Fundamentals of Inorganic Chemistry

738 Pages·102.024 MB·English

by  Asim Kumar Das

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Fundamental
Concepts of
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Inorganic a
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Chemistry
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SECOND EDITIOcN
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Volume 3
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Revised SecondcEdition
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Aesim K. Dos
MSc(GoldMemdalist,CU), PhD(CU), DSc(VisvaBharan)
Professorof Chemistry
Visva.Bharati University, Santiniketan 731235
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West Bengal (India)
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MSC(CU), PhD(VisvaBharati)
H FormerResearchAssociate, DepartmentofChemistry
Visva BharatiUniversity, Santiniketan 731235

West Bengal (India)
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Dr. A.V. Saha, DSc
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Head ofthe DepartmentofChemistry
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Ramakrishna MissionbResidential College
P.O. Narendrapuri743508, 24-Parganas (8)
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West Bengal, India
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Foreword
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Present-day inorganicchemistry is nomoreacollectionofunrelated facts. Thescenariohasundergone
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a.drasticchangeoverthe lastfifteentotwent/yyearswiththeapplicati~n'ofkinetic,thermodynamicand
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structural studies to inorganic substances and with newer techniques providing newer information.
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Oftentheinformationgathered,hasmadetheoreticiansdevelop/modifyvalencytheoriesandprinciples.
In this situation every teacher an.d student realise the importance ofa textbook that will help them
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developtheconceptsandunder standingofthesubject.Thereareattemptsbyafewauthorsatachieving
this goal but those seldom coeverthe wholecurricula followed by most ofthe Indian Universities and
Institutes. In many oftherse books the authors virtually neglect the evolutionary developments ofthe
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subject,creatingundesirablelacunaeinthereaders'understanding.Hereisanhonestandsincereattempt
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at bridgingthese gaps and presentinga comprehensive textbookon concepts and understandingtothe
readers. The tre atment ofevery topic is elaborate and is marked by remarkable clarity and the author
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has notcompromised herewiththe volume ofhis work. ThebookFundamentalConcepts ofInorganic
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Chemistrycovers the inorganic chemistry curriculaat the BSc (honours) and MSc preliminaries.
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A llarge number ofexercises and problems essential for modern teaching, have been incorporated
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meticulously at the end ofeach chapterto bridge the gaps, ifany, in the understandingofthe subject.
Hope this earnest effort ofDr. Das, a teacher ofdistinction, will receive well-deserved acclaim from
the students and teachers ofthis subject.
A.V. Saha
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my teacherts and well-wishers
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whoepaved the way
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One who h~s shraddha acquires knowledge
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Preface to the Seclond Edition
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Ido endeavour. Hegives thestrengthandpatience.
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My beloved readers are requested first to accept my unconditional apology for this long timetaken to
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shape the second edition of the book. Though the second edition incorporates some aspects of
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coordinationchemistry,thereadersdesirethecompleteCoordinationChemistrywhichisexpectedto
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appear in the next volumes and the process/is in progress.
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Ifeel delighted to record the warm response which the first edition ofthe book has received from
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thestudentsandteachersthroughoutthecountry. Ihavetriedmybestto incorporateall thesuggestions
received from the readers. The pre.sentedition has been thoroughly revised and substantiallyenlarged
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and, in fact, no single page has been left untouched. However, Ihave taken all the measures to retain
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the features for which the first edition has been so popular.
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In thissecondeditionofthebook,scopeofthe book has been broadened byaddingnewtopicsand
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revisionsoftheearliersections. The newtopics areatomic units; NMRactive nucleiand principlesof
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NMR spectroscopy; nucleosynthesis ofelements after big bang; nuclear waste management; Bose

Einstein condensate (BEC): fifth state ofmatter; bonding properties ofd- and}-orbitals: comparison;
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application ofWoodward-Hoffmann orbital symmetry rules; structure and properties oftluoroalkyl
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radicalsiand ions; structure and properties ofzeolites and clay materials; aluminosilicates and surface
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acids;Cheteropoly and isopoly acid anions; hypervalency; molecular orbital diagrams of polyatomic
molecules in terms of group orbitals (i.e. TASOs); 3c-4e versus 3c-2e bondingsystems; geometry of
·the molecules in terms ofWalshdiagrams; isolobal fragments; reaction-mechanism ofthe main group
elements;differentaspectsofmaterialscience;PSPET-Wade'srule,Jemmi'srule;chemistryofboranes
andcarboranes; metalclustersandcarbonylclusters;Zintleions;symmetryelementsand pointgroups;
fullerenes; intercalationcompoundsofgraphite;bandtheoryofsolids- bandsplittingandbandbending;
electrical and magnetic properties ofsolids; piezoelectric solids; organic metals and organic semi
conductors; superconductivity; supra~olecularchemistry; aqueouschemistry ofamino acids; surface
viii Fundamental Concepts of Inorganic Chemistry
acids and solid acids; agostic interaction; ionic equilibria and related numerical problems; inorganic
photochemistry;lithiumbattery;fuelcells;solarcells;EMFdiagrams- Frostdiagram,Pourbaixdiagram;
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Tafel equation; stability field of water; chemistry of explosives; electroanalytical techniques
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polarography,coulometry,ampereometry,LSV, CV,polarography;chemicalclockreC\cationsandoscilla
ting chemical reactions. r
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In preparing the revised manuscript, I have freely consulted the books and reviews ofdifferent
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authors and I have borrowed their ideas whenever it has been required. Ilam extremely grateful and
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indebted to these authors. In fact, I have picked up the flowers from these gardens to prepare the
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garland to worship the goddess oflearning.
The golden period ofmy student life at Ramakrishna MissioneResidential College, Narendrapur,
gives the foundation ofmy career. There I got a gifted teacherh, Prof. AV Saha whose teaching in the
subject is still remaining vibrant in my memory and his tecaching is reflected at many places.ofthis
book. l
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TheauthoristhankfultoProf.KLSebastian,IPC,IISc,Bangalore;Prof. SBasu,BurdwanUniversity;
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Prof. GN Mukherjee, Sir Rashbehari Ghose, Professor ofChemistry; Dr A Sen, Ramakrishna Mission
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Centenary College, Rahara, 24 Parganas; Dr MN Bishnu, City College, Kolkata; Prof. RN Mukherjee,
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lIT, Kanpur; Dr SP Banerjee, Retired Pro/fessor, Vivekananda Mahavidyalaya, Burdwan; Dr S Roy
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Chowdhury, Dinabandhu Andrews College, Garia, Kolkata; Prof. K Dey, Kalyani University; Prof. A
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Sarkar, Kalyani University; Dr. GMukherjee, KalnaCollege, Burdwan; DrN' Koley, Retired Professor,
Raghunathpur College, Purulia; Prof. B Pathak, Retired Professor, Presidency College, Kolkata; Dr B
.
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Saha,BurdwanUniversity;DrHKarak,StPaul'sCollege,Kolkata,fortheirencouragementandsuggestion.

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Iam thankful to all mycolleagues for extendingtheirmoral support. Iam speciallythankful to my
colleague DrM Seikh forr discussion on many topics and procuring some reference materials.
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I ~m extremely grateful to Mr SK Jain, Managing Director, CBS Publishers and Distributors,
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NewDelhiforhiscontinuedsupport. I amalsothankfultoMrYNArjuna,SeniorDirector(Publishing,

Editorial and Publicity)and the staffinvolved in DTP for takingthe troubles in processingthe revised
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manuscript.
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Iamithankful to my PhDstudents, DrM Islamand Sri RBayenfortheircooperation. Iam indebted
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tomyCfamilymembersDr (Mrs)MahuaDas(wife),AnkitaDas(elderdaughter)andUditaDas(younger
daughter) for their moral support without which it would have been impossible to do this task.
Despite my best efforts, some mistakes and misconceptions might have crept in and forthese incon
veniences, I begto be pardoned. Suggestions and criticisms are always welcome from the readers.
Santiniketan Asim K. Das
Preface to the First Edyition
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- "No great work can be achieved by humbug. It is through love, apassionfor truth; and
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tremendous energy, thatallundertakingsareaccomplished." y
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:-"Iholdevery man a traitor who, having been educatedat their expensepay not the least
heedto them. " SwamiVivekananda
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As a studentand alsoas ateacher, theauthorhas experiencedthat forasystematicand comprehensive
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coverageofthepresentsubject,oneisforcedtoconsultvariousbooksondifferentdisciplinestocollect
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the reading materials. Consequently, the students are speciallyconstrained. Keepingthis idea in mind,
it has been attempted here to present a complete texetbook on the subject. In a logical sequence, the
book deals extensively with different aspects shuch as atomic structure (both classical and wave
mechanical) and atomic spectra, fundamentalstofquantum mechanics and wave mechanics, nuclear
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chemistry and radiation chemistry, differenet theories ofvalence for~es and chemical forces including
band and Blochtheoryofsolids,solid-stmatechemistry,acidsandbases,nonaqueoussolventsandredox
potentials. It also covers the different aspects of materials science which is emerging with a great
.
promise. Thus the present book ctovers the curricula followed by most ofthe Indian Universities and

Institutes at the SSc and MSc levels. It also aims to help the students preparing for competitive
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examinations like NET, GATE, SLET, etc. Adequate stress on the basic theories and concepts has
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beengiveneverywheretoerationalisethepresentation.Theideashavebeenveryoftenillustratedthrough
solution ofrelated nHumerical problems. Each chapter is ended with various types ofquestions and
problems to afford an opportunity to the students for self-evaluation.

In writing akbookofthis nature, one accumulates indebtednessto the previous authors ofdifferent
books. The cbooks which have been consulted are listed separately and gratefully acknowledged.
Thelaiuthor expresses his deep sense ofgratitude to DrAV Saha, a gifted teacher, from whom the
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author had started to learn and understand the subject in his student life in Ramakrishna Mission
Residential College, Narendrapur, for writingthe foreword. The author's association for a fairly long
period with the said Institute was highly fruitful in shaping the present ideas and the author must
express his indebtednessto histeachersandthe authoritiesofthe Institute. Theauthor isgratefultohis
wife, Dr M Das for various types ofhelp, assistance and cooperation.