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83% found this document useful (6 votes)
10K views834 pagesSelected Topics in Inorganic Madan Tuli @EngineeringEntrance
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Priyasu GuinCopyright
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SELECTED TOPICS -
IN
-- INORGANIC CHEMISTRY
[For B.Sc. (Hons.) and M.Sc. students]
WAHID U. MALIK ?1.D., D.Sc. GD. Tuli M.Sc., PhD.
Vice Chancellor Formerly Principal, Shyam Lal College
University of Kashmir Delhi University
SRINAGAR DELHI
R.D. MADAN M.Sc, Ph.D.
Deptt. of Chemistry
N.RE.C. College
KHURJA
Dear Students, :
Beware of fake/pirated editions. Many of our best selling titles have been
unlawfully printed by unscrupulous persons. Your sincere effort in this direction
may stop piracy and save intellectuals’ rights. 7
Forthe genuine book check the 3-D hologram which gives a rainbow effect. Preface to the Seventh Edition
In this edition the style of the presentation and arrangement of differ-
ent topics of sixth edition has been kept unchanged.
Main Features:
Main features of this new edition are:
© In this edition a new chapter entitled as “Electrode Potential and
Their Applications” (Chapter 22) has been added at the end of the
book. This chapter has been introduced by many Indian Universi-
ties in the syllabus of their B.Sc. (Honours) Course. The study of
this chapter is very important since the knowledge of electrode
potentials has been used to predict whether a given redox reaction
will take place in the forward direction or not.
© InChapter 22 a large number of numerical problems, along with
their solution, has also been given. Solving these problems involves
the use and application of various concepts studied in this chapter.
© The printing mistakes noted so far have been corrected.
Acknowledgement:
‘We express our sincere thanks to our students and fellow-teachers
who have been sending us their valuable suggestions for the improvement of
the book. We are extremely grateful to our respected Managing Director,
Shri Ravindra Kumar Gupta, Shri R.S. Saxena (Advisor), Shri Navin Joshi,
General Manager (Sales & Marketing), and Shri Dharmendra Jha (Asstt.;
Editor), S. Chand & Company Ltd. for the valuable and active cooperation
they have extended during the publication of this new edition. .
Our thanks are also due to Shri Virender Singh, DTP operator who has
taken pains in composing and designing the book according to our instruc-
tions and to our complete satisfaction. He has thorough knowledge of com-
posing chemistry books.
A Request:
‘We humbly request our students and chemistry teachers to send us their
constructive criticism and suggestions which we shall be using in the publi-
cation of the next edition.
Delhi Authors
June, 2001 . Preface to the First Edition
During the last few years, the Boards of Studies in Chemistry.
of the various universities in Indja havé been trying to overhaul and
mndernise. the syllabi at the under-graduate and post-graduate level.
There has accordingly been a distinct.e¥ange in approach and con-
teut with the result that a shortage of sunable texts written on these
dines was being keenly felt,, The authors seek justification in present~
ing the present voreme in the sincere, attempts that they have made
fo fill up the gap.
Considerable thought has been given to the selection orqopits
for-discussion. As the bvok’has been wristen primarily for the us¢.of
B.Sc, (Hons:) aod M.Sc, ‘students, most of the topics deal with the
theoretical sépecrs of Inorganic Chemistry, Great care has been taken
to elucidate ee fu entals and the approach to discussion is
modern thfoughoyl. Particular sention-may be le in this connec-
ston of the Chapters on Structure of the Atom, Chemical ‘bonding,
{nner Tragsistion elements and Coordination Chemistry.
A speciatfeatite of the book is that the text has been iflus-
trated witb g large number of line diagrams and the data presented
in shie-forni of numerous tables for reference and comparison.
In the preparation of the text, standard works and reviews vy
fesbsmned authors have been freely. consulted and. the references
Bree chapterewise at the end of the book will be found useful by
ose who wish to make a more detailed study of the topics
distussed.
. The authors ‘Wish to thank all those who letped in the pre-
patation.of the text and illustrations. Since drawbacks anid better
methods of wagion are always there, suggestions . ‘for iasptoye- ~-
ment and ‘will be gratefully received and acknowledged.
Novimber- 20, 1975." Auruors ‘Contents
Chapter
List of Abbreviations of Chemicals, Ligands,
Radicals, etc.
Miscellaneevs Abbreviations and Important Relitions
given chapter-wise
Values of some Physical Constants a
Energy Corversion Factors -
Length Conversion Fac-ors
Numerical prefixes
Prefixes for naming multiples and sub-muttiples of
units
Greak Alphabets
‘Structure of the Atom
(Quantum Mechanical and Wave-Mechanical Approach)
Plank’s quantum theory of radiation and Einstein's extension
—1; The hydrogen spectrum—1; Bohr’s atomic model ~ quantum
mechanical concept-3; Bohr's theory of hydrogen atom—5;
Electronic transition and origin of the spectral lines of hydrogen
atom—10; Bohr-Sommerfeld’s atomic model—14: Quantum
numers—15; Pauli’s exclusion principle—18; Russel-Saunder’s
or L S coupling scheme and determination of the ground state
terms of free atoms or ions—21; Wave mechanical concept of
the atoni—24; Heisenberg's uncertainty principle—26:
Uncerjainty principle and Bohr's theory — Probability and charge
cloud concept—26; Schrodinger wave equation—28; Probability
distribution curves—33; Energy level diagrams—-37; Rules for
filling the orbitals with clectsons and electronic configuration of
elements—38; Hund’s rule of maximum multiplicity—40;
Ground state electronic configuration of elements—42 (Table
1.6); References — 44.
Extended or Long Form of Periodic Table
Mendeleef’s delcef periodic law and Mendeleef’s periodic tatle—
45; Moders, periodic law—45; Extended or long form of peri-
odic table — 45; Electronic configuration of the elements and
the build-up of the periodic table—49; Types of elements on the
basis of their electronic configurations—51; Reférences—55.
Pages
(xiii)
(xxi)
(xxxii)
(xxxiii)
(xxxivy
(xxxiv)
(xxxiv)
(xxxyv)
1—4
45—55 wi)
Chapter
3. Periodic Properties
Atomic and Ionic radii—S6; Determination of covalent
radii—61 ;\ lonic_radii—61; Determination’ of ionic
radii—62 ; Crystal coordination number—64; Radius
ratio—64;. Factors {influencing the magnitud of ionic
radii—66 ; Periodic variations of atomic and ionic radii—
66 ; Ionisation potential or’ ionisation energy—69 ;
Factors affecting the magnitude of ionisation potential
and its periodic variations—71 ; Applications of the con-
cept. of ionisation \poteatial_ 74; Electron, afin oF
affinity enc ;.Factors influencing the i of
: elect
ical
Peric yariation ron
affinity—77 ; Experimental det tion of electron affi-
nity—79 ; Impact of electron_ affinity‘ ‘on chemical
behaviour—79 ; Electronegatiyity—79; Scales of electro-
negativity—79 ; Periodic variations of electronegativity—
84; Correlation of ionisation potential and electron
affinity with electronegativity—85 ; Relation between the
oxidation state of the element and its electronegativity—
853 Applications of electronegativity concept—86 ; Refe-
rences—91.
4. Chemical Bonding
Tonic or electrovalent bond—92 ; Variable electrovalency—
94; Inert pair effect—96 ; Lattice energy of ionic
crystals—98 ; lon deformation or polarisation of ions—
106; Fajans’s rules—107; Covalent bond—110 ; Coor-
dinate or dative bond—116 ;-Hydrogen bond—117; Odd
clectron bonds—127 ; Bonding in rnetals-metallic bond—
130; References—141.
5. Natare of-Covalent Bond and Shapes of Molecules
Nature of covalent bond—143; Valance Bond Theory
(VBT)—143; Concept of resonance—145; Molecular
Orbital Theory (MoT) 154 3,Molecular orbital configura-
tion of some. nuclear diatomic specics—159 ; Bond
ordé or bond mnltiplicity—461; “Molecular orbital
configuration of some hetro-nuclear diatomic species—
166; Shapes of covalent molecutes—171 ; ‘Valence Shell
Electron Pair Repulsion (VSEPR) Theory—171 ; Hybri-
disation of atomic orbitals—174 ; hy lisation
and shapes of spme common molegules with o-or o+n-
bonds—176 ;\ Delocalised or extended -MO’s—194:
Electron deficient ¢ompounds—1I96; Structure and bond-
ing of diborane (BzH_)—196 5, References—199.
6. Modern Concepts of Acids and Bases
Arrhenius concept—The water ion system—200 ; Brons-
ted-Lowry theory—The proton:donor-acceptor sys-
‘tem—201 ¢ General theory of solvent system—209; The
Lewis gancent The electron-donor-concept system—
210 ; SHAB inte and stability of the complex A : B—
215; fhe. Usano' pt—The positive —weégative
system—216 : References—217 4
Pages
-- 56-91
92142
143199
. 200—217 Qwr&
(vii) Y
Chapter - Pages
7. Non-aqueous Solvents eee 218—249
Classification of solevents—218 ; General properties of
ionising solvents—220 ; Chemical reactions—222 ; Liquid
ammonia as solvent—224; Liquid sulphur dioxide as.
solvent—235 ; Liquid dinitrogen tetra oxide {tig 120—
240; Liquid hydrogen fluoride ie HF)—242; Liquid
bydrogen sulphide (lig. H2S)—244; Liquid hydrogen
cyanide (lig. HCN) 2445 Acetic acid (CHyCOOH,—246 ;
Piguid bromine trifluoride (/ig. BrFs)—247 ; Oxyhalides—
; References—249,
8. Transition Elements (d-Block Elements) vee, 250—273
Definition and electronic configurations of atoms—250 ;
General characteristics of transition elements—2§2 ;
Comparison of the elements of first transition series (3¢-
series) with those of second (4d-series) and third (Sd
series) series—272; References—273-
9. Lanthanides or Rare Earths (4f Block Elements) «- 274—310
Definition—274 ; Position of lanthanides in the periodic
table—275 ; Occurence of lanthanides—275 ; Extraction
of Janthanides from monazite mineral—278 ; ration
of individual rare-earth elements—280; Preparation of
the metals—288 ; General properties of lanthanides—289 ;
Atomic and ionic radii—lanthanide contraction—295 ;
Cause of lanthanide contraction—297 ; Consequences of
lanthanide contraction—298 ; Uses of lanthanides and
their compounds—307 ; Comparison between d-and f-
block elements (particularly between 3d-and 4f-block ele-
ments)—308; References—310,
10. Actinides (5f-block elements) we 311-331
Definition—311 ; Position of actinidesin the periodic
table—311 ; Identification and nuclear synthesis of trans-
uranium elements—314 ; Separation of actinide elements—
314; General characteristics of actinides and their com-
parison with lanthanides—318 ; References—331,
11. Basic Concepts of Co-ordination Chemistry we 332374
Definition of some terms—332 ; Classification of ligands—
334; Chelation—340; Coordination number and stereo-
chemistry of complexes—342; Nomenclature of coordi-.
nation compounds—345 ; Detection and structure deter-
mination of complexes—352 ;.Polynuclear or bridged com-
plexes—355 ; Inner-metailic complexe*—363; Werner's
Coordination Theory—365 3 Sidgwick’s electronic inter-”
Bygtation of coordination—369 ; Sidgwic’’s Concept of
ren
fective Atomic Number—EAN concept—370; Refe-
ces—374,
12, Nature of Metal-Ligand Bonding in Complexes... 375451
Valence Bond Theory \VBT)_ 375 3 Formation of Octa-
Redral Complexes on the basis of VBT—378 ; Outer-
orbital and Inner-orbital Octeahedral Complexes+382 ;
Formation of tetrahedral and square planar complexes
on the basis of VBT—386 ; Limitation of VBT—390..
Crystal Field Theory (CFT)—393 ; Important features of
of crystal field theory- 391 ; Crystal field splitting.of or.’ (viii)
Chapter
15.
bitals in octahedral, tetragonal, square planar and tetrahedral com-
plexes—392, 395; Factors influencing the magnitude of
4,—399; Strong (er) and weak (er) ligands and Spectrochemical se-
ries — 401; Distribution of d-electrons in #,, and e, orbitals in octa-
hedral complexes—403; Number of unpaired electrons (n) and high
spin (HS) and low spin (LS) Complexes—405; Distribution of d-
electrons in f,g and e, orbitals in tetrahedral complexes—407; Some
applications of CFI—408; Colour of the transition metal .com-
plexes—408; Number of unpi clectrons and magnetic properties
of octahedral complexes—4 11; Distortion of octahedral, complexes
and Jahn-Teller Theorem—414; Cause of distortion with some ex-
amples—416; Crystal Field Stabilisation Energies (CFSE’s}—422;
Uses of CFSE values—425; Limitations of CFT—429; Experimen-
tal evidence for metal-ligand covafent bonding in complexes—430.
Ligand Field Theory (LFTY6r Molecular Orbital Theory (MOT)}—
430; MOT as applied to octahedral complexes—431; x-bonding on
the Values’ of Ay—445; Relation between.
-n-bonding ability of ligands and spectro-chemical series—447; Effect
of charge on the central metal in on the magnitude ‘of Aj—447;
Comparison of different theories —448, References—450.
Pages
Vv
Isomerism Among Inorganic Complexes we 452—484
Structural isomerism—452; Stereoisomerism or space isomerism—
456; Geomertical isomerism in 4- and 6- coordination compounds—
456; To distinguish between cis and trans-isomers—467, Optical
or mirror-image isomerism—470; Conditions for a molecule to
show optical isomerism—471, Optical isomerism in 4- and 6-
coordination compounds—47 1, Resolution of recemic mixtures—
482: References—484.
Stability of Campiexes in Aqueous Solstion ”~
Definition of stability—485; Stepwise formation of complexes,
stepwise formation constants and overall formation constants—
‘ASG, Kinetic V's thermodynamic ‘stability—488; Labile and insert
octahedral complexes according to VBT—490; Labile and inert
octahedral complexes according to CFT 491; Other factors affecting
the Lability of a complex—44; Factors affecting the stability of
complexes—496; Natural order (also called Irving-William order) ~
of stability —498; Experimental determination of stability constant
and composition of a complex—505; References—509.
Ligand Substitution-Reactions in Octahedral Complexes
Transition state or activated complex—510; Substrate—5S
Attacking reagents; electrophilic reagents—512, nucleophilic
reagents 2.2; Types of: substitution reactions; nucleophilic ligand
substitutiun (Sy) reactions—513; electronhilic or metal substitution
(S_) reacsions~-513; Sy1 or dissociation meckanism—513; SN?
or.association or displacement mechanism—514; Labile and inert
complexes—516; Hydrolysis reactions—516; Aquation or acid
hydroly.is reactions of six co-ordinated Co (Hl) ammine:
compleacs—517; Base hydrolysis reactions of
485—S09
£10526 (a)
Chapter
six co-ordinated Co (HY ammine complexes—S21 ; Ana-
tion reactions—$24 ; Substitution reactions without break-
ing metal-ligand bond—S525 ; References—526,
16. Ligand Substitution Reactions in Square-plazar
Complexes wee
The trans-effect—527 ;_ Trans-effect series—S$28 ; Uses
of trans-effect—529 ; Theories of trans-effect: electro-
static polarisation theory—533 ; =-bonding theory—535 ;
lechanism of substitution reactions—537 ; Factors
affecting the rates of substitution reactions in square
planar complexes—539 ; * Cis-trans isomerisation in planar
complexes—S42 ; References—S42.
17 Electron-transfer (or oxidation-reduction) Reactions
in Coordination Compounds ae
Mechanism of one-electron transfer reactions: Atom
{or group)—transfer or inner-sphere mechanism—543 ;
Direct electron trans-sphere mechanism—5, 6; Factors
affecting the rates of direct electron-transfer reactions—
548; Two electron transfer reactions—349 ; Comple-
mentary electron-transfer reactions—$49 ; Mechanism—
549; References—550.
18. Electron-deficient Compounds : Boranes
What are electron-deficient compounds ?—551; Examples
of electron-deficient compounds 551; Hydrides of boron:
boranes—55i ; General methods of preparation of boranes
552; General properties of boranes—553 ;| Diborane
(BzHe)—5S5 ; Types of bonds found in higher boranes
—562; Structure and bonding in higher boranes—563.
19, Metallic Carbonyls and metallic nitrosyls
Metallic carbonyls: General methods of preparation—$67 :
General properties—569 ; Structure and nature of M-CO
bonding in carbonyls—S71 ; Effective atomic number (EAN)
rule as applied to metallic carbonyls—S75 ; 18 electron
tule as applied to metallic Carbonyls—577; Sone Carboniys
—578;_ Metallic nitrosyls—591 ; Some metallic nitrosyis
592; Effective atomic (EAN) rule as applied to metallic
nitrosyls—S95.
20. Basic properties of iodine, interbalogen compounds,
polyhalides and pseudohalogens
Basic properties of iodine—596 ; Interhalogen compounds
599; Some important interhalogen compounds—604 ;
Polyhalide ions and polyhalides—616, Pseudohalide ions,
pseudohalides and pseudohalogens—624 ; Cynogen (CN):
—628 ; Thiocyanogen, (SCN)s—631 ; ocyanogen
(SeCN)-~633 ; Oxycyanogen, (OCN),—-633 ; Azidocarbon
disulphide, (SCSN3jz—634.
ion and its Effects on the Living World i
* Paine aad pollutants- 635; Types of pollutants- £35, Air
pollution-636, Green house effect- 639; Smog- 649; ater
pollution- 650; Soil pollution-653; Radioactive pollution- 653;
Industrial poliution- 654; Noise pollution-657.
Pages
527—S42
543—550
551—366
567—595
596—634
635—657 @)
Chapter
22.
Electrode Potentials and their Applications oe
Electrochemical Cell—658; What is electrode potential of an
electrode (E, ge OF E)? — 660; Oxidation or reduction elec-
trode potentials (E,, or E,.,) — 661; What is standard electrode
potential (E°)? — 661; Positive and negative values of standard
electrode potentials (E° values) of electrodes— 661; Metal-
metal ion electrodes— 662; Gas-gas ion electrodes — 662; Hy-
drogen electrode —662; Chlorine electrode— 663; Oxygen elec-
trode — 663; Metal-metal insoluble salt-anion electrodes— 663;
Silver -silver chloride electrode — 663; Calomel electrode—
664; Antimony-antimony trioxide electrode— 664; Mercury-
mercuric oxide electrode—664; Oxidation-reduction electrodes—
664; To construct a galvanic cell for a given redox reaction —
665: To construct a galvanic cell , if two electrodes with their E°
values are'given — 669; To write cell reaction (redox reaction)
for a given cell—669; EMF or e.m,f. (E.,,,) of a given galvanic cell
— 673; Solved examples — 674; To calculate standard e.m,f. (or
Econ reaction) Of @ given redox reaction, if E°values of two elec-
trodes or half reactions are given—674; Solved examples — 675;
To determine e.m.f. of a redox reaction (cell reaction) formed by
combining two elelctrodes—678; Summary of the main points
about a galvanic (electro chemical ) cell—678; Electrochemical *
series—681; Applications of E° values—684; To determine the
increasing or decreasing order of oxidising/reducing power of
elements/ions, if their E°values are given —684; To explain why
among alkali metals, lithium in aqueous solution is the strongest
reducing agent—687; Reducing power of alkaline earth metals in
aqueous solution—687; To determine the relative order of
oxidising power of halogens (X,) and reducing power of halide
ions (X°) in aqueous solution — 688; Solved examples— 689;
To determine the conditions for the feasibility of metal-metal
displacement reactions (Redox reactions) — 696; Summary—
697; Solved examples— 699; Metal-metal displacement reac-
tions in the electrochemical series — 704; To determine the
conditions of the feasibility of halogen-halogen displacement
reactions or to determine the conditions of the feasibility of a
redox reaction involding oxidation of a halide by another halogen
—706; Solved examples — 709; Halogen-halogen displacement
reactions in electrochemical series —-711; To determine condi-
tion s for feasibility of metal-hydroger displacement reactions
(Redox reactions) —712; Production of H, gas by the action of
transition metals on HCI : Reducing property of transition met-
als— 714; Solved examples —-715; Metal-hydrogen displace-
ment reactions in electrochemical series— 716; Solved examples
— 716; Electropositive and electronegative character of elements
— 721; Reactivity of metals — 723; Rectivity of halogens —
723; To predict the relative stability of different oxidation states
Pages
658—784 Gi)
Chapter
of an element in aqueous soltuion—724; Solved examples—
724; Nernst equation—725; To calculate the electrode potential
of a given electrode with the help of Nernst equation—725;
Relation between E°,..ag> Ey sagas (K,.) 727; Solved
examples — 728; To calculate the value of electorode potential
of hydrogen electrode : To calculate the value of pH of an acid
solution — 734; To calculate emf (E,,,) ofan electro-chemical
cell with the help of Nernst equation — 735; To calculate e.m,f-
ofa given redox reaction taking place at 298K in electro-chemical
cell—736; Solved examples — 736; Concentration cells— 747;
To calculate e.m/. of a given concentration cell at 298K— 748;
Solved examples— 748; Equilibrium constant of redox reaction
— 752; To calculate the equilibrium constatn «.) of a given
redox reaction at equilibrium by Nemst equation—752; Solved
examples — 753; Standard free energy change (AG°}— 757; To
calculate standard free energy (AG°) fora given electrode or for
its half-cell reaction (electrode reaction}— 758; Solved examples
— 758; Relation between AG and K, — 761; Solved examples
— 762; EMF diagram — 763; To calculate the value of E° of a
given half-cell reaction from the values of E° of other given half-
cell reactions — 764; Solved examples — 765; Electrolysis —
715; Electrolysis of some electrolytes — TIT, Some commercial
cells/batteries— 783; Primary cells — 784; Mercury cell —
785; Secondary cells — 786; Lead acid storage battery — 786;
Recharging of the discharged battery/cell— 787; Nickel-cad-
mium (Nicad) cell — 788; Fuel cells - 788; Hydroge-oxygen
(H,/O,) fuel cell — 789; Propane-oxygen (C,H,/O,) fuel cell—
789; Methyl! alcohol-oxygen (CH,OH/O,) fuel cell — 790; Im-
portant questions — 790
Subject Index we
Pages
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iuogd
pular
SIP oua[AyIaAqroourmy) spy,
uo!
OJBUIXO. JO UO! OJEUIoUINbAxo1pAY-g
ad
ud
uayd-0 10 uayd
ud
uajuad
_(arourcg) 10 -(upxo} ( xix )
‘CHN—HO—'HO—HN—"HO—"HO)HN
Jo
*HN—CHO)—HN
—HHO)-UN—*HO)—-HN—*HO)—"HN
(S
cane
*(OWSV"HO'HO"HO)d
€UNCHO—"HO—"N)
*(qasv"H°O-O)sV
x
N'H'Q 40 D
7
ourmeyusdous|Aqyoes391,
ouiprskdis}-,,2 42 ‘7%
ouryd
-soyd (jAdosdoutssejAqyounrp-¢)-s74
dnoss [Are Jo |AXIV
auisiu(|Auoydoutsse]Auaqdip-o) s14y
ouIpikg
wapiyay
day 30 Aduay
dvi
uarpry
svd oes ss ee
|
“9 Ig ‘TD ussoreEy x
‘HN’SO“HN vamory], m
- surydsond(|AuaqdormyAqyout-o)-s45 ash
‘SHN*HO'HOHN'HD)
Jo"
7 "EN—“C*HO)—BN—4HD)—HN—'HO)—-N' suremeNo;o02]AQIOET, ae
x
eurmre({Aq}ourure uaa
N‘CHO—'HO—HND O-*ME 30. auroreApoLjoururenty,
‘AN ‘HN auedosdourmenp-¢ “| us
"HO—'HO-"HO
€ z I
O'H"D wemnjoupAqenoy, aHL
"AN—(*HO)O—CtHO)IO—N'H ourarerpons/éqie-AqiomENnoy, uoousosja} (xxi)
(B) Miscellaneous Abbreviations aud important Relations
These are given chapter-wise as follows :
v (Nu,
Chapter 1. Structure of the Atom
Plank’s constant (== 6-62 x 10-*7 ergs)
Wave number :
herz, sec"?
Frequency (cm? or Hz)
Velocity of light
4 (Lambda, ®t) Wave length
v
Ez
Ru
Ac orA
“a mer gy
tay OF dy
, or d,
Wave number
Energy
Rydberg constant or Rydberg number for hydro-
gen (= 109,679 cm") -
Angstrom unit (1 A° = 10°%¢m)
picometer
nanometer
Radius of the ath orbit of hydrogen atom
Radius of the Jst orbit (called Bohr radius)
Energy of an electron revolving in the nth orbit
Energy of an electron revolving in the Ist orbit.
Principal quantum number
Azimuthal quantum umber (Also called orbital
angular momentum quantune number)
Magnetic quantum. nuinbet (m also denotes the
mass.of an electron)
Spin quantum number (Also called spin angular
momentum quantum ’
Resultant spin angular momentum quantum
number
Resultant orbital angular momentym mg
number
Resultant inner quantum number (also called
angular momentum quantum number)
Aset_ of orbitals consisting of dy, and dyy
atomic orbitals.) (These are cal non-axial
orbitals)
A set of orbitals consisting of d,s_ys and djs
atomic orbitals. (These are called exial orbitals). (xxii)
(Relations : . 7
(1) Einstein's mass-energy relationship : E = me*
(2) Plank’s equation : E = hv
(3) Rydberg’s formula: vy = + = Ru( see ) cem-?
(4) Angular momentum of an electron, mvr = 7 Z
This equation represents the principle of quphtisation of angular
momentum of an electron with mass m and revolving in an orbit
of radius ¢ with velocity »
(5) Radius of nth orbit, r, = we
(6) Radius of the first orbit of
hydrogen atom (called Bohr radius), ry
(or riz or ag) = 0°53 A®
(7) rq and ry are related as :
Tn = (1X n%) A? = (053 Xn) A?
3.
(8) Centrifugal force = + =
(9) Centripetal force = -£
(10) Energy of an electron revolving in the nth orbit,
(12) ‘Energy of an electron revolving in the first orbit,
E, = +21-79x 10-8 ergs/atom
== —13-6 cV/atom
= —313-6 kcal/mole
(13) E, and Ey are related as .
z= fxd eV/atom
—13-6x i eVjatom
7
2n%e4m Inge
(4) (Ra) = i = 109,679,cm-?
; 2ntetm 11
15) Y= lak ae
> _l ae (gen)
a6) OR Be Mink nyt ( xxiii )
— 1 it
or v -4+- RAs)
— 4 11
or 7 =f = 109,679 Fes emt
(17) Principal quantum number, 1 =
Azimuthal quantum number, / =
Magnetic quantum nuniber, m = 0, +1, +2, ..
Spin quantum number, s = +4, —+
(18) Multiplicity = 2841 = 2x5 +1—= "+1
(19) - Ground state term of an atom or an ion
Multiplicity
el= 2S+I1Ly = stLy ~*
(20) Heisenberg’s uncertainty relation: Axx Ap >t
: or AEX AT >t
(21) Schrodinger wave equation
TY OY OY A E-PE) ¥ = 0
7 a dd
Laplacian operator, V7 = ate +or
Schrodinger wave equation for hydrogen atom +
ay ay aY 8n'm/ .
Orie tare (EFS) Yao
(22) Order of energy of various atomic’ orbitals for poly-
electron atoms (Aufbue Principle) .
_————Energy increasing —————_—————_—>
ls < 2s < tp <3s< < 3p <'4s< 3d< 4p < 5s < 4d
< 5p < 65 < 4f < Sd < Op < 78 < Sf < Sd < 7s < 8s.
(23) Order of filling of atomic orbitals with electrons :
_—_--—--—Orbitals being filled -——— ~—-———————-—>
1s? (He,), 2s? (Be,), 2p* (Nea), 35% (MBia)» 3p* (Aria), 45% (Caso),
3d¥ (Zngo), 4p* (Krze)s 55% (Sta)s 402° (Cugels Sp* (Xesa)» 75* (Basa),
Sd? (Las), 4f% (Lun), Sd? 010 (Hifze to HB so)s-e+-0e :
Chapter 2. Extended or Long Form of Periodic Table
n Number of the period
TE’s Transitional Elements
Zz Atomic number. | « ( xxiv )
Chapter 3. Periodic Properties
Abbreviations :
TA Radius of an atom A (called atomic radius)
re Radius of a cation, ct (called cationic radius)
tT. Radius of an anjgn, a” (called anionic radius)
ta Approximately
dae Toternuclear distance between atoms A and B (called bond
length) .
XA Electronegativity of atom A
(Zey)** Effective nuclear charge Acting on the cation, c+
GN. Coordination Numbef
R Radius ratio
hor
(IP), Tonisation potential (or ionisation energy) of atom A
E, or
(EA), Electron affinity of atoms A
Eas Energy of A—B bond
Aas Tonic-resonance energy of A—B bond
Keal Kilo calories
ev Electron volts
MeV Million electron volts
KJ mol-? Kilojoules per mole
ecp Cubic close packed 7
hep Hexaganal close packed
Relations :
Q) daa = ratra et Ora
(2, Schomaker and Stevenson equation :
dnp = TrA+1a+0°09 (Xa—2p)
(3) Radius ratio, Ry = ret
(4) Pauling’s scale of electronegativity :
xannn = 026 Exa—a/ Ex aXxEon AxEn
(5) % ionic character in A—B bond = 16 (xa—xp)4+3'5
te
(Xa—n)* (xxv )
Chapter 4. Chemical Bonding
Abbreviations :
(U)mx Lattice energy (also called crystal energy) of MX crystal
n Born exponent
b " Repulsion coefficient
24,2. Charges carried by cations and anions respectively
A Mandelung constant
oust a potential (also called charge density) of cation,
(s) Solid state
(J) or (ig) Liquid state
(g) Gaseous state
( AH rex Heat of formation of MX crystal
(Alu ),, Heat of sublimation of one mole of solid M
(Ae cg Heat of dissociation of one mole of X,.
Relations :
(1) Born-Lande equation: U = MAet. ( 1-})
(2) Born-Haber cycle equation for MX crystal :
(Are )oe = (AH oe )yp HH (AHeu),
+ (IP Ing +(EA)x +(U)rax
(3) Tonic potential (or charge density), ¢= Rae opsation
Chapter 5. -Nature of Covalent Bond and Shapes of Molecules,
Abbreviations :
VBT Valence Bond Theory
MOT Molecular Orbitat Theory
LCAO Linear Combination of Atomic Orbitals
AO Atomic Orbital
MO Molecular Orbital
o’-MO Sigma t=ndig molecular orbital
o*-MO Sigma‘ antibonding molecular orbital
-MO pi bonding molecular orhi?al
x*-MU pl ant-ponding morecular orbital
VSEPR Valence Shel Electron Pair Repulsion xxvi )
bp Bonaing pair of electrons
Ip Lone pair of electrons .
BO. Bond Order (Also called bond multiplicity)
mp Number of electrons in bonding molecular orbitals
nN Number of electrons in antibonding molecular orbitals
(2c—2e) tond Two-cenire-two-electron bond
(3c—2e) bond Three-centre-two-electron bond
Relations :
(1) Bond order, B.O. = $ (t—Ma)
(2) Order of energy of molecular orbitals of a homo-
nuclear diatomic molecule (A; type molecule) :
-—_—__—_ - —. ———Energy increasing: i —
On, < Oy,* < ai? = Ty? < GP < ryt (ip—bp) > (bp—hpy
Chapter 6. Modern Concepts of Acids and Bases
(1) SHAB Principle of Soft and Hard Acids and Bases
(2) Conjugate acid-base pair :
Conjugate acid-base pair
Acid, + Base, = Acid, + Base,
(e.g. HCl) (eg Heo: (H;O*) (Cl)
Conjugate acid-base pair’
(3) A salt containing (hard acid+ hard base) or (soft acid+ soft. base)
1s.nore Stable than that containing (hard acid + soft-buse) or (soft
acid hard base)
Chapter 8. Transition Elements (d-Blotk Elements)
Abbreviations
TE’s Transition elements
I Magnetic moment per unjt ore
B Total magnetic induction’ or thagnetic flux
H Strengtn of a magnetic field
P Magnetic permeability |
X (Chi, sr€) Voliune- susceptibility Xe
Xm
Xs
» (Mu; *)
Pert
B.M.
o
Reiations :
Q) +
Q)
(2)
@
(ss
(6)
(7)
(xxvii )
Gram, specific or weight suscepgyoiliiy
. Molar susceptibility
Paramagnetic susceptibility
Magnetit moment in Bohr magnetons
Effective magnetic moment
Bohr magneton (1 BM)
Curie’s or Weiss constant( = Net) %
Avogadro’s number
Boltzman constant
Absolute temperature *
Weiss constant
Spin multiplicity
Lande splitting factor’
Number of unpaired electrons
Resultant spin aggular momentum quantum number
Resultant orbitaf. angular momentum quantum
number
Resultant angular momentam quanium ‘number (also
called resultant inner quantury number) ~
Magnetié permeability, P = B/H
Volume susceptibility,..y = 1/H
Total magnetic induction,
~ Bs H+4rl
B I
or . Wom et
or P= 144nx%
Gram susceptibility, %, = Fa = density)
Molat susceptibility, -Am = %xM (M =.melecular
weight)
Paramagnedt eusceptibility,
Curie’s equation :
com: Ne
ty xT=C= “e-
: corr _-Natege
or it xT mh. !
or wn = fe. ty XT
B.M.
or Bary = 284 J tan xT BM.
48) _ Curie-Weiss equation :
corr
ly X(T-8) = C
Also parr = 2846/0" x(T—8)
B.M.
eh 27° 10°
9) 1B.M. 7 tanc = 9-27 10: * ergs/gauss
(10) S= np
(uy Spin multiplicity = 2541 = 2 x-541 = n+l
(12) Lande splitting factor,
i 14 LGEDtS(S4+ HL (L+1)
ae 25 +1)
(13) Ground state term of an atom or ion
= 2SHLy = HL,
. (14) (a) When the spin-orbit (LS) coupling of unpaired electrons
is strong as in case of tripositive ions of lanthanides (with
the exception of Sm*+ and Eu*+ ions), effective magnetic
moment, pes, is given by :
: Hooe = BE = B VJ (+1) BM.
(6) When spin-orbit (L—S) coupling is weak as in case of
some ions of the metals of first transition series, effective
magnetic moment. j,, is given by ;
bere = VEO-FI+48(S41) BM.
For the ions which have S ground state terms [e.z. Mn*+
(Sua), Fet¥ (*S5)), La** (Sq), Gd? (*Syq) and Lu** (S,)],
=.0 and Heyy *S given by:
Mery = psy = VL (L41)+4S (S+1) B.M.
= sie = VOXO+D+4S(S+1)
<1 = VISSTT =f ax ($41)
= V nF 2) BM.
: or spin only = / a8 S(S+1) BM, } (Spin-only. formula)
\ . =a Vn(n+1) BM. -Creix j
Chapter 10. Actinides (5/-block elements)
Molar susceptibility, Xm of an actinide ion is given by :
Xu = Net) Na
where N = Avogadro’s number, g = Lande splitting factor, B =
Bohr magneton, J = Total angular momentum of atom = | L+S|,
& = Boltzman constant, T =, Absolute temperature and « = Small,
temperature independent term due to second order Zeeman effect.
Chapter 11. Busic Concepts of Coordination Chemistry
CN. Coordination number (or ligancy of the central
metal cation)
TUPAC International Union of Pure,and Applied Chemistry
EAN concept Effective Atomic Number‘Goncépt (also called Nobile
Gas Rule) :
Chapter 12. Nature of Metal-Ligand Bonding in Complexes
Abbreviations :
vVBT Valence Bond Theory
CFT Crystal Field Theory
LFT Ligand Field Theory
MOT Molecular Orbital
ACFT Adjusted Crystal Field Theory
a Number of unpaired electrons
Herp Experimental value of magnetic’: moment
M+ Central] metal cation
L A monodentate ligand
Qo or Dq Energy difference between 2, and e, sets of orbitals
in octahedral complexes (A, or Dq is called octa-
a crystal field splitting ‘energy or orbital separa-
tion)
Energy difference between 1, and e sets of orbitals
in tetrahedral comolexes
nergy ditterence between the highest d,s_ys orbita:
and lowest dys, dys pair of orbitals is square planar
complexes
Resultant spin
Energy required ‘tc ‘pair two electrons in the same
‘orbital (called average or mean pairing energy)
High snin
‘Low spin
symmetrical
‘unsyminetrical
Crystal Field Stabilisation Energy
> BP
5
pice
é ( xx 5
Relations :
dQ) Splitting power of the following common ligands to
split the d-orbitals into t,, and e, sets increases from
left to right
TTT ——Splitting power increasing———————____,
I- < Br- < Cl’: ~SCN- ~N;- < (CoH5O) 2PS.- < Fo < (NH2)s,
CO < OH" < C0" ~ H,O < NCS” ~H- < NH,CH,CO,” <
NH, ~ C;H;N < en < SO,* < NH,OH < NO,- < o-phen <
< CHs” < CN-,CO.
This series is called spectro-chemical series or Fajans-Tsuchida.
series
(2) Resultant spin, S = x
@) 10 Da = Ao
(S) CESE for an ion having f,"e,? configuration
= [—0-4p+0°6 9) Ao
= [—4p-+ 69] Da
(5) Order of MO’s and AO’s of an octahedral complex
of a cation trom 3d-series
(@) When ihe ligands are strong(er)
+ Energy increasing—-——— ——— - ____-__,
6° < o,? = a,” = a, < Gy2_yoo= 022° < Bdey = 3dy, = 3dze <
O,a_ya® = 2" < G,* < og* = 0,* = ,*
(6) When the ligands are weaker)
—--——- — ~—Energy increasing ——————_________.__,
ay? = oF < a48_ ya” = G2 > < By = 3dy, = 3drz
=0,8_ys* = 8,2 * Ka> Ky dca... Ku.) > Ky
(a Bn and Ky, K, ...... K, are related-as :
Ba = KixKex ss. xKeaixK,
or 1oBse Ba = login Kit logig Kat ....-lOBi9 Kn 1 +]ogig Kn
(5) Natural order (also called Irving- William order) of
stability of the high-spin complexes of the ions
between Mn*+ and Zn: with a given ligand is as
follows : :
Mni+ -< Fett < Cot < Nitt < Cut < Zntt
o —RTinp= AG*=AH'—T .AS*( AU? is negative)
(7), Absorbance. A. of a complex = ¢ Jc (Beer’s Law) XXxii
Chapter 15. Ligand Subsiliution Reactions in Octahedral Complexes .
X.Y...
. Sy
Sz
Syt
Sy?
One
Reaction energy
Transition state or activated complex
Nucleophilic or ligand substitution reactions
Electrophilic or metal substitution reactions
Substitution (S) nucleophilic (N) uni-molecular or
first order (1) reactions (Also called dissociation
unimolecular reactions)
Substitution (S) nucleophilic (N) biziolecular or
second order (2) reactions (Also called association
or bimolecular displacement reacilonst
Conjugate base
Values of some physical constants
‘Bohr magnetek- (IBM)
= 9-27 x 10-*! engs/gauss
Planck’s constant (gas constant per molecule) (A),
. -= 66256 x 10°27 ergs-sec
Kyqberg’s constant for hydrogen (Ru)
= 109,679 cm-?
soltzman constant (A)
= 1:38 107% ergs/deg/mole
Universa! gas constant (R)
= 19872 cal/deg/mole
== 8-31434 Joule/deg/mole
Radius of :
Hydrogen atom (Bohr radius) (r; of rH OF a)
== 0°5297A°
= 0:529] x 16-* cm =
Proton == 10-* cm (calculated)
Electron = 10-33 cm (calculated)
Rest mass of :
neutron, 179 (m,) = = 1675 x 10°" kg
== 1-0087 amu
= 939°6 MeV
proton, 4p; or 7H, (7p)
r= 1-67 10-*7 kg
= 1:0073 amu
== 938°3 MeV (xsi)
electron, *e.,(m.) = 9:11 x 10-7 kg
w= $487 x 10-4 ama
= 0-511 Mev
Jretium nucleus, ‘He,
wa 40028 conn
Charge on: \
electron = 480298 x 10° esu
= 160210 x 10° coulombs
proton : = 160210 x 10° coulombs
Velocity of light in vacuum (c)
exe 2997225 x 10° cm/sec
Avogadro's number (N)
== 6-023 x 10" per g-mole or B-atom
= 6-023 x 10 per kg-molewr kg-afom
1 Atomic mass unit (amw)
=h = 146610 the
= 931 MeV
Energy of the electron revolving inthe Zot orbit (E.t
es 21-79 x10°M ergs atom
ae + 136.e¥/alom
— +336 ealymole,
pi{n) i a 34
Knorgy. Geavertta Factors
1 kcal/mole ea 380-00 'om™ (wave nriehber)
ea. OO4KS eV particle
x 6-9468 310°" ergsjmle
a= 4:1840 Idules;moie
1 em-? (wave.number)
mm. 2:8993.x 10° Tkcal/mole
= 1-299 x 10-4 eV /particle
= 1996 x.10-® ergs/mote
es 1 $63: Joulesitiote
1 cV/particle = 23. 460. keal/mpie
_ = 8065-7 cit \ Rakiv )
= 5-602 x 10-4 ergs/mole
== 1:602 x 10" Joules/mole
== 2390 x 10°! keal/mole
= 5.0348 x 1025 cm-2
= 6242 100 eV/particle
= 10-7 Joules/mole
1 Joule/mole = 0:239 kcal/mole
==00835 cm-1
= 6242 x 10!8 eV/particle
: =. 10" ergs/moie
1 kJ/mole = 83-54 cm?
} erg/mole
Lengs. Conversion Factors
1 angstrom aA ortA..
= 0-tem
“1 nanometer (1 sini = JOA = 10°? cm
1 picometer (1 pnt) = 10-%A* = 10° cm.
Numerical prefixes
(The prefixes in parentheses ‘are Tese used)
}-henti or semi ; -1—moio or. uni; 1}—sesqui; 2—Di or Bi
{bis) ; 3—tti or ter (tris); 4—tetra or quadri (tet okis); 5—penta or
iiinque (pentakis) ; 6—hexa or sexa (hexeki3) ; 7- —hepta or septa ;
* —octa ; 9—nona or canea'; 10—deca or decena ; 11—undeca or
henadeca ; 12—dodeca ; ete.
Prefixes for naming multiples: ‘ted sub-maltiples o1 waits
ap yo
ann g> AON MD Iw D>
Been COLMA ORDA
(xxxv)
Greek Alphabets
Alpha
Beta
Gamma
Delta
Epsilon
Zeta
Eta .
Theta
Tota
Kappa
Lambda
Mu
pgXeota MnO Z
EENKCAASTA OME
3
Nu
Xi
Omicron
Rho
Sigma
Upsilon
Chi
Psi
Omega Structure of the Atom
QUANTUM MECHANICAL AND WAVE”
| MECHANICAE APPROACH .
PLANK’S QUANTUM. THEORY OF RADIATION AND. EINSTEIN'S
EXTENSION. :
Plank in 1901 studied the energy of light of different frtqwencies’
iadiated from hot (black) bodies and on the basis of these studies he
put forward a, theory known as Plank’s Quantum Theoty oS 4
according to which a black body emits (i.e. radiases) of, absorbs the.
energy such as' light and heat not continuously but jn wi
small packet of energy. called a quantum The gy ofeach quantum -
is equal to the produ of Plank’s constant, h 62 x 10" “erg-sec)
and the frequency,.¥ radiation. Thus :+ \ .
E=hyv.or rae ( v =§) or Eeehey
v=) where c= velocity of radiation (em/see)
-. f
A=warclength (in cms):and-v.=wave pumber./ ©
In 1905 Einstein vgtended thy: tut tatory, by /postulating
that the cnergy,.like ight, 1s no? WS lemitred or a in packets
but is also propagated in space in packets. Each pac! et he called a
photon. According to-thds extension’ light has wave as well as particle
characteristics. The énergy,.B and the mass, m of a photon, are given
by : E=hy and E=mc? where ¢==velocity of light. The relation
between the mass and energy js called Einstein’s mass-energy relation-
ship. x
THE HYORGGEN SPECTRUM, »
When an electric cuerent is passed through h pogen gas. kept
at low pressure, we get hydrogen spectrum which is found ‘to consat
of a number of tfies in the visible ultraviolet: and infra-red regions.
Rach line of the spectrum corresponds to a perticular frequency. . 2 Structure of the Atom
It was found that these lines could be 8rouped into a definite
number of Spectral series. These are five series and are known after
their discoverers : (i) Balmer series £1885) appearing in
the visible region (ji Paschen series (1896) (in the infra-red region)
(it Lyman series'(1896) (in the ultra-violet region) (iv) Brackett series
¢ we the infrasited region) ( v) Pfund series (1925) (in the infra-red
region)
Balmer's formula. In 1885 Balmer, while analysing the hydro-
8en spectrum in the: visible region (Balmer series), found that the
Wwavelétigth, A-ahd the wave number, v of each spectral line of
ner series sgiven by -
‘yl J 1
, ~7-®( 3-7)
where Ru=consiant. known as Ryd! constant or Rydbe:
number for- hydrogen and n=an integrate 4, 5 and 6 for
a Het and-He lines.tespectively in the hydrogen spectrum. (See
Continuous
_ Fig. 1-1. Balmer series of atomic hydrogen in the excited state. The dark
: lines show the bright emission lines of the spectrum.
The experimental. value of Ru for the visible lines of hydrogen
Spectrum has been. found to equal tc 109,678 cm7},
Rydberg’s formula. Balmer’s formula as given above served
asa valuable clue to Rydberg who made a detailed study of the
Spectrum and gave in 1889 a general: relationship for the wave
number ¥ for the spectral lines. This formula; known as Rydberg’s
formula, can be written in a simple form as :
— 1 1 1 =
v= yoke a —) em?
2 varies fiom line to line in the same series, e.g. for the six lines of
Balmer series, m=2.and-n for the successive six lines is 3, 4,5,6,7 Structute of the Atom 3
The values of m for various series and those of m for thé sac-
cessive lines in the same series are given below in Table 1-1.
‘Table 1:1 Valuce of m and n for various series
Spectral Series | Value af | tgccm th, Cat Dyer} | Spectrat Region
Lyman Series 1 2,3,4,5.. | Ultraviolet region
Balmer Series 2 3,4, 5, 60 Visible region
Paschen Series 3 4,5, 6, To Infra-red region
Brackett Series 4 5,6, 7,8. Infrared region
fund Series s 6, 7, 8.0. ‘| Tofra-red region
Thus by assigning suitable values tom and n as indicated ia
the Table we can calculate the value of the wave number, v and the
wavelength, A of the spectral lines.
Ritz Combination Principle. This principle states that by combin-
ing the two terms that occur in Rydberg’s or ‘Balmer’s formula, other
relations can be obtained which will represent new lines and even new
spectral series, e.g. series other than that of Balmer in ‘the hydrogen
spectrum were predicted evén before they were actually discovered
by Paschen and Brackett. Considering the first two lines viz H, and
He of the'Balmer series, we can get the wave mimbér of a new line
as follows: .
rota) a nota)
Thus va—Ve =Ra( 3 -+)
This equation gives the wave number, (vg a) of a new line
which is actually the first line in a new series namely Paschen series
ing in the infra-red‘region. Similarly it can be shown that
the wave number of the second line of the same series is equal to
¥y—ve and so on. In the same, manner another series namely
Brackett series discovered by Bratket can be obtained.
BOHR'S ATOMIC MODEL—QUANTUM MECHANICAL CONCEPT
Rutherford’s planet-like model of the atom was gontests@ by ¢ Structure of the Atom
Bobs in 1913 on two, grounds:
. ( According to jflassical mecha:
- @ics, whenever a charged particle
is subjected to acceleration, it cmits
radiation and loses crergy. At
-80 electron revolving round the nucleus
tro, sue. therefore, be continually
Nucleus lerated. towards the centre
: dd of the orbit’ and consequently emit-
: Fig. 12. ‘An eiection ia the ting radiation. The result of this
soltaltinurthe nitius t's, Would be that the radius of curva-
tadiales .q@urgy due io ture of its path (i.e. orbit) would go- .
acceleration. ‘en’ - decreasing and due to spiral
motion, the clectron would finally
fall into the nucleus when all its'retational encfgy has becn spent on
the electromagnetic radiation and the atom would collapse. (See
Fig. 1:2). Ne such thing is, however, observed.
(iP If the electrons lose energy continuously, the observed
aiowme spectra should be ‘continuous, consisting of broad bands
‘metging one into the othar, The observed atomic spectra, however,
eonsists of well defined lines of definite frequencies.
To ‘overcome tnesy two. objections. and also to explain the
‘spectra of hydrogen atom he pro) @ qaentum mechanical model
Of the atom based on Quantum of Radiation.
Pustalates'Jf Boar's Theory. (i) Each orbit round the nuclcus
ig associated with a definite amount of energy and the orbits arc,
therefore, are ‘called energy tevels or main energy shells. These
shells are numbered as 1, 2, 3,...... starting from the nucleus and arc
designated by capital letters : K, L, M.....:respectively. The energy
associated with a certain energy level increases with the increase of its
distance from the nucleus. Thus, if E,, Ey, Ey......! denote the energies
associated with the energy levels numbered as 1 (K-shell), 2 (L-shcll),
3 (M-shell)....... , these are in the order :
E,
