>] [Lx\]n
Stability of the complex can be explained in terms of K. Higher the value of K larger is the thermodynamic
stability of the complex hence K is called stability constant, and denoted by Kstab.
The equilibria for the complex formation with the corresponding K values are given below.
Ag>;2CN\ & [Ag(CN) ]\ K:5.5;10

Cu>;4CN\ & [Cu(CN) ]\ K:2.0;10

Co>;6NH & [Co(NH ) ]> K:5.0;10

From the above data, the stability of the complexes is [Co(NH ) ]> [Cu(CN) ]\ [Ag(CN) ]\. ■

★ Q. 62. Name the factors governing the equilibrium constants of the coordination compounds. (2 marks)
Ans. The equilibrium constant of the complex depends on the following factors :
(a) Charge to size ratio of the metal ion : Higher the ratio greater is the stability. For the divalent metal ion
complexes their stability shows the trend : Cu> Ni> Co> Fe> Mn> Cd>. The above stability
order is called Irving-William order. In the above list both Cu and Cd have the charge ;2, however, the ionic
radius of Cu> is 69 pm and that of Cd> is 97 pm. The charge to size ratio of Cu> is greater than that of Cd>.
Therefore the Cu> forms stable complexes than Cd>.
(b) Nature of the ligand : A second factor that governs stability of the complexes is related to how easily the ligand
can donate its lone pair of electrons to the central metal ion that is, the basicity of the ligand. The ligands those are
stronger bases tend to form more stable complexes. ■

(Textbook page 201)
● The stability constant K of the [Ag(CN) ]\ is 5.5;10 while that for the corresponding [Ag(NH ) ]> is

1.6;10. Explain why [Ag(CN) ]\ is more stable.

Ans. Stability constant of [Ag(CN) ]\ is larger than that of [Ag(NH ) ]> and hence [Ag(CN) ]\ is more stable.

Also, CN\ is a stronger ligand than NH .

Units
9.9 Theories of bonding in complexes
9.9.1 Valence Bond Theory (VBT)
Q. 63. Explain the steps involved in describing the bonding in coordination compounds using valence bond
theory. (3 marks)
Ans.
(1) Vacant d-orbitals of metal ion form coordination bonds with ligands.
(2) s, p orbitals along with vacant d-orbitals of metal ion take part in hybridisation.
(3) The number of vacant hybrid orbitals formed is equal to number of hybridising orbitals which is equal to the
number of ligand donor atoms or coordination number of the metal.
(4) The metal-ligand coordination bonds are formed by the overlap between the vacant hybrid orbitals of metal
and the filled orbitals of the ligands.
(5) The hybrid orbitals used by the metal ion point in the direction of the ligands.
(6) When inner (n91) d orbitals of metal ion are used in the hybridisation then the complex is called (a) inner orbital
complex while when outer nd orbitals are used, complexes are called (b) outer orbital complexes. ■
Q. 64. Explain the steps involved in the metal-ligand bonding. (3 marks)

Ans.
(1) Find the oxidation state of central metal ion in the complex.
(2) Write the valence shell electronic configuration of metal ion.
(3) From the formula of the complex determine the number of ligands and find the number of metal ion orbitals
required for bonding.
(4) Find the orbitals of metal ion available for hybridisation and the type of hybridisation involved.
(5) Represent the electronic configuration of metal ion after hybridisation.
(6) Exhibit filling of hybrid orbitals after complex formation.
(7) Determine the number of unpaired electrons and predict magnetic property of the complex.
(8) Find whether the complex is low spin or high spin (applicable for octahedral complexes with d or d electronic
configuration.)
■
Q. 65. What are the salient features of valence bond theory (VBT) ? (3 marks)
Ans. The salient features of valence bond theory (VBT) are as follows :
(1) According to this theory, a central metal atom or ion present in a complex provides a definite number of vacant
orbitals (s, p, d and f ) to accommodate the electrons from the ligands for the formation coordinate bonds with the
metal ion / atom.
(2) The number of vacant orbitals provided by the central metal atom or ion is the same as the coordination number of
the metal. For example : Cu> provides 4 vacant orbitals in the complex. [Cu(NH ) ]>.

(3) The vacant orbitals of metal atom or ion undergo hybridisation forming the same number of hybridised orbitals,
since the bonding with the hybrid orbitals is stronger.
(4) Each ligand has one or more orbitals containing one or more lone pairs of the electrons.
(5) The shape or geometry of the complex depends upon the type of hybridisation of the metal ion / atom.
(6) When inner orbitals namely (n91) d orbitals in transition metal atom or ion hybridise, the complex is called inner
complex and when outer orbitals i.e., nd orbitals hybridise then the complex is called outer complex.
(7) When the central metal atom or ion in the complex contains one or more unpaired electrons the complex is
paramagnetic while if all the electrons are paired, the complex is diamagnetic. ■
★ Q. 66. What is the shape of a complex in which the coordination number of central metal ion is 4. (1 mark)
Ans. A complex with the coordination number of central metal ion equal to 4 may be tetrahedral or square planar.
■
★ Q. 67. What are strong field and weak field ligands ? Give one example of each.
Ans. The ligands are then classified as (a) strong field and (b) weak field ligands. Strong field ligands are those in which
donor atoms are C,N or P. Thus CN\, NC\, CO, HN , EDTA, en (ethylenediammine) are considered to be strong

ligands. They cause larger splitting of d orbitals and pairing of electrons is favoured. These ligands tend to form
low spin complexes. Weak field ligands are those in which donor atoms are halogens, oxygen or sulphur. For
example, F\, Cl\, Br\, l\, SCN\, C O \. In case of these ligands the R parameter is smaller compared to the

energy required for the pairing of electrons, which is called as electron pairing energy. The ligands then can be
arranged in order of their increasing field strength as
I\ Br\ Cl\ S\ F\ OH\ C O \ H O NCS\ EDTA NH en CN\ CO.
■
★ Q. 68. [CoCl ]\ is a tetrahedral complex. Draw its box orbital diagram. State which orbitals participate in

hybridisation. (2 marks)
Ans. Co [Ar] 3d 4s

Oxidation state of Co: ;2
Co> [Ar] 3d 4s
Since Cl\ is a weak ligand, there is no pairing of electrons. Since C.N. is 4, there is sp hybridisation.

★ Q. 69. With the help of crystal field energy level diagram explain why the complex [Cr(en) ]> is coloured ?

(2 marks)
Ans. Cr>:[Ar]3d4s
Since (en) is a strong field ligand there is pairing of electrons. The electrons occupy the t g orbitals of lower energy.

It has one unpaired electron. Due to d-d transition, it is coloured. ■
Q. 70. What is the spin pairing process in the coordination compound ? (3 marks)
Ans. When the ligands approach the metal atom or ion for the formation of a complex, they influence the valence
electrons of metal atom or ion. Accordingly the ligands are classified as (A) strong ligands and (B) weak ligands.
(A) Strong ligands :
(i) They cause the pairing of unpaired electrons present in the metal atom or ion.
(ii) Spin pairing process :
(a) The process of pairing of unpaired electrons in metal atom or ion due to the presence of ligands in the
complex is called spin pairing process.
(b) This spin pairing process decreases the number of unpaired electrons and hence decreases the
paramagnetic character of the complex.
(c) The strong ligands also promote the outer ns electrons to the vacant inner (n91)d orbitals.
(B) Weak ligands : The weak ligands have no effect on the electrons in the valence shell of a metal atom or ion.
\ , ethylenediammine (en), NH , EDTA, etc.
Strong ligands : CO, CN

Weak ligands : Cl\, I\, OH\, etc.
[Note : If a complex has n number of unpaired electrons then the magnetic moment, is given by ‘spin only’ formula :( n(n;2) B.M.
where B.M. (Bohr Magneton) is the unit of magnetic moment. Hence from the magnitude of , the number of unpaired electrons in the complex
and its structure can be evaluated.] ■
Units
9.9.2 Octahedral complexes
9.9.3 Tetrahedral complexes
9.9.4 Square planar complex
9.9.5 Limitations of VBT
Q. 71. Explain the structure of octahedral complex, [CO(NH ) ]> on the basis of valence bond theory.

(3 marks)
Ans.
(1) Hexaamminecobalt(III) ion, [CO(NH ) ]> is a cationic complex, the oxidation state of cobalt is ;3 and the

coordination number is 6.
(2) Electronic configuration : Co [Ar] 3d 4s

Electronic configuration : Co> [Ar] 3d 4s 4p
3d 4s 4p
Co> (Ground state)
2/Navneet Chemistry Digest : Std. XII (Part II) E0289 33

(3) Since NH is a strong ligand, due to spin pairing effect, all the four unpaired electrons in 3d orbital are paired

giving two vacant 3d orbitals.
3d 4s 4p
Co> (Excited state)
ZIIIII dsp hybridisation IIIIIJ
(4) Since the coordination number is 6, Co> ion gets six vacant orbitals by hybridisation of two 3d vacant orbitals,
one 4s and three 4p orbitals forming six dsp hybrid orbitals giving octahedral geometry. It is an inner complex.
Co>
3d dsp hybrid orbitals
(5) 6 lone pairs of electrons from 6NH ligands are accommodated in the six vacant dsp hybrid orbitals. Thus six

hybrid orbitals of Co> overlap with filled orbitals of NH forming 6 coordinate bonds giving octahedral geometry

to the complex.
Co> NH NH NH NH NH NH

[Co(NH ) ]> ;; ;; ;; ;; ;; ;;

Since the complex has all electrons paired, it is diamagnetic.
[Co(NH ) ]>

Fig. 9.5 : Structure of [Co(NH ) ]>

Complex Hybridisation Geometry Magnetic property
[Co(NH ) ]> dsp (inner) Octahedral Diamagnetic (:0)

■
Q. 72. Explain the geometry of [CoF ]\ on the basis of valence bond theory. (3 marks)

Ans.
(1) Hexafluorocobaltate(III) ion, [CoF ]\ is an anionic complex, the oxidation state of cobalt is ;3 and the

coordination number is 6.
(2) Electronic configuration : Co [Ar] 3d 4s 4p 4d

Electronic configuration : Co> [Ar] 3d 4s 4p 4d
3d 4s 4p 4d
Co> (Ground state)
ZIIIIII spd hybridisation IIIIIIJ
(3) Since F\ is a weak ligand, there is no spin pairing effect and Co> possesses 4 unpaired electrons.
(4) Since the coordination number is 6, the Co> ion gets six vacant orbitals by hybridisation of one 4s orbital, three 4p
orbitals and two 4d orbitals forming six spd hybrid orbitals giving octahedral geometry.
Co>
3d spd hybrid orbitals

(5) 6 lone pairs of electrons from 6F\ ligands are accommodated in the six vacant spd hybrid orbitals. Thus six
hybrid orbitals of Co> overlap with filled orbitals of F\ forming 6 coordinate bonds giving octahedral geometry
to the complex. It is an outer complex.
Co> F\ F\ F\ F\ F\ F\
[CoF ]\ ;; ;; ;; ;; ;; ;;

3d spd hybrid orbitals
As the complex has 4 unpaired electrons it is paramagnetic.
Magnetic movement is, :(n(n;2):(4(4;2):4.9 B.M.
[CoF ]\

Fig. 9.6 : Structure of [CoF ]\

[CoF ]\ spd (outer) Octahedral Paramagnetic (:4.9 B.M.)

■
Q. 73. Explain the structure of tetrachloronickelate(II) [NiCl ]\ on the basis of valence bond theory.

(3 marks)
Ans.
(1) Tetrachloronickelate(II) ion is an anionic complex, oxidation state of Ni is ;2 and the coordination number is 4.
(2) Electronic configuration : Ni [Ar] 3d 4s 4p

Electronic configuration : Ni> [Ar] 3d 4s 4p
3d 4s 4p
Ni> (Ground State)
sp hybridisation
(3) Since the coordination number is 4, it gets 4 vacant hybrid orbitals by sp-hybridisation of one 4s and three
4p orbitals giving tetrahedral geometry to the complex.
Ni>
3d sp hybrid orbitals
(4) As Cl\ is a weak ligand, 2 unpaired electrons in Ni> remain undisturbed.
(5) 4 lone pairs of electrons from 4Cl\ ligands are accommodated in the vacant four sp hybrid orbitals. Thus four
sp hybrid orbitals of Ni> overlap with filled orbitals of Cl\ forming 4 coordination bonds, giving tetrahedral
geometry to the complex.
Ni> Cl\ Cl\ Cl\ Cl\
[NiCl ]\ ;; ;; ;; ;;

3d sp hybrid orbitals
Since the complex has 2 unpaired electrons, it is paramagnetic.
Magnetic moment is, :(n(n;2):(2(2;2):2.83 B.M.
Fig. 9.7 : Structure of [NiCl ]\

Hybridisation Geometry Magnetic property
sp Tetrahedral Paramagnetic (:2.83 B.M.)
■
Q. 74. Explain the structure of [Ni(CN) ]\ on the basis of valence bond theory. (3 marks)

Ans.
(1) Tetracyanonickelate (II) ion, [Ni(CN) ]\ is an anionic complex, oxidation state of Ni is ;2 and the coordination

number is 4.
(2) Electronic configuration : Ni [Ar] 3d 4s 4p

Electronic configuration : Ni> [Ar] 3d 4s 4p
3d 4s 4p
Ni> (Ground state)
(3) Since CN\ is a strong ligand, one of the unpaired electrons in 3d orbital is promoted giving two paired electrons
and one vacant 3d orbital.
3d 4s 4p
Ni> (Excited state)
< dsp hybridisation ;
(4) Since the coordination number is 4, Ni> gets 4 vacant hybrid orbitals by hybridisation of one 3d, one 4s and two
4p orbitals forming four dsp hybrid orbitals. This has square planar geometry.
Ni>
(5) 4 lone pairs from 4CN\ ligands are accommodated in the vacant four dsp hybrid orbitals. Thus four dps hybrid
orbitals of Ni> overlap with filled orbitals of CN\ forming 4 coordinate bonds giving square planar geometry to
the complex. It is an inner complex.
Ni> CN\ CN\ CN\ CN\
[Ni(CN) ]\ ;; ;; ;; ;;

Since the complex ion has all electrons paired, it is diamagnetic.
Fig. 9.8 : Structure of [Ni(CN) ]\


[Ni(CN) ]\ dsp (inner) Square planar Diamagnetic (:0)
■
Remember ...
(Textbook page 202)
Complete the missing entries.
Coordination number Geometry of complex Hybridisation
2 Linear sp
4 Tetrahedral sp
4 Square planar dsp
6 Octahedral dsp/spd
(Note : The missing entries are underlined.)
Table 9.3 : Type of hybridisation and geometry of a complex

Type of hybridisation sp sp sp dsp dsp
Geometry Linear Triangular plane Tetrahedral Square planar Trigonal bipyramidal
Type of hybridisation dsp, spd dsp
Geometry Octahedral Pentagonal bipyramidal
(Note : Number of hybridised orbitals:Coordination number)

Q. 75. What are the limitations of valence bond theory ? (3 marks)
Ans. In case of the coordination compounds, the valence bond theory has the following limitations :
(1) It cannot explain the spectral properties (colours) of the complex compounds.
(2) Even if the magnetic moments can be calculated from the number of unpaired electrons, it cannot explain the
magnetic moment arising due to orbital motion of electrons.
(3) It cannot explain why the metal ions with the same oxidation state give inner complexes and outer complexes with
different ligands.
(4) In every complex, it cannot explain magnetic properties based on geometry of the complex.
(5) Quantitative interpretations of thermodynamic and kinetic stabilities of the coordination compounds cannot be
accounted.
(6) The complexes with weak field ligands and strong field ligands cannot be distinguished.
(7) It cannot predict the tetrahedral and square planar geometry of complexes with coordination number 4.
(8) The order of reactivity of inner complexes of d, d, d and d metal ions cannot be explained.
(9) It cannot explain the rates and mechanisms of reactions of the coordination compounds. ■
Try this …
(Textbook page 204)
Q. Based on the VBT predict structure and magnetic behaviour of the [Ni(NH ) ]> complex.

Ans. Ni [Ar] 3d 4s

Ni> [Ar] 3d 4s
Hybridisation : spd
Geometry : Octahedral
Magnetic property : Paramagnetic
Units
9.9.6 Crystal field theory (CFT)
9.9.7 Factors affecting Crystal Field splitting parameter ( )

9.9.8 Colour of the octahedral complexes
9.9.9 Splitting of d-orbitals in tetrahedral and octahedral complexes
Q. 76. What are the assumptions of Crystal Field Theory (CFT) ? (3 marks)
Ans. Bethe and van Vleck developed Crystal Field Theory (CFT) to explain various properties of coordination
compounds. The salient features of CFT are as follows :
(1) In a complex, the central metal atom or ion is surrounded by various ligands which are either negatively charged
ions (F\, Cl\, CN\, etc.) or neutral molecules (H O, NH , en, etc.) and the most electronegative atom in them

points towards central metal ion.
(2) The ligands are treated as point charges involving purely electrostatic attraction between them and metal ion.
(3) (i) The central metal ion has five, (n91) d degenerate orbitals namely d , d , d , d(x9y) and dz.
VW WX XV
(ii) When the ligands approach the metal ion, due to repulsive forces, the degeneracy of d-orbitals is destroyed
and they split into two groups of different energy, t g and eg orbitals. This effect is called crystal field splitting

which depends upon the geometry of the complex.
(iii) The d-orbitals lying in the direction of ligands are affected to a greater extent while those lying in between
the ligands are affected to a less extent.
(iv) Due to repulsion, the orbitals along the axes of ligands acquire higher energy while those lying in between the
ligands acquire less energy.
(v) Hence repulsion by ligands give two sets of split up orbitals of metal ion with different energies.
(vi) The energy difference between two sets of d-orbitals after splitting by ligands is called crystal field splitting
energy (CFSE) and represented by or by arbitrary term 10Dq. The value of or 10Dq depends upon the

geometry of the complex.
(4) The electrons of metal ion occupy the split d-orbitals according to Hund’s rule, aufbau principle and those orbitals
with minimum repulsion and the farthest away from the ligands.
(5) CFT does not account for overlapping of orbitals of central metal ion and ligands, hence does not consider covalent
nature of the complex.
(6) From the crystal field stability energy, the stability of the complexes can be known.
Fig. 9.9 : Shapes of d–orbitals ■

Q. 77. What is crystal field splitting ? (1 mark)
Ans. The splitting of five degenerate d-orbitals of the transition metal ion into different sets of orbitals (t2g and eg)
having different energies in the presence of ligands in the complex is called crystal field splitting. ■
Try this …
(Textbook page 202)
Q. Give VBT description of bonding in each of following complexes. Predict their magnetic behaviour.
(a) [ZnCl ]\

(b) [Co(H O) ]> (high spin)

(c) [Pt(CN) ]\ (square planar)

(d) [CoCl ]\ (tetrahedral)

(e) [Cr(NH ) ]>

Ans.
Complex ion Hybridisation Geometry Magnetic property
(a) [ZnCl ]\ sp Tetrahedral Diamagnetic

(b) [Co(H O) ]> spd Octahedral Paramagnetic

(c) [Pt(CN) ]\ dsp Square planar Diamagnetic

(d) [CoCl ]\ sp Tetrahedral Paramagnetic

(e) [Cr(NH ) ]> dsp Octahedral Paramagnetic

Q. 78. What is crystal field stabilisation energy ? (1 mark)

Ans. Crystal field stabilisation energy (CFSE) : It is the change in energy achieved by preferential filling up of the
orbitals by electrons in the complex of metal atom or ion.
CFSE is expressed as a negative quantity i.e., CFSE 0. Higher the negative value more is the stability of the
complex. ■
Q. 79. Explain the factors affecting Crystal Field Splitting parameter ( ). (2 marks)

Ans. Crystal Field Splitting parameter ( ) depends on, (a) Strength of the ligands and (b) Oxidation state of

the metal.
(a) Strength of the ligands : Since strong field ligands like CN\, en, etc. approach closer to the central metal ion, it
results in a large crystal field splitting and hence has higher values.

(b) Oxidation state of the metal : A metal ion with the higher positive charge draws the ligands closer to it which
results in large separation of t g and eg set of orbitals. The complexes involving metal ions with low oxidation state

have low values of . For example [Fe(NH ) ]> has higher than [Fe(NH ) ]>.
■
Q. 80. Explain the octahedral geometry of complexes using crystal field theory. (3 marks)
Ans.
(1) In an octahedral complex [MX ]n<, the metal atom or ion is placed at the centre of regular octahedron while six

ligands occupy the positions at six vertices of the octahedron.
(2) Among five degenerate d-orbitals, two orbitals namely dx9y and dz are axial and have maximum electron density
along the axes, while remaining three d-orbitals namely dxy, dyz and dzx are planar and have maximum electron
density in the planes and in-between the axes.
(3) Hence, when the ligands approach a metal ion, the orbitals dx9y and dz
experience greater repulsion and the orbitals dxy, dyz and dzx experience less
repulsion.
(4) Therefore the energy of dx9y and dz increases while the energy of dxy, dyz and
dzx decreases and five d-orbital lose degeneracy and split into two point groups.
The orbitals dxy, dyz and dzx form t g group of lower energy while dx9y and dz

form eg group of higher energy.
Thus t has three degenerate orbitals while eg has two degenerate orbitals.
g
(5) Experimental calculations show that the energy of t g orbitals is lowered by
Fig. 9.10 : Octahedral geometry
0.4o or 4Dq and energy of eg orbital is increased by 0.6o or 6Dq. Thus energy
having central metal (M) at the
difference between t g and eg orbitals is or 10Dq which is crystal field
centre and six ligands (L) at the
splitting energy. vertices of the octahedron.
Fig. 9.11 : Crystal field splitting in octahedral complex
(6) CFSE increases with the increasing strength of ligands and oxidation state of central metal ion. ■
Q. 81. Explain the tetrahedral geometry of complexes using crystal field theory. (3 marks)
Ans.
(1) In the tetrahedral complex, [MX ]n<, the metal atom or ion is placed at the centre of the regular tetrahedron and the

four ligands, are placed at four corners of the tetrahedron.
(2) The ligands approach the central metal atom or ion in-between the three coordinates x, y and z. The orbitals dxy , dyz
and dzx are pointed towards ligands and experience greater repulsion while the axial orbitals dx–y and dz lie
in-between metal –ligand bond axes and experience comparatively less experience.
(a) (b)
Fig. 9.12 (a) and (b) : Tetrahedral geometry having central metal atom (M) at the centre and four ligands (L) at the four corners
(3) Therefore energy of dxy , dyz and dzx orbitals is increased while that of dx-y and dz is lowered. Hence 5d-orbitals lose
their degeneracy and split into two point groups, namely t g of higher energy (dxy, dyzand dzx ) and eg of lower energy

(dx9y and dz ).

Fig. 9.13 : Crystal field splitting in tetrahedral complex
(4) The experimental calculations show that the energy of t g orbitals is increased by 0.4 or 4Dq and energy of eg is

lowered by 0.6 or 6Dq. Thus energy difference between t g and eg orbitals is or 10Dq which is crystal field

splitting energy (CFSE).
(5) This explains that the entry of each electron in eg orbitals, stabilises the complex by 0.6 or 6Dq. While the entry

of each electron in t g orbitals destabilises tetrahedral complex by 0.4 or 4Dq.

(6) In case of strong field ligands, the electrons prefer to pair up in eg orbitals giving low spin (LS) complexes while in
case of weak field ligands, the electrons prefer to enter higher energy t g orbitals giving more unpaired electrons

and hence form high spin (HS) complexes.
Table 9.4 : Properties of complexes
(1) [NiCl ]\ sp Tetrahedral Paramagnetic

(2) [Ni(CO) ] sp Tetrahedral Diamagnetic

(3) [Ni(CN) ]> dsp Square planar Diamagnetic

(4) [CuCl ]\ sp Tetrahedral Paramagnetic

(5) [Cu(NH ) ]> dsp (inner) Square planar Paramagnetic

(6) [Fe(H O) ]> spd (outer) Octahedral Paramagnetic

(7) [Fe(CN) ]\ dsp (inner) Octahedral Paramagnetic

(8) [Fe(CO) ] dsp (inner) Trigonal bipyramidal Diamagnetic

(9) [Cr(H O) ]> spd (outer) Octahedral Paramagnetic

(10) [Co(NH ) ]> dsp (inner) Octahedral Diamagnetic

■
★ Q. 82. What are high spin and low spin Complexes ? (2 marks)
Ans.
(1) High spin complex (HS) :
(i) The complex which has greater number of unpaired electrons and hence higher value of resultant spin and
magnetic moment is called high spin (or spin free) or HS complex.
(ii) It is formed with weak field ligands and the complexes have lower values for crystal field splitting energy
(CFSE), o.
(iii) The paramagnetism of HS complex is larger.
(2) Low spin complex (LS) :
(i) The complex which has the least number of unpaired electrons or all electrons paired and hence the lowest
(or no) resultant spin or magnetic moment is called low spin (or spin paired) or LS complex.
(ii) It is formed with strong field ligands and the complexes have higher values of crystal field splitting
energy (o ).
(iii) Low spin complex is diamagnetic or has low paramagnetism. ■
Table 9.5 : d-orbital diagrams for high spin and low spin complexes
d-orbital
High spin Low spin
electronic
configuration
d eg
t
g
d eg
t
g
d eg
t
g
d eg
t
g
(Only the electronic configurations d to d render the high spin and low spin complexes)
Try this...
(Textbook page 206)
Q. Sketch qualitatively crystal field d orbital energy level diagrams for each of the following complexes :
(a) [Ni(en) ]> (b) [Mn(CN) ]\ (c) [Fe(H O) ]>

Predict whether each of the complexes is diamagnetic or paramagnetic.
Ans.
(a) The complex ion, [Ni(en) ]> is octahedral.

Ni [Ar] 3d 4s

Ni> [Ar] 3d 4s
Since en is a strong ligand there is pairing of electrons.

Number of unpaired electrons:n:2 in t g orbitals

Magnetic moment::(n(n;2)
:(2(2;2):2.83 B.M.
The complex ion is paramagnetic.

(b) The complex ion [Mn(CN) ]\ is octahedral.

Mn [Ar] 3d 4s

Mn> [Ar] 3d 4s
Since CN\ is a strong ligand there is pairing of electrons.

Number of unpaired electrons:n:2 in t g orbitals

:(2(2;2):2.83 B.M.
(c) The complex ion [Fe(H O) ]> is octahedral.

Fe [Ar] 3d 4s

Fe> [Ar] 3d 4s
Since H O is a weak ligand, there is no pairing

of electrons.
Number of unpaired electrons:n:4 in t g

and eg orbitals.
:(4(4;2)
:4.90 B.M.
★ Q. 83. Give valence bond description for the bonding in the complex [VCl ]\. Draw box diagrams for free

metal ion. Which hybrid orbitals are used by the metal ? State the number of unpaired electrons. (3 marks)
Ans. V [Ar] 3d 4s

V> [Ar] 3d 4s
Since Cl\ is a weak ligand, there is no pairing of electrons.

Number of unpaired electrons:2
Type of hybridisation:sp
Geometry of complex ion:Tetrahedral
The complex ion is paramagnetic. ■
★ Q. 84. (A) Draw qualitatively energy-level diagram showing d-orbital splitting in the octahedral environment.
(B) Predict the number of unpaired electrons in the complex [Fe(CN) ]\. (C) Is the complex diamagnetic

or paramagnetic ? (D) Is it coloured ? Explain. (4 marks)
Ans. (A) d-orbital splitting in the octahedral environment :
(B) [Fe (CN) ]\ is an octahedral complex.

(C) Since CN\ is a strong ligand, there is pairing of electrons and the complex is diamagnetic.
(D) The complex exists as lemon yellow crystals.
(In the complex all electrons in t
are paired and requires high radiation energy for excitation.) ■
g
Q. 85. Write a note on colour in coordination compounds. (3 marks)
Ans.
(1) A large number of coordination compounds show wide range of colours due to d-d transition of electron and this
can be explained by crystal field theory (CFT).
(2) The complex absorbs the light in one visible region (400 nm to 700 nm) and transmits the light in different visible
region giving complementary colour.
(3) Consider an octahedral purple coloured complex of [Ti(H O) ]> which absorbs green light and transmits purple

colour. Similarly [Cu(H O) ]> absorbs the light in the red region of radiation spectrum and transmits in the blue

region, hence the complex appears blue.
(4) The absorption of light arises due to d-d transition of electron from lower energy level (t g ) to higher energy level

(eg) in octahedral complex.
(5) The energy required for transition depends upon crystal field splitting energy . If :E, then the energy of an

absorbed photon (h) is
hc
E:h:

where , and c are wavelength, frequency and velocity of the absorbed light.
(6) Higher the magnitude of or E, higher is the frequency or lower is the wavelength of the absorbed radiation.

(7) Since depends upon nature of metal atom or ion, its oxidation state, nature of ligands and the geometry of the

complex, different coordination compounds have different colours. ■
Q. 86. Explain the purple colour of the complex, [Ti(H O) ]> with the help of crystal field theory. (3 marks)

Ans.
(1) [Ti(H O) ]> is an octahedral complex, oxidation state of titanium is ;3 (Ti>) and the coordination

number is 6.
(2) Electronic configuration: Ti [Ar] 3d 4s

Electronic configuration:Ti> [Ar] 3d OR

(3) According to crystal field theory, 3d orbitals undergo crystal field splitting giving higher energy eg, two orbitals and
lower energy t g , three orbitals.

Fig. 9.14 : Crystal field splitting in [Ti(H O) ]>

(4) The crystal field splitting energy (CFSE), is found to be 3.99;10\ J/ion from the spectrochemical studies.

(5) The absorption of radiation of wavelength or frequency results in the transition of one unpaired electron from
t g orbital to eg orbital.

t2g eg ----E t g eg

Lower energy configuration Higher energy configuration
Fig. 9.15 : Photon absorption and the absorption spectrum of [Ti(H O) ]>

(6) The wavelength of the absorbed radiation will be,
hC
: E:h:

Js ms\
hC 6.63;10\;3;10
: :
E 3.99;10\
J / ion
:4.98;10\ m :498 nm
(7) Hence the complex [Ti(H O) ]> absorbs the green radiation of wavelength 498 nm in the visible region and

transmits the complementary purple light. Therefore the complex is purple coloured. ■
Q. 87. An octahedral complex absorbs the radiation of wavelength 620 nm. Find the crystal field splitting energy.
(2 marks)
Ans. Crystal field splitting energy is given by,

Js ms\
hC 6.63;10\;3;10
: E: :
620;10\
m
:3.2;10\ J ■
Unit
9.10 Applications of coordination compounds
Q. 88. What are the applications of coordination compounds ? (1 mark for each application)
Ans.
(1) In biology : Several biologically important natural compounds are metal complexes which play an important role
in number of processes occurring in plants and animals.
For example, chlorophyll in plants is a complex of Mg> ions, haemoglobin in blood is a complex of iron, vitamin
B is a complex of cobalt.

(2) In medicine : The complexes are used on a large scale in medicine. Many medicines in the complex form are more
stable, more effective and can be assimilated easily.
For example, platinum complex [Pt(NH ) Cl ] known as cisplatin is effectively used in cancer treatment.

EDTA is used to treat poisoning by heavy metals like lead.
(3) To estimate hardness of water :
(1) The hardness of water is due to the presence Mg> and Ca> ion in water.
(2) The strong field ligand EDTA forms stable complexes with Mg> and Ca>. Hence these ions can be removed
by adding EDTA to hard water.
Similarly these ions can be selectively estimated due to the difference in their stability constants.
(4) Electroplating : This involves deposition of a metal on the other metal. For smooth plating, it is necessary to
supply continuously the metal ions in small amounts.
For this purpose, a solution of a coordination compound is used which dissociates to a very less extent. For
example, for uniform and thin plating of silver and gold, the complexes K[Ag(CN) ] and K [Au(CN) ] are used.

■
★ Q. 89. Mention two applications of coordination compounds. (2 marks)

Ans. For answer refer to Q. 88. ■
Activity : (Textbook page 209)

(1) The reaction of chromium metal with H SO in the absence of air gives blue solution of chromium ion.

Cr(s) ;2H>(aq) ; Cr>(aq) ;H (s)

Cr> forms octahedral complex with H O ligands.

(a) Write formula of the complex.
(b) Describe bonding in the complex using CFT and VBT.
Draw crystal field splitting and valence bond orbital diagrams.
(2) Reaction of complex [Co(NH ) (NO ) ] with HCl gives a complex

[Co(NH ) H OCl ]> in which two chloride ligands are trans to one another.

(a) Draw possible stereoisomers of starting material
(b) Assuming that NH groups remain in place, which of two starting isomers would give the observed

product ?
(Note : Students are supposed to carry out these activity on their own.)

...
... ★ 7. When an excess of AgNO is added to the complex
...
... one mole of AgCl is precipitated. The formula of
Q. 90. Select and write the most appropriate answer ...
... the complex is
from the given alternatives for each subquestion : ...
... (a) [CoCl (NH ) ]Cl
(1 mark each) ...
... (b) [CoCl(NH ) ]Cl
...
★ 1. The oxidation state of cobalt ion in the complex ... (c) [CoCl (NH ) ]
...
[Co(NH ) Br]SO is ... (d) [Co(NH ) ]Cl
...
(a) ;2 (b) ;3 ... ★ 8. The sum of coordination number and oxidation
...
(c) ;1 (d) ;4 ... number of M in [M(en) C O ]Cl is
...
... (a) 6 (b) 7 (c) 9 (d) 8
★ 2. IUPAC name of the complex [Pt(en) (SCN) ]> is ...
...
(a) bis(ethylenediamine dithiocyanatoplatinum ... 9. The coordination number of cobalt in the complex
... [Co(en) Br ]Cl is
(IV) ion ...
... (a) 4 (b) 5 (c) 6 (d) 7
(b) bis(ethylenediamine) dithiocyantoplatinate ...
...
(IV) ion ... 10. EDTA combines with cations to form
...
(c) dicyanatobis(ethylenediamine)platinate(IV) ... (a) chelates
...
ion ... (b) polymers
...
(d) bis(ethylenediammine)dithiocynatoplatinate ... (c) clathrates
...
(IV) ion ... (d) non-stoichiometric compounds
...
... 11. Which one of the following compounds can exhibit
★ 3. Formula for the compound sodium hexacynofer- ...
... coordination isomerism ?
rate (III) is ...
... (a) [Co(en) Cl ]Br
(a) [NaFe(CN) ]

(b) Na [Fe(CN) ]

...
... (b) [Co(NH ) ] [Cr(CN) ]
(c) Na[Fe(CN) ]

(d) Na [Fe(CN) ]

...
... (c) [Co(en) ]Cl
...
★ 4. Which of the following complexes exist as cis and ... (d) [Co(NH ) NO ]Cl
...
trans isomers ? ...
... 12. Which of the following compounds can exhibit
(1) [Cr(NH ) Cl ]\ ...
... linkage isomerism ?
(2) [Co(NH ) Br]> ...
... (a) [Co(en) ]Cl (b) [Co(en) Cl ]Cl
(3) [PtCl Br ]\ (square planar) ...
... (c) [Co(en) NO Br]Cl (d) [Co(NH ) Cl]Br
(4) [FeCl (NCS) ]\ (tetrahedral) ...
... 13. Oxidation number of cobalt in K[CoCl ] is
(a) 1 and 3 (b) 2 and 3 ...
... (a) ;1 (b) 91 (c) ;3 (d) 93
(c) 1 and 2 (d) 4 only ...
... 14. The correct structure of [Cr(H O) ]> is ...
...
★ 5. Which of the following complexes are chiral ? ... (a) octahedral
...
(1) [Co(en) Cl ]> (2) [Pt(en)Cl ] ...
... (b) tetrahedral
(3) [Cr(C O ) ]\ (4) [Co(NH ) Cl ]> ...
... (c) square pyramidal
(a) 1 and 3 (b) 2 and 3 ... (d) trigonal bipyramidal
...
(c) 1 and 4 (d) 2 and 4 ...
... 15. Amongst the following ions which one has the
...
★ 6. On the basis of CFT predict the number of un- ... highest paramagnetism ?
...
paired electrons in [CrF ]\ . ... (a) [Cr(H O) ]> (b) [Fe(H O) ]>
...
(a) 1 (b) 2 (c) 3 (d) 4 (c) [Cu(H O) ]> (d) [Zn(H O) ]>

...
16. The geometry of [Ni(CN) ]\ and [NiCl ]\ are ... 24. The strongest ligand in the following is
...
(a) both tetrahedral ... (a) CN\ (b) Br\ (c) HO\ (d) F\
...
(b) both square planar ... 25. Magnetic moment of (NH ) (MnBr ) is ...... BM
...
(c) tetrahedral and square planar respectively ... (a) 5.91 (b) 4.91 (c) 3.91 (d) 2.91
...
(d) square planar and tetrahedral respectively ...
... 26. The complex which violates EAN rule is
...
17. The complex cis-[Pt(NH ) Cl ] is used in treat- ... (a) Fe(CO) (b) [Fe(CN) ]\
...
ment of cancer under the name. ... (c) Ni(CO) (d) [Zn(NH ) ]Cl
...
(a) Aspirin (b) Eqanil ... 27. EDTA is a ligand of the type
...
(c) cisplatin (d) transplatin ... (a) bidentate (b) tridentate
...
18. [Co(NH ) ]> is an ....... orbital complex and is ... (c) tetradentate (d) hexadentate
...
...... in nature. ...
... 28. The cationic complex among the following is
(a) inner, paramagnetic ...
... (a) K [Fe(CN) ] (b) Ni(CO)
...
(b) inner, dimagnetic ... (c) K HgI (d) [Co(NH ) ]Cl
...
(c) outer, paramagnetic ...
... 29. If Z is the atomic number of a metal, X is number
(d) outer, dimagnetic ... of electrons lost forming metal ion and Y is the
...
19. The IUPAC name of [Ni(Co) ] is ... number of electrons from the ligands then EAN is
...
(a) tetra carbonyl nickel (O) ... (a) Z;X;Y (b) X9Z;Y
...
(b) tetra carbonyl nickel (II) ... (c) Z9X;Y (d) X;Z9Y
...
(c) tetra carbonyl nickelate (O) ...
... 30. Octahedral complex has hybridisation,
(d) tetra carbonyl nickelate (II) ...
... (a) dsp (b) dsp (c) dsp (d) dsp
...
20. The number of ions produced by the complex ... 31. Inner complex has hybridisation,
...
[Co(NH ) Cl ] Cl is ... (a) dsp (b) spd (c) spd (d) spd
...
(a) 1 (b) 2 (c) 3 (d) 4 ...
... 32. The number of unpaired electrons in
21. The dimagnetic species is ... [Co(NH ) ]> is
...
(a) [Ni(CN) ]\ (b) [NiCl ]\ ... (a) 0 (b) 1 (c) 2 (d) 4
...
(c) [CoCl ]\ (d) [CoF ]\ ...
... 33. The number of unpaired electrons in [NiCl ]\

...
22. Which one of the following is an inner orbital ... and [Ni(CN) ]\ are respectively,
...
complex as well as dimagnetic in behaviour ... (a) 2, 2 (b) 2, 0 (c) 0, 0 (d) 1, 2
...
(Atomic no. Zn:30, Cr:24, Co:27, Ni:28) ... 34. Among the following complexes, the highest
...
(a) [Zn(NH ) ]> (b) [Cr(NH ) ]> ... magnitude of crystal field stabilisation energy will
...
(c) [Co(NH ) ]> (d) [Ni(NH ) ]> ... be for
...
... [Co(H O) ]>, [Co(CN) ]\, [Co(NH ) ]>,
23. Among [Ni(Co) ], [Ni(CN) ]\, [NiCl ]\ ...
...
Species, the hybridisation states at the Nickel atom [CoF ]\
...
... (a) [Co(H O) ]> (b) [Co(CN) ]\
are respectively ...
... (c) [Co(NH ) ]> (d) [CoF ]\
(a) sp, dsp, sp ...
...
(b) sp, dsp, dsp ... 35. The number of unpaired electrons in a low spin
...
(c) dsp, sp, sp ... octahedral complex ion of d is
...
(d) sp, sp, dsp (a) 0 (b) 1 (c) 2 (d) 3

..
36. The number of unpaired electrons in a high spin ... 11. (b) [Co(NH ) ] [Cr(CN) ]
...
octahedral complex ion of d is ... 12. (c) [Co(en) NO Br]Cl
...
(a) 0 (b) 1 (c) 2 (d) 3 ... 13. (b) 91
..
37. Ligand used in the estimation of hardness of water .... 14. (a) octahedral
...
is ...
... 15. (b) [Fe(H O) ]>
(a) EDTA (b) DBG (c) chloride (d) bromo ...
... 16. (d) square planar and tetrahedral respectively
38. Which of the following complexes will give a ...
... 17. (c) cisplatin
white precipitate on treatment with a solution of ...
... 18. (b) inner, dimagnetic
barium nitrate ? ...
... 19. (a) tetra carbonyl nickel (O)
(a) [Cr(NH ) SO ] Cl ...
... 20. (b) 2
(b) [Co(NH ) Cl ] NO ...
... 21. (a) [Ni(CN) ]\
(c) [Cr(NH ) Cl ] SO
...
(d) [CrCl (H O) ] Cl ... 22. (c) [Co(NH ) ]>
...
... 23. (a) sp, dsp, sp
39 What is effective atomic number of Fe (z:26) in ...
[Fe(CN) ]\ ?
... 24. (a) CN\
...
(a) 12 (b) 30 (c) 26 (d) 36 ... 25. (a) 5.91
...
... 26. (b) [Fe(CN) ]\
40. Cisplatin compound is used in the treatment of ...
(a) malaria (b) cancer ...
... 27. (d) hexadentate
(c) AIDS (d) yellow fever ...
... 28. (d) [Co(NH ) ]Cl
...
Answers ... 29. (c) Z9X;Y
...
... 30. (d) dsp
1. (b) ;3 ...
... 31. (a) dsp
2. (a) bis(ethylenediamine dithiocyanatoplatinum (IV) ...
... 32. (a) 0
ion ...
... 33. (b) 2, 0
3. (d) Na [Fe(CN) ] ...
... 34. (b) [Co(CN) ]\
4. (a) 1 and 3 ...
... 35. (b) 1
5. (a) 1 and 3 ...
... 36. (d) 3
6. (c) 3 ...
... 37. (a) EDTA
7. (a) [CoCl (NH ) ]Cl ...
... 38. (c) [Cr(NH ) Cl ] SO
8. (c) 9 ...
...
... 39. (d) 36
9. (c) 6 ...
... 40. (b) cancer
10. (a) chelates ...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
.
10. HALOGEN DERIVATIVES
10 HALOGEN DERIVATIVES
CHAPTER OUTLINE
Page No.
.... Important Definitions and Reactions … 51
.... Exercises
10.1 Classification of halogen derivatives … 53

10.1.1 Classification of monohalogen compounds … 54
10.2 Nomenclature of halogen derivatives … 56
10.3 Methods of preparation of alkyl halides/aryl halides … 63
10.3.1 From alcohol … 63
10.3.2 From hydrocarbon … 66
10.3.3 Halogen exchange … 70
10.3.4 Electrophilic substitution … 71
10.3.5 Sandmeyer’s reaction … 71
10.4 Physical properties … 71
10.4.1 Nature of intermolecular forces … 71
10.4.2 Boiling Point … 71
10.4.3 Solubility … 71
10.5 Optical isomerism in halogen derivatives … 73
10.5.1 Chiral atom and molecular chirality … 73
10.5.2 Plane polarized light … 73
10.5.3 Optical activity … 73
10.5.4 Enantiomers … 73
10.5.5 Representation of configuration of molecules … 77
10.6 Chemical properties … 78
10.6.1 Laboratory test of haloalkanes … 78
10.6.2 Nucleophilic substitution reaction of haloalkanes … 78
10.6.3 Mechanism of SN reaction … 84
10.6.4 Factors influencing SN1 and SN2 mechanism … 87
10.6.5 Elimination reaction : Dehydrohalogenation … 91
10.6.6 Reaction with active metals … 96
10.6.7 Reaction of haloarenes … 98
10.7 Uses and environmental effects of some polyhalogen compounds … 108
10.7.1 Uses of some polyhalogen compounds … 108
10.7.2 Environmental effects of some polyhalogen compounds … 110
.... Multiple Choice Questions … 111

1. Classification of Halogen derivatives :
Halogen derivatives
!
!D !D !D !D
Haloalkanes Haloalkenes Haloalkynes Haloarenes
Halogen derivatives
!
!D !D !D
Monohalogen compounds Dihalogen compounds Trihalogen compounds
Alkyl halides or Haloalkanes

!
!D !D !D
Primary alkyl halide Secondary alkyl halide Tertiary alkyl halide
Alkyl halides (Based on halogen atom bonded to sp, sp and sp hybridised carbon)
!
!D !D !D !D !D
Allylic halide Benzylic halide Vinylic halides Haloalkyne Aryl halides
2. Preparation and Reactions of alkyl halides :

Preparation methods Reactions
Hx aq. NaOH or aq. KOH

IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIJ R9OH alcohols
PCl
R9OH R9ONa ;
SOCl R9OR Ethers

IIIIIIIIIIIIIIIIIIJ
X RCOOAg
Alkanes
IIIIIII IIIIIIIIIIJ RX IIIIIIIIIIJ
IIIIIIIIIIIIIIIIIIJ R9COOR Ester
light
Alkyl halide NH
R9NH Amine

IIIIIIIIIIIIIIIIIIJ
HX excess
Alkenes IIIIII
aq. KCN
IIIIIIIIIIIIIIIIIIJ R9CN Alkyl cyanide
Alkyl halide NaI
AgCN
IIIIIIIIIIIJ R9NC Alkyl isocyanide
KO9N:O
IIIIIIIIIIIIIIIIIIIIIJ R9O9N:O Alkyl nitrite
;
Ag9O9N:O O
IIIIIIIIIIIIIIIIIIIIIIIIIIJ R9N 9Nitroalkane
O
Alc. KOH
IIIIIIIIIIIIIIIIIJ Olefins (alkenes)
Mg, ether
IIIIIIIIIIIIIIIIIJ RMgX (Grignard reagent)
Na, dry ether
IIIIIIIIIIIIIIIIIIIIIIJ R9R Higher alkane (Wurtz reaction)
10. HALOGEN DERIVATIVES 51

3. Preparation of haloarenes :
4. Reactions of chlorobenzene :

(i)
(ii)
(iii)
5. Uses and environmental effects :

(1) Dichloromethane (CH Cl ) (2) Chloroform (CHCl ) (3) Carbon tetrachloride (CCl )

(4) Iodoform (CHI ) (5) Freons (CCl F ) (6) Dichlorodiphenyltrichloro ethane (DDT)

(★ ) Indicates questions from the textbook.
Unit
10.1 Classification of halogen derivatives
Q. 1. What are halogen derivatives of hydrocarbons ? (1 mark)

Ans. The replacement of hydrogen atom/s in aliphatic or aromatic hydrocarbons by halogen atom/s results in the
formation of halogen derivatives of hydrocarbons. ■
Q. 2. How are halogen derivatives of hydrocarbons classified ? (3 marks)

Ans. Halogen derivatives of alkane are classified as :
Halogen derivatives
!
!D !D
Monohalogen derivatives Polyhalogen derivatives

(Alkyl halides) !
!D !D !D
Dihalogen Trihalogen Tetrahalogen

derivatives derivatives derivatives
!
!D !D
Vicinal Geminal
dihalides dihalides

(1) Monohalogen derivative (or alkyl halide) : It is a halogen derivative of an alkane in which one hydrogen atom is
replaced by one halogen atom and it is also called alkyl halide. E.g. C H Br.

(2) Polyhalogen derivatives : These are halogen derivatives in which more than one hydrogen atoms of an alkane
are substituted by corresponding number of halogen atoms.
They are classified as follows :
(i) Dihalogen derivatives : The compounds formed by the substitution of two hydrogen atoms of an alkane by
two halogen atoms are called dihalogen derivatives. E.g. CH Cl .

They are further classified as :
(a) Vicinal dihalides : CH 9CH (Two halogen atoms on vicinal or adjacent carbon atoms)

Cl Cl
(b) Geminal dihalides : CH 9CHCl (Two halogen atoms on the same carbon atom)

(ii) Trihalogen derivatives : The compounds formed by the substitution of three hydrogen atoms of an alkane
by three halogen atoms are called trihalogen derivatives. E.g. CHCl , CH 9CH 9CH ,

Cl Cl Cl
(iii) Tetrahalogen derivatives : The compounds formed by the substitution of four hydrogen atoms of an alkane
by four halogen atoms are called tetrahalogen derivatives. E.g. CCl . ■

Unit
10.1.1 Classification of monohalogen compounds
Q. 3. What are alkyl halides ? How are they classified ? (3 marks)

Ans. The compound formed by the replacement of one hydrogen atom in an alkane by a halogen atom is called an alkyl
halide. The halogen atom is bonded to sp hybridised carbon. Alkyl halides are classified into the following three
classes depending on the type of the carbon to which halogen atom is bonded.
(1) Primary (1°) alkyl halide : Alkyl halide in which a halogen atom is bonded to a primary carbon atom is called
primary alkyl halide.
[Primary (1°) carbon atom i.e., the carbon atom which is attached to only one carbon atom.]
CH CH
° ° °
CH CH – CH –Cl CH – CH– CH –Br CH – C— CH –Br

ethyl chloride isobutyl bromide
CH

neopentyl bromide
°

They are represented by the general formula R– CH –X.

(2) Secondary (2°) alkyl halide : Alkyl halide in which a halogen atom is bonded to a secondary carbon atom is
called secondary alkyl halide. [Secondary (2°) carbon i.e., the carbon atom which is attached to two other carbon
atoms.]
° °
CH – CH –CH CH –CH – CH –CH

Br Cl
iso-propyl bromide sec-butyl chloride

°
They are represented by the general formula R– CH –X (R and R can be same or different)

R
(3) Tertiary (3°) alkyl halide : Alkyl halide in which halogen atom is bonded to a tertiary carbon atom is called
tertiary alkyl halide. [Tertiary (3°) carbon i.e., the carbon atom which is attached to three other carbon atoms.]
CH C H
° °
CH – C –Br CH – C –CH

CH Cl

tert-butyl bromide tert-pentyl chloride
R

They are represented by the general formula R– C–X (R, R and R may be same or different) ■

R
Q. 4. Explain the following :

(1) Alkyl halide or haloalkanes (2) Allylic halides (3) Benzylic halide (4) Vinylic halide
(5) Haloalkyne (6) Aryl halide or haloarenes. (1 mark each)
Ans.
(1) Alkyl halide or haloalkanes : In alkyl halides or haloalkanes the halogen atom is bonded to sp hybridized carbon
which is a part of saturated carbon chain.
Example : CH 9CH 9CH 9Br

n-proyl bromide
(2) Allylic halides : In allylic halides, halogen atom is bonded to a sp hybridized carbon atom next to a
carbon-carbon double bond.
Example :
CH :CH9CH 9Br

Allyl bromide
(3) Benzylic halide : In benzylic halides, halogen atom is bonded to a sp hybridized carbon atom which is further
bonded to an aromatic ring.
Example :
(4) Vinylic halides : In vinylic halides, halogen atom is bonded to a sp hybridized carbon atom of aliphatic chain.
Vinylic halide is a haloalkene.
Example : CH :CH9Br

Vinyl bromide
(5) Haloalkyne : In haloalkynes, halogen atom is bonded to a sp hybridized carbon atom.

Example : CH Y C9Cl
Chloro acetylene

(6) Aryl halides or haloarenes : In aryl halides, halogen atom is directly bonded to the sp hybridized carbon atom of
aromatic ring.
Example :
■
Unit
10.2 Nomenclature of halogen derivatives
Q. 5. Give the IUPAC names of the following : (1 mark each)
Compound Ans. names

Ans. IUPAC
(1) CH – Br Bromomethane

(2) CH – CH – Br Bromoethane

(3) CH – CHCl 1,1-Dichloroethane

(4) Cl – CH – CH – Cl 1,2-Dichloroethane

(5) CH Cl Dichloromethane

(6) Cl – CH – CH – CH – Cl 1,3-Dichloropropane

(7) CHCl Trichloromethane

(8) CHI Triiodomethane

CH

(9) (CH ) C – Cl OR CH 9C9Cl 2-Chloro-2-methylpropane

CH

4 3 2 1
(10) CH – CH – CH – CH – Br 1-Bromobutane

1 2 3 4 5
(11) CH – CH – CH – CH – CH 2-Chloropentane

Cl
CH

(12) (CH ) CH – CH – Cl OR CH 9 CH9CH 9Cl 1-Chloro-2-methylpropane

(13) CH – Cl

(13) CH – CH – CH 2-Chloropropane

1 2 3 4 5
(14) CH – CH – CH – CH – CH 3-Bromo-2-chloropentane

Cl Br
(15) CH – CH – CH – CH 2,3-Dichlorobutane

Cl Cl

Compound IUPAC names
(16) CH – CH – CH – CH 2-Chloro-3-methylbutane

Cl CH

3 2 1
(17) Cl – CH – CH – CH – Br 1-Bromo-3-chloropropane

CH

(18) CH – CH – C – CH – Cl 1-Chloro-2, 2-dimethylbutane

CH

(19) sec-butyl chloride CH – CH – CH – CH 2-Chlorobutane

Cl
CH

(20) tert-butyl bromide H C – C–Br 2-Bromo-2-methylpropane

CH

(21) n-Butyl bromide CH 9CH 9CH 9CH 9Br 1-Bromobutane

(22) sec-Butyl bromide CH 9CH9 CH 9CH 2-Bromobutane

Br
CH

(23) Tertiary butyl iodide CH 9 C9 I 2-Iodo-2-methylpropane

CH

CH

(24) neo pentyl bromide CH – C–CH –Br 1-Bromo-2, 2-dimethyl propane

CH

(25) CH :CH–Cl Chloroethene

(26) 1,3,5-tribromobenzene
(27) Bromophenyl methane

Q. 6. Draw the structures of the following compounds : (1 mark each)
Compound Ans. Structures
H

(1) Dibromomethane Br9 C9 Br (CH Br )

H
(2) 3-Bromopentane CH – CH – CH – CH – CH

Br
CH – Br

(3) 2-Bromo-2-methylpropane CH – C – CH

CH

CH – Cl

(4) 2,2-Dichloropropane CH – C – CH

Cl
(5) Iodoethane CH – CH – I

(6) 1,1-Dibromopropane CH – CH – CHBr

(7) 1,1,1-Trichloroethane CH – CCl

(8) 1,2-Dichloropropane Cl – CH – CH – CH

Cl
1 2 3 4 5
(9) 1-Bromo-4-methylpentane Br – CH – CH – CH – CH – CH

CH

(10) 2-Chlorobutane CH – CH – CH – CH

Cl
(11) 1,2-Diiodoethane I – CH – CH – I

(12) Tetrachloromethane CCl

(13) 1,2,3-Trichloropropane Cl – CH – CH – CH – Cl

Cl
(14) 1-Iodobutane CH – CH – CH – CH – I

(15) n-Butyl bromide CH – CH – CH – CH – Br

(16) isobutyl bromide CH – CH – CH Br

CH


Compound Structures
CH – CH

(17) 1-Chloro-2, 2-dimethylpropane CH – C – CH – Cl

CH

CH – CH
C – CH – CH
C–
5
4 3 2 1
(18) 1-Bromo-2, 2, 4, 4-tetramethylpentane CH – C – CH – C – CH – Br

CH CH

CH – CH

(19) 2-Chloro-2-methylpropane CH – C – CH

Cl
CH – CH

(20) 1-Chloro-3, 3-dimethylbutane CH – C – CH – CH – Cl

CH

CH – CH
C – CH – CH
C–

(21) 1-Iodo-2, 2, 4, 4-tetramethylpentane CH – C – CH – C – CH – I

CH CH

CH – Br

(22) tertiary butyl bromide CH – C – CH

CH

CH – I

(23) isopropyl iodide CH – CH – CH

(24) sec-butyl chloride CH – CH – CH – CH

Cl
CH

(25) 3-Bromo-2-methyl pentane CH –CH –CH– CH–CH

Br
CH C H

(26) 2-Bromo-3-ethyl-2-methyl hexane CH – C—– CH–CH –CH –CH

Br
(27) 1-Chlorobutane CH –CH –CH –CH –Cl


Compound Structures
(28) p-dichlorobenzene
Cl

(29) 1,1,1-trichloroethane CH – C–Cl

Cl
■
Q. 7. Write the structure of –
(a) 3-chloro-3-ethylhex-1-ene (b) 1-Iodo-2, 3-dimethylbutane (c) 1, 3, 5-tribromobenzene (3 marks)
Ans.
Cl

(a) 3-Chloro-3-ethylhex-1-ene : CH – CH – H C– C– CH:CH

CH – CH

CH CH

(b) 1-Iodo-2, 3-dimethylbutane : CH – CH – CH – CH – I

(c) 1, 3, 5-Tribromobenzene :
★ Q. 8. Write IUPAC name of the following compounds. (1 mark each)
Compound Ans. IUPAC names
(1) CH 9CH:C 9 CH9Br 4-Bromo-3, 4 dimethyl but-2-ene

CH CH

(2) CH 9CH9 CH9CH 9CH 2-Chloro-3-methyl pentane

Cl CH

(3) 1-Chloro-4-ethyl cyclohexane

Compound Ans. IUPAC names
(4) 1,4-Dichloro-2-methyl benzene
Q. 9. Write structures of
(a) 2-iodo-3-methyl pentane (b) 3-chlorohexane
(c) 1-chloro-2, 2-dimethyl propane (d) 1-chloro-4-ethyl cyclohexane. (1 mark each)
Ans. (a) H C–HC–CH–H C–CH (b) H C–H C–HC–H C–H C–CH

I CH Cl

2-iodo-3-methyl pentane 3-chlorohexane
CH

(c) H C– C–CH –Cl (d)

CH

1-chloro-2, 2-dimethyl propane
1-chloro-4-ethyl cyclohexane
Q. 10. Write the possible isomers of monochloroderivatives of 2,3-Dimethylbutane and write their IUPAC
names. (2 marks)
Ans. The given parent hydrocarbon has molecular formula, C H . The monochloroderivative of this compound has

molecular formula C H Cl.

The parent hydrocarbon is,
CH 9CH9CH9CH 2,3-Dimethylbutane

CH CH

Hence the structures of isomers of monochloroderivative are,
(1) CH 9CH9CH9CH Cl 1-Chloro-2, 3-dimethylbutane

CH CH

Cl

(2) CH – C 9 CH – CH 2-Chloro-2, 3-dimethylbutane

CH CH

Hence C H Cl has two isomers. ■


Q. 11. Write structures and IUPAC names of all possible isomers of C H Br and classify them as 1° / 2° / 3°.

(1 mark each)
Ans. C H Br is a monohalogen derivative.

Isomer IUPAC name Type
Br
1°
(1) CH 9CH 9CH 9CH 9CH 1-Bromopentane (1°) Primary alkyl halide

Br

(2) CH 9CH9CH 9CH 9CH 2-Bromopentane (2°) Secondary alkyl halide
2°
Br

(3) CH 9CH 9CH9CH 9CH 3-Bromopentane (2°) Secondary alkyl halide
2°

Br

(4) CH 9CH9CH 9CH 1-Bromo-2-methylbutane (1°) Primary alkyl halide
1°

CH

Br
3°
(5) CH 9C9CH 9CH 2-Bromo-2-methylbutane (3°) Tertiary alkyl halide

CH

Br

(6) CH 9CH9CH9CH 2-Bromo-3-methylbutane (2°) Secondary alkyl halide
2°

CH

1°
(7) CH 9CH9CH 9CH 9Br 1-Bromo-3-methylbutane (1°) Primary alkyl halide

CH

CH
1°
(8) CH 9C9CH 9Br 1-Bromo-2, 2-dimethylpropane (1°) Primary alkyl halide

CH


(Textbook page 212)
Write IUPAC names of the following :
(i) CH 9CH9 CH (ii) CH 9CH9CH I (iii) CH 9CH:CH9CH Cl

Br CH

(iv) CH 9C Y C9CH 9Br (v) (vi)

Ans. (i) CH 9CH9 CH 2-Bromopropane

Br
(ii) CH 9CH9CH I 1-Iodo-2-methyl propane

CH

(iii) CH 9CH:CH9CH 9Cl 1-Chloro-but-2-ene

(iv) CH 9C Y C9CH 9Br 1-Bromo-but-2-yne

(v) Bromobenzene
(vi) 1, 4-Dibromobenzene (p-dibromobenzene)
Unit
10.3 Methods of preparation of alkyl halides/aryl halides
10.3.1 From alcohol
Q. 12. How are following compounds obtained from alcohols :

(1) ethyl chloride C H Cl (2) isopropyl chloride (CH 9CHCl9CH ) (3) tert-butyl chloride (CH ) –Cl ?

(1 mark each)
Ans. Alcohols in the presence of Lucas reagent which is a solution of concentrated HCl and ZnCl form alkyl halides.

Hydrogen chloride is used with zinc chloride (Grooves’ process) for primary and secondary alcohols.
anhydrous ZnCl
(1) C H 9OH ; HCl C H 9Cl ; H O

J
conc.
ethyl alcohol chloroethane
anhydrous ZnCl
(2) CH 9CH 9CH ; HCl CH 9CH 9CH ; H O

J
conc.
OH Cl
isopropyl alcohol isopropyl chloride

(3) Tertiary alcohols don’t need ZnCl to react with HCl.

CH CH

CH 9 C9 OH ; HCl CH 9 C9 Cl ; H O

J
CH CH

tert-butyl alcohol tert-butyl chloride
The order of reactivity of alcohols with a given halo acid is 3°2°1°. ■
Do you know ?
(Textbook page 212)
Zinc chloride is a Lewis acid and consequently can coordinate with the alcohol, weakening R-O bond. Mixture of
concentrated HCl and anhydrous ZnCl is called Lucas reagent.

Q. 13. How are following compounds prepared from alcohols :
(1) ethyl bromide (C H Br) (2) isopropyl bromide (CH 9CHBr9CH )

(3) tert-butyl bromide (CH ) C–Br ? (1 mark each)

Ans.
(1) Ethyl alcohol on heating with conc. hydrobromic acid (48%) forms ethyl bromide. OR
When ethyl alcohol is treated with a mixture of NaBr and H SO , ethyl bromide is formed. Here HBr is generated

in situ.
NaBr;conc. H SO
C H 9OH ; HBr C H 9Br ; H O

IIIIIIIIIIIIIIIIIIIIIIIIJ
ethyl alcohol ethyl bromide
(2) Isopropyl alcohol, on reaction with NaBr and dil. H SO forms isopropyl bromide.

NaBr;H SO
CH 9CH 9CH ; HBr CH 9CH9 CH ; H O

IIIIIIIIIIIIIIIIIIJ
conc.
OH Br
isopropyl alcohol isopropyl bromide
(3) Tertiary alcohol on reaction with sodium bromide and dil. H SO forms tert-butyl bromide.

CH CH
NaBr;dil. H SO
CH – C–OH ; HBr CH – C–Br ; H O

IIIIIIIIIIIIIIIIIIIIIIJ
CH CH

tert-butyl alcohol tert-butyl bromide ■
Q. 14. How is ethyl iodide obtained from ethyl alcohol ? (1 mark)

Ans. When ethyl alcohol is treated with sodium or potassium iodide in 95% phosphoric acid, ethyl iodide is formed.
Here HI is generated in situ.
NaI/H PO
CH 9CH 9OH;HI CH 9CH 9I;H O

ethyl alcohol ethyl iodide ■
Q. 15. How will you prepare the following : (1 mark each)

(1) Ethyl chloride (chloroethane) from ethyl alcohol using (i) PCl (ii) PCl and (iii) SOCl .

Ans.
(i) When ethyl alcohol is refluxed with phosphorus trichloride, ethyl chloride is formed.

3CH CH OH ; PCl 3CH CH Cl ; H PO

IIIIIJ
ethyl alcohol ethyl chloride phosphorus acid

(ii) When ethyl alcohol is refluxed with phosphorus pentachloride, ethyl chloride is formed.

CH CH OH ; PCl CH CH Cl ; POCl ; HCl

IIIIIJ
ethyl alcohol ethyl chloride phosphoryl chloride

(iii) When ethyl alcohol is refluxed with thionyl chloride, in the presence of pyridine, ethyl chloride is formed.
The by-products obtained are gases. Therefore, this method is preferred for preparation of alkyl chloride.
pyridine
CH CH OH ; SOCl CH CH Cl ; SO ! ; HCl !

IIIIIIIIIJ
reflux
ethyl alcohol ethyl chloride
(2) Isopropyl chloride (2-chloropropane) from isopropyl alcohol using (i) PCl (ii) PCl (iii) SOCl .

Ans. When isopropyl alcohol is refluxed with phosphorus trichloride, isopropyl chloride is formed.

(i) 3CH –CH–CH ;PCl 3CH –CH–CH ;H PO

IIIIIJ
phosphorus acid
OH Cl
When isopropyl alcohol is refluxed with phosphorus pentachloride, isopropyl chloride is formed.

(ii) CH –CH–CH ;PCl CH –CH–CH ;POCl ;HCl

IIIIIJ

OH Cl
When isopropyl alcohol is refluxed with thionyl chloride, in the presence of pyridine, isopropyl chloride is formed.
The by-products obtained are gases. Therefore, this method is preferred for preparation of alkyl chloride.
pyridine
(iii) CH –CH–CH ;SOCl CH –CH–CH ;SO !;HCl !

IIIIIIIIIJ
reflux

OH Cl
(3) Ethyl bromide (bromoethane) from ethyl alcohol.
Ans. When ethyl alcohol is treated with a mixture of red phosphorus and bromine or hydrobromic acid (phosphorus
tribromide is generated in situ), ethyl bromide is formed.
2P ; 3Br 2PBr

IIIIIJ

3CH CH OH ;PBr 3CH CH Br ; H PO

IIIIIJ
ethyl alcohol ethyl bromide
(4) Ethyl iodide (iodo ethane) from ethyl alcohol.

Ans. When ethyl alcohol is heated with a mixture of red phosphorus and iodine, (phosphorus triiodide is generated in
situ), ethyl iodide is formed.
2P ; 3I 2PI

IIIIIJ
3CH CH OH ; PI 3CH CH I;H PO

IIIIIJ
ethyl alcohol ethyl iodide ■

Unit
10.3.2 From hydrocarbon
Q. 16. Explain halogenation of methane. (2 marks)

Ans. Halogenation : A reaction of alkanes with halogens (Cl , Br , I ) in the presence of appropriate conditions

forming a mixture of alkyl halides.
(1) Chlorination :
UV light
CH ;Cl CH 9Cl ; HCl

IIIIIIIIIIIIJ
(excess) methyl
methane chloride
(major product)
(2) When excess of chlorine is used, tetrachloro methane, a major product is obtained. When excess of methane is
used, chloromethane, a major product is obtained. The order of reactivity of halogens towards alkane is
F Cl Br I .

UV light
CH ;Cl CH Cl;CH Cl ;CHCl ; CCl ; HCl
or
IIIIIIIIIIIIIIJ
excess methyl methylene chloroform Carbon tetrachloride

chloride dichloride (major product)
(3) Iodination :
CH ;I & CH –I;HI

methyl iodide
However, iodination reaction is a reversible reaction. HI being a strongest reducing agent reduces methyl iodide
back to methane.
(4) Fluorination : A reaction of alkane with fluorine is explosive and also hydrofluoric acid is poisonous and
corrosive. Hence, alkyl fluorides are not prepared by halogenation of alkane. ■
Q. 17. Predict the possible products of the following reaction :

(1) Bromination of propane (2) Bromination of n-butane (3) Bromination of 2-Methyl propane.
(3 marks)
Ans.
(1) Bromination of propane
Br
CH 9CH 9CH CH 9CH 9CH 9Br ; CH 9CH9CH
UV light
IIIIIIIIIIIJ
Propane 1-Bromopropane (3%) Br

2-Bromo propane (97%)
(2) Bromination of n-butane
Br
H C9CH 9CH 9CH H C9CH 9CH 9CH 9Br ; H C9CH 9CH9CH
UV light
IIIIIIIIIIIJ

n-Butane Br
1-Bromobutane (2%)
2-Bromobutane (98%)
(3) Bromination of 2-Methyl propane
CH CH CH
Br
H C9 CH9CH H C9 CH9CH 9Br ; H C9 C9 CH
UV light
IIIIIIIIIIIJ

2-Methylpropane 1-Bromo-2-methylbutane Br
(trace) 2-Bromo-2-methylpropane (over 99%)
■

Do you know ?
(Textbook page 213)
Some times during replacement of – OH by – X, alcohols tend to undergo rearrangement. This tendency can be
minimized by use of phosphorous halides. Straight chain primary alcohols react with phosphorous trihalide to give
unrearranged alkyl halides.
Q. 18. How are following compounds prepared by halogenation of ethane :

(1) Chloroethane (2) Bromoethane (3) Iodoethane ? (1 mark each)
Ans.
(1) Chlorination of ethane : When ethane (excess) is reacted with a limited quantity of chlorine in the presence of
diffused sunlight or U.V. light or at high temperature, chloroethane is obtained.
diffused
sunlight
C H ;Cl C H 9Cl ; HCl

IIIIIIIIIIIIJ
(excess) Chloroethane
ethane
(2) Bromination of ethane : When ethane is heated with Br in the presence of anhydrous AlBr , bromoethane is

obtained.
Anhydrous AlBr
C H ;Br C H 9Br ; HBr

IIIIIIIIIIIIIIIIIIIIIIJ
ethane Bromoethane
(3) Iodination : When ethane is reacted with I in the presence of suitable oxidising agents like–HgO or HIO or

dilute HNO iodoethane is obtained.

2 C H ;2I ;HgO ; 2C H 9I ; HgI ; H O

ethane
mercuric Iodoethane

oxide
5C H ;2I ;HIO ; 5C H 9I ; 3H O

ethane iodic acid Iodoethane
8C H ;4I ;HNO ; 8 C H 9I ; 3H O ; NH

ethane Iodoethane ■
Q. 19. Explain :
(1) Halogenation of alkanes is not a good method of preparation of alkyl halides. (2 marks)
Ans.
(1) Direct fluorination of alkanes is highly exothermic, explosive and invariably leads to polyfluorination and
decomposition of the alkanes. It is difficult to control the reaction.
(2) Direct iodination of alkanes is highly reversible and difficult to carry out.
(3) In direct chlorination and bromination, the reaction is not selective. It can lead to different isomeric
monohalogenated alkanes (alkyl halides) as well as polyhalogenated alkanes.
Hence, halogenation of alkanes is not a good method of preparation of alkyl halides.
(2) Direct iodination of alkanes is not possible. (2 marks)

Ans.
(1) Direct iodination of alkanes using iodine is highly reversible.
RH ; I & RI ; HI

(2) Hydroiodic acid HI being strong reducing agent, it reduces RI to alkane RH.

(3) The reaction takes place only in the presence of a suitable oxidizing agent like HgO, HIO or dilute HNO

which decomposes HI.
Hence, direct iodination of alkanes is not possible.
(4) 5C H ;2I ;HIO ; 5C H 9I;3H O

ethane iodoethane ■
Q. 20. How are following compounds obtained from alkenes :

(1) C H Cl (2) C H Br (3) CH 9CH 9CH (4) CH –CH –CH –CH ? (1 mark each)

I I
Ans.
(1) Ethene on reaction with hydrogen chloride forms C H Cl.

H C:CH ;HCl ; CH 9CH 9Cl

Ethene Chloroethane
(2) Ethene on reaction with hydrogen bromide forms C H Br.

H C:CH ;HBr ; CH 9CH 9Br

Ethene Bromoethane
(3) Propene on reaction with hydrogen iodide forms CH 9CHI9CH .

CH 9CH:CH ;HI ; CH 9CH9CH

propene
I
2-Iodopropane
(4) but-2-ene on reaction with hydrogen iodide forms 2-iodobutane.

CH –CH:CH–CH ;HI CH –CH –CH–CH

IIIIIJ

but-2-ene
I 2-iodobutane ■
Q. 21. State and explain Markovnikov’s rule. (2 marks)

Ans. Markovnikov’s rule : When an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part of
the reagent gets attached to that carbon atom of the double bond which carries less number of hydrogen atoms.
Example : Addition of HBr to unsymmetrical alkene like propene gives two products.
; CH –CH–CH (Major product)

Br
CH –CH:CH ;HBr
Propene Isopropylbromide
IIIII
; CH –CH –CH –Br (Minor product)

n-propylbromide
Isopropyl bromide is the major product, since the negative part (Br\) of HBr is attached to carbon atom of a
double bond with less number of hydrogen atoms. ■
Q. 22. Explain peroxide effect. OR Write a note on Kharasch-Mayo effect. OR

Explain the addition of HBr to (unsymmetrical alkene) propene in the presence of benzoyl peroxide.
(2 marks)
Ans. The addition of HBr to an unsymmetrical alkene (propene) in the presence of benzoyl peroxide takes place in the

opposite orientation to that of Markovnikov’s rule and this is known as Kharasch-Mayo effect or peroxide effect or
Anti-Markovnikov addition.
(C H CO) O
H C9CH:CH ;H9Br H C9CH 9CH 9Br

IIIIIIIIIIIIIIIIIIIIIJ
Benzoyl peroxide
Propene 1-Bromopropane ■
Q. 23. Write the structure of alkyl halide obtained by the action hydrogen bromide on 2-Methylprop-
1-ene in the presence of peroxide. (1 mark)
Ans. In the presence of peroxide, HBr to 2-Methyl prop-1-ene forms 1-Bromo-2-methylpropane.
CH CH
(C H CO) O

H C9 C:CH ;H9Br H C9 C9 CH 9Br

IIIIIIIIIIIIIIIIIIIIJ
Benzoyl peroxide

Z-Methylprop-1-ene H
1-Bromo-2-methylpropane ■

How will you obtain 1-bromo-1-methylcyclohexane from alkene ?
Write possible structures of alkene and the reaction involved.
Answer :
(1) (2)

(Textbook page 213)
Rewrite the following reaction by filling the blanks :
(1) CH 9CH:CH ;HBr ; ……;……

(major) (minor)
peroxide
(2) (CH ) C:CHCH ;HBr ……;……

IIIIIIIIIIIIJ
(major) (minor)
peroxide
(3) CH 9CH:CH ;HBr ……;……

IIIIIIIIIIIIJ
(major) (minor)
Ans.
(1) CH 9CH:CH ;HBr ; CH 9CH9CH ;CH 9CH 9CH 9Br

Propene n-propyl bromide
Br
(minor)
isopropyl bromide
(major)
CH CH CH
peroxide

(2) CH 9 C:CH9CH ;HBr CH 9 CH9 CH9CH ; CH 9 C9 CH 9CH

IIIIIIIIIIIIJ

2-methyl but-2-ene
Br Br
2-bromo-3-methyl butane 2-bromo-2-methyl butane
(major) (minor)

peroxide
(3) CH 9CH:CH ;HBr CH 9CH 9CH 9Br ; CH 9CH9CH

IIIIIIIIIIIIJ
Propene n-propyl bromide isopropyl bromide

(major) (minor)
Do you know ?
(Textbook page 213)
Alkenes form addition product, vicinal dihalide, with chlorine or bromine usually in inert solvent like CCl at room

temperature.
(X:Cl, Br)
Do you know ?
(Textbook page 214)
When alkenes are heated with Br or Cl at high temperature, hydrogen atom of allylic carbon is substituted with

halogen atom giving allyl halide.
CH :CH9CH ;Cl ; CH :CH9CH Cl;HCl

Unit
10.3.3 Halogen exchange
Q. 24. How are alkyl iodides prepared from alkyl chlorides/bromides ? (2 marks)
Ans. Alkyl iodide is prepared by treating alkyl chloride or alkyl bromide with sodium iodide, in the presence of dry
acetone, sodium chloride or sodium bromide precipitates from the solution and can be separated by filtration.
This reaction is known as Finkelstein reaction.
dry ether
RX;NaI IIIIIIIIIIJ RI;NaX
dry acetone
R–Cl ; NaI IIIIIIIIIIIIIIIJ RI ; NaCl
alkyl chloride alkyl iodide
dry acetone
R–Br ; NaI IIIIIIIIIIIIIIIJ RI ; NaBr
alkyl bromide alkyl iodide
dry acetone
C H Br ; NaI C H I ; NaBr

IIIIIIIIIIIIIIIJ
ethyl bromide ethyl iodide ■
Q. 25. How are alkyl fluorides prepared with alkyl chlorides / alkyl bromides ? (2 marks)
Ans. When alkyl chloride or alkyl bromide is heated with metallic fluorides like AgF, CaF , CoF or Hg F , alkyl

fluoride is formed.

R–X;AgF IIIIIJ R–F;AgX

CH –Cl ; AgF CH F ; AgCl

IIIIIJ
methyl methyl
chloride fluoride
This reaction is known as Swarts reaction. ■

Units
10.3.4 Electrophilic Substitution
10.3.5 Sandmeyer’s reaction
Q. 26. Explain the preparation of haloarenes using electrophilic substitution. (1 mark)

Ans. When arene is treated with chlorine or bromine in dark at ordinary temperature in the presence of lewis acid as a
catalyst like Fe, FeCl or anhydrous AlCl , aryl chloride or aryl bromide is formed.

When toluene is brominated in dark at ordinary temperature in the presence of iron, a mixture of ortho and para
bromo tolerene is obtained.
Ortho and para isomers can be easily separated as there is large difference in melting points of ortho and para
isomers. ■
Q. 27. Write a note on Sandmeyer’s reaction. (3 marks)

Ans. Aryl halides are most commonly prepared by replacement of nitrogen of diazonium salt. The replacement of
diazonium group by –Cl or –Br using cuprous salt is called Sandmeyer’s reaction. When a primary aromatic amine
(like aniline) suspended in cold HCl, is treated with sodium nitrite, a diazonium salt (benzene diazonium chloride)
is formed. When diazonium salt is treated cuprous chloride or cuprous bromide, aryl halide (chlorobenzene or
bromobenzene) is formed.
When benzene diazonium salt is mixed with potassium iodide, iodobenzene is formed.
Units
10.4 Physical properties
10.4.1 Nature of intermolecular forces
10.4.2 Boiling point
10.4.3 Solubility

Q. 28. Give reasons : (2 marks each)
★ (1) Alkyl halides through polar are immiscible with water.
Ans.
(1) In alkyl halide, the halogen atom is more electronegative than carbon atom, the C9X bond is polar.
(2) Though alkyl halide is polar, it is insoluble in water because alkyl halide is not able to form hydrogen bonds with
water. Attraction between alkyl halide molecule is stronger than attraction between alkyl halide and water.
(2) C–F bond in CH F is the strongest bond and C–I bond in CH I is the weakest bond. Explain.

Ans.
(1) Methyl fluoride (CH F) is highly polar molecule and has the shortest C–F bond length (139 pm) and the strongest

C–F bond due to greater overlap of orbitals of the same principal quantum number i.e., overlap of 2sp orbital of
carbon with 2pz orbital of fluorine.
(2) Methyl iodide (CH I) is much less polar and has the longest (C–I) bond length (214 pm) and the weakest C–I bond

due to poor overlap of 2sp orbital carbon with 5pz orbital of iodine i.e., 2sp orbital of carbon cannot penetrate into
larger p-orbitals.
(3) The boiling point of alkyl iodide is higher than that of alkyl fluoride.
Ans. For a given alkyl group, the boiling point increases with increasing atomic mass of the halogen, because magnitude
of van der Waals force increases with increase in size and mass of halogen. Therefore, boiling point of alkyl iodide
is higher than that of alkyl fluoride.
(4) The boiling point of isopropyl bromide is lower than that of n-propyl bromide.
Ans. For isomeric alkyl halides (isopropyl bromide and n-propyl bromide), the boiling point decreases as the branching
increases, surface area decreases on branching and van der Waals forces decrease, therefore, the boiling point of
isopropyl bromide is lower than that of n-propyl bromide.
(5) p-Dichlorobenzene
has m.p. higher than those of o-and m-isomers.
Ans. p-Dichlorobenzene has higher melting point than those of o-and m-isomers. This is because of its symmetrical
structure which can easily fits in crystal lattice. As a result intermolecular forces of attraction are stronger and
therefore greater energy is required to overcome its lattice energy. ■
★ Q. 29. Arrange the following in the increase order of boiling points :

(a) 1-Bromopropane (b) 2-Bromopropane (c) 1-Bromobutane (d) 1-Bromo-2-methylpropane (2 marks)
Ans. 1-Bromo-2-methylpropane, 2-Bromopropane, 1-Bromopropane, 1-Bromo butane ■

Arrange the following compounds in order of increasing boiling points : bromoform, chloromethane,
dibromomethane, bromomethane.
Ans. The comparative boiling points of halogen derivatives are mainly related with van der Waals forces of
attraction which depend upon the molecular size. In the present case all the compounds contain only one carbon.
Thus the molecular size depends upon the size of halogen and number of halogen atoms present.
Thus increasing order of boiling point is,
CH Cl CH Br CH Br CHBr


Units
10.5 Optical isomerism in halogen derivatives
10.5.1 Chiral atom and molecular chirality
10.5.2 Plane polarized light
10.5.3 Optical activity
10.5.4 Enantiomers
Try this ...

(Textbook page 216)
(1) Make a three-dimensional model of 2-chlorobutane.
(2) Make another model which is a mirror image of the first model.
(3) Try to superimpose the two models on each other.
(4) Do they superimpose on each other exactly ?
(5) Comment on whether the two models are identical or not.
Ans. (1) (2) and (3)
Fig : Nonsuperimposable mirror images

(4) Two models are nonsuperimposable mir ror images of each other called enantiomers.
(5) Two enantiomers are identical. Theyhave the same physical properties (such as melting points, boiling points,
densities refractive index). They also have identical chemical properties. The magnitude of their optical
rotation is equal but the sign of optical rotation is opposite.
Do you know ?
(Textbook page 217)
Nicol prism is a special type of prism made from pieces of calcite, a crystalline form of CaCO , arranged in a

specific manner. Nicol prism is also called polarizer.
Q. 30. Define the following : (1 mark each)

Ans.
(1) Monochromatic light : It consists of rays of single wavelength vibrating in different planes perpendicular to the
direction of propagation of the light.
(2) Plane polarized light : A light having oscillations only in one
plane perpendicular to direction of propagation of light is known
as plane polarized light.
Fig. Plane polarized light
Fig. Rotation of plane polarized light

due to optically active substance

(3) Optical isomerism : The steroisomerism in which the isomers have different spatial arrangements of
groups/atoms around a chiral atom is called optical isomerism.
(4) Optical activity : The property of a substance by which it rotates plane of polarization of incident plane polarized
light is known as optical activity.
(5) Optically active compound : The compound which rotate the plane of plane polarized light is called optically
active compound.
(6) Enantiomers : The optical isomers which are non-superimposable mirror images of each other are called
enantiomers or enantiomorphs or optical antipodes.
Example : 2-chlorobutane, lactic acid
(7) Chiral carbon atom : Carbon atom in a molecule which carries four different groups/atoms is called chiral carbon
atom.
Chiral atom in a molecule is marked with asterisk ( * )
*
For example : C in lactic acid
CH
*
H9 C 9OH

COOH
(8) Chiral molecule : When a molecule contains one chiral atom, it acquires a unique property i.e. it is non-
superimposable with its mirror image is said to be chiral molecule.
(9) Chirality : The relationship between a chiral molecule and its mirror image is similar to the relationship between
left and right hands. Therefore it is called handedness or chirality.
(10) Dextrorotatory substance or d-Isomer : An optically active substance (or isomer) which rotates the plane of a
plane polarized light to the right hand side (RHS) is called dextrorotatory substance (or isomer) and denoted by d or
(;) sign.
(11) Laevorotatory substance or l-Isomer : An optically active substance (or isomer) which rotates the plane of a
plane polarized light to the left hand side (LHS) is called laevorotatory substance (or isomer) and denoted by l or
(9) sign.
(12) Racemic mixture or Racemate : A mixture containing equimolar quantities of dextro (d) and laevo (l) optical
isomers which is optically inactive due to molecules of one enantiomer is cancelled by equal and opposite optical
rotation due to molecules of the other enantiomer is called a racemic mixture or racemate. It is represented as (dl )
or (<). ■
Q. 31. Calculate the number of isomers for 2-chlorobutane. (1 mark)

n
Ans. The number of optical isomers possible for a compound is 2 where n:number of asymetric carbon atoms.
As n:1 for 2-chlorobutane, 2n :2:2. Hence, it has two optical isomers. ■
Q. 32. How many optical isomers are possible for C H Cl ? (1 mark)

Ans. The number of optical isomers : 3. ■
Q. 33. How many optical isomers are possible for glucose ? (1 mark)
Ans. The number of optical isomers : 16. ■
Remember ...
(Textbook page 217)
The phenomenon of optical isomerism in organic compounds was observed first and its origin in molecular
chirality was recognized later

Remember ...
(Textbook page 218)
● Optical activity is an experimentally observable property of compounds. Chirality is a description of molecular
structure. Optical activity is the consequence of chirality.
● Molecules which contain one chiral atom are chiral, that is, they are nonsuperimposable on their mirror image.
● The two non-superimposable mirror image structures are called pair of enantiomers.
● Enantiomers have equal and opposite optical rotation. Thus, enantiomers are a kind of optical isomers.
Q. 34. Draw the structures and indicate the chiral carbon atoms in (1) Lactic acid (2) 2-Chlorobutane.
(2 marks each)
Ans.
*
(1) In lactic acid structure, CH – CH – COOH, the starred carbon atom is chiral carbon atom as it is attached to

the starred OH
four different substituents, COOH, OH, CH and H.

Cl

(2) In 2-chlorobutane structure, CH – CH – CH – CH the starred carbon atom is chiral carbon atom as it is

*
attached to four different substituents, – CH – CH (ethyl), CH (methyl), Cl and H.

(The carbon atom marked with an asterisk (*) is an asymmetric carbon atom.) ■
Q. 35. Identify chiral and achiral molecules. (1 mark each)
(1) CH –CH–CH –CH (2) CH –CHBr (3) CH –CH(OH)Br (4)

Br
Ans. Chiral Ans. Achiral Ans. Chiral Ans. Chiral
■
★ Q. 36. Explain optical isomerism in 2-chlorobutane. (3 marks)
Ans.
(1) 2-Chlorobutane contains an asymmetric.
Cl

CH – CH–CH –CH carbon atom (the starred
*
carbon atom) which is attached to four different
groups, i.e., ethyl (– CH – CH ), methyl (CH ),

chloro (Cl) and hydrogen (H) groups.
(2) Two different arrangements of these groups
around the carbon atom are possible as shown in
the figure. Hence, it exists as a pair of enanti-
omers. The two enantiomers are mirror images of
each other and are not superimposable.
(3) One of the enantiomers will rotate the plane of Fig. Enantiomers of 2-Chlorobutane
(with structural and Fischer’s projection formula)
plane-polarized light to the left hand side and is
called the laevorotatory isomer (l-isomer). The
other enantiomer will rotate the plane of plane-polarized light to the right hand side and is called the dextrorotatory
isomer (d-isomer).

(4) Equimolar mixture of the d- and the l-isomers is optically inactive and is called the racemic mixture or the racemate
(dl-mixture). The optical inactivity of the racemic mixture is due to external compensation. ■
Q. 37. Complete the following reactions and explain optical activity of the products formed : (1 mark each)
(i) Pent-1-ene with HBr
Ans. CH –CH –CH –CH:CH ;HBr CH –CH –CH –CH–CH

IIIIIJ
Pent-1-ene Br
2-bromopentane
H

CH –CH –H C– C–CH

Br
2-bromopentane
(Optically active)
(ii) Pent-2-ene with HBr
Ans. CH –CH –CH:CH–CH ;HBr CH –CH –CH–CH –CH

IIIIIJ
Pent-2-ene
Br
3-bromopentane
H

H C–H C– C–CH –CH

Br
3-bromopentane
(Optically inactive) ■
Q. 38. C H (A) on treatment with HCl produced a compound Y. Which is optically active, what is structure A?

(2 marks)
Ans. CH –CH –CH:CH–CH –CH ;HCl CH –CH –CH–CH –CH –CH

IIIIIJ
hex-3-ene Cl
3-chloro hexane
The structure of A:CH –CH –CH:CH–CH –CH

hex-3-ene
Optically active compound:CH –CH –CH–CH –CH –CH

Cl
3-chloro hexane ■
★ Q. 39. Identify chiral molecule/s from the following : (1 mark each)
(a) CH 9CH9CH 9CH (b) CH 9CH 9CH9CH 9CH

OH Br
(c) CH 9CH 9CH 9CH Br (d) CH 9CH9CH 9CH

CH


Ans. Chiral molecule
H

(a) CH 9 C9CH 9CH

OH ■
Q. 40. A racemic mixture is optically inactive. Explain. (2 marks)

Ans.
(1) A racemic mixture contains equimolar (or equimolecular) quantities of the dextrorotatory (d-) and laevorotatory
(l-) isomers (enantiomers) of a compound.
(2) The d-enantiomer rotates the plane of plane-polarized light to the right, while the l-enantiomer rotates the same to
the left to the same extent.
(3) The quantities of the d- and l-enantiomers being the same, both the rotations are of the same magnitude, but of
opposite directions. Hence, they cancel each other.
Hence, a racemic mixture is optically inactive.
(4) It is represented as dl or (<). Example : (<) lactic acid ■
Unit
10.5.5 Representation of configuration of molecules
Q. 41. Explain fischer projection formula with illustration. OR

Write a note on fischer projection formula. (3 marks)
Ans. Fischer projection formula or cross formula : The three dimensional (3–D) view of a molecule is presented on
plane of paper. A Fischer projection formula can be drawn by visualizing the main carbon chain verical in the
molecule. Each carbon on the vertical chain is represented by a cross.
Conventionally the horizontal lines of the cross represent bonds projecting up from the carbon and the vertical lines
represent the bonds going below the carbon. ■
Q. 42. Explain Wedge formula with illustration OR Write a note on Wedge formula. (3 marks)
Ans. Wedge formula : When a tetrahedral carbon is imagined to be
present in the plane of paper all the four bonds at this carbon cannot
lie in the same plane. The bonds in the plane of paper are represented
by normal lines, the bonds projecting above the plane of paper are
represented by solid wedges (or simply by bold lines) while bonds
going below the plane of paper are represented by broken wedges
(or simply by broken lines).
■

Try this ...
(Textbook page 219)

CH 9CH9COOH
(1) Draw structures of enantiomers of lactic acid using Fischer projection formulae.
OH
(2) Draw structures of enantiomers of 2-bromobutane using wedge formula.

Ans.
(1) Fischer projection formula : CH 9CH9COOH

OH
(2) Wedge formula : 2-bromobutane
Units
10.6 Chemical properties
10.6.1 Laboratory test of haloalkanes
10.6.2 Nucleophilic substitution reaction of haloalkanes
Q. 43. Give a laboratory test to confirm the presence of halogen in the original organic compound. (1 mark)
Ans. Haloalkanes are of neutral type in aqueous medium. On warming with aqueous sodium or potassium hydroxide the
covalently bonded halogen in haloalkane is converted to halide ion.

R9X;OH*
9
IIIIIJ R9OH;X*
9
When this reaction mixture is acidified by adding dilute nitric acid and silver nitrate solution is added a precipitate
of silver halide is formed which confirms presence of halogen in the original organic compound.
Ag*
;
(aq);X*
9
(aq) IIIIIIIJ AgX (s)
silver halide ■

(1) Mechanism of a reaction : It is a step by step description of exactly how the reactants are transformed into
products in as much details as possible.
(2) Substitution reaction : When a group bonded to a carbon in a substrate is replaced by another group to get a
product with no change in state of hybridization of that carbon, the reaction is called substitution reaction. ■

Q. 45. Describe the action of aqueous KOH (or NaOH) on :
(1) ethyl bromide (2) isopropyl bromide (3) tert-butyl chloride (4) methyl bromide
(5) 2-chlorobutane. (1 mark each)
Ans.
(1) Ethyl bromide : When ethyl bromide (bromoethane) is refluxed with aqueous potassium hydroxide, ethyl alcohol
is formed. The reaction is called a hydrolysis reaction.
boil
CH – CH – Br; KOH CH – CH – OH;KBr

J
(aq)
ethyl bromide ethanol
(2) Isopropyl bromide : When isopropyl bromide (2-bromopropane) is boiled with aqueous potassium hydroxide,
isopropyl alcohol is formed.
CH – CH – CH ; KOH boil CH – CH – CH ; KBr
(aq) J
Br OH
isopropyl bromide isopropyl alcohol
(3) Tert-butyl chloride : When tert-butyl chloride is refluxed with aqueous potassium hydroxide, tert-butyl alcohol is
formed.
CH CH
boil

CH – C – Cl ; KOH CH – C – OH ; KCl

J
(aq)
CH CH

tert-butyl chloride tert-butyl alcohol
(4) Methyl bromide : When methyl bromide (bromomethane) is heated with aq. KOH, it is hydrolysed to methyl
alcohol (methanol).
boil
CH – Br ; KOH CH – OH ; KBr

J
(aq)
methyl bromide methyl alcohol
(5) 2-chlorobutane : When 2-Chlorobutane is boiled with aqueous KOH, Butan-2-ol is obtained.
Cl OH
boil
CH – CH – CH – CH ; KOH CH – CH – CH – CH ; KCl

J
2-Chlorobutane (aq) Butan-2-ol ■
Q. 46. Describe the action of sodium ethoxide on (1) ethyl bromide (2) methyl bromide : OR
Write a note on Williamson’s synthesis. (2 marks) OR How are ethers prepared from alkyl halides ?
(2 marks)
Ans. Williamson’s synthesis : When an alkyl halide (R9X) is heated with sodium alkoxide (R9O9Na), an ether
is obtained. In this reaction halide (–X) of alkyl halide is replaced by an alkoxy group (–OR). This reaction is
known as Williamson’s synthesis. This method is used to prepare simple (or symmetrical) ethers and mixed
(or unsymmetrical) ethers.
Sodium alkoxide is obtained by a reaction of sodium with an alcohol.
9 ;
2R9OH ; 2Na 2R9O Na ; H

IIIIIJ
9 ;
E.g. 2C H OH ; 2Na 2 C H O Na ; H

IIIIIJ
(1) Simple (symmetrical) ether : When an alkyl halide and sodium alkoxide having similar alkyl groups are heated,
symmetrical ether is obtained.

R9O9Na ; RX IIIIJ R9O9R ; NaX
e.g., When ethyl bromide is heated with sodium ethoxide, diethyl ether is formed.

C H 9O9Na ; C H 9Br C H 9O9C H ; NaBr

IIIIJ
sodium ethoxide Bromoethane diethyl ether

(2) Mixed (unsymmetrical) ether : When an alkyl halide and sodium alkoxide having different alkyl groups are
heated, unsymmetrical ether is obtained.

R9O9Na ; R9X IIIIJ R9O9R ; NaX
When methyl bromide is heated sodium ethoxide, ethyl methyl ether is formed.

C H 9O9Na ; CH 9Br C H 9O9CH ; NaBr

IIIIJ
sodium ethoxide methyl ethyl methyl ether

bromide
When ethyl bromide is heated with sodium methoxide, ethyl methyl ether is formed.

CH –O–Na;C H Br C H –O–CH ;NaBr

IIIIJ
ethyl
Sodium methoxide ethyl methyl ether ■
bromide
Q. 47. What is the action of silver salt of carboxylic acid on alkyl halide ? (1 mark)
Ans. When an alkyl halide (R9X) is heated with silver salt of carboxylic acid (R9COOAg), an ester is obtained.

R9COOAg;RX IIIIIIIIIJ R9COOR;Agx
alcohol
silver salt of Ester
■
carboxylic acid
Q. 48. Describe the action of alcoholic silver acetate on (1) methyl bromide (2) ethyl bromide. (1 mark each)
Ans.
(1) Methyl bromide : When methyl bromide is heated with an alcoholic silver acetate, methyl acetate is formed.

CH – COOAg;CH – Br CH – COO – CH ;AgBr

IIIIIIIIIIJ
alcohol
silver acetate methyl acetate
(2) Ethyl bromide : When ethyl bromide is heated with an alcoholic silver acetate, ethyl acetate is formed.

CH – COOAg ; CH – CH – Br CH – COO9CH 9CH ;AgI

IIIIIIIIIIJ
alcohol
silver acetate ethyl acetate ■
Q. 49. What is the action of alcoholic silver propionate on ethyl bromide ? (1 mark)
Ans. When ethyl bromide is heated with an alcoholic silver propionate, ethyl propionate is formed.

C H –Br;C H COOAg C H –COO–C H ;AgBr ■

IIIIIIIIJ
alcohol
Q. 50. Describe the action of excess of ammonia on (1) ethyl bromide (2) n-propyl bromide. (1 mark each)
Ans.
(1) Ethyl bromide : When ethyl bromide is boiled under pressure with an excess of alcoholic ammonia, ethylamine
(ethanamine) is formed. This is known as ‘ammonolysis’ of ethyl bromide.
413 K
CH – CH – Br ; NH CH – CH – NH ; HBr

IIIIIIIIIIIIJ
pressure
(alc.)
ethyl bromide ethyl amine
(excess)
(2) n-propyl bromide : When n-propyl bromide is boiled under pressure with an excess of ammonia, n-propyl amine
(propanamine) is formed.

413 K
CH – CH – CH – Br;NH CH – CH – CH – NH ;HBr

IIIIIIIIIIIIJ
pressure
n-propyl bromide (alc.) n-propyl amine
(excess) ■
Q. 51. What is ammonolysis ? Give a suitable example for the reaction. (2 marks)
Ans. When an alkyl halide is boiled under pressure with an excess of alcoholic solution of ammonia (NH ),

corresponding (primary amine) alkyl amine is formed. This reaction is known as ammonolysis of alkyl halide.
pressure
R9X ; NH R9NH ; HX

J
(alc.)
alkyl halide alkyl amine
(excess) (primary amine)
Further refer to Q. 45. ■
Q. 52. Describe the action of aqueous alcoholic potassium cyanide on (1) ethyl bromide (2) methyl iodide.
(2 marks)
Ans.
(1) Ethyl bromide : When ethyl bromide (bromoethane) is boiled with alcoholic solution of potassium cyanide
in aqueous ethanol, ethyl cyanide (ethyl nitrile) is formed.
boil
CH – CH – Br ; KCN CH – CH – CN ; KBr

J
(alc.)
ethyl bromide ethyl cyanide
(2) Methyl iodide : When methyl iodide is boiled with alcoholic solution of potassium cyanide, methyl cyanide is
formed.
boil
CH –I;KCN CH –CN;KI

IIIIIJ
(alc.) methyl cyanide ■
Q. 53. Describe the action of alcoholic silver cyanide on (1) ethyl bromide (2) methyl chloride. OR
Explain isocyanide reaction of (1) ethyl bromide (2) methyl chloride. (2 marks)
Ans.
(1) Ethyl bromide : When ethyl bromide is heated with alcoholic silver cyanide, ethyl isocyanide is formed.
heat
CH – CH – Br;AgCN CH – CH – NC;AgBr

J
ethyl bromide (alc.) ethyl isocyanide (ethyl carbylamine)

(2) Methyl chloride : When methyl chloride is heated with alcoholic silver cyanide, methyl isocyanide is formed.
heat
CH – Cl;AgCN CH – NC;AgCl

J
(alc.)
methyl chloride methyl isocyanide
The above reactions (1) and (2) are called isocyanide reaction. ■
Q. 54. Describe the action of potassium nitrite on (i) ethyl bromide. (ii) methyl chloride. (2 marks)
Ans.
(1) Ethyl bromide : When ethyl bromide is treated with potassium nitrite, ethyl nitrite is formed.
;9
CH 9CH 9Br ; K O 9N:O CH 9CH 9O9N:O;KBr

IIIIIJ
ethyl bromide potassium ethyl nitrite

nitrite
(2) Methyl chloride : When methyl chloride is treated with potassium nitrite, methyl nitrite is formed.
;9
CH 9CH 9Cl ; K O 9N:O CH 9 O9N:O;KCl

IIIIIJ
methyl chloride potassium methyl nitrite

■
nitrite

Q. 55. Describe the action of silver nitrite on (1) ethyl chloride (2) n-propyl bromide. (2 marks)
Ans.
(1) Ethyl chloride : When ethyl chloride is treated with silver nitrite, nitroethane is obtained.
(2) n-Propyl bromide : When n-propyl bromide is treated with silver nitrite, nitropropane is obtained.
Do you know ?
(Textbook page 220)
Cyanide ion is capable of attacking through more than one site (atom).
Such nucleophiles are called ambident nucleophiles. KCN is predominantly ionic (K* ; *
C9 Y N) and provides
cyanide ions. Both carbon and nitrogen are capable of donating electron pair. C9C Bond being stronger than C–N
bond, attack occurs through carbon atom of cyanide group forming alkyl cyanides as major product. However
AgCN (Ag9C Y N) is mainly covalent compound and nitrogen is free to donate pair of electron. Hence attack
occurs through nitrogen resulting in formation of isocyanide.
Another ambident nucleophile is nitrite ion, which can attack through ‘O’ or ‘N’.
Can you tell ?

(Textbook page 220)
Alkyl halides when treated with alcoholic solution of silver nitrite give nitroalkanes whereas with sodium nitrite
they give alkyl nitrites. Explain.
Ans. Nitrite ion is an ambident nucleophile, which can attack through ‘O’ or ‘N’.
Both nitrogen and oxygen are capable of donating electron pair. C9N bond, being stronger than N9O bond,
attack occurs through C atom from alkyl halide forming nitroalkane.
However, sodium nitrite (NaNO ) is an ionic compound and oxygen is free to donate pair of electrons. Hence,

attack occurs through oxygen resulting in the formation of alkyl nitrite.
★ Q. 56. Write structure and IUPAC name of the major product in each of the following reaction. (1 mark each)
Ans. Structure and IUPAC name
Acetone
(1) CH 9CH9CH Cl;NaI CH 9CH9CH I;NaCl

IIIIIIIIIIIIJ
CH CH

1-Iodo-2-methyl propane

(2) CH 9CH Br;SbF F 9 CH9 CH 9Br

IIIIIIIJ
1,1-difluoro-2-bromoethane
Peroxide
(3) CH 9CH9CH:CH ;HBr CH 9CH9CH 9CH 9Br

IIIIIIIIIIIIJ

CH CH

1-Bromo-3-methyl butane
(4)
(5)
Q. 57. How will you convert the following : (1 mark each)

(1) Ethyl bromide to ethanol.

Ans. C H Br ; NaOH C H OH ; NaBr

IIIIJ
ethyl bromide ethanol

(2) Ethyl bromide to propane nitrile.

Ans. C H Br ; KCN C H CN ; KBr

IIIIJ
ethyl bromide (alc.) propane nitrile

(3) Ethyl bromide to ethyl amine.

Ans. C H Br ; NH C H NH ; HBr
pressure
IIIIIIIIIIIJ
ethyl bromide (alc.) ethyl amine

(4) Ethyl bromide to ethyl acetate.

Ans. CH COOAg ; C H Br CH COOC H ; AgBr

IIIIJ
silver acetate ethyl bromide ethyl acetate

(5) Ethyl bromide to ethyl isocyanide.

Ans. C H Br ; AgCN C H NC ; AgBr

IIIIJ
ethyl bromide (alc.) ethyl isocyanide

(6) Ethyl bromide to ethyl methyl ether.

Ans. C H Br ; CH –ONa C H –O–CH ; NaBr

IIIIJ
ethyl bromide ethyl methyl ether

(7) Ethyl bromide to n-butane.
dry ether
Ans. C H Br ; Na ; C H Br CH 9CH 9CH 9CH ; 2NaBr

IIIIIIIIIIIIJ
ethyl bromide n-butane

(8) Ethyl bromide to Ethyl magnesium bromide.
dry ether
Ans. C H Br ; Mg C H MgBr

IIIIIIIIIIIIJ
ethyl bromide ethyl magnesium bromide ■

Unit
10.6.3 Mechanism of SN reaction

Ans.
(1) Nucleophilic bimolecular reaction (SN) : The substitution reaction in which a nucleophile reacts with the
substrate and the rate of the reaction depends on the concentration of the substrate and the nucleophile is called a
nucleophilic bimolecular reaction.
Example : CH Br ; OH 9 ; CH OH ; Br 9

substrate nucleophile
(2) SN reaction : The substitution reaction in which a nucleophile reacts with the substrate and the rate of the
reaction depends only on the concentration of the substrate is called nucleophilic unimolecular or first order
reaction or SN reaction. ■
Q. 59. Explain, the mechanism of alkaline hydrolysis (reaction with aqueous KOH) of tert-butyl bromide
(2-Bromo-2-methylpropane) with energy profile diagram. (4 marks) OR
Explain only reaction mechanism for alkaline hydrolysis of tert-butyl bromide. (2 marks)
Ans.
(i) Consider alkaline hydrolysis of tert-butyl bromide (2-Bromo-2-methylpropane) with aqueous NaOH or KOH.
CH CH

9
CH – C – Br ; OH CH – C – OH ; Br9

IIIIIIJ
CH CH

tert-butyl bromide nucleophile tert-butyl alcohol
(substrate)
(ii) Kinetics of the reaction : Due to steric hindrance of voluminous three methyl groups around carbon, nucleophile
OH9 cannot attack carbon atom directly. Hence, the reaction takes place in two steps.
Step I : This involves heterolytic fission of C9Br covalent bond in the substrate forming carbocation and Br9.
This is a slow process.
CH CH
slow
CH – C – Br CH – C ; ; Br9
RDS
CH CH

Carbonium ion
Step II : This step involves attack of nucleophile OH9 or carbocation forming C9OH bond and product tert-butyl
alcohol. Since it involves ionic charge neutralisation, it is a fast step.
CH CH
fast
; 9
CH – C ; OH CH – C – OH

IIIIIIJ
CH CH

Rate Determining Step (R.D.S.) : Since the first step is a slow step, it is R.D.S., and therefore the rate of the
reaction depends on the concentration of only one reactant, (CH ) C9Br.

Rate:R:k [(CH ) C9Br] where k is a rate constant of the reaction.

SN reaction : The reaction between tert.butyl bromide and hydroxide ion to form tert.butyl alcohol follows
a first – order kinetics. The rate of this reaction depends only on the concentration of one substance (tert-butyl

bromide) and is independent of concentration of alkali added. It is unimolecular first (1st) order Nucleophilic
Substitution reaction denoted as SN reaction.
Stereochemistry and mechanism of the reaction : The reaction takes place in two steps and both the steps
involve formation of transition states (T.S.).
T.S. – I for first step :
Fig. : Formation of carbocation intermediate
In this transition state, C9Br bond is partially broken, so that carbon atom carries partial positive charge
(;) and Br carries partial negative charge (9) which further breaks forming carbocation and Br9. Tert-butyl
cation (carbocation) has a planar structure and the CH –C–CH bond angle is 120°. It is the intermediate of the

reaction. It is unstable. In this step, hybridisation of carbon atom changes from sp (tetrahedral geometry) to sp
(planar geometry).
T.S. – II for second step :
Fig. : SN mechanism
In this transition state, C9OH bond is partially formed so that carbon atom carries partial positive charge
(; ) and OH carries partial negative charge (9 ) which further forms tert-butyl alcohol.
Formation of a racemic mixture : Since OH9 has equal probability of the attack on carbocation from
frontside and from backside, the products obtained are equal. In case of optical active alkyl halide, a racemic
mixture is obtained. ■
Q. 60. Discuss SN mechanism of methyl bromide using aqueous KOH. Draw energy profile diagram. OR
Discuss the mechanism of alkaline hydrolysis of methyl bromide or Bromomethane. (4 marks)
Ans.
(1) Consider alkaline hydrolysis of methyl bromide (Bromomethane), CH Br with aqueous NaOH or KOH.

CH 9Br ; OH 9 ; CH 9OH ; Br 9

Bromomethane nucleophile Methanol
substrate
(2) Stereochemistry and Kinetics of the reaction (R.D.S.) : This hydrolysis reaction takes place only in one step
which is a rate determining step i.e. R.D.S. The rate of hydrolysis reaction depends on the concentration of CH Br

and OH 9 which are present in the R.D.S. of the reaction.
Rate:R:k [CH Br] [OH 9 ]

where k is rate constant of the reaction.

SN reaction : The reaction between methyl bromide and hydroxide ion to form methanol follows a second order
kinetics, since the rate of the reaction depends on the concentrations of two reacting species, namely methyl
bromide and hydroxide ion it is bimolecular second order (2nd) Nucleophilic Substitution reaction denoted by SN.
(3) Mechanism of the reaction :
(i) It is a single step mechanism. The reaction takes place in the following steps :
Fig. : Backside attack of nucleophile in SN mechanism

(ii) Backside attack of the nucleophile : Nucleophile, OH9 attacks carbon atom of CH Br from back side

i.e. from opposite side to that of the leaving group i.e. Br\ to experience minimum steric repulsion and
electrostatic repulsion between the incoming nucleophile (OH\) and leaving Br\.
(iii) Transition state : When a nucleophile, OH 9 approaches carbon atom of CH Br, the potential energy of the

system increases until a transition state (T.S.) of maximum potential energy is formed in which C9Br bond is
partially broken and C9OH bond is partially formed. The negative charge is equally shared by both
incoming nucleophile –OH\ and outgoing, leaving group –Br\. (Thus, the total negative charge is diffused.)
(iv) In CH Br, carbon atom is sp-hybridized and CH Br molecule is tetrahedral. The hybridisation of carbon

atom changes to sp hybridisation. The transition state contains pentacoordinate carbon having three (sigma)
bonds in one plane making bond angles of 120° with each other i.e., H , H and H atoms lie in one plane

while two partial covalent bonds containing Br and OH lie collinear and on opposite sides perpendicular to the
plane.
(v) Inversion of configuration : The transition state decomposes fast by the complete breaking of the C–Br
bond and the new C–OH bond is formed on the other side. The breaking of C–Br bond and the formation of
C–OH bond take place simultaneously. The energy required to break the C–Br bond is partly obtained from
the energy released when C–OH bond is formed. The formation of product CH OH is accompanied by

complete or 100% inversion of configuration forming again sp-hybridized carbon atom giving tetrahedral
CH OH molecule. But in this structure the positions of H and H atoms in the reactant (CH Br) and in

product are on the opposite side. This inversion of configuration is called Walden inversion. ■

(Textbook page 222)
● Draw the Fischer projection formulae of two products obtained when compound (A) reacts with OH*
9
by
SN1 mechanis.
C H

H C9 C9Br (A)

n– C H

C H C H C H

9
*
Ans. CH 9 C9Br ; OH H C9 C9OH ; HO9 C9CH

IIIIIIJ

n– C H n– C H n– C H

I II
(Racemic mixture)

● Draw the Fischer projection formula of the product formed when compound (B) reacts with OH*
9
by SN2
mechanism.
CH

H9 C9Cl (B)

C H

CH CH

Ans. H9 C9Cl ;OH*
9
IIIIIIIJ HO9 C9H ;Cl 9

C H C H

Unit
10.6.4 Factors influencing SN1 and SN2 mechanism
Q. 61. Discuss the factors influencing SN1 and SN2 mechanism. (4 marks)
Ans.
(1) Nature of substrate : SN2 : The transition state (T.S.) of SN2 mechanism < is pentacoordinate, it is crowded. As a
result SN2 mechanism is favoured in primary halides and least favoured in tertiary halides.
SN1 : A planar carbocation intermediate is formed in SN1 reaction. Bulky alkyl groups can be easily accommodated
in planar carbocation and it has no steric crowding. As a result SN1 mechanism is favoured in tertiary halides and
least favoured in primary halides.
The carbocation intermediate is stabilized by;effect of alkyl substituents and also by hyperconjugation
effect of alkyl substituents containing -hydrogens. As a result, SN1 mechanism is favoured in tertiary halides and
least favoured in primary halides.
SN1 rate increases
CH 9X
IIIIIIIIIIIIIIIIIIIIIIIIIJ
1° 2° 3°

ZIIIIIIIIIIIIIIIIIIIIII
SN2 rate increases

Thus, tertiary alkyl halides undergo nucleophilic substitution by SN1 mechanism while primary halides follow SN2
mechanism.
(2) Nucleophilicity of the reagent : A strong nucleophile attacks the substrate faster and favours SN2 mechanism. The
rate of SN1 mechanism is independent of the nature of nucleophile. Nucleophile does not react in the 1st step (slow
step) of SN1. Nucleophile reacts fast after the carbocation intermediate is formed.
(3) Solvent polarity : (1) SN1 reaction proceeds more rapidly in polar protic solvents than in aprotic solvent. Polar
protic solvent decreases the rate of SN2 reaction. (2) In SN2 mechanism, rate depends on substrate as well as
nucleophile. A polar solvent stabilizes nucleophile by solvation. Thus solvent deactivates the nucleophile by
stabilizing it. Hence, aprotic solvents or solvent of low polarity will favour SN2 mechanism. ■

Allylic and benzylic halides show high reactivity towards the SN1 mechanism than other primary alkyl
halides. Explain. (2 marks)
Ans. In allylic and benzylic halide, the carbocation formed undergoes stabilization through the resonance. Hence,
allylic and benzylic halides show high reactivity towards the SN1 reaction. The resonating structures are
Resonance stabilization of allylic carbocation
Resonance stabilization of benzylic carbocation
Do you know ?
(Textbook page 224)
1. A negatively charged nucleophile is more powerful than its conjugate acid. For example, R9O*
9
is better
nucleophile than R9OH.
2. When donor atoms are from same period of periodic table, nucleophilicity decreases from left to right in a
period. For example, H O is less powerful nucleophile than NH .

3. When donor atoms are from same group of the periodic table, nucleophilicity increases down the group. For
example, 1*
9
is better nucleophile than Cl*
9
.

Which of the following two compounds would react faster by SN2 mechanism and Why ?
CH 9CH 9CH 9CH Cl CH 9CH9CH 9CH

Cl
1-Chlorobutane 2-Chlorobutane
Answer : In SN2 mechanism, a pentacoordinate T.S. is involved. The order of reactivity of alkyl halides towards
SN2 mechanism is,
Primary Secondary Tertiary, (due to increasing crowding in T.S. from primary to tertiary halides.
1-Chlorobutane being primary halide will react faster by SN2 mechanism, than the secondary halide
2-chlorobutane.)

★ Q. 62. Distinguish between SN1 reaction and SN2 reaction : (2 marks)
Ans. Factor SN1 SN2
(1) Number of steps Two steps One step
(2) Molecularity/Order Unimolecular/1st order Bimolecular/2nd order
(3) Reaction rate Depends upon concentration of one reacting Depends upon concentration of two
species reacting species
(4) Attack of a nucleo- Back side attack and front side attack on a Only back side attack on a substrate
phile substrate with equal probability
(5) Transition state Two steps, two transition states One step, one transition state
(6) Type of substrate Mainly tertiary (3°) substrate Mainly primary (1°) substrate
(7) Stereochemistry 50% inversion and 50% retention of configur- 100% inversion of configuration
ation
(8) Enantiomer Forms racemic mixture Forms opposite enantiomer
(9) Solvent Polar solvent favourable Nonpolar solvent favourable
(10) Energy of activation Two values of energies of activation One value of energy activation
(11) Intermediate Carbocation intermediates No intermediate
(12) Nucleophile Weak nucleophile favourable Strong nucleophile favourable
(13) Order of reactivity Tertiary Secondary Primary Primary Secondary Tertiary

in alkyl halides
Q. 63. How does relative reactivity for alkaline hydrolysis with respect to SN2 and SN1 vary in the following alkyl
halides :
(1) Bromomethane (2) Bromoethane (3) 2-Bromopropane (4) 2-Bromo-2-methylpropane ?
(2 marks each)
Ans.
(A) Relative reactivity for SN2 mechanism decreases in the order of :
Bromomethane Bromoethane 2-Bromopropane 2-Bromo-2-methyl propane
CH

CH Br CH 9CH 9Br CH 9CHBr9CH CH – C – Br

CH

(B) Relative reactivity for SN1 mechanism decreases in the order of :
2-Bromo-2-methylpropane 2-Bromopropane Bromoethane Bromomethane
CH

CH – C – Br CH 9CHBr9CH CH 9CH 9Br CH Br

CH

■

Q. 64. Explain with reason the relative order of reactivity of 1°/2°/3° alkyl halides by SN1 mechanism. (2 marks)
Ans. In alkaline hydrolysis of an alkyl halide by SN1 mechanism, the formation of carbocation as an intermediate
product is involved.
The increasing order of a stability of carbocation is,
(1°) primary (2°) secondary (3°) tertiary

CH

CH 9 >
CH CH 9>
CH 9CH CH –>C

CH

(less stable) (most stable)
The stability order for carbocation is 3° 2° 1°.

Therefore the increasing order of reactivity by SN1 mechanism of alkyl halides is
(1°) primary (2°) secondary (3°) tertiary ■
Q. 65. Which one of the following is more easily hydrolysed in SN1 and SN2 reaction by aqueous KOH,
C H CHCl C H and C H CH Cl ? (1 mark each)

Ans. In SN1 reaction C H CHCl C H will be more easily hydrolysed than C H CH Cl

In SN2 reaction C H CH Cl will be more easily hydrolysed than C H CHCl C H . ■

★ Q. 66. Which one compound from the following pairs would undergo SN2 faster ? (2 marks)
(1)
(2) CH CH CH I and CH CH CH Cl

Ans.
(1) Since is a primary halide it undergoes SN2 reaction faster than .
(2) Since iodine is a better leaving group than chloride, 1-iodo propane (CH CH CH I) undergoes SN2 reaction faster

than 1-chloropropane (CH CH CH Cl). ■

Q. 67. Choose the member that will react faster than the following pairs by SN1 mechanism. (2 marks each)
(1) 1-bromo-2, 2-dimethyl propane or 2-bromopropane.
CH

CH – C— CH –Br CH – CH–CH

CH Br

1-bromo-2, 2-dimethyl propane 2-bromopropane
Ans. The reactivity of SN1 reaction depends on the steric hindrance, in 2-bromopropane, -carbon atom is attached to
two methyl groups suffers greater steric hindrance to nucleophilic attack than 1-bromo-2, 2-dimethyl propane.
Hence, 2-bromopropane react faster by SN mechanism.
(2) 2-Iodo-2-methyl butane or 2-iodio-3-methyl butane.
CH CH

CH –CH – C–CH CH – CH–CH–CH

I I
2-Iodo-2-methyl butane 2-Iodo-3-methyl butane

Ans. Since, 2-Iodo-2-methyl butane is a tertiary alkyl halide, it undergoes SN reaction faster than 2-iodo-3-methyl
butane.
(3) 1-Chloro propane or 2-chloropropane.
CH –CH –CH –Cl CH –CH–CH

1-chloropropane
Cl
2-chloropropane
Ans. Since, 2-chloropropane is a secondary alkyl halide, it undergoes SN reaction faster than 1-chloropropane.
(4) 2-Iodo-2-methyl butane or tert-butyl chloride.

I CH

CH – C–CH –CH CH – C–Cl

CH CH

2-Iodo-2-methyl butane tert-butyl chloride
Ans. Since, iodine is a better leaving group than chloride 2-iodo-2-methyl butane undergo SN reaction faster than
tert-butyl chloride. ■
★ Q. 68. Observe the following and answer the questions given below :
;
*
CH :CH9 X:* 9
CH 9CH:X:

(1) Name the type of halogen derivative
(2) Comment on the bond length of C9X bond in it
(3) Can react by SN1 mechanism ? Justify your answer.
Ans.
(1) Vinyl halide
(2) C9X bond length shorter in vinyl halide than alkyl halide. Vinyl halide has partial double bond character due to
resonance.
In vinyl halide, carbon is sp hybridised. The bond is shorter and stronger and the molecule is more stable.
(3) Yes, It reacts by SN1 mechanism. SN1 mechanism involves formation of carbocation intermediate. The vinylic
carbocation intermediate formed is resonance stabilized, hence SN mechanism is favoured. ■
Unit
10.6.5 Elimination reaction : Dehydrohalogenation
Q. 69. Write a note on elimination reaction. OR Explain dehydrohalogenation reaction. (2 marks)

Ans. When alkyl halide having at least one
-hydrogen is boiled with alcoholic solution of potassium hydroxide (KOH),
an alkene is formed due to elimination of hydrogen atom from
-carbon and halogen atom from -carbon, is called
dehydrohalogenation.
H X

9 C99 C 9 ; KOH 9C :C 9 ; KX;H O

J
(alc.)
For example,

CH 9CH 9Br ; KOH H C:CH ;KBr;H O

J
ethyl bromide (alc.) ethylene

Tertiary butyl bromide when heated with alcoholic solution of potassium hydroxide forms isobutylene.
CH CH

CH – C– CH ; KOH CH – C:CH ;KBr;H O
(alc.)
IIIIIJ
isobutylene
Br
This reaction is called

-elimination (or 1,2-elimination) reaction as it involves elimination of halogen and a

-hydrogen atom.
As hydrogen and halogen is removed in this reaction it is also known as dehydrohalogenation reaction. ■
Remember ...
(Textbook page 225)
The carbon bearing halogen is commonly called -carbon (alpha carbon) and any carbon attached to -carbon is

-carbon (beta carbon). Hydrogens attached to
-carbon are
-hydrogens.
Q. 70. Describe the action of alcoholic potassium hydroxide (alc. KOH) on

(1) ethyl bromide (2) n-propyl bromide (3) isopropyl bromide (4) tert-butyl chloride. (1 mark each)
Ans.
(1) Ethyl bromide : When ethyl bromide (bromoethane) is heated with alcoholic potassium hydroxide (alcoholic
alkali), ethene (gas) is formed by the dehydrobromination reaction.
heat
CH – CH – Br ; KOH CH :CH ; KBr ; H O

J
ethyl bromide (alc.) ethene
(2) n-Propyl bromide : When n-propyl bromide is heated with alcoholic potassium hydroxide, propene is formed.
heat
CH –CH –CH –Br;KOH CH – CH:CH ;KBr;H O

J
n-propyl bromide (alc.) propene
(3) Isopropyl bromide : When isopropyl bromide (2-bromopropane) is boiled with alcoholic potassium hydroxide,
propene is formed.
heat
CH – CH – CH ; KOH CH – CH:CH ; KBr ; H O

J
(alc.) propene
Br
isopropyl bromide
(4) Tert-butyl chloride : When tert-butyl chloride (2-chloro-2-methyl propane) is heated with alcoholic KOH,
2-methyl propene is formed.
CH CH
heat
CH – C – Cl;KOH
CH – C :CH ;KBr;HO

J
(alc.) 2-methyl propene

CH

tert-butyl chloride ■
Q. 71. Describe the action of alc.KOH on 2-bromobutane. (1 mark)

When 2-bromobutane is boiled with alc.KOH on 2-bromobutane, a mixture of but-1-ene and but-2-ene is
formed.

Ans.

CH 9 CH 9CH 9 CH

Br
(2-bromobutane)
alc. KOH
loss of
-hydrogen loss of
-hydrogen
HC 9CH 9CH:CH CH 9CH:CH9CH

(But-1-ene) (But-2-ene) ■
Q. 72. Explain Saytzeff’s rule with suitable example. (2 marks)

Ans. Saytzeff’s rule : In dehydrohalogenation reaction the preferred product is that alkene which has the greater
number of alkyl groups attached to the doubly bonded carbon atoms.
Hence the number of alkyl substituents on doubly bonded carbon atoms increases, the stability of the alkene
giving its major products.
Hence the increasing stability of alkenes is,
R R R
CH :CH CH :CH9R R9CH:CH9R C:CH9R C:C
R R R
Monosubstituted Disubstituted Trisubstituted Tetrasubstituted
alkene alkene alkene alkene
There are two types of

hydrogens (
and
) therefore two alkenes are expected.

2CH – CH – CH –CH ;2KOH H C–CH:CH–CH ;H C:CH–CH –CH ;2KBr;2H O

IIIIJ
(alc.) But-2-ene (Disubstituted alkene) (80%) But-1-ene (20%)

Cl
(Monosubstituted alkene) ■
2-chlorobutane
Do you know ?
(Textbook page 225)
Elimination versus substitution :
Alkyl halides undergo substitution as well as elimination reaction. Both reactions are brought about by basic
reagent, hence there is always a competition between these two reactions. The reaction which actually
predominates depends upon following factors.
(a) Nature of alkyl halides : Tertiary alkyl halides prefer to undergo elimination reaction whereas primary alkyl
halides prefer to undergo substitution reaction.
(b) Strength and size of nucleophile : Bulkier electron rich species prefers to act as base by abstracting proton,
thus favours elimination. Substitution is favoured in the case of comparatively weaker bases, which prefer to
act as nucleophile.
(c) Reaction conditions : Less polar solvent, high temperarture favours elimination whereas low temperature,
polar solvent favours substitution reaction.

Q. 73. Answer the following :
★ (1) HCl is added to a hydrocarbon ‘A’ (C H ) to give a compound ‘B’ which on hydrolysis with aqueous alkali

forms tertiary alcohol ‘C’(C H O). Identify ‘A’, ‘B’ and ‘C’. (3 marks)

CH CH

Ans. CH 9 C:CH ;HCl CH 9 C9CH

IIIIIJ
Cl
(A) (B)
2-methyl propene tert.butyl chloride
CH CH

CH 9 C9CH ;aq.KOH H C9 C9CH

IIIIIIIIJ

Cl OH
(B) tert. butyl alcohol
(C)
CH CH CH

A:CH 9 C:CH B:CH 9 C9CH C:CH 9 C9OH

Cl CH

★ (2) Complete the following reaction sequences by writing the structural formulae of the organic compounds
‘A’, ‘B’ and ‘C’.
alc.KOH
(1) 2-Bromobutane IIIIIIIIIIIIIJ A IIIIIIIIIIIIJ B IIIIIIIIIIIIJ C (3 marks)
Br NaNH

(2) Isopropyl alcohol IIIIIIIIIJ A IIIIIIIIIIIIIIIJ B (2 marks)
PBr NH excess

Ans.
alc. KOH
(1) CH 9CH9CH 9CH CH 9CH:CH9CH ;CH 9CH 9CH:CH ;2KBr;2H O

IIIIIIIIIIIIIIJ
80% 20%
Br
But-2-ene But-1-ene
2-Bromobutane
(A)
CH 9CH:CH9CH ;Br CH 9CH9CH9CH

IIIIIIIIIIIJ

Br Br
2,3-Dibromobutane
(B)
CH 9CH9CH9CH ;2NaNH CH 9CH9CH9CH ;2NaBr

IIIIIIIIJ

Br Br NH NH

2,3-diaminobutane
(C)
A:CH 9CH:CH9CH

B:CH 9CH9CH9CH C:CH 9CH9CH9CH

Br Br NH NH

NH
(2) CH 9CH9CH CH 9CH9CH CH 9CH9CH

IIIIIIIIIIIJ IIIIIIIIIIIJ
PBr excess

OH Br NH

(A) (B)
isopropyl bromide isopropyl amine
A:CH 9CH9CH isopropyl bromide

Br
B:CH 9CH9CH isopropyl amine ■

NH

★ Q. 74. Convert the following :
(1) Propene to propan-1-ol (2 marks)
peroxide
Ans. CH 9CH:CH ;HBr CH 9CH 9CH

IIIIIIIIIIIIJ
Propene n-propyl bromide

CH 9CH 9CH 9Br;aq. KOH CH 9CH 9CH 9OH;KBr

IIIIIIIJ
Propan-1-ol
(2) Benzyl alcohol to benzyl cyanide (2 marks)

Ans.
(3) Ethanol to propane nitrile. (2 marks)
Ans. CH 9CH 9OH;HBr CH 9CH 9Br;H O

IIIIIIJ
Ethanol (48%) Ethyl bromide
alc.
CH 9CH 9Br;KCN CH 9CH 9CN;KBr

IIIIIIIIJ
Propane nitrile
(4) But-1-ene to n-butyl iodide. (2 marks)
Ans. 6CH 9CH 9CH:CH ;B H 2 (CH 9CH 9CH 9CH ) B

IIIIIIIJ
But-1-ene Tributyl borane

OH 9
(CH 9CH 9CH 9CH ) B;3H O 3CH 9CH 9CH 9CH 9OH;B (OH)
H O
IIIIIIIJ
Butan-1-ol
red P/I
3CH 9CH 9CH 9CH 9OH;PI 3CH 9CH 9CH 9CH I;H PO

IIIIIIIIIIIIJ
n-butyl iodide

(5) 2-Chloropropane to propan-1-ol. (3 marks)

Ans. CH 9CH9CH ;alc.KOH CH 9CH:CH ;KCl;H O

IIIIIJ
Propene
Cl
6CH 9CH:CH ;B H 2 (CH 9CH 9CH ) B

IIIIIIJ
Propene tripropyl borane

OH 9
(CH 9CH 9CH ) B;3H O 3CH 9CH 9CH 9OH;B(OH)
HO
IIIIIIIIJ

Propan-1-ol
(6) tert. butyl bromide to isobutyl bromide. (2 marks)
CH CH

Ans. CH 9 C9 Br;alc.KOH CH 9 C:CH ;KBr;H O

IIIIIIIJ
2-Methyl prop-1-ene
CH

tert. butyl bromide
CH CH
Peroxide

CH 9 C:CH ;HBr CH 9 C9CH Br

IIIIIIIIIIIIJ
isobutyl bromide
(7) Aniline to chlorobenzene. (2 marks)

Ans.
(8) Propene to 1-nitropropane. (2 marks)

Peroxide
Ans. CH 9CH:CH ;HBr CH 9CH 9CH 9Br

IIIIIIIIIIIIJ
Propene 1-bromopropane

CH 9CH 9CH 9Br;AgNO CH 9CH 9CH 9NO ;AgBr(s)
9NaCl
IIIIIIIIIJ
1-nitropropane ■
Unit
10.6.6 Reaction with active metals
Q. 75. What is a Grignard reagent ? (2 marks)

Ans. Grignard reagent : An organometallic compound in which the divalent magnesium is directly linked to an alkyl
group (R9) and a halogen atom (X), and has general formula R9Mg9X is called Grignard reagent. OR
When alkyl halide is treated with magnesium in dry ether as solvent, it gives alkyl magnesium halide. It is known as
Grignard reagent.

dry ether
R9X;Mg IIIIIIIIIIIIJ R9Mg9X
alkyl magnesium halide
(Grignard reagent)

\ > \
E.g. CH 9 Mg 9 I

The carbon-magnesium bond is highly polar and magnesium-halogen bond is in ionic in nature. Grignard
reagent is highly reactive. It is an important reagent and used in the preparation of a large number of organic
compounds. ■
Q. 76. How is Grignard reagent prepared ? (2 marks)

Ans. Grignard reagent is an alkyl magnesium halide, R9Mg9X obtained by the reaction of alkyl halide R9X with
magnesium (Mg) in dry ether.

dry ether \ > \
R9X ; Mg IIIIIIIIIIIJ
R 9 Mg 9 X
alkyl halide alkyl magnesium halide
When an alkyl halide like CH I is added from a dropping funnel to a flask containing pieces of pure Mg in pure

and dry ether (diethyl ether) and a trace of iodine, Grignard reagent, CH 9Mg9I is formed.

dry ether \ > \
\ > \
CH 9I ; Mg CH 9 Mg 9 I OR ( CH 9 Mg9 I )

IIIIIIIIIIIJ
methyl iodide methyl magnesium iodide
Ethyl iodide when treated with magnesium in presence of dry ether forms ethyl magnesium iodide.

dry ether \ 2
> \
C H I;Mg C H –Mg–I OR ( C H 9 Mg9 I )

IIIIIIIIIIIJ
ethyl magnesium
iodide ■
Q. 77. Write a note on Grignard reagent. (2 marks)

Ans. For the answer refer to Qs. 70 and 71. ■
Do you know ?
(Textbook page 226)
Carbon-magnesium bond in Grignard reagent is a polar covalant bond. The carbon pulls electrons from the
electropositive magnesium. Hence carbon in Grignard reagent has negative polarity and acts as a nucleophite.
Victor Grignard received Nobel Prize in 1912 for synthesis and study of organomagnesium compounds. Grignard
reagent is a very versatile reagent used by organic chemist. Vinyl and aryl halides also form Grignard reagent.
Q. 78. Describe the action of water on (1) methyl magnesium iodide (2) ethyl magnesium iodide. (2 marks)
Ans.
(1) Methyl magnesium iodide : When methyl magnesium iodide is treated with water, methane is obtained
OH
CH 9Mg9I;H9OH CH ;Mg

IIIIIIJ
I
Methane
(2) Ethyl magnesium iodide : When ethyl magnesium iodide is treated with water, ethane is obtained.
OH
CH 9CH 9Mg9I;H9OH CH 9CH ;Mg
I
IIIIIIIJ
Ethane ■

Q. 79. Describe the action of ammonia on (1) ethyl magnesium bromide (2) n-propyl magnesium chloride.
(2 marks)
Ans.
(1) Ethyl magnesium bromide : When ethyl magnesium bromide is treated with ammonia, ethane is formed.
Br
CH 9CH 9Mg9Br;H9NH CH 9CH ;Mg

IIIIIIIJ
NH

ammonia Ethane
(2) n-Propyl magnesium chloride : When n-propyl magnesium chloride is treated with ammonia, propane is formed.
Br
CH 9CH 9CH 9Mg9Br;H9NH CH 9CH 9CH ;Mg

IIIIIIIJ
NH

ammonia Propane ■
Q. 80. Explain Wurtz reaction. (2 marks) OR Explain the action of sodium with alkyl halides. (2 marks)
Ans.
(1) When an alkyl halide is treated with metallic sodium in dry ether, the corresponding higher alkane is formed. This
is called Wurtz reaction or Wurtz coupling reaction.
ether
R – X ; 2Na ; X – R IIIIIIIJ R – R ; 2NaX
alkane
(2) In this reaction the alkyl radicals from two molecules of the reacting alkyl halide combine or couple to form the
higher alkane.
(3) Thus, methyl bromide reacts with sodium in ether to form ethane (C H ), while ethyl bromide under the same

conditions forms n-butane (C H ).

ether
2 CH – Br ; 2Na CH – CH ; 2NaBr

IIIIIIIIJ
methyl bromide ethane

ether
2 CH – CH – Br ; 2Na CH – CH – CH – CH ; 2NaBr

IIIIIIIIJ
ethyl bromide n-butane
(Zinc metal can also be used in place of sodium.)

(4) If a mixture of two different alkyl halides is treated with Na in dry ether, then a mixture of alkanes is obtained
called self coupling products. For example, a mixture of CH Br and C H Br gives propane along with C H and

C H .

dry ether
CH Br ; 2Na ; C H Br C H ; C H ; C H ; NaBr

J
methyl bromide major major minor ■
Unit
10.6.7 Reaction of haloarenes
Q. 81. Explain the reaction of haloarene with alkyl halide and sodium metal. OR
Write a note on Wurtz–Fittig reaction. (2 marks)
Ans. When an alkyl halide and an aryl halide is treated with sodium metal in dry ether the corresponding alkylarene
(alkyl benzene) is formed. The reaction is known as Wurtz-Fittig reaction. This reaction allows alkylation of alkyl
halides.

■
Q. 82. Describe the action of aryl halide on sodium metal. (1 mark)

Ans. Aryl halide reacts with sodium metal in dry ether, biphenyl is formed. This reaction is known as Fittig reaction.
Can you tell ?

(Textbook page 227)
Conversion of chlorobenzene to phenol by aqueous sodium hydroxide requires high temperature of
about 623K and high pressure. Explain.
Ans. Due to partial double bond character in chlorobenzene, the bond cleavage in chlorobenzene is difficult and
are less reactive. Hence, during the conversion of chlorobenzene to phenol by aq. NaOH requires high
temperature & high pressure.
Electrophilic substitution (SE) in aryl halides

Q. 83. Identify the product A of following reaction. (Textbook page 228)
(1 mark)
Ans.
Remember ...
(Textbook page 228)
The 9I effect of Cl is more powerful than its ;R effect. Therefore Cl is o-/p- directing but ring deactivating
group.

Do you know ?
(Textbook page 228)
Occurrence of nucleophilic substitution in p-nitrochlorobenzene can be explained on the basis of resonance
stabilization of the intermediate.
The resonance structure (III) shows that the electron withdrawing nitro group (9NO ) in the p-position

extends the conjugation. As a result, the intermediate carbanion is better stabilized which favours nucleophilic
substitution reaction.
Q. 84. Explain the following substitution reactions of chlorobenzene :

(1) Halogenation (2) Nitration (3) Sulphonation. (1 mark each)
Ans.
(1) Halogenation : When chlorobenzene is reacted with chlorine in presence of anhydrous ferric chloride, a mixture
of ortho and para-dichlorobenzene (major product) is formed.
(2) Nitration : When chlorobenzene is heated with nitrating mixture (conc. nitric acid;conc. sulphuric acid) a
mixture of 1-chloro-4-nitro benzene (major product) and 1-chloro-2-nitrobenzene is formed.
(3) Sulphonation : When chlorobenzene is heated with concentrated sulphuric acid, a mixture of 4-chlorobenzene
sulphonic acid (major product) and 2-chlorobenzene sulphonic acid is formed.

Q. 85. Describe the action of the following on chlorobenzene :
(1) Methyl chloride in the presence of anhydrous AlCl

(2) Acetyl chloride in the presence of anhydrous AlCl . (1 mark each)

Ans.
(1) Methyl chloride in the presence of anhydrous AlCl : When chlorobenzene is treated with methyl chloride in

the presence of anhydrous AlCl , a mixture of 1-chloro-4-methyl benzene (major product) and 1-chloro-2-methyl

benzene is formed. Since, the alkyl group is introduced in the benzene ring, the reaction is termed as Friedel Craft’s
alkylation.
(2) Acetyl chloride in the presence of anhydrous AlCl : When chlorobenzene is reacted with acetyl chloride in the

presence of anhydrous AlCl , a mixture of 2-chloro acetophenone and 4-chloro acetophenone (major product) is

formed. Since, the acetyl group is introduced in the benzene ring, the reaction is termed as Friedel Craft’s acylation.
Q. 86. Write a note on Friedel Craft’s reaction. (2 marks)

Ans. For answer refer to Q. 85. ■
Q. 87. Give reasons : ★ (1) Haloarenes are less reactive than haloalkanes. (3 marks)
Ans. Haloarenes (Aryl halides) are less reactive than (alkyl halides) haloalkanes due to the following reasons :
(1) Resonance effect : In haloarenes, the electron pairs on halogen atom are in conjugation with -electrons of the
benzene ring. The delocalization of these electrons C-Cl bond acquires partial double bond character.
Due to partial double bond character of C-Cl bond in aryl halides, the bond cleavage in haloarene is difficult and
are less reactive. On the other hand, in alkyl halides, carbon is attached to chlorine by a single bond and it can be
easily broken.
(2) Aryl halides are stabilized by resonance but alkyl halides are not. Hence, the energy of activation for the
displacement of halogen from aryl halides is much greater than that of alkyl halides.

(3) Different hybridization state of carbon atom in C-X bond :
(i) In alkyl halides, the carbon of C-X bond is sp-hybridized with less s-character and greater bond length of
178 pm, which requires less energy to break the C-X bond.
(ii) In aryl halides, the carbon of C-X bond is sp-hybridized with more s-character and shorter bond length which
requires more energy to break C-X bond. Therefore, aryl halides are less reactive than alkyl halides.
(iii) Polarity of the C-X bond : In aryl halide C-X bond is less polar than in alkyl halides. Because sp-hybrid
carbon of C-X bond has less tendency to release electrons to the halogen than a sp-hybrid carbon in alkyl
halides. Thus halogen atom in aryl halides cannot be easily displaced by nucleophile.
(2) Aryl halides are extremely less reactive towards nucleophilic substitution reactions. (3 marks)
Ans. Aryl halides are extremely less reactive towards nucleophilic substitution reaction due to the following reasons :
(1) Resonance effect : In haloarenes, the electron pairs on halogen atom are in conjugation with -electrons of the
benzene ring. The delocalization of these electrons C-Cl bond acquires partial double bond character.
Due to partial double bond character of C-Cl bond in aryl halides, the bond cleavage in haloarene is difficult
and are less reactive towards nucleophilic substitution.
(2) Sp hybrid state of C : Different hybridization state of carbon atom in C-X bond : In aryl halides, the carbon of
C-X bond is sp-hybridized with more s-character and shorter bond length of 169 pm which requires more energy
to break C-X bond. It is difficult to break a shorter bond than a longer bond, in alkyl chloride (bond length 178 pm)
therefore, aryl halides are less reactive towards nucleophilic substitution reaction.
(3) Instability of phenyl cation : In aryl halides, the phenyl cation formed due to self ionisation will not be stabilized
by resonance which rules out possibility of SN1 mechanism. Also backside attack of nucleophile is blocked by the
aromatic ring which rules out SN2 mechanism. Thus cations are not formed and hence aryl halides do not undergo
nucleophilic substitution reaction easily.
(4) As any halides are electron rich molecules due to the presence of -bond, they repel electron rich nucleophilic.
attack. Hence, aryl halides are less reactive towards nucleophilic substitution reactions. However, the presence of
electron withdrawing groups at o/p position activates the halogen of aryl halides towards substitution.
(3) Aryl halides undergo electrophilic substitution reactions slowly. (3 marks)

Ans. Aryl halides undergo electrophilic substitution reactions slowly and it can be explained as follows :
(1) Inductive effect : The strongly electronegative halogen atom withdraws the electrons from carbon, atom of the
ring, hence aryl halides show reactivity towards electrophilic attack.
(2) Resonance effect : The resonating structures of aryl halides show increase in electron density at ortho and para
position, hence it is o, p directing.

The inductive effect and resonance effect compete with each other. The inductive effect is stronger than
resonance effect. The reactivity of aryl halides is controlled by stronger inductive effect and o, p orientation is
controlled by weaker resonating effect.
The attack of electrophile (Y) on haloarenes at ortho and para positions are more stable due to formation of
chloronium ion. The chloronium ion formed is comparatively more stable than other hybrid structures of
carbonium ion.
★ (4) Reactions involving Grignard reagent must be carried out under anhydrous condition. (2 marks)
Ans.
(1) Grignard reagent (R Mg X) is an organometallic compound. The carbon-magnesium bond is highly polar and
magnesium halogen bond is in ionic in nature. Grignard reagent is highly reactive.
(2) The reactions of Grignard reagent are carried out in dry conditions because traces of moisture may spoil the
reaction and Grignard reagent reacts with water to produce alkane. Hence, reactions involving Grignard reagent
must be carried out under anhydrous condition.
★ (5) Alkyl halides are generally not prepared by free radical halogenation of alkane. (2 marks)
Ans.
(1) Free radical halogenation of alkane gives a mixture of all different possible Monohaloalkanes as well as
polyhalogen alkanes.
(2) In this method, by changing the quantity of halogen the desired product can be made to predominate over the other
products. Hence, alkyl halides are generally not prepared by free radical halogenation of alkane. ■
★ Q. 88. Complete the following reactions giving major product.

HBr alc.KOH
(1) CH 9CH:CH A B (2 marks)
Peroxide
IIIIIIIIIIIJ IIIIIIIIIIIIJ
HBr alc.KOH
Ans. CH 9CH :CH CH 9CH 9CH 9Br CH 9CH:CH ;KBr;H O
Peroxide
IIIIIIIIIIIJ IIIIIIIIIIIIJ
(A) (B)
1-Bromopropane Propene
(major product)
A:CH 9CH 9CH 9Br

B:CH 9CH:CH


Red P/Br Ag O/H O
(2) CH 9CH:CH A B (2 marks)

IIIIIIIIIIIIIIJ IIIIIIIIIIIIIIJ
OH
Red P/Br Ag O/H O

Ans. CH 9CH:CH CH 9CH 9CH 9Br CH 9CH 9CH 9OH

IIIIIIIIIIIIIIJ IIIIIIIIIIIIIIJ
OH OH OH
(A) (B)
A:CH 9CH 9CH 9Br, B:CH 9CH 9CH 9OH

OH OH
CH
Na/dry ether
(3) CH 9 C9 CH 9Cl A (1 mark)

IIIIIIIIIIIIIIIJ
CH

CH CH CH
Na/dry ether

Ans. CH 9 C9 CH 9Cl CH 9 C9 CH 9CH 9 C9 CH

IIIIIIIIIIIIIIIJ
CH CH CH
(A)

2,2,5,59tetramethylhexane
CH CH

A:CH 9 C9 CH 9CH 9 C9 CH

CH CH

(4) (1 mark)
Ans.
Q. 89. Name the reagent used to bring about the following conversions.
★ (1) Bromoethane to ethoxyethane ★ (2) 1-Chloropropane to 1 nitropropane ★ (3) Ethyl bromide to ethyl
isocyanide ★ (4) Chlorobenzene to biphenyl (5) Ethyl iodide to ethyl magnesium iodide (6) Ethyl chloride to
ethyl iodide (7) Toluene to a mixture of ortho and para bromo toluene. (1 mark each)

Ans.
Reactant Ans. Reagent Product

(1) Bromoethane IIIIIIIIIIIIIIIIIIIJ ethoxy ethane
Sodium alkoxide
Silver nitrite
(2) 1-Chloropropane IIIIIIIIIIIIIIIIIIIJ 1-nitropropane
alcohol
Alcohol
(3) Ethyl bromide IIIIIIIIIIIIIIIIIIIJ Ethyl isocyanide
AgCN
Na
(4) Chlorobenzene IIIIIIIIIIIIIIIIIIIJ Biphenyl
dry ether
Mg
(5) Ethyl iodide IIIIIIIIIIIIIIIIIIIJ Ethyl magnesium iodide
dry ether
NaI
(6) Ethyl chloride IIIIIIIIIIIIIIIIIIIJ Ethyl iodide
acetone
Fe
(7) Toluene;Br ortho and para bromo toluene

IIIIIIIIIIIIIIIIIIIJ
dark
Q. 90. Convert 1-chlorobutane into the following compounds :

(1) butan-1-ol
(2) 1-iodobutane (3) CH –CH –CH –CH –CN

O

(4) CH –CH –CH –CH –O– C–CH . (1 mark each)

Ans.
(1) 1-Chlorobutane to butan-1-ol :

CH –CH –CH –CH –Cl;aq·KOH CH –CH –CH –CH –OH;KCl

IIIIJ
1-chlorobutane butan-1-ol
(2) 1-Chlorobutane to 1-iodobutane :

(i) CH –CH –CH –CH –Cl;aq·KOH CH –CH –CH –CH –OH;KCl

IIIIJ
1-chlorobutane butan-1-ol
red P;I
(ii) 3CH –CH –CH –CH –OH;PI 3–CH –CH –CH –CH –I;H PO

IIIIIIIIIIIIIJ
butan-1-ol 1-iodobutane
(3) 1-Chlorobutane to n-butyl cyanide (CH –CH –CH –CH –CN) :

alcohol
CH –CH –CH –CH –Cl;KCN CH –CH –CH –CH –CN;KCl

IIIIIIIIJ
1-chlorobutane potassium n-butyl cyanide

cyanide
O

(4) 1-Chlorobutane to CH –CH –CH –CH –O– C–CH :

O O

CH –CH –CH –CH –Cl;Ag–O– C–CH CH –CH –CH –CH – C–O–CH ;AgCl .

IIIIJ
1-chlorobutane silver acetate butyl acetate ■

Q. 91. Predict the expected product of substitution reactions : (1 mark each)
(1) Isobutyl chloride;sodium ethoxide.
CH CH

Ans. CH – CH–CH –Cl;NaOC H CH – CH–CH –OC H ;NaCl

IIIIIJ
Isobutyl chloride Sodium ethoxide Ethyl isobutyl ether

CH

Product : CH – CH–CH –OC H

ethyl isobutyl ether
(2) n-butyl chloride;sodium.

dry ether
Ans. 2CH –CH –CH –CH –Cl;2Na C H ;2NaCl

IIIIIIIIIJ
n-butyl chloride sodium n-octane
Product : C H

n-octane
(3) 1-chloropropane ; aq. potassium hydroxide.

Ans. CH –CH –CH –Cl;aq. KOH CH –CH –CH –OH;KCl

IIIIJ
1-chloropropane propan-1-ol
Product : Propan-1-ol
(4) Aniline;NaNO / HCl.

Ans. Product :
Q. 92. Write the products : (1 mark each)

Br

(1) C H –CH –CH:CH ;HBr C H –CH – CH–CH

IIIIIJ
3-phenyl prop-1-ene 2-Bromo-3-phenyl propane

(Product)
Peroxide
(2) C H –CH:CH ;HBr C H –CH –CH –Br

IIIIIIIIIIIJ
Phenyl ethene 1-Bromo-2-phenyl ethane

(Product)
CH CH CH

(3) CH – C: C–CH ;HBr CH – C–CH –CH

IIIIIJ
2,3-dimethyl but-2-ene Br
2-Bromo-2-methyl butane
(Product)

CH CH

(4) CH – C:CH–CH ;HBr CH – CH–CH–CH

IIIIJ

Br
2-Methyl but-2-ene 2-Bromo-3-methyl butane
(Product)
(5)
Q. 93. Identify A and B in the following : (2 marks each)
(1)
Ans.
(2)
Ans.
Na C H Br
(3) C H OH A B.

IIIIIJ IIIIIIIIIIJ
C H Br
Ans. 2C H OH;2Na C H ONa C H OC H ;NaBr

IIIIIIJ IIIIIIIIIIJ
–H

(A) C H ONa (B) C H OC H

Sodium ethoxide Diethyl ether
Ag C H Br
(4) CH COOH A B.

IIIIIJ IIIIIIIIIIJ

Ans. 2CH OOH;2Ag CH COOAg ; C H Br CH COOC H ;AgBr

IIIIIIJ IIIIJ
–H

(A) CH COOAg (B) CH COOC H

silver acetate ethyl acetate

Na Cl
(5) CH –CH –CH –Cl A B.

IIIIIJ IIIIIIJ
Cl
Ans. 2CH –CH –CH –Cl;2Na C H C H Cl
–2NaCl\
IIIIIIIIIIJ IIIIIIJ
(A) C H (B) C H Cl

n-Hexane n-Hexyl chloride
HBr alc. KOH
(6) CH –CH:CH A B.

IIIIIIJ IIIIIIIIIIIIIJ
alc. KOH
Ans. CH –CH:CH ;HBr CH –CH–CH CH –CH:CH ;KBr

IIIIIJ IIIIIIIIIIIIJ
Br
(A) CH –CH–CH (B) CH –CH:CH

propene
Br
isopropyl bromide ■
★ Q. 94. Match the pairs : (3 marks)
Column I Column II
(1) CH 9CH9CH (a) vinyl halide Ans. (1) CH 9CH9CH – (b) alkyl halide

(b) alkyl halide
X X
(c) allyl halide
(2) CH :CH9CH X (2) CH :CH9CH X – (c) allyl halide
(d) benzyl halide
(3) CH :CH9X (3) CH :CH9X – (a) vinyl halide
(e) aryl halide
■
Units
10.7 Uses and environmental effects of some polyhalogen compounds
10.7.1 Uses of some polyhalogen compounds
Q. 95. State the uses of the following compounds :

(1) Dichloromethane (CH Cl ) (2) Trichloromethane or Chloroform (CHCl )

(3) Tetrachloromethane or carbon tetrachloride (CCl ) (4) Iodoform (CHI )

(5) Freons (6) DDT (p, p-Dichlorodiphenyl trichloroethane). (2 marks each)
Ans.
(1) Dichloromethane (CH Cl ) :

(1) Dichloromethane dissolves wide range of organic compounds, hence it is used as solvent for many chemical
reactions.
(2) It is used as a solvent as a paint remover and degreaser.
(3) It is used as propellant in aerosols and as a fumigant pesticide for grains and strawberries.
(4) It is used to decaffinate tea or coffee.
(2) Trichloromethane or Chloroform (CHCl ) :

(1) Chloroform in the production of chlorofluoromethane, freon refrigerant R-22.
(2) It is used as solvent in pharmaceuticals, pesticides, gums, fats, resins and dye industry.
(3) It is a good source of dichlorocarbene species.

(3) Tetrachloromethane or carbon tetrachloride (CCl ) :

(1) Carbon tetrachloride is used in the manufacture of refrigerants.
(2) It is used as a dry cleaning agent and as a pesticide for stored grains.
(3) It is very useful solvent for oils, fats and resins. It serves as a source of chlorine.
(4) Iodoform (CHI ) :

(1) Iodoform is used as antiseptic, dressing of wounds and sores.
(2) On small scale it is used as disinfectant.
(5) Freons :
(1) Freons are widely used as propellants in aerosol, products of food, cosmetics and pharmaceutical industries.
(2) Freons containing bromine in their molecules are used as fire extinguishers.
(3) They are used in aerosol insecticides, solvent for cleaning clothes and metallic surfaces. It is used as foaming
agents in the preparation of foamed plastics and in production of certain fluorocarbons.
(4) It is used as refrigerants and air conditioning purposes. ■
Do you know ?
(Textbook page 230)
How do CFC destroy the ozone layer in the atmosphere ?
When ultraviolet radiation (UV) strikes CFC (CFC13) molecules in the upper atmosphere, the carbon-chlorine
bond breaks and produces highly reactive chlorine atom (Cl).
CFCl CFCl ;Cl

IIIIIJ
This reactive chlorine atom decomposes ozone (O ) molecule into oxygen molecule (O ).

O ;Cl O ;ClO

IIIIIJ
ClO;O O ;Cl

IIIIIJ
One atom of chlorine can destroy up to 100,000 ozone molecules.
(6) p, p-Dichlorodiphenyl trichloroethane (DDT) :

(1) DDT is used as insecticide against malaria and typhus.
(2) It is used to kill various insects like housefly and mosquitoes. ■
Do you know ?
(Textbook page 230)
DDT, the first chlorinated organic insecticides, was originally prepared in 1873, but it was not until 1939 that
Paul Muller of Geigy Pharmaceuticals in Switzerland discovered the effectiveness of DDT as an insecticide. Paul
Muller was awarded the Nobel Prize in Medicine and Physiology in 1948 for this discovery. The use of DDT
increased enromously on a worldwide basis after World War II, primarily because of its effectiveness against the
mosquito that spreads malaria and lice that carry typhus. Many species of insects developed resistance to DDT, and
it was also discovered to have a high toxicity towards fish. DDT is not metabolised very rapidly by animals;
instead, it is deposited and stored in the fatty tissues. The use of DDT was banned in the United States in 1973,
although it is still in use in some other parts of the world.

Unit
10.7.2 Environmental effects of some polyhalogen compounds
Q. 96. State the environmental effects of the following compounds :

(1) Dichloromethane (CH Cl ) (2) Trichloromethane or chloroform (CHCl )

(3) Tetrachloromethane or carbon tetrachloride (CCl ) (4) Iodoform (CHI )

(5) Freons (CCl F , CCl F, CHClF ) (6) DDT (2 marks each)

Ans.
(1) Dichloromethane (CH Cl ) :

(1) Higher levels of dichloromethane in air causes nausea, numbness in fingers and toes, dizziness.
(2) Lower levels of dichloromethane causes impaired vision and hearing.
(3) Direct contact with eyes can damage cornea.
(2) Trichloromethane or chloroform (CHCl ) :

(1) When chloroform is exposed to air in the presence of sunlight, it slowly oxidised to phosgene, a poisonous
compound, therefore it is stored in dark, amber coloured bottles.
(2) Chloroform vapour when inhaled for a short time causes dizziness, headache and fatigue and if inhaled for a
long time affects central nervous system.
(3) Tetrachloromethane or carbon tetrachloride (CCl ) :

(1) Exposure to carbon tetrachloride causes eye irritation, damages nerve cells, vomiting sensation, dizziness,
unconciousness or death. Long exposure to chloroform may affect liver.
(2) When mixed with air it causes depletion of the ozone layer, which affects human skin leading to cancer.
(4) Iodoform (CHI ) : Iodoform has a strong smell. It causes irritation to skin and eyes. It may cause respiratory

irritation or breathing difficulty, dizziness, nausea, depression of central nervous system, visual disturbance.
(5) Freons (CCl F , CCl F, CHClF ) :

(1) Freon as refrigerant causes ozone depletion.
(2) Freons have low toxicity and low biological activity.
(3) Freons from propane group are more toxic in nature.
(4) Regular large inhalation of freon results in breathing problems, organ damage, loss of consciousness.
(6) DDT :
(1) DDT is not readily metabolised by animals.

(2) It is deposited and stored in fatty tissues.
(3) Exposure to high doses of DDT may cause vomiting, tremors or shakiness.

(4) Laboratory animal studies showed adverse effect of DDT on liver and reproduction.
(5) DDT is a pressistent organic pollutant, readily absorbed in soils and tends to accumulate in the ecosystem.
(6) When dissolved in oil or other lipid, it is readily absorbed by the skin. It is resistant to metabolism. There is a
ban on use of DDT due to all these adverse effects. ■
Q. 97. What is the chemical name of freon ? (1 mark)

Ans. The chemical name of freon is Dichlorodifluoro methane.
■
Q. 98. What is the chemical name of DDT ? (1 mark)

Ans. The chemical name of DDT is p, p-Dichlorodiphenyltrichloroethane. ■
Activity : (Textbook page 233)

(1) Collect detailed information about Freons and their uses.
(2) Collect information about DDT as a persistent pesticide.
Reference books :
(1) Organic chemistry by Morrison, Boyd, Bhattacharjee, 7th edition, Pearson.
(2) Organic chemistry by Finar, Vol 1, 6th edition, Pearson
(Note : Students are supposed to do these activity on their own.)
★ 3. Which of the following is likely to undergo
racemization during alkaline hydrolysis ?
Q. 99. Select and write the most appropriate answer
from the given alternatives for each sub-question : CH 9CH9C H

(1 mark each) Cl
★ 1. The correct order of increasing reactivity of C-X
(I) (II)
bond towards nucleophile in the following
compounds is CH

CH 9 CH

CH Cl

(III) (IV)
(I) (II) (a) Only I (b) Only II

(c) II and IV (d) Only IV
(CH ) C9X (CH ) CH9X

(III) (IV)
★ 4. The best method for preparation of alkyl fluorides
(a) I II III IV (b) II I III IV
is
(c) III IV II I (d) IV III I II
Hl
(a) Finkelstein reaction
★ 2. CH 9CH:CH
peroxide (b) Swartz reaction
IIIIIIIIIIIIJ
The major product of the above reaction is, (c) Free radical fluorination
(a) I9CH 9CH:CH
(d) Sandmeyer’s reaction
(b) CH 9CH 9CH I

★ 5. Identify the chiral molecule from the following :
(c) CH 9CH 9CH

(a) 1-Bromobutane
I
(b) 1, 1-Dibromobutane
(d) CH 9CH 9CH

(c) 2, 3-Dibromobutane
I OH (d) 2-Bromobutane

★ 6. An alkyl chloride on Wurtz reaction gives 2, 2, 5, 11. The rate of SN2 reaction depends on the concentra-
5-tetramethylhexane. The same alkyl chloride on tion of
reduction with zinc-copper couple in alcohol give (a) only the substrate
hydrocarbon with molecular formula C H . What (b) only the reagent

is the structure of alkyl chloride (c) both the substrate and the reagent
CH

(d) neither the substrate nor the reagent
(a) CH 9 C9 CH Cl 12. In SN2 reaction, the hydrolysis of alkyl halide

CH shows

(a) the retention of configuration
CH
(b) the inversion of configuration
(b) CH 9 C9 CH CH (c) both retention and inversion of configuration

Cl (d) no change in the configuration
13. The one step exothermic reaction is
(c) CH 9CH 9CH9Cl (a) SN1 (b) SN2 (c) SN (d) S2N

CH 14. Which of the following is correct about SN2

mechanism ?
(d) CH 9CH9 CH9CHCl (a) Two step reaction

(b) Complete inversion of configuration
CH CH
(c) Formation of carbonium ion
★ 7. Butanenitrile may be prepared by heating (d) Favoured by polar solvent
(a) Propanol with KCN
15. Which of the following is not a nucleophile ?
(b) butanol with KCN
(a) Ammonia (b) Ammonium ion
(c) n-butyl chloride with KCN
(c) Primary amine (d) Secondary amine
(d) n-propyl chloride with KCN
16. Which of the following undergoes nucleophilic
★ 8. Choose the compound from the following that will
substitution exclusively by SN2 mechanism ?
react fastest by SN1 mechanism
(a) ethyl chloride (b) isopropyl chloride
(a) 1-iodobutane
(c) chlorobenzene (d) benzyl chloride
(b) 1-iodopropane
(c) 2-iodo-2 methylbutane 17. Which of the following is most reactive towards
(d) 2-iodo-3-methylbutane nucleophilic substitution reaction ?
(a) CH :CH–Cl (b) CH CH:CHCl

★ 9.
(c) C H Cl (d) ClCH –CH:CH

The product ‘B’ in the above reaction sequence is, 18. The stability order of carbocation is
(a) 2° 3° 1° (b) 3° 2° 1°
(a) (b) (c) 3° 1° 2° (d) 1° 3° 2°
Alc. KOH HBr
(c) (d) 19. CH – CH – Br B C

IIIIIIIIIIIIJ IIIIIJ
★ 10. Which of the following is used as source of Na Ether

IIIIIIIIIIJ D the compound D is :
dichlorocarbene
(a) tetrachloromethane (b) chloroform (a) ethane (b) propane
(c) iodoform (d) DDT (c) n-butane (d) n-pentane

20. Which of the following characteristic properties of 27.
the enantiomers is correct?
(a) The enantiomers possess same physical and
chemical properties
(b) The enantiomers are optically active compounds
(c) The enantiomers have different optical rotations The above reaction is known as
(d) All of these (a) Wurtz-Fittig reaction (b) Friedel Craft’s reaction
21. The optically inactive compound is (c) Sandmeyer’s reaction (d) Swarts reaction
(a) glucose (b) lactic acid
(c) isopropyl alcohol (d) 2-bromo butane 28. Iodoform is used as
22. A compound with the molecular formula (a) an anaesthetic (b) an antiseptic
CH OH(CHOH) CH OH has ……… optically (c) an analgesic (d) an antibiotic

active forms
(a) 3 (b) 4 (c) 6 (d) 8 29. p, p-dichlorodiphenyl trichloroethane is used as
23. A racemic mixture consists of (a) insecticide (b) anaesthetic
(a) equal amount of d and l isomers (c) antiseptic (d) refrigerant
(b) unequal amounts of d and l isomers
(c) unknown amounts of d and l isomers 30. The order of reactivity in nucleophilic substitution
(d) only d isomers reaction is
24. Which of the following compounds is not optically (a) CH F CH Cl CH I CH Br

active? (b) CH F CH Cl CH Br CH I

(a) Lactic acid (b) Secondary butyl chloride (c) CH F CH Br CH Cl CH I

(c) n-propyl iodide (d) Glucose (d) CH I CH Br CH Cl CH F

25. Which of the following compounds shows optical
activity ? 31. Racemate is
(a) n-butyl chloride (b) isobutyl chloride (a) optically active (b) optically dextro rotatory
(c) sec-butyl chloride (d) t-butyl chloride (c) optically inactive (d) optically laevorotatory
26. The major product of the following reaction is
32. The number of asymmetric carbon atoms in
glucose are
(a) 2 (b) 3 (c) 4 (d) 5
33. The geometry of carbonium ion is

(a) Tetrahedral (b) planar
(c) linear (d) pyramidal
34. In its nucleophilic substitution reaction, aryl halide

resembles
(a) Vinyl chloride
(b) allyl chloride
(c) Benzyl chloride
(d) ethyl chloride

35. The weakest C-Cl bond is present in 42. Carbon atom in methyl carbocation contains how
many pairs of electrons ?
(a) 8 (b) 4 (c) 3 (d) 5
43. The optically inactive compound is
(a) Glucose (b) Lactic acid
(c) 2-Chlorobutane (d) 2-Chloropropane
44. The hydrogen halide which does not obey
Markownikv rule in presence of a peroxide is
(a) HCl (b) HBr (c) HF (d) HI
45. Which one of the following is NOT used to prepare
36. Which alkyl halide among the following com-
alkyl halide from an alcohol ?
pounds has the highest boiling point ?
(a) SOCl (b) PCl (c) HCl;ZnCl (d) NaCl
(a) (CH ) CCI (b) CH CH CH CH Cl
46. The total number of electrons present in the central
(c) CH CH CH Cl (d) CH CH(CH )CH Cl
carbon atom of a free radical is
37. It is difficult to break C-Cl bond in CH :CH-Cl
(a) 7 (b) 8 (c) 9 (d) 6
due to
47. In which of the following pairs both are
(a) Hyper conjugation (b) Resonance nucleophiles ?
(c) Electromeric effect (d) Inductive effect (a) BF , AlCl (b) NO> , Cl\

38. Which one of the following when heated with (c) CN\, NH (d) Br>, BCl

metallic sodium will not give the corresponding 48. Which one of the following alkane is NOT formed
alkane ? in Wurtz reaction ?
(a) CH –CH–Cl (b) CH –CH –CH –Cl (a) Methane (b) Ethane (c) Propane (d) Butane

CH 49. Which of the following groups has highest priority

according to R, S convention?
CH
(a) CH OH

(b) COOH
(c) CH – C–Cl (d) CH –CH –CH –CH –Cl (c) COCH (d) COOCH

CH 50. The halogen atom in aryl halides is

39. The most reactive alkyl halide towards SN2 reac- (a) o- and p-directing (b) m-directing
tion is (c) o, m and p-directing (d) only m-directing
(a) CH X (b) R CX (c) R CHX (d) RCH X 51. Chlorobenzene can be obtained by benzene

40. The number of electrons surrounding the carbon- diazonium chloride by
ium ion is (a) Friedel Craft’s reaction (b) Wurtz reaction
(a) 6 (b) 8 (c) 10 (d) 7 (c) Gatterman’s reaction (d) Fittig reaction
52. Which of the following carbocations is least stable ?
41. The lowest stability of carbocation among the
(a) CH 9CH 9CH 9CH
compounds

(a) CH 9CH 9 C>

CH 9CH

(b) CH 9CH 9>CH9CH 9CH

chloride with KCN 8. (c) 2-iodo-2-methyl butane
(c) CH 9CH 9>CH

(d) CH 9CH 9>CH9H 9. (d) 10. (b) chloroform 11. (c) both

the substrate and the reagent 12. (b) the inversion of
(d) CH 9CH 9>CH9C9CH
configuration 13. (b) SN2 14. (b) Complete inver-

CH sion of configuration 15. (b) Ammonium ion

16. (d) benzyl chloride 17. (d) ClCH –CH:CH
53. But-1-ene on reaction with HCl in the presence of
sodium peroxide yields 18. (b) 3° 2° 1° 19. (c) n-butane 20. (d) All of
(a) n-butyl chloride (b) isobutyl chloride these 21. (c) isopropyl alcohol 22. (d) 8
(c) secondary butyl chloride (d) tertiary butyl chloride 23. (a) equal amount of d and l isomers
54. Carbon tetrachloride is used as 24. (c) n-propyl iodide 25. (c) sec-butyl chloride
(a) anaesthetic (b) antiseptic

(c) dry cleaning agent (d) fire extinguisher 26. (c) 27. (b) Friedel Craft’s reaction
55. Identify the product D in the following sequence of

reactions :
Alc. KOH HBr
H C – CH – CH – Cl B C 28. (b) an antiseptic 29. (a) insecticide

IIIIIIIIIIIIJ IIIIIJ
Na
D 30. (b) CH F CH Cl CH Br CH I

IIIIIIJ
Ether
31. (c) optically inactive 32. (c) 4 33. (b) planar
(a) 2, 2-dimethyl butane (b) 2, 3-dimethyl butane
(c) hexane (d) 2, 4-dimethylpentane
34. (a) Vinyl chloride 35. (d)
56. The preparation of alkyl fluoride from alkyl chlor-
ide, in presence of metallic fluorides is known as
36. (b) CH CH CH CH Cl 37. (b) Resonance
(a) Williamson’s reaction
CH
(b) Finkelstein reaction
(c) Swarts reaction 38. (c) CH – C–Cl 39. (a) CH X 40. (a) 6

(d) Wurtz reaction CH

57. IUPAC name of the following compound is
41. (a) 42. (b) 4 43. (d) 2-Chloropropane

(a) 3-Bromo-3, 4-dimethylheptane
(b) 3,4-dimethyl-3-bromoheptane 44. (b) HBr 45. (d) NaCl 46. (a) 7
(c) 5-Bromo-4,5-dimethylheptane
47. (c) CN\, NH 48. (a) Methane
(d) 4,5-dimethyl-5-bromoheptane
49. (d) COOCH 50. (a) o- and p-directing

Answers 51. (c) Gatterman’s reaction
1. (d) IV III I II 2. (b) CH 9CH 9CH 9I 52. (c) CH 9CH 9>CH

3. (a) Only I 4. (b) Swartz reaction 5. (d) 2-Bro- 53. (c) secondary butyl chloride
CH 54. (c) dry cleaning agent

mobutane 6. (a) CH 9 C9 CH Cl 7. (d) n-propyl 55. (b) 2, 3-dimethyl butane 56. (c) Swarts reaction

57. (a) 3-Bromo-3, 4-dimethylheptane
CH


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Based on the Board's New Textbook

★ Navneet Bhavan, Bhavani Shankar Road, Dadar (West),

Published by : Navneet Education Limited, Dantali, Gujarat. 2001

9. Coordination Compounds  . . . 155

10. Halogen Derivatives . . . 150

11. Alcohols, Phenols and Ethers . . . 116

12. Aldehydes, Ketones and Carboxylic Acids . . . 189

13. Amines . . . 277

14. Biomolecules . . . 339

15. Introduction to Polymer Chemistry . . . 383

Chapter Nos. 1 to 8 are included in Chemistry Digest: Part 1, published separately.

6 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

(1) For octahedral complex :

(2) For tetrahedral complex :

(★ ) Indicates question from the textbook.

Q. 1. What are double salts ? (1 mark)

Q. 2. Define coordination compound. (1 mark)

Ans. Cisplatin : or Pt(NH ) Cl .

8 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

Use your brain power !

Q. 8. Define coordination sphere. Give example. (2 marks)

Q. 12. Calculate the oxidation state of a metal in the following complexes :

Can you tell ?

10 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

(a) [Cu(NH ) ]Cl 2 4 4

Use your brain power !

Can you tell ?

Ans. Double salt Coordination compound (complex)

12 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

Question 9.1 : (Textbook page 194)

Q. 18. Define the following terms. (2 marks)

★ Q. 21. Classify following complexes as homoleptic and heteroleptic complex :

14 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

Q. 22. Summarise the rules of IUPAC nomenclature of coordination compounds. (3 marks)

Try this ...

Anionic ligand IUPAC name Anionic ligand IUPAC name

Br\, Bromide Bromo CO \, Carbonate Carbonato

F\, Fluoride Fluoro C O \, Oxalate Oxalato

SO \, Sulphate Sulphato SCN\, Thiocyanate Thiocyanato (For ligand

NO \, Nitro Nitrato NCS\, Thiocyanate Isothiocyanato (For ligand

Neutral ligand IUPAC name Neutral ligand IUPAC names

NH , Ammonia Ammine (Note the spelling) H O, water Aqua

Table 9.2 : IUPAC names of anionic complexes

Metal Name Metal Name Metal Name

Al Aluminate Fe Ferrate Zn Zincate

Table 9.3 : IUPAC names of some complexes

Complex IUPAC name

(i) Anionic complexes :

(a) Na [Co(NO ) ] Sodium hexanitrocobaltate(III)

16 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

(iii) Cationic complexes :

(a) [Cu(NH ) ]> Tetraamminecopper(II) ion

(iv) Compounds containing complex cation and anion :

(a) [PtBr (NH ) ]Br Tetraamminedibromoplatinum(IV) bromide,

(a) Co(NO ) (NH ) Triamminetrinitrocobalt(III)

★ Q. 24. Write formula of the following complexes :

Q. 25. State effective atomic number (EAN). (1 mark) OR

Use your brain power !

Q. 26. Find effective atomic number (EAN) in the following complexes :

(1) [Ni(CO) ] Ni 28 0 4;2:8 2890;8:36 (Kr)

18 NAVNEET CHEMISTRY DIGEST : STANDARD XII (PART II)

(1) [Fe(CN) ]\ Fe 26 3 6;2:12 2693;12:35

Q. 28. Calculate EAN in the following complexes :

(2) [Ni(en) ]SO Ni 28 2 2en:8 2892;8:34

9. Coordination Compounds . . . 155

10. Halogen Derivatives . . . 150

11. Alcohols, Phenols and Ethers . . . 116

12. Aldehydes, Ketones and Carboxylic Acids . . . 189

13. Amines . . . 277

14. Biomolecules . . . 339

15. Introduction to Polymer Chemistry . . . 383

Br\, Bromide Bromo CO \, Carbonate Carbonato

F\, Fluoride Fluoro C O \, Oxalate Oxalato

SO \, Sulphate Sulphato SCN\, Thiocyanate Thiocyanato (For ligand

(a) [Cu(NH ) ]> Tetraamminecopper(II) ion

(1) [Fe(CN) ]\ Fe 26 3 6;2:12 2693;12:35

(3) Na [Cr(C O ) ] Cr 24 3 3C O \ :12 2493;12:33

Fig. 9.3 : Optically active forms of [Co(en) ]> ■

Fig. 9.5 : Structure of [Co(NH ) ]>

[Co(NH ) ]> dsp (inner) Octahedral Diamagnetic (:0)

Fig. 9.6 : Structure of [CoF ]\

[CoF ]\ spd (outer) Octahedral Paramagnetic (:4.9 B.M.)

Fig. 9.7 : Structure of [NiCl ]\

Fig. 9.8 : Structure of [Ni(CN) ]\

4 Square planar dsp

(a) [ZnCl ]\ sp Tetrahedral Diamagnetic

(1) [NiCl ]\ sp Tetrahedral Paramagnetic

Ans. V [Ar] 3d 4s

V> [Ar] 3d 4s

(B) [Fe (CN) ]\ is an octahedral complex.

Fig. 9.14 : Crystal field splitting in [Ti(H O) ]>