Concise Inorganic Chemistry for IIT-JEE
J.D.Lee Concise Inorganic Chemistry for IIT-JEE
Sudarsan Guha
Wiley India Pvt. Ltd.
J.D. Lee Concise Inorganic Chemistry for IIT-JEE Copyright © 2011 by Wiley India Pvt. Ltd., 4435-36/7, Ansari Road, Daryaganj, New Delhi-110002. All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or scanning without the written permission of the publisher. Limits of Liability: While the publisher and the author have used their best efforts in preparing this book, Wiley and the author make no representation or warranties with respect to the accuracy or completeness of the contents of this book, and specifically disclaim any implied warranties of merchantability or fitness for any particular purpose. There are no warranties which extend beyond the descriptions contained in this paragraph. No warranty may be created or extended by sales representatives or written sales materials. The accuracy and completeness of the information provided herein and the opinions stated herein are not guaranteed or warranted to produce any particular results, and the advice and strategies contained herein may not be suitable for every individual. Neither Wiley India nor the author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Disclaimer: The contents of this book have been checked for accuracy. Since deviations cannot be precluded entirely, Wiley or its author cannot guarantee full agreement. As the book is intended for educational purpose, Wiley or its author shall not be responsible for any errors, omissions or damages arising out of the use of the information contained in the book. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered. It is sold on the understanding that the Publisher is not engaged in rendering professional services. Trademarks: All brand names and product names used in this book are trademarks, registered trademarks, or trade names of their respective holders. Wiley is not associated with any product or vendor mentioned in this book. Other Wiley Editorial Offices: John Wiley & Sons, Inc. 111 River Street, Hoboken, NJ 07030, USA Wiley-VCH Verlag GmbH, Pappellaee 3, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 42 McDougall Street, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada, M9W 1L1 First Edition: 2011 ISBN: 978-81-265-2009-1 www.wileyindia.com Printed at: Kay-Kay Printers, Delhi
Preface Concise Inorganic Chemistry by J.D. Lee is a book widely used by students preparing for IIT-JEE as the most comprehensive and authentic text for understanding Inorganic Chemistry. The purpose of adaptation of this book is to provide a complete textbook of Inorganic Chemistry that covers the entire syllabus of IITJEE in proper sequence of topics and provides in-depth explanation of topics. The use of book should give confidence to the students to apply their knowledge to problem-solving and attempting IIT-JEE. This adaptation consists of three completely new chapters, i.e., Hydrolysis, Metallurgy and Qualitative Salt Analysis. Along with this, several changes have been made in the topics as per IIT-JEE syllabus. This includes new additions to Coordination Compounds; reorganization and additions in Chemical Bonding; deletion of irrelevant topics from p- and d-block elements; and complete deletion of chapters not required as per syllabus (f-block elements, Atomic Nucleus and Spectra). A new set of exercises have been added at the end of each chapter, comprising all types of questions asked in IIT-JEE, i.e., single correct choice type questions, multiple correct choice type questions, comprehension type questions, assertion– reasoning type questions, integer answer type questions and matrix-match type questions. I would like to acknowledge my students for their intellectual doubts and my colleagues for their valuable arguments in various aspects of the subject. This enhanced my understanding of the subject and helped me to teach better. I am especially indebted to my college Belur Ram Krishna Mission, Calcutta University for teaching me ‘How to read and learn chemistry?’ and Bansal classes where I have got the opportunity to apply my knowledge and teach chemistry. I am thankful to Mr. Ankur Padia who linked me with Wiley India. It is my promise to make this book as ‘only one book for Inorganic Chemistry’ for students aspiring for IIT-JEE. For the future also, any suggestions for the improvement of this book are welcome by the author. Sudarsan Guha M. Tech. (IIT-Kanpur)
Note to the Student The IIT-JEE is one of the hardest exams to crack for students, for a very simple reason – concepts cannot be learned by rote, they have to be absorbed, and IIT believes in strong concepts. Each question in the IIT-JEE entrance exam is meant to push the analytical ability of the student to its limit. That is why the questions are called brainteasers! Concise Inorganic Chemistry by J.D. Lee has been the definitive text for learning Inorganic Chemistry since its first edition appeared about 45 years ago. The book captures the fundamentals of the subject in a simple and logical framework of factual knowledge. The description is long enough to cover the essentials, yet short enough to be interesting. Its unparalleled approach to teaching Inorganic Chemistry is the reason why it is probably the most favoured resource for an IIT aspirant like you today. In collaboration with expert in IIT-JEE coaching, the fifth edition of the original book has now been adapted to give you the best book available in Inorganic Chemistry for preparing for the toughest engineering entrance exam in India. This adaptation offers the dual advantage of unmatched explanation of concepts as developed by “Master teacher” and appropriate applications of the concepts to problem solving as developed by an expert in this area. Let’s walk through some of the special book features that will help you in your efforts to take the IIT-JEE with confidence.
A.
STRUCTURE OF THE BOOK
1. Atomic Structure and the Periodic 2. General Properties of the Elements 3. Chemical Bonding 4. Hydrolysis 5. Coordination Compounds 6. Metallurgy 7. Qualitative Salt Analysis 8. Hydrogen and its Hydrides 9. The s-Block Elements and their compounds 10. The p-Block Elements and their Compounds 11. The d-Block Elements and their Compounds
The original book has been reorganized in a manner to provide more structured approach as per the IIT-JEE syllabus requirement. The progression is from basic concepts such as Atomic Structure, General Properties of Elements and Chemical Bonding to practical aspects of Metallurgy and Qualitative Salt Analysis. This is followed by description on Hydrogen and its compounds and some compounds and properties of s-, p- , d-block elements.
B.
PEDAGOGY
Chapter Opener
5 x
x
t2g orbitals (de)
Coordination Compounds
y
dxy
y
z
dxz
x
eg orbitals (dg)
Each chapter starts with an opening vignette related to the topic, and listing of contents of that chapter. This gives you an overview of the chapter and helps to identify the extent of coverage.
z
dyz
z
5.9
y
Crystal Field Theory
15
Table 5.6 Colours absorbed and colours observed d
2
2
x −y Colour absorbed
dz 2
Shapes of d orbitals. 5.1 | DOUBLE SALTS AND COORDINATION COMPOUNDS
Yellow–green
Yellow Contents
Wavenumber observed (cm-1)
Colour observed Red–violet
24 000–26 000
Indigo
23 000–24 000
5.1Orange Double Salts and Blue 21 000–23 000 Coordination Compounds Addition compounds are formed when stoichiometric Red Blue–green 20 000–21 000 5.2 Werner’s Work amounts of two or more stable compounds join together. 18 000–20 000 5.3Purple More Recent Methods of Green For example: Studying Complexes Red–violet Yellow–green 17 300–18 000 KCl + MgCl 2 + 6H 2 O → KCl MgCl 2 6H 2 O 5.4 Classification of Ligands (carnallite) 16 400–17 300 5.5Indigo Effective Atomic NumbersYellow 5.6Blue Shapes of d Orbitals K 2 SO4 + Al 2 (SO4 )3 + 24H 2 O → K 2 SO4 Al 2 (SO4 )3 24H 2 O Orange 15 300–16 400 5.7 Bonding in Transition (potassium alum) Blue–green Red 12 800–15 300 Metal Complexes 5.8 Valence Bond Theory + + → CuSO4 4NH 3 H 2 O CuSO4 4NH 3 H 2 O Field on Theory (tetrammine copper(II) The magnitude 5.9 of Δ Crystal depends three factors: 5.10 оEffects of Crystal Field sulphate monohydrate) Splitting 1. The nature of the ligands. Fe(CN)2 + 4KCN → Fe(CN)2 4KCN 5.11 Tetragonal Distortion of 2. The charge on the metal ion. Octahedral Complexes (potassium ferrocyanide) (Jahn-Teller Distortion) 3. Whether the metal is in the first, second or third row of transitions elements. Addition compounds are of two types: 5.12 Square Planar 1. Those which lose their identity in solution (double salts) Arrangements Examination of the spectra of a series of complexes of the same metal with different ligands shows that Tetrahedral Complexes 2. Those which retain their identity in solution (complexes) the position of 5.13 the absorption band (and hence the value of Δо) varies depending on the ligands which are 5.14 Magnetism When crystals of carnallite are dissolved in water, the solution attached (Table5.15 5.7).Extension of the Crystal + 2+ shows the properties of K , Mg and Cl ions. In a similar way, Field Theory to Allow for a solution of potassium alum shows the properties of K+, Al3+ Table 5.7 Crystal field splittings by various ligands Some Covalency and SO2− 4 ions. These are both examples of double salts which 5.16 Nomenclature exist only in the crystalline state. Complex Absorption peak of Coordination When the other two examples of coordination comCompounds -1 pounds dissolve they do not form simple ions - Cu2+, or Fe2+ (kJ mol-1) (cm ) and CN- - but instead their complex ions remain intact. 5.17 Isomerism Thus the cuproammonium ion [Cu(H2O)2(NH3)4]2+ and the 13 640 163 [CrIIICl6]3•
•
•
•
•
•
•
Lee_Chapter 05.indd 1
concept explanation
[CrIII(H2O)6]3+
17 830
213
[CrIII(NH3)6]3+
21 680
259
[CrIII(CN)6]3-
26 280
314
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Ligands which cause only a small degree of crystal field splitting are termed weak field ligands. Ligands which cause a large splitting are called strong field ligands. Most Δ values are in the range 7,000 cm-1 to 30,000 cm-1. The common ligands can be arranged in ascending order of crystal field splitting Δ. The order remains practically constant for different metals, and this series is called the spectrochemical series. Spectrochemical series
Concepts are explained in a manner easy to read and understand. They are descriptive to the extent required and provide reasons for the structure, properties and reactions of compounds. Many fascinating applications of inorganic compounds are also explained.
weak field ligands I − < Br − < S 2 < Cl − < NO3− < F − < OH − < EtOH < oxalate < H2O < EDTA < (NH3 and pyridine) < ethylenediamine < dipyridyl < o-phenanthroline < NO2− < CN −< CO strong field ligands The spectrochemical series is an experimentally determined series. It is difficult to explain the order as it incorporates both the effects of s and p bonding. The halides are in the order expected from electrostatic effects. In other cases we must consider covalent bonding to explain the order. A pattern of increasing s donation is followed: halide donors < O donors < N donors < C donors The crystal field splitting produced by the strong field CN − ligand is about double that for weak field ligands like the halide ions. This is attributed to p bonding in which the metal donates electrons from a filled t2g
Lee_Chapter 05.indd 15
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5.13 | TETRAhEDRAL COMPLExES A regular tetrahedron is related to a cube. One atom is at the centre of the cube, and four of the eight corners of the cube are occupied by ligands as shown in Figure 5.19. The directions x, y and z point to the centres of the faces of the cube. The eg orbitals point along x, y and z (that is to the centres of the faces). The t2g orbitals point between x, y and z (that is towards the centres of the edges of the cube) (Figure 5.20). z
5.5
Figures 9
Effective Atomic Number (EAN)
The text is sprinkled with multiple figures x 1. All donations contribute two electrons, while NO is considered as a 3-electron donor. which two-di 2. For p-donors, the number of p-electrons involved in donation from a particular ligand present are to be cony sidered. For example, mensional representation dz dx −y − of compounds and their is a 6-electron donor. structures. This visual − is a 4-electron donor. representation enhances understanding and helps is a 2-electron donor. dxy dyz dxz − the student visualize what CH 2 = CH − C H 2 is a 2-electron donor. a molecule may look like. Figure 5.20 Orientation of d orbitals relative to a cube. The following points need to be noted with regard to EAN.
2
z x y
Figure 5.19 Relation of a tetrahedron to a cube.
2
2
3. For the compounds having d bond, for example, Mn 2 (Co)10, the EAN of each Mn atom is calculated as:
The direction of approach of the ligands does not coincide exactly with either the eg or the t2g orbitals. The 1 EAN of Mn = °28 [2 ×′ /25 0 +°44 10 ′×. 2 + 2* ] = 36 2 =−54 angle = 109 angle between an eg orbital, the central metal and the ligand is half the tetrahedral 2 The angle between a t2g orbital, the central metal and the ligand is 35°16′. Thus the t2g orbitals are nearer to the direction of the ligands than the eg orbitals. (Alternatively t2g orbitals are half for thed-bond. side of the cube *These two the electrons are considered orbitals half metal the diagonal the cube away.) The away from the approach of the ligands, whilst the egThe EAN are of some atoms inof different complexes are given in Table 5.5. approach of the ligands raises the energy of both sets of orbitals. The energy of the t2g orbitals is raised most because they are closest to the ligands. This crystal field splitting is the opposite way round to that in Table 5.5 Effective atomic numbers of some metals in complexes octahedral complexes (Figure 5.21). Thenumber t2g orbitals of are tables 0.4Δt above the weighted average of the two groups (the Bari centre) and the lost Atom energy Atomic Complex Electrons Electrons gained A large capture number in ion formation by coordination eg orbitals are 0.6Δt below the average (Figure 5.22).
Tables
Cr
24
[Cr(CO)6]
Fe
26
[Fe(CN)6]4-
Fe
26
Co
27
[Fe(CO)5] +0.4) ]∆3+t [Co(NH
Ni
28
[Ni(CO)4]
29
[Cu(CN)4]3-
Cu Pd
Metal ion in tetrahedral field
Figure 5.21 Crystal field splitting of energy levels in a tetrahedral field.
t 2g
3 6
∆t
Average energy level (Bari centre)
0
12
36
2
12
36
0
10
3
12
36
(Kr)
0
8
36 36
1
8
36
46
[Pd(NH3)6]4+
4
12
54
(Xe)
Pt
78
4
12
86
(Rn)
Fe
26
[PtC6]2−0.6 ∆t [Fe(CN)6]3-
3
12
35
Ni
28
[Ni(NH3)6]2+
2
12
38
Pd
46
[PdCl4]2-
2
8
52
2
8
84
4
16
34
2
12
36
0
10
36
-1
8
36
-1
12
36
Pt Free metal ion (five degenerate d orbitals)
Energy
Energy
data on structure, properties and other such parameters. Thet2gtabular representation supports comparad orbitals are split into two tive study of properties and draws groups out changing trends in them. The trends of various propertieseg of elements along the periodic table are also amply illustrated.
EAN
Ti Fe Fe Co V
eg 78 [Pt(NH3)4]2+ 0 ion Average 22 energy[Ti(s -CMetal H ) (p -C 5 5 2 5 H5)2] in tetrahedral of metal ion 0 26 [Fe(p -Cfield in spherical 5 H5)2] field26 [Fe(CO) (NO) ] 0 2
2
-
27 5.22 Energy [Co(CO)4levels ] Figure for d orbitals in 23 a tetrahedral field. 6][V(CO)
Sidgwick EAN rule
Lee_Chapter 05.indd 23
C.
In 1927, Sidgwick suggested that electron pairs from ligands were added to the central metal atom until the central atom was surrounded by the same number of electrons as the next noble gas. The stability of the resulting state can be explained on the basis of the molecular orbital theory. However, this rule fails in 2011-05-17 4:35:38 PM many cases and works best for metals in low oxidation state.
ASSESSMENT – AS PER IIT-JEE PATTERN
Application of concepts to problem solving is the core of IIT-JEE, so it is imporLee_Chapter 05.indd 9 tant to test our understanding of concepts. For the test to be effective, the assessment technique should be comprehensive and in the context of this book, also in resonance with the IIT-JEE paper pattern. Each part of the assessment should be modeled on the actual IIT-JEE paper pattern because unless the student practices the IIT-JEE way, he/she will not be sufficiently equipped to take the exam. Keeping this in mind the assessment has been divided into:
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9. Be salts are extensively hydrolyzed. 10. Be salts are among the most soluble known. 11. Beryllium forms an unusual carbide Be2C, which, like Al4C3, yields methane on hydrolysis. There is plainly a diagonal similarity between beryllium in Group 2 and aluminium in Group 3. Just as was the case with lithium and magnesium, the similarity in atomic and ionic sizes is the main factor underlying this relationship.
Multiple Correct Choice Type Questions 45 Single Correct | SinGle CorreCt ChoiCe type QueStionS Choice 13. Among LiCl, RbCl, BeCl , MgCl , the compounds 9. Which of theType following is the most soluble in water? (B) KOH is a stronger base than NaOH. 1. Aqueous solution Na SO and is crystallized above respectively (A) CsClO withofgreatest least ionic out character Questions (C) KHCO is soluble in water and NaHCO is insoluand below 32 °C. The respective products are are (B) NaClO 2
2
4
2
4
4
(A) RbCl (A) Na2SO4 and NaLiCl ⋅ 10H 2SO4and 2O (B)2O RbCl BeCl (B) Na2SO4 ⋅ 10H and and Na2SO 4 2 (C) and MgCl2 (C) Na NaRbCl 4 and 2SO4 Compounds These are of the mul- 38 Chapter 5 2SO Coordination 10. Which the regular following statements is correct? (D)2O MgCl and BeCl2 2O (D) Na SO ⋅ 10H and 2Na 2SO4 ⋅ 10H (A) NaHCO and KHCO have similar crystal structure. 2 4 (C) KClO4 (D) LiClO4
3
3
ble in water. (D) KOH is cheaper than NaOH.
6. Ozonized oxygen is passed through dry powdered
KOH. Which option is not correct regarding the tiple choice questions with product obtained in complexes the above process? (B) Li CO decomposes to give Li O and CO . Which of 14. Which of the followingdoes properties show a reverse following compounds not have (C) Trivalent silver (coordination number 4. 2. Which of thethe following statements is/are correct for (C) Li CO provided. trend on moving fromthree Mg to Ba within the group? is soluble in water. (A) It andiamagnetic. orange coloured solid. four choices Only similarity in structure with the other compounds? 4)isare ferrocene? (A) (D) All are correct. (B) It is paramagnetic in nature. FeSO ⋅ 7H O Density. (D) AgO is diamagnetic. (A)(A) The dipole moment of the eclipsed form of ferroone among the four choices (B)OSolubility of sulphate. (C) It is used in submarines for oxygenating the air. (B) Na is CO ⋅ 7H 11. If Na ion is larger than Mg and S ion is larger than cene zero? (C) of oxalate. It isofalso passing Ohave in blue solution 9. (D) Which theprepared followingbycomplexes geometrical (C) MgSO ⋅ 7H O Solubility will be correct Cl the ion, which of theanswer. following will be least(B) soluble indipole The moment of of the staggered form of (D) Basicity M(OH) . of K that in liquid isomers are NH optically inactive due to the pres3
2
3
2
3
3
2
2
4
+
2+
2-
2
12.
2
3
-
2
4
2
2
2 3 (D) ZnSO 2O water? ferro cene4 ⋅is7H non-zero? enceNof centre of symmetry? 2+ leaves no residue and (A) NaCl 15.point Compound M on 7. A + H O → NaOH 3. of a mixture ofheating NaFe CO + K CO is (C)The Allmelting C atoms are equidistant from ion. 2 2 2 3 2 3 (B) Na2S isthat alsotakes Aqueous solution reacts [Pt°(Cbn)2 ]2+ H2 O higher than ofnot Naobtained. CO3. in the π * orbital (D)(A) Synergic bonding of of M(A) 2place A 400 → B → NaOH + O2 with alkali and all the gases are evolved. The result(C) MgCl2 (B) higher than that of K CO . C atoms. (B) [ Fe(gly)3 ]0 at 25 °C 2 3 ing solution isNa treated with Al in alkaline medium to (D) MgS B is used for oxygenating in submarines. A and B are (C) lower than that of both CO and K CO . 2 3 2 3 5. Which of following IUPAC names is/are correct for (C) [Cr(H 2O)3 Cl 3 ]0 a gas that produces a deep blue solution with respectively: lower thanliberate that K2CO 0 3 only. In which of following cases is the value of x maximum? the(D) complex [Co(NH ) ( tn ) σ − ( C H ) ] NO ? (D) Na [PdO(NH 3 2 ) solution. 3 M 5 is 2 3 2 − CH(CH 3 ) − (CO 2 )2 ] Ni(NO (A) 2 2 and Na2O (A) CaSO4 ⋅ xH2O 4. of the following3 2statements is not correct? (A)Which Diallyldiamminetrimethylenediaminecobalt (III) 10. (B) (A) NH4NO3 Na2O Which ofand theNa following complexes is/are optically 2O2 (B) BaSO4 ⋅ xH2O (A) Common salt absorbs water because it is hygroscopic. nitrate. (B) NH4NO2 (C) Na2Odue 2 and 2 inactive toOthe presence of plane of symmetry? (C) MgSO4 ⋅ xH2O (B) Common salt is used to clear snow on the road. (C) NH Cl (B) 1,3-Diaminopropanediaminediallylcobalt (III) nitrate (D) Na2O and O2 (D) All have the same value of x. (C) Anhydrous MgCl2 4 can be prepared by heating a NH Br (C) Diammine-1,(D)3-diaminopropanedicyclopropyl A (A) a n± n ± (B) double salt of it, i.e.4 MgCl2 ⋅ NH4Cl ⋅ 6H2O. 8. Na2O cannot be prepared by cobalt (III) nitrate. A a a (D) CaSO4 and BaSO4 are reacted with coke to produce A (A) Na O + CO → 2 2 (D) Diallyldiammine-1, 3-diaminopropanecobalt (III) CaS and BaS respectively. (B) Na + NaNO 3 → M M nitrate.type QueStionS multiple CorreCt ChoiCe (C) Na + NaNO2 → 3+ 5. KOH is preferably used to absorb CO because 2 of Co 6. A complex compound consists of 1 mole ion, A bNa2O2 + Na c→ (D) A (A) KOH is more soluble than −NaOH water. 6 moles of NH 6 moles 1 in mole of are Cr 3+ MgO can be used as refractory material because 6.3, Which of of theNO following in the increasing 2 and properties A b ion. The complexorder has from neither thebottom highest top to forvalue metal nor ions in Group 1? (A) it has a very high melting point. the lowest value (A) of electrical conductivity. The possiIonic radius. (B) it has a very low vapour pressure. A (C) n± (B) complex Hydrated radius. is/are B (C) it is a very good conductor of heat. ble formulae for the Aare multiple choice These (C) Ionic mobility. (D) it is chemically inert. Lee_Chapter 09.indd 44 (A) [Cr( NH 3 )5 ( NO 2 )][Co( NH 3 )( NO 2 )5 ] 2011-05-02 M (D) Hydration number. questions with four choices (B) [Co(NH 3 )6 ][Cr (NO2 )6 ] B The temporary hardness of water is caused by which A Which of the following hydrides are electron deficient? (C) [Cr(NH 3 )7. 4 ( NO 2 )2 ][Co( NH 3 )2 ( NO 2 )4 ] of the following compound(s). provided. One or more of B (A) )][ BeH 2 (D) [Co(NH 3 )5 (NO Cr(NH 2 3 )( NO 2 )5 ] (A) CaCl2 (B) CaH2 the four choices provided (B) Mg(HCO3)2 7. Which of the following complexes is/are square planar? (D) Me Me (C) AlH 3 (C) Ca(HCO3)2 (A) [Ag F4 ]− H N NH 2 2 may be correct. (D) KH − (D) MgSO4 (B) [AuCl 4 ] 8. In which of the following cases, does N2 evolve as a (C) [NiCl 2 (PPh 3 )2 ] H H Pt2+ When KO2 reacts with water, the products are gaseous product? H H (D) [ NiCl ( PMe )2 ] KNO reacts with K on heating. 2 3(A) (A) KOH
Multiple Correct Choice Type Questions
|
1.
2.
3.
2:31:01 PM
3
NH2 H2N 8. Choose the correct from following: (B)statement(s) Na2O2 reacts withthe NH 3. Me Me (A) Monovalent (C) silver complexes (coordination NH3 reacts with bleaching powder. (D) None of these. number 2) are diamagnetic. (B) Bivalent silver complexes (coordination number 9. Which of the following elements liberate H2 on reac4. KO3 or Na2O2 is used in submarines or space capsules 4 and 6) are paramagnetic with µ = 1.73 BM . tion with NaOH? because (A) Be (A) it absorbs CO2. (B) Al (B) it releases O2. (C) B (C) it produces corresponding carbonate on reacCOMPREhENSION TyPE qUESTIONS (D) None of these tion with CO2. 10. Which of the following statements are correct regard(D) None of these. Passage 1: foringquestions 1–3 the diagonal relationship between Al and (C) Be? [ Ni(NH 3 )4 ](NO3 )2 ⋅ 2 H 2O; square planar. 5. Electrolysis of KH produces H2 (A) BeO and Al2O3 are amphoteric in nature. (D) [Ni(NH 3 )4 (H 2O)2 ](NO3 )2 ; octahedral. The magnetic moment for two complexes of empiri(A) at the cathode. (B) Carbides of both produce the same gas on Comprehension-type cal formula Ni(NH 3 )4 (NO (B) at the anode. 3 )2 ⋅ 2 H 2 O is zero and 2.84 hydrolysis. 3. Which of the following statements are true for the BM respectively. The complex is not a neutral (C) either at the cathode or at the anode. questions consist of a small (C)second Both can form complexes. second complex? complex. (D) Cannot be predicted. (D) Hydrides of both the elements are covalent m(A) nature. It has the EAN value of 36. passage, followed by three/ 1. The number of water molecules of crystallization are (B) It can show optical isomerism. respectively four multiple choice ques(C) It cannot show geometrical isomerism. (A) zero, two. (D) It produces three-fold freezing point depression. tions based on it. The ques(B) zero, zero. Passage 2: for questions 4–6 (C) two, zero. are of single correct Lee_Chapter 09.inddtions 45 2011-05-02 2:31:01 PM (D) two, two. Some ligands not only donate their lone pair to the central answer type (with some metal atom but also accept the electron cloud from the 2. The correct formula and geometry of the first complex is central metal atom. This is known as synergic bonding. exceptions). (A) [Ni(H O) (NO ) ] ⋅ 4 NH ; tetrahedral.
(B) H2O2 (C) K2O2 (D) O2
Comprehension Type Questions
|
2
2
3 2
3
(B) [Ni(NH 3 )4 ](NO3 )2 ⋅ 2 H 2O; tetrahedral.
Lee_Chapter 05.indd 38
4. In which of the following cases is the bond energy of C - O bond minimum?
2011-05-09 2:33:13 PM
Assertion–Reasoning Type Questions 12
Chapter 4
Hydrolysis
These questions check the analytical and reasoning | ASSErtion–rEASoninG tYPE QuEStionS skills of the students. Two 12 Chapter 4 Hydrolysis In the following set of questions, a Statement I is given 3. Statement I: SiH 4 is prone towards hydrolysis while statements are provided – and a corresponding Statement II is given below it. Mark SnH 4 is inert. the correct answer as: | ASSErtion–rEASoninG tYPE QuEStionS Type Questions Statement II: Sn–HMatrix–Match bond has insufficient polarity 47 Statement I and Statement (A) If both Statement I and Statement II are true compared to Si–H bond. II. The student is expected and Statement II is the correct In explanation of set of questions, a Statement I is given 3. Statement I: the following is prone towards hydrolysis while TeFand H 2 TeO as2O, hydrolyzed 5. Statement I: Na alkaline in 4.9.Statement catch fire. SiH 4 StatementI:I: Na K on reaction with4 H 6 produces Statement I. 2CO3 solution is strongly and a corresponding Statement II is given below it. Mark SnH 4 is inert. to verify if (A) both stateproduct. nature. (B) If both Statement I and Statementthe II are trueanswer but as: Statement II: The reaction is highly exothermic, as a correct Statement II: Sn–H ments bond has polarity 2− Statement II: Te ( OH ) exists and there is no steric areinsufficient true and if both CO Statement II is not the correct explanation for ions Statement II: Hydrolysis of 6 (A) produces If both Statement I and Statement II are true 3 result of which the remaining solid metal melts and – compared to Si–H bond. crowding to accommodate six OH groups around it. Statement H I. 2CO3 and OH ions in solution. undissociated and Statement II is the correct of released H2 catches local heating is soexplanation high that the true,Hverify if statement Statement I: TeF6 are produces 2 TeO 4 as hydrolyzed If Statement true but Statement is2+false. Statement I: P4S10 produces H 3 PO44.and H 2S, not fire. is much I.5. Statement 6. (C) Statement I: TheI ishydration energy of IIBe product. + (D) If Statement I is false but Statement II is true. I follows from statement and , on hydrolysis. PH H SO (B) If both Statement Statement II+ are but + higher as compared to that of Li . 3 2 I and 4 10. Statement I: NaOH NHtrue ↑ +Na+ +H2O 4 - salt → NH3 Statement II: Te(OH)6 exists and there is no steric Statement II isStatement not the correct explanation forelectronegative, the 1. Statement I: Mg C and Al C both produce the II: S atom being more 2 3 4 3 Statement II: First ionization energy of Be is greater II; (B) statements to accommodate six both OH– groups around it. are OH-→place H2O;on it P is atom the crowding strong acid – Statement II: H++ takes same gaseous products on their hydrolysis. Statement I. nucleophilic attack and protothan that of Li. strong base reaction which releases more energy and (C) If Statement I isnation true but Statement II is false. true and if both true, 5. Statement I: H PO Hare produces and P S takes place on S atom. 3 4 2 S, not 4 10 The nature of hydrocarbonstomach produced or 7. Statement Statement II: I: BaSO 4 is used in diagnosing towards greater (D) If Statement I is shifts false but Statement II stability. is true. H 2SO4 and PH 3, on hydrolysis. from a particular carbide depends upon the anionic 6. Statement I: Silicones are resistant towards hydrolysis. duodenal ulcers. verify if statement II is not 1. Statement I: Mg and Al 4CI: produce are the stronger 11. Superoxides oxidizing part present in it. Statement II: S atom being more electronegative, the 2 C 3Statement 3 both Statement II:hydrolysis. +I effect of CH 3 groups reduces the d(+) and gaseous in sev- products Statement II: BaSO4 is insoluble in watersame on their the correct reasoning agents than peroxides. nucleophilic attack takes place on P atom and proto- for 2. Statement I: isHydrolysis of Al 2 (CH 3 )6 is highly character of Si atoms. eral acids and opaque to X-rays. nation takes place on S atom. Statement II: The nature of hydrocarbon produced spontaneous. Statement II: Superoxides accept electrons in the same statement I; (C), (D) which the 8. Statement I: When an electron is added tofrom Na+ ion, a particular carbide upon anionic 6. Statement I: Silicones are resistant towards hydrolysis. energydepends level, i.e. p * the orbital while peroxides accept Statement 2 (CH 3 )6 gives Al(OH)3 (white ppt.) size of theII: ionAl decreases. * of the statements is untrue. part present in it. electrons in the higher energy σ 2p orbital. Statement II: +I effect of CH groups reduces the d(+) and CH (gaseous product) on hydrolysis. 4
the inter-I: Hydrolysis of Al 2 (CH 3 )6 is highly Statement II: In the process of Na+ → 2. Na, Statement electric repulsion increases. spontaneous.
Integer Answer Statement II: Al (CH ) gives Al(OH) (white ppt.) anSWer type QueStionS and CH (gaseous product) on hydrolysis. Type|| inteGer Questions intEGEr AnSWEr tYPE QuEStionS 2
3 6
character of Si atoms.
3
3
4
The answer to each of the following questions is a non5. Cl2 gas is passed through a compound A and proThe answer to each of the following questions is a non- 4. Among the following orders, numberofofprotons incorrect negative integer. duces bleaching powder. Thethenumber in The questions negative integer. in this secorders with respect to rate of hydrolysis is ___________. A is ___________. 21. The number of rings formed in [Ca(EDTA)] is SnCl 2 > SnCl 4 tYPE QuEStionS (i) AnSWEr intEGEr tion arenumber numerical prob- among the following, 1. The of compounds ___________. 6. The ratio of the number of water of crystallization in (ii) BBr3 > BI 3 forming oxyacids from the central atom on hydrolysis gypsum and that in plaster Paris is4.___________. Themolecule answer toofeach of the following questions is aofnonAmong the following orders, the number of incorrect lems for which no of choices 2. isThe total number electrons in one ___________. (iii) SeF6 > TeF6 negative integer. orders with respect to rate of hydrolysis is ___________. Mg2C3 is ___________. 7.(iv) Among following elements, the number of eleare provided. The students SiCl 4 the < SiBr 4 SnCl 2 >isSnCl 4 (i) NaOH AsClthe SbCl SiF ments thatamong releasetheH2following, on reaction with 1.pairs number 3 , NCl 3 , PCl 3 ,the 3 , PCl 5 ,of 4The of 3. Among following number com- of compounds (v) SiH 4 > GeH 4 are required to find theamong (ii) BBr3 > BI 3 ___________. forming oxyacids from the central atom on hydrolysis pounds, for which the thermal stability order is that correct 2. The number of compounds the following do (vi) SF6 < SeF6 is ___________. (iii) SeF6 > TeF6 Be, Al, B, Mg, Ca, Zn, Sn is ___________. notanswers produce only product(s) on their hydrolysis is exact toacidic numeri(a) BeCO3 > SrCO3 SiCl < SiBr 5. When SnCl 4 is converted into [SnCl 6 ]2− (iv) by the nucle___________. The number of bicarbonates that do not exist in 4solid 4 AsCl 3 , NCl 3 ,8.PCl 3 , SbCl 3 , PCl 5 , SiF4− cal problems which can (b) MgO >BaO ophilic additon of Cl , the coordination is 4 SiH 4 > GeH (v)number form among the following is ___________. , XeF (c) LiSO < Cs 2 , 3SO 2 Cl 2 , NCl 3 , SeCl 4 , TeF6 2. 4 . number of compounds increased by___________. The among the following that do 2CO 2CO 3 (vi) SF6 < SeF6 be one-digit or two-digit LiHCO3 , NaHCO (HCO3 )is2 , KHCO3 , NH 4 HCO3 , Ba(HCO3 )2 Mg(HCO3 )2 (d) CaSO < hydrolyzed, BaSO4 3 , Ca not produce on their hydrolysis SF4 4 is 3. When the change in oxidation stateonly acidic product(s) 2− (e)S Li Na3N the numerals. LiHCO (HCO3 )2 , KHCO3 , NH 4 HCO3 , Ba(HCO3 )2 Mg(HCO3 5. )2 When SnCl 4 is converted into [SnCl 6 ] by the nucle3N > 3 , NaHCO 3 , Ca___________. of atom during process is ___________. − ophilic additon of the coordination number is Cl , (f ) LiClO4 < KClO4 is The3 , number of 6planes [BeH4]2-by___________. SO2 , SO2Cl 29. , NCl SeCl 4 , TeF , XeF4 . of symmetry in increased 4. Among the following compounds, the number of ___________. 3. or When 4 is hydrolyzed, the change in oxidation state compounds which do not produce acidic basicSF solu10. The percentage water loss when gypsum is heated to of SQuEStionS atom during the process is ___________. MAtriX–MAtcH tYPE tions when dissolved in water is ___________. get plaster of Paris is ___________. NaCl, BeCl 2 , BaCl 2 , Li 2O, MgO, CaH 2 , CaSO4 In each of the following questions, statements are given (R), (S) and (T). Any given statement in Column I can These questions are the in two columns, which have to be matched. The state- have correct matching with one or more statements in ments in Column I are labelled as (A), (B), QueStionS (C) MAtriX–MAtcH and Column II. tYPE QuEStionS matrix–matCh type regular “Match the Follow(D), while those in Column II are labelled as (P), (Q), statement in Column I can In each of the following questions, statements are given (R), (S) and (T). Any given ing” variety. Two columns In each of the following questions, statements are given in two columns, which have to be matched. The statements in two columns, which have to be matched. The state- have correct matching with one or more statements in in Column I are labelled as (A), (B), (C) and (D), while those in Column II are labelled as (P), (Q), (R), (S) and (T). each containing 4 subdiviments in Column I are labelled as (A), (B), (C) and Column II. Any given statement in Column I can have correct matching with one or more statements in Column II. (D), while those in Column II are labelled as (P), (Q),
|
Matrix–Match Type Questions
|
|
|
1. Match the chemical properties with the compounds.
2. Match the compounds with their characteristics.
Column I
Column II
Column I
Column II
(A) Ca
(P) Produces H2 on reaction with H2O. (Q) Produces Ca(OH)2 on reaction with H2O. (R) The compound is ionic. (S) Can absorb N2 under not conditions.
(A) BeCO3 (B) MgCO3 (C) CaCO3
(P) Least soluble in water. (Q) Least thermally stable. (R) Produces MO + CO2 on heating with the help of bunsen burner. (S) Produces basic oxides on thermal decomposition.
(B) CaH2 Lee_Chapter 04.indd 12
(C) CaO (D) CaC2
Lee_Chapter 04.indd 12
Lee_Chapter 09.indd 47
sions or first column with four subdivisions and second column with more subdivisions are given and the student should match of column I to 2011-05-17 elements 5:00:15 PM that of column II. There can be one or more matches.
2011-05-17 5:00:15 PM
2011-05-02 2:31:02 PM
D.
USe of SI UNITS
SI units for energy are used throughout this edition, thus making a comparison of thermodynamic properties easier. Ionization energies are quoted in kJ mol–1, rather than ionization potentials in eV. Older data from other sources use eV and may be converted into SI units (1 kcal = 4.184 kJ, and 1 eV = 23.06 × 4.184 kJ mol–1). Meters are strictly the SI units for distance, and bond lengths are sometimes quoted in nanometers (1 mm = 10–9 m). However Ångström units Å (10–10 m) are a permitted unit of length, and are widely used by crystallographers because they give a convenient range of numbers for bond lengths. Most bonds are between 1 and 2 Å (0.1 to 0.2 nm). Ångström units are used throughout for bond lengths. The positions of absorption peaks in spectra are quoted in wave numbers cm–1, because instruments are calibrated in these units. It must be remembered that these are not SI units, and should be multiplied by 100 to give SI units of m–1, or multiplied by 11.96 to give J mol–1. The SI units of density are kg m–3, making the density of water 1000 kg m–3. This convention is not widely accepted, so the older units of g cm–3 are retained so water has a density of 1 g cm–3. In the section on magnetism both SI units and Debye units are given, and the relation between the two is explained. For inorganic chemists who simply want to find the number of unpaired electron spins in a transition metal ion, Debye units are much more convenient.
E.
NOMENCLATURE Followed IN THE PERIODIC TABLE
For a long time chemists have arranged the elements in groups within the periodic table in order to relate the electronic structures of the elements to their properties, and to simplify learning. There have been several methods of naming the groups. A number of well known books name the main groups and the transition elements as A and B subgroups, which dates back to the older Mendeleef periodic table of more than half a century ago. Its disadvantages are that it may overemphasize slight similarities between the A and B subgroups, and there are a large number of elements in Group VIII. In earlier versions of this book the s-block and the p-block were numbered as groups I to VII and 0, depending on the number of electrons in the outer shell of the atoms, and the transition elements were dealt with as triads of elements and named as the top element in each group of three. The IUPAC has recommended that the main groups and the transition metals should be numbered from 1 to 18. This system has gained acceptance, and has now been adopted throughout this book.
I IA H Li Na K Rb Cs 1
II IIA Be Mg Ca Sr Ba 2
IIIB
Sc Y La 3
IVB
Ti Zr Hf 4
F. APPENDICES
VB
V Nb Ta 5
VIB
Cr Mo W 6
VIIB
Mn Tc Re 7
<…VIIIB…>
Fe Ru Os 8
Co Rh Ir 9
Ni Pd Pt 10
IB
Cu Ag Au 11
IIB
III IIIA
IV IVA
V VA
VI VIA
VII VIIA
Zn Cd Hg 12
B Al Ga In Tl 13
C Si Ge Sn Pb 14
N P As Sb Bi 15
O S Se Te Po 16
F Cl Br I At 17
0 VIIIA He Ne Ar Kr Xe Rn 18
F.
APPENDICES
Appendix A
Abundance of the elements in the Earth’s crust
Appendix B
Melting points of the elements
Appendix C
Boiling points of the elements
Appendix D
Densities of solid and liquid elements
Appendix E
Electronic structures of the elements
Appendix F
Some average single bond energies and some double and triple bond energies
Appendix G
Solubilities of main group compounds in water
Appendix H
Atomic weights based on 12C= 12.000
Appendix I
Values of some fundamental physical constants
Appendix J
Electrical resistivity of the elements at the stated temperature
Appendix K
Hardness of minerals — Mohs’ scale
Contents Preface
v
Note to the Student 1. Atomic Structure and the Periodic Table 1.1 The Atom as a Nucleus with Orbital Electrons 1.2 Atomic Spectra of Hydrogen and the Bohr Theory 1.3 Refinements to the Bohr Theory 1.4 The Dual Nature of Electrons—Particles or Waves 1.5 The Heisenberg Uncertainty Principle 1.6 The Schrödinger Wave Equation 1.7 Radial and Angular Functions 1.8 Pauli Exclusion Principle 1.9 Build-up of the Elements, Hund’s Rule 1.10 Sequence of Energy Levels 1.11 Arrangement of the Elements in Groups in the Periodic Table Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
2. General Properties of the Elements 2.1
Size of Atoms and Ions Size of atoms Size of ions Problems with ionic radii Trends in ionic radii 2.2 Ionization Energies 2.3 Electron Affinity 2.4 Electronegativity Pauling Mulliken Allred and Rochow 2.5 Metallic Character 2.6 Variable Valency and Oxidation States 2.7 Horizontal, Vertical and Diagonal Relationships in the Periodic Table Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
3. Chemical Bonding 3.1 3.2
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Attainment of a Stable Configuration Types of Bonds
vii 1 1 2 6 7 7 8 10 14 14 16 17 18 19 20 21 21 21 22
23 23 23 23 24 25 25 28 29 29 31 32 32 33 34 35 36 37 38 38 39 39
41 42 42
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Contents
3.3
3.4
3.5
3.6
3.7 3.8 3.9 3.10
3.11 3.12
3.13
3.14
3.15 3.16
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Transitions Between the Main Types of Bonding Ionic bonds Covalent bonds Oxidation numbers Coordinate bonds Double and triple bonds Metallic bonds and metallic structures The Covalent Bond The Lewis theory Sidgwick–Powell theory Valence Bond Theory What is the essence of hybridization? Features of hybrid orbitals Calculation of steric number Valence Shell Electron Pair Repulsion (VSEPR) Theory Effect of lone pair Effect of double bond Effect of electronegativity Back bonding The Extent of d Orbital Participation in Molecular Bonding Types of Covalent Bonds (Sigma (s ) and Pi (p ) Bonds) Bridge bonding Molecular Orbital Method LCAO Method s–s combinations of orbitals s–p combinations of orbitals p–p combinations of orbitals p–d combinations of orbitals d–d combinations of orbitals Non-bonding combinations of orbitals Rules for Linear Combination of Atomic Orbitals Examples of Molecular Orbital Treatment for Homonuclear Diatomic Molecules H2+ molecule ion H2 molecule + He2 molecule ion He2 molecule Li2 molecule Be2 molecule B2 molecule C2 molecule N2 molecule O2 molecule O-2 ion F2 molecule Examples of Molecular Orbital Treatment for Heteronuclear Diatomic Molecules NO molecule CO molecule The Ionic Bond Radius ratio rules Calculation of some limiting radius ratio values Close Packing Ionic Compounds of the Type AX (ZnS, NaCl, CsCl) Structures of zinc sulphide Sodium chloride structure Caesium chloride structure
43 43 44 45 45 46 46 46 46 48 48 48 49 50 51 51 55 55 57 61 62 65 67 67 68 69 70 71 71 71 72 74 75 75 75 76 76 76 76 76 76 77 77 77 78 79 79 80 80 81 82 84 84 84 84
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Contents
3.17
Ionic Compounds of the Type AX2 (CaF2, TiO2, SiO2) Calcium fluoride (fluorite) structure Rutile structure b-cristobalite (silica) structure 3.18 Layer Structures (CdI2, CdCl2, [NiAs]) Cadmium iodide structure Cadmium chloride structure Nickel arsenide structure 3.19 Lattice Energy 3.20 Stoichiometric Defects Schottky defects Frenkel defects 3.21 Nonstoichiometric Defects Metal excess Metal deficiency 3.22 Born–Haber Cycle 3.23 Polarizing Power and Polarizability – Fajans’ Rules Properties of ionic compounds affected by polarization 3.24 Melting Point of Ionic Compounds 3.25 Solubility of Ionic Compounds Prediction of solubility order in ionic compounds 3.26 Electrical Conductivity and Colour 3.27 Acidic Nature of Oxides 3.28 Thermal Stability of Ionic Compounds 3.29 Weak Forces Attractive intermolecular forces Repulsive intermolecuar forces Lennard–Jones potential 3.30 Interactions Between Ions and Covalent Molecules 3.31 The Metallic Bond Conductivity Lustre Malleability and cohesive force Crystal structures of metals Bond lengths 3.32 Theories of Bonding in Metals Free electron theory Valence bond theory Molecular orbital or band theory 3.33 Conductors, Insulators and Semiconductors Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
4. Hydrolysis 4.1 4.2 4.3 4.4 4.5
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Introduction Hydrolysis through SN1 Mechanism Hydrolysis through SN2 Mechanism Hydrolysis through Addition–Elimination Mechanism Hydrolysis through Addition Mechanism
xvii
85 85 86 86 86 86 87 87 87 91 91 91 92 93 94 94 96 97 97 100 101 103 103 104 105 105 107 107 107 108 108 109 109 112 113 113 113 113 114 116 117 119 120 122 123 124 125
127 127 127 128 132 133
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Contents
4.6 Hydrolysis through Redox Reaction 4.7 Hydrolysis through Push–Pull Mechanism 4.8 Hydrolysis through Mixed Mechanism Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
5. Coordination Compounds 5.1 5.2 5.3 5.4 5.5
Double Salts and Coordination Compounds Werner’s Work More Recent Methods of Studying Complexes Classification of Ligands Effective Atomic Number (EAN) Sidgwick EAN rule 5.6 Shapes of d Orbitals 5.7 Bonding in Transition Metal Complexes Valence bond theory Crystal field theory Molecular orbital theory 5.8 Valence Bond Theory 5.9 Crystal Field Theory Octahedral complexes 5.10 Effects of Crystal Field Splitting 5.11 Tetragonal Distortion of Octahedral Complexes (Jahn-Teller Distortion) 5.12 Square Planar Arrangements 5.13 Tetrahedral Complexes 5.14 Magnetism 5.15 Extension of the Crystal Field Theory to Allow for Some Covalency 5.16 Nomenclature of Coordination Compounds 5.17 Isomerism Polymerization isomerism Ionization isomerism Hydrate isomerism Linkage isomerism Coordination isomerism Coordination position isomerism Geometrical isomerism and optical isomerism Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
6. Metallurgy 6.1 6.2 6.3
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Types of Ores Principal Steps in the Recovery of a Metal from its Ore Concentration or Dressing of Ore Gravity separation or levigation
133 133 134 136 136 137 138 138 138 139
141 141 142 143 145 148 149 150 151 151 151 151 151 152 153 158 159 161 163 165 166 166 169 169 169 169 170 170 171 171 176 177 178 179 179 180 181
183 184 185 185 186
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Contents
Magnetic separation Froth floatation or oil floatation Chemical method of separation: Leaching 6.4 Conversion of Concentrated Ore into its Oxide Calcination Roasting 6.5 Different Reduction Processes Carbon reduction Self reduction Thermite reduction (or Goldschmidt-Thermite process) Metal replacement method (Hydrometallurgy) Electrolytic reduction Thermal decomposition method 6.6 Purification or Refining of metal Thermal refining Electrorefining 6.7 Theromodynamics of Reduction Process 6.8 Alloys and Amalgams Classification of alloys Characteristics of alloys Preparation of alloys Amalgam 6.9 Different Types of Furnaces Used in Metallurgy 6.10 Extraction of Silver Refining of Ag 6.11 Extraction of Gold by Cyanide Process Refining of Au 6.12 Extraction of Tin Refining of Sn 6.13 Extraction of Magnesium Electrolytic reduction Carbon reduction process Other processes 6.14 Extraction of Aluminium Beneficiation of bauxite Electrolytic reduction of pure Al2O3 Electrorefining of aluminium 6.15 Extraction of Lead Carbon reduction Self reduction process Refining of lead 6.16 Extraction of Copper Refining of blister copper 6.17 Extraction of Zinc 6.18 Extraction of Iron Purification of iron or preparation of wrought iron Steel making Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
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186 186 188 188 188 188 189 189 190 190 191 191 192 192 192 194 195 197 197 198 198 199 199 200 201 201 201 202 203 203 203 205 205 205 206 208 209 210 210 212 212 212 214 214 216 217 218 219 220 221 222 223 223 224
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Contents
7. Qualitative Salt Analysis Tests for Acid Radicals 7.1 Action of Dilute Acids 7.2 Tests for CO32-/HCO3- and SO32-/HSO3- Radicals Distinction between carbonate and bicarbonate Detection of carbonate and bicarbonate when both are present together Distinction between sulphite and bisulphite Some other tests for SO32- ions 7.3 Tests for Sulphide (S2-) Radical 7.4 Tests for Thiosulphate (S2O23 ) Radical 7.5 Tests for Nitrite (NO-2) Radical 7.6 Tests for Acetate, Formate and Oxalate Radicals Specific test for acetate (cacodyl oxide test) Specific test for formate (mercury (II) formate test) Specific tests for oxalate 7.7 Tests for Halide (Cl-, Br-, I-) Radicals Specific test for Cl - (chromyl chloride test) Specific test for Br- and I - (layer test) Other test for Br− Other tests for I − 7.8 Tests for Nitrate (NO-3) Radical 7.9 Tests for Sulphate (SO42-) Radical 7.10 Tests for Borate (BO33- ) Radical 7.11 Tests for Phosphate (PO43-) Radical 7.12 Tests for Chromate (CrO42-) And Dichromate (Cr 2O72-) Radicals 7.13 Tests for Permanganate (MnO-4) and Manganate (MnO42-) Radicals
226 226 227 228 229 232 232 234 235 237 239 241 241 242 242 244 244 244 245 246 247 248 249 250 252
Tests for Basic Radicals 7.14 Dry Tests for Basic Radicals Heating effects on the dry sample Flame test Borax bead test Sodium carbonate bead test 7.15 Wet Tests for Basic Radicals Classification of cations (group analysis) 7.16 Some General Tests for Cations Tests for group V cations Tests for group VI and zero group cations 7.17 Specific Tests for Some Cations
253 253 253 255 255 256 256 256 258 266 267 268
Heating Effects Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
269 272 274 275 278 279 279 280
8. Hydrogen and the Hydrides 8.1 8.2 8.3 8.4 8.5
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225
Electronic Structure Position in the Periodic Table Abundance of Hydrogen Preparation of Hydrogen Properties of Molecular Hydrogen
283 283 284 284 284 285
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Contents
8.6 8.7 8.8
Isotopes of Hydrogen Ortho and Para Hydrogen Hydrides Ionic or salt-like hydrides Covalent hydrides Metallic (or interstitial) hydrides Intermediate hydrides 8.9 The Hydrogen Ion 8.10 Hydrogen Bonding 8.11 Acids and Bases Arrhenius theory Acids and bases in proton solvents Bronsted–Lowry theory Lewis theory The Lux–Flood definition Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
9. The s-Block Elements and their Compounds Group 1 – The Alkali Metals 9.1 General Properties Electronic structure Size of atoms and ions Density Ionization energy Electronegativity and bond type 9.2 Born–Haber Cycle: Energy Changes in the Formation of Ionic Compounds 9.3 Structures of the Metals, Hardness and Cohesive Energy Melting and boiling points 9.4 Flame Colours and Spectra 9.5 Colour of Compounds 9.6 Chemical Properties Reaction with water Reaction with air Reaction with dinitrogen 9.7 Oxides, Hydroxides, Peroxides and Superoxides Reaction with air Normal oxides – monoxides Hydroxides Peroxides and superoxides 9.8 Sulphides 9.9 Oxosalts – Carbonates, Bicarbonates, Nitrates, Nitrites and Sulphates 9.10 Halides and Polyhalides 9.11 Hydrides 9.12 Solubility and Hydration 9.13 Solutions of Metals in Liquid Ammonia 9.14 Compounds with Carbon 9.15 Complexes, Crowns and Crypts 9.16 Biological Importance 9.17 Differences Between Lithium and the Other Group 1 Elements
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286 288 289 289 290 292 292 292 292 295 295 296 298 299 300 300 301 301 302 303 303 303
305 306 306 306 306 307 307 307 308 310 311 311 312 312 313 313 313 314 314 314 314 315 316 317 318 318 319 322 323 323 325 326
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The Chlor-Alkali Industry 9.18 Sodium Hydroxide 9.19 Leblanc Process 9.20 Weldon and Deacon Processes 9.21 Electrolytic Processes Diaphragm cell Mercury cathode cell Quantities 9.22 Sodium Carbonate 9.23 The Solvay (or Ammonia – Soda) Process
327 327 328 328 329 329 330 331 331 332
Group 2 – The Alkaline Earth Elements 9.24 General Properties Electronic structure Size of atoms and ions Ionization energy Electronegativity Hydration energies Solubility and lattice energy Solutions of the metals in liquid ammonia 9.25 Anomalous Behaviour of Beryllium 9.26 Chemical Properties Reaction with water 9.27 Hydroxides 9.28 Hardness of Water 9.29 Reaction with Acids and Bases 9.30 Oxides and Peroxides 9.31 Sulphates 9.32 Nitrates 9.33 Hydrides 9.34 Halides 9.35 Nitrides 9.36 Carbides 9.37 Complexes 9.38 Biological Role of Mg2+ and Ca2+ 9.39 Differences Between Beryllium and the Other Group 2 Elements Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
332 333 333 333 334 334 334 335 335 335 337 337 338 338 339 339 341 341 342 343 344 344 345 347 348 348 349 350 350 351 351 352
10. The p-Block Elements and their Compounds The Group 13 Elements 10.1 Oxidation States and Types of Bonds The (+III) oxidation state The (+I) oxidation state – the ‘inert pair effect’ 10.2 General Properties Melting points, boiling points and structures Size of atoms and ions Electropositive character Ionization energy 10.3 Reactions of Boron
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353 354 354 354 355 355 355 356 357 358 359
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Contents
10.4
10.5
10.6 10.7 10.8
10.9 10.10 10.11
10.12
10.13 10.14
Reactions of the Other Elements Reaction with water and air Reaction with acids and alkalis Reaction with dioxygen Reaction with the halogens and sulphate Alums Cement Compounds of Boron and Oxygen Boron sesquioxide and the borates Acidic properties of H3BO3 or B(OH)3 Structures of borates Borax Sodium peroxoborate Isopolyacids of B, Si and P Qualitative analysis of boron compounds Fluoboric acid Borides The Other Group 13 Oxides Amphoteric behaviour – aluminates Tetrahydridoborates (Borohydrides) Halides Trihalides Dihalides Monohalides Complexes Differences Between Boron and the Other Elements Boron Hydrides Compounds known Preparation Reactions of the Boranes Hydroboration Reaction with ammonia Some other reactions of boranes Structures of the Boranes Organometallic Compounds
The Group 14 Elements 10.15 Structure and Allotropy of the Elements 10.16 Differences between Carbon, Silicon and the Remaining Elements Carbon dating 10.17 Physical Properties Covalent radii Ionization energy Melting points Metallic and non-metallic character Four-covalent compounds 10.18 Chemical Reactivity Inert pair effect Standard reduction potentials (volts) 10.19 Graphite Compounds 10.20 Carbides Salt-like carbides Interstitial carbides Covalent carbides 10.21 Oxygen Compounds of Carbon
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359 359 360 360 360 360 361 361 361 362 363 364 365 365 365 366 366 367 367 368 369 369 371 372 372 373 373 373 373 375 375 376 377 377 378 379 379 381 382 382 382 382 382 383 383 383 384 384 384 386 386 387 387 387
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Contents
10.22 10.23 10.24 10.25 10.26 10.27
10.28
10.29 10.30
10.31 10.32 10.33 10.34
10.35 10.36 10.37
Carbon monoxide CO Carbon dioxide CO2 Carbon suboxides Carbonates The Carbon Cycle Sulphides of Carbon Oxides of Silicon Oxides of Germanium, Tin and Lead Silicates Occurrence in the Earth’s crust Soluble silicates Principles of silicate structures Classification of Silicates Orthosilicates (neso-silicates) Pyrosilicates (soro-silicates, disilicates) Cyclic silicates Chain silicates Sheet silicates (phyllo-silicates) Three-dimensional silicates Glass Organosilicon Compounds and the Silicones Organosilicon compounds Preparation of organosilicon compounds Silicones Hydrides of Silicon Complexes Internal π Bonding Using d Orbitals Halides Tetrahalides Catenated halides Dihalides Cluster Compounds Reaction Mechanisms Organic Derivatives
The Group 15 Elements 10.38 General Properties and Structures of the Elements Nitrogen Phosphorus Bond type Metallic and non-metallic character Reactivity 10.39 Hydrides Ammonia NH3 Phosphine PH3 Arsine AsH3, stibine SbH3 and bismuthine BiH3 Structure of the hydrides Donor properties Hydrazine N2H4 Hydroxylamine NH2OH 10.40 Liquid Ammonia as a Solvent 10.41 Hydrogen Azide and the Azides 10.42 Nitrogen Fixation Cyanamide process Haber–Bosch process
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388 390 391 392 392 393 394 395 396 396 397 397 397 397 398 399 399 401 403 404 405 405 405 406 408 410 411 411 411 414 414 415 415 416 416 417 417 418 419 420 420 421 421 422 422 423 423 424 425 426 427 428 429 429
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Contents
10.43
10.44
10.45
10.46
10.47
10.48
10.49
Fertilizers Urea Phosphate fertilizers Halides Trihalides Pentahalides Oxides of Nitrogen Nitrous oxide N2O Nitric oxide NO Nitrogen sesquioxide N2O3 Nitrogen dioxide NO2 and dinitrogen tetroxide N2O4 Dinitrogen pentoxide N2O5 Oxoacids of Nitrogen Nitrous acid HNO2 Nitric acid HNO3 Oxides of Phosphorus, Arsenic and Bismuth Trioxides Pentoxides Other oxides Oxoacids of Phosphorus The phosphoric acid series The phosphorous acid series Major Uses of Phosphates
The Group 16 Elements – Chalcogens 10.50 General Properties Electronic structure and oxidation states Acid rain and SO2 Uses of sulphur 10.51 Structure and Allotropy of the Elements Oxygen Ozone Sulphur 10.52 Physical Properties 10.53 Chemical Reactivity Standard reduction potentials (volts) Oxidation states (+II), (+IV) and (+VI) Bond lengths and pπ – dπ bonding Differences between oxygen and the other elements 10.54 General Properties of Oxides Normal oxides Peroxides Suboxides Basic oxides Amphoteric oxides Acidic oxides Neutral oxides Reactions between oxides 10.55 Oxides of Sulphur Dioxide SO2 Trioxides SO3 Other oxides Detergents 10.56 Oxoacids of Sulphur Sulphurous acid series
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430 431 431 431 431 432 434 434 435 436 436 437 438 438 439 441 441 442 443 443 443 449 450 450 451 451 451 452 452 452 453 454 455 456 456 456 457 457 457 457 458 458 458 458 459 459 459 460 460 462 463 463 464 465
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Contents
10.57
10.58
10.59 10.60
Sulphuric acid series Thionic acid series Peroxoacid series Oxohalides Thionyl compounds Sulphuryl compounds Hydrides Water Other hydrides Peroxides and polysulphides Hydrogen peroxide Halides Organo Derivatives
The Group 17 Elements – The Halogens 10.61 Extraction and Uses of the Elements Fluorine Chlorine Bromine Iodine 10.62 General Properties Size of atoms and ions Ionization energy Type of bonds formed and oxidation states Melting and boiling points Bond energy in X2 molecule Oxidizing power 10.63 Reaction with Water 10.64 Reactivity of the Elements 10.65 Hydrogen Halides HX HF HCl HBr and HI 10.66 Halides Ionic halides Molecular (covalent) halides Bridging halides Preparation of anhydrous halides 10.67 Halogen Oxides Oxygen difluoride OF2 Dioxygen difluoride O2F2 Dichlorine monoxide Cl2O Chlorine dioxide ClO2 Chlorine perchlorate Cl · ClO4 Dichlorine hexoxide Cl2O6 Dichlorine heptoxide Cl2O7 10.68 Oxoacids Hypohalous acids HOX Halous acids HXO2 Halic acids HXO3 Perhalic acids HXO4 Strength of the oxoacids 10.69 Interhalogen Compounds AX compounds AX3 compounds
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466 468 469 469 469 470 470 471 472 473 474 475 477 478 479 479 481 482 482 483 483 483 484 485 486 486 487 488 489 490 490 491 494 494 494 494 495 496 496 496 496 497 498 498 498 499 499 500 501 502 503 503 504 505
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Contents
AX5 compounds AX7 compounds 10.70 Polyhalides 10.71 Basic Properties of the Halogens 10.72 Pseudohalogens and Pseudohalides 10.73 Occurrence and Recovery of the Elements 10.74 Uses of the Elements 10.75 Physical Properties 10.76 Special Properties of Helium 10.77 Chemical Properties of the Noble Gases Molecular ions formed under excited conditions Clathrate compounds 10.78 Chemistry of Xenon Xenon fluoride complexes 10.79 Structure and Bonding in Xenon Compounds XeF2 XeF4 XeF6 10.80 Valediction Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
11. The d-Block Elements and some of their Compounds 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8
11.9 11.10 11.11 11.12 11.13
11.14
11.15 11.16
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Variable Oxidation State Stability of the various oxidation states Complexes Size of Atoms and Ions Density Melting and Boiling Points Reactivity of Metals Ionization Energies Colour Polarization Incompletely filled d or f shell Magnetic Properties Catalytic Properties Nonstoichiometry Abundance Chromate and Dichromate Preparation Properties Manganate and Permanganate Preparation Properties Silver and its Compounds Silver nitrate (AgNO3) Zinc Compounds Zinc Oxide (ZnO) Zinc chloride (ZnCl2) Zinc sulphate (ZnSO4)
xxvii
507 508 509 510 512 513 514 514 515 515 515 515 516 518 519 519 521 521 522 523 527 528 530 531 532 533
535 536 537 537 538 538 539 539 539 540 540 540 541 542 542 542 543 543 543 544 544 544 545 546 547 547 548 549
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11.17
Copper Compounds Copper oxide (CuO) Copper chloride (CuCl2) Copper Sulphate (CuSO4) 11.18 Iron Compounds Iron sulphate (FeSO4.7H2O) Iron oxide (FeO) Iron chloride (FeCl2) Single Correct Choice Type Questions Multiple Correct Choice Type Questions Comprehension Type Questions Assertion–Reasoning Type Questions Integer Answer Type Questions Matrix–Match Type Questions Answers
Appendices Appendix A Appendix B Appendix C Appendix D Appendix E Appendix F Appendix G Appendix H Appendix I Appendix J Appendix K
Index
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549 549 550 550 551 551 552 552 553 554 554 556 556 557 557
559–577 Abundance of the Elements in the Earth’s Crust Melting Points of the Elements Boiling Points of the Elements Densities of the Solid and Liquid Elements Electronic Structures of the Elements Some Average Single Bond Energies and Some Double and Triple Bond Energies Solubilities of Main Group Compounds in Water Atomic Weights Based on 12 C = 12.000 Values of Some Fundamental Physical Constants Electrical Resistivity of the Elements at the Stated Temperature Hardness of Minerals – Mohs’ Scale
559 561 562 563 564 568 569 571 573 574 576
579
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