Inorganic - Chemistry # Brahmastra

Inorganic Chemistry
Index
Sr. Topics Name Page
1. Periodic Table 1
2. Chemical Bonding 9
3. s-block 19
4. p-block 25
5. d-Block Elements 46
6. co-ordination compound 51
7. Metallurgy 58
8. Hydrogen and It’s Compounds 66

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Earlier Attempt of Periodic Table
 Earlier Attempt Periodic Table • Li, Be, B, C, N, O, F
Periodic table is the systematic arrangement of Na, Mg, Al, Si, P, S, Cl
elements in tabular form to make the study of Limitation :
elements easier.
a) He could not arrange the elements after
1. Lavoisier
calcium.
• He classified the elements into metals of non-metal
b) After the discovery of noble gases, the law of
Metal - losses e– octave gets failed.
Non-metal - gains e– 4. Lother - Mayer Curve
• After the discovery of metalloids, this • Peaks : Alkali Metals.
classification get discarded.
• Ascending : Halogens
2. Dobereiner’s Traid
• Descending : Alkaline Earth Metals.
• All triad consists of three elements and follows
two rules • Similar elements occupy similar position in the
curve.
a) All three element of triad have similar
properties. • On the basis of above graph he concluded that
physical properties of elements are periodic
b) At wt of middle element are average of At.
function of atomic mass.
wt of first and last element.
Limitation : Could not arrange all elements into triad. Limitation :
3. Newland’s Law of Octave a) He was unable to include all elements into

his graph.
• He arrange the elements into increasing atomic
mass and found that property of every 8th element b) Graphical representation does not make study
is similar to 1st element just like 8th note of musical of elements easier.
octave.
Mendleev’s Periodic Table
• He arranged elements in increasing order of these ii. He corrected atomic mass of following elements.
atomic mass.
Element U Be In Au Pt
• All 63 elements known at his time, were included
in his PT. Trick You beiman insan aur pito
• There are 7 periods and 8 groups Demerits.
• Gr-1 to 7 are further devided into 2 subgroup (A He could not justify
& B) while gr-8 has 3 subgroup and each
• Position of hydrogen.
subgroup has 3 elements like (Fe, Co, Ni), (Ru,
Rh, Pd) and (Os, Ir, Pt) • Position of Isotopes
Merits • Anomalous pair of elements.
i. He left some vacant space for undiscovered element. Ar 39.9 K 39.1 Amir Khan
18 19
Trick
Te 128 I 127 Teri Iccha
Eka 'Al'  Gallium (Ga) Aliya - Galiya 52 53
Eka 'B' Scandium (Sc) B.Sc. 89

Th 232 90
Pa 231 Thanda Pepsi
58.9 58.7
Eka 'Si' Germenium (Ge) Sita-Geeta 27
Co 28
Ni Cola Nahi
Eka 'Mn'  Technitium (Tc) M.Tech
Prof.Motegaonkar
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Modern Periodic Table
• It is based on mosley’s x-ray experiment. • There are 7 periods & 18 groups in modern PT.
vz
P-1 2 element (H – He) Very short
P-2 8 element (Li – Ne) Short
v  az  b
P-3 8 element (Na – Ar) Short
v  frequency of emitted P-4 18 element (K – Kr) Long
x-ray
P-5 18 element (Rb – Xe) Long
z  Atomic number P-6 32 element (Cs – Rn) Very long
a, b  constant P-7 Incomplete (Fr....) Incomplete
z • Magic Number
G-1 2, 8, 8, 18, 18, 32
• Modern Periodic Law - G-2 8, 8, 18, 18, 32
Physical and chemical properties of elements are G-3 18, 18, 32
periodic function of their atomic number. G-4 to G-12 18, 32, 32
G-13 to G-17 8, 18, 18, 32, 32
G-18 8, 8, 18, 18, 32, 32
Blockwise Clsassification of Modern Periodic Table
1. s-block 5th period - 4d - series 39Y – 48Cd
• Contains two group i.e. gr-1 (Alkali Metals) & 6th period - 5d - series 57La – 80Hg
gr-2 (Alkaline earth metal) 4. f-block
• GEC : ns1 to 2 • Outermost, penultimate as well as Anti
• All metals penultimate shells are incompletley filled and last
• Fixed valancy - G-I, V=1 and G-II, V=2 e– enters into (n-2) f.
2. p-block • GEC : (IG) ns2 (n-1)d0, 1 (n-2)f1-14
• Contains 6 group (from gr-13 to gr-18) • Also known as inner transition elements.
• GEC : ns2 np1 to 6 • Contains two sereis of elements
G - 18 Inert gas/Noble gas 4f - series Lanthanides (58Ce – 71Lu)
G - 17 Halogens (Salt producing) (Rare earth metal)
G - 16 Chalcogens (Ores producing) 4f - series Actinides (90Th – 103Lr)
• Elements can be metals, non-metals as well as • All f-block elements belongs to gr-3 or IIIB.
metalloids.
• All are metals, shows variable valancy.
• Elements can be solid, liqide or gas.
• Elements after uranium (U) are called transuranic
• Shows variable valancy. or artificial or synthetic or manmade elements.
3. d-block • Determination of Block, Period and Group
• Outermost as well as penultimate shells are Step-I : Block - The subshell in which last e– enters.
incompletly filled
Step-II : Period - Maxm value of principle ON (n)
• Differentiating e– (last e–) enters into d-subshell
Step-III : Group -
of penultimate shell i.e., (n–1)d.
a) If element is of s-block
• Total 10 groups (gr-3 to gr-12)
gr no = no. of e– in ns
• GEC :- (IG) ns0, 1 or 2 (n–1)d1 to 10
b) If element is of d-block
• All metals, shows variable valancy, Paramagnetic,
Colourfull, used in making catalysts and complex gr no = no. of e– in ns + (n–1) d
compounds. c) If element is of p-block
• Contains 3-series gr no = no. of e– in np + 12
4th period - 3d - series 21Sc – 30 Zn d) If element is of f-block - gr no = 3
Page: 2 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

• Gr.No. in IUPAC 1 2 3 4 5 6 7 IUPAC Nomenclature of Elements having Z > 100
I A II B IIIB IV B V B VI B VII B Number Name Symbol Number Name Symbol
Gr.No. in CAS
0 Nil N 5 Pent P
Gr.No. in IUPAC 8 9 10 11 12 13 14
1 Un U 6 Hex H
Gr.No. in CAS VIII VIII VIII I B II B IIIA IVA 2 Bi B 7 Sept S
Gr.No. in IUPAC 15 16 17 18 3 Tri T 8 Oct O
Gr.No. in CAS VA VIA VIIA VIIIA 4 Quad Q 9 Enn E
Periodic Properties Part-I (Effective Nuclear Charge Zeff and Atomic Radius)
1. Effective Nuclear Charge (Zeff) • Ionic Radius
+ve charge ; r 
Z eff  z  
–ve charge ; r 
 Slatter’s constant • Radius of isoelectronic species
Z  Atomic Number
2. Screening / Shielding Effect of e– in 1 +ve charge ; r
r
S>P>d>f Z –ve charge ; r
3. Atomic Radius • Size of hydrated ion
Distance between nucleous and outermost shell G-1 : Li aq   N a aq   K aq   R b aq   Cs aq 
containing e–.
G-2 : Be 2aq
 2 2 2 2
  M g  aq   Ca  aq   Sr aq   Ba  aq 
   
M g 2aq
 3
  Al  aq 
r r
• Conductivity in solution  Ionic Mobility
Covalent Radius Metallic Radius
1
• Ionic Mobility  size of ion .
 Exceptions of Atomic or Ioic Radius
r i. Inert gas has largest radius in its period due to
Vanderwaal Radius Vanderwaal Radius.
Note : In case of inert gases Vanderwaal radius ii. d-block
is considered. Sc Ti V Cr Mn Fe Co Ni Cu Zn
r  Cov. radius < Metallic Radius < Vanderwall Radius r r = same r
• Covalant Radius iii. Boron family : r  B < Ga < Al < In  Tl In  Tl
a) Same atom
iv. Carbon family : r  C<Si<Ge<Sn  Pb Sn  Pb
d
rC = v. Lanthanide Contraction
2
Radius of lanthanides decreases on moving from
b) Different atom left to right due to poor screening effect.
dA – B = rA + rB – 0.9 (EN) Due to Lanthanides contraction
EN  difference of EN; rA = dA–A / 2; a) In d-block
rB = dB–B / 2 Gr no- 3 - SC < Y < La
P-1 r  H < He  V.wall radius Gr no- 4 to 12
P-2 r  Ne > Li > Be > B > C > N > O > F. Size of 4d series  5d series
P-3 r  Ar > Na > Mg > Al > Si > P > S.... b) Stability of Tl+ > Tl+3 (inert pair effect)
c) Stability of Pb+2 > Pb+4 (inert pair effect)
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Periodic Properties Part-II (Ionisation Energy)
Ionisation Energy (HI.P. / I.E.)
P-2 I.E  Li < B  Be < C < O  N < F < Ne
• Minimum amount of energy required to remove
an electron from gaseous isolated atom is called P-3 I.E  Na < Ag < Mg < Si < S  P < Cl < Ar
ionisation energy.
Exceptions in ionisation energy
• Ionisation process is endothermic. i.e. H = +ve.
i. Boron Family :
 
Ag   A g  e ; HI.P. = +ve I.E  B > Tl > Ga > Al > In
Successive I.E. band karke tala gaya ali India
ii. Carbon Family :
A g   x KJ  A g   e  ; I.E 1  x
C > Si > Ge > Pb > Sn
2 
A g   y KJ  A g   e ; I.E 2  y iii. d-block:
A 2   z KJ  A 3g  e  ; I.E 3  z g-3 Sc < Y > La
gr-4, 5, 6, 10 5d > 4d > 3d
I.E1  I.E 2  I.E 3 ..... gr-7,8, 9, 11, 12 5d > 3d > 4d
Application
Factors effecting I.E
i. Basic strength of metal oxide  1/I.E
1
1. I.E  e– relasing tendency  1/I.E
r
2. I.E.  Zeff Metallic characteristics  1/I.E
3. I.E  penetrating effect of valance e– Electropositive characteristics  1/I.E
4. I.E.  +ve charge Tendency to oxidise itself  1/I.E
Reducing power  1/I.E
1
5. I.E.  charge ii. Types of oxide
 ve
6. I.E.  Stable Electronic configuration Baisc : Metal oxides
Variation in PT Acidic : Non-metal oxides
G-1 I.E  Li > Na > K > Rb > Cs Amphoteric : BeO, Al2O3, ZnO, SnO, SnO2, PbO,
PbO2, TiO2, V2 O5, Cr2O3, CrO4
G-2 I.E  Be > Mg > Ca > Sr > Ba
Neutral : CO, N2O, NO.
P-1 I.E  H < He
iii. Highest I.E  He, Lowest I.E.  Cs
Periodic Properties Part-III (Electron Gain Enthalpy)
Electron Gain Enthalpy(Heg) / Electron Factors effective electron affinity
Affinity (EA)
1
• Energy change when an e– is added to gasious i. EA 
isolated atom is called electron gain enthalpy. size
A(g) + e–  A(g ) ; + xKJ, Heg = –x ii. EA  Zeff

1
iii. Electronic configuration - Half filled and full filled
2
A(g ) + e–  Ag  ;  y KJ, H eg 2 = –y orbitals are stable, So they show less interest
towards incoming e–.
A2g + e–  A 3g ;  z KJ, H eg 3 = –z
Variation in PT
• Heg1 of most of atoms are negative (Except P-1 :- EA : H > He
Atoms having stable configuration), but
P-2 : gr  18  gr  15  gr  2 < G  13  G  1 <
Heg2 , Heg3 , H eg 4 .... are always positive.
< G-14 < G-16 < G  17
EA  Heg
P-3 : gr  18  gr  15  gr  2 < G  13  G  1 < G-16 S > Se > Te > PO > O
< G-14 < G-16 < G  17 G-15 P > As > Sb > Bi > N
Ne < N < Be < B < Li << < O < F Highest EA  Cl (Most –ve Heg)
Ar < P < Mg < Al < Na < Si < S < Cl Lowest EA  Ne (Most +ve Heg)
G-17 Cl  F > Br > I > At

Periodic Properties Part-IV (Electronegativity)
Electronegativity (EN) ii. Mulliken’s Scale
• Tendency of bonded atom to pull shared pair I.E  EA
electron towards itself. EN 
2
Factors : I.E.  Ionisation energy (ev/atom)
1 E.A.  Electron Affinity (ev/atom)
i. EN 
size
ii. EN  Zeff  EN  Mulliken Scale
 EN 
Pauli 's Scale
 2.8
iii. EN  % s-character
iii. Allred & Rochow’s Scale
EN : sp  sp2  sp3
Z eff
EN  0.359  0.744
iv. EN  +ve charge r2
1 r = radius in Å
v. EN  Application of electronegativety
 ve charge
a) Non- Metallic character  EN
i. Pauli’s Scale
b) Bond polarity EN
c) % Ionic character = 16 × EN + 3.5 (EN)2
xA  xB  0.208 EAB  E AA  E BB
Some Important Definitions
Reference Element (xB) = 'H' a) Typical element :
xA  EN of A 3rd period element except inert gas. e.g. Na,
xB  EN of B Mg, Al, Si, P, S and Cl.
EA–B  Bond enegy of A – B bond b) Representative element :
EA–A  Bond enegy of A – A bond ‘s’ and ‘p’ block element (except inert gas)
EB–B  Bond enegy of B – B bond c) Transition element :
Note :- B.E most be in k.cal/ml d-block elements except e.g. Zn, Cd & Hg.
H All transition elements are d-block element
2.1
but all d-block elements are not transition
Li Be B C N O F element.
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Si P S Cl d) Bridge element : Mg & Ca

1.8 2.1 2.5 1.5
Br Mg Ca
2.8
I Na Cu K Ag
2.1
(I A) (I B) (I A) (II B)
Same EN :
e) Diagonal Relationship :
Nakli - N = Cl (3.0)
Ishk - I = S = C (2.5) Li Be B
Pachano - P=H (2.1)
Mg Al Si
EN of F > O > N = Cl > Br > I = S = C > P = H
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General Trend of Different Properties in the Period and Groups
Periodic Properties Group Periods
Atomic radius Increases Decreases
Ionisation potential Decreases Increases
Electronegativity Decreases Increases
Electron affinity Decreases Increases
Covalent character Decreases Increases
of halides
Metallic nature Increases Decreases
Oxidising nature Decreases Increases
Reducing nature Increases Decreases
Screening effect Increases Increases
Effective nuclear charge (Zeff) Constant Increases
Valency w.r.t. oxygen Constant Increases
Basic character (Metals) Decreases
of hydrides Increases
Basic character of oxides (Non metal) Decreases Decreases
(Metals) Increases
Basic character of Increases Decreases
oxy acids
Strenth of oxy acids Decreases Increases
Thermal stability of sulphate Increases Decreases
Thermal stability of carbonates Increases Decreases
Thermal stability of nitrates Increases Decreases
Thermal stability of hydroxide Increases Decreases
Density Increases First increass then decreases
Electro positivity Increases Decreases
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Prof.Motegaonkar
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S.R.
M.Sc.Chem.Gold
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IMPORTANT INCREASING TRENDS IN INORGANIC CHEMISTRY
1) Atomic/Ionic Size (Increasing order)  p, m, o-dichlorobenzene
 Mg2+, Na+, F–, O2–, N3– (Hint : Isoelectric series)  CH3I, CH3Br, CH3F, CH3Cl
2+ – 2–
 Ca , Ar, Cl , S  O, C, S, Se  NH3, SO2, H2O, HF
 B, Be, Li, Na  F, O, F–, O2–  H2 S, H2 O
2) Ionic Radii in Water (Increasing order)  HI, HBr, HCl, HF
+ + + +
 Cs , Rb , K , Na , Li +
 +
Li , Be +2  PH3, AsH3, SbH3, NH3
 Na+, Mg+2, Al+3  H2O, H2O2
3) Melting Point (Increasing order) 10) Strength of H-bonding (Increasing order)
 S, Cl, N, O, F
 Cs, Rb, K, Na, Li
 NH3, H2O, HF
 Mg, Ba, Sr, Ca, Be
11) Abundance of Element (Increasing order)
 CaI2, CaBr2, CaCl2, CaF2
 Element of earth crust - Fe, Al, Si, O
 BeCl2, MgCl2, CaCl2, SrCl2, BaCl2
 Metals of earth crust - Ca, Fe, Al
 NaI, NaBr, NaCl, NaF
 Non-Metals - Si, O
 CsCl, RbCl, KCl, NaCl
 In atmosphere - O, N
 AlCl3, MgCl2, NaCl
 In universe - He, Si, H
4) Density (Increasing order) 12) Electric Conductivity (Increasing order)
 Na, Al, Fe, Pb, Au  Li, K, Na, Rb, Cs  Cr, Pt, Fe, Al, Au, Cu, Ag
 Ca, Mg, Be, Sr, Ba  Max. density = Os/Ir 13) Molar Conductivity in Water (Increasing order)
 Min. density = H  Metal of min.density = Li  LI+, Na+, K+, Rb+, Cs+
5) Boiling Point (Increasing order) 14) Covalent character (Increasing order)
 PH3AsH3, NH3, SbH3  H2S, H2 Se, H2 O  LiCl, BeCl2, BCl3, CCl4
 HCl, HBr, HI, HF  NH3, HF, H2O  SrCl2, CaCl2, MgCl2
 He, Ne, Ar, Kr  H2O, D 2 O  TiCl2, TiCl3, TiCl4  LiCl, LiBr, LiI
 H2, Cl2, Br2  Na2O, Na2 S  AlF3, Al2O, AlN
6) Electronegativity (Increasing order)  HF, HCl, HBr, HI
 As, P, S, Cl  I, Br, Cl, F 15) Ionic Character (Increasing order)
 C, N, O, F  sp3 < sp2 < sp  LiBr, NaBr, KBr, RbBr, CsBr
 LiF, NaF, KF, RbF, CsF
7) Electron Affinity (Increasing order)
 BeCl2, MgCl2, CaCl2, SrCl2, BaCl2
 I, Br, F, Cl  Cu, Ag, Au
 BCl3, AlCl3, GaCl3  VCl4, VCl3, VCl2
(EA of Au is very high = 222 kJ mol–1)
 AlF3, MgF2, NaF  AlN, Al2O3, AlF3
 O, S, F, Cl  N, P, O, S
 HI, HBr, HCl, HF  CuCN, AgCN
8) Ionization Energy (Increasing order)
 AgCl, KCl
 Na, Al, Mg, Si
16) Acidic Property (Increasing order)
 Li, B, Be, C, O, N, F, Ne, He (Ist I.P.)  SiO2 , CO2, N2O, SO3
 Be, C, B, C, F, O, Ne, Li, He (IInd I.P.)  MgO, Al2O3, SiO2, P4O10
9) Dipole Moments (Increasing order)  HClO, HClO2, HClO3, HClO4
 CCl4, CHCl3, CH2Cl2, CH3Cl  CH4, NH3, H2O, HF  SiH4, PH3, H2S, HCl
 NF3, NH3, H2O, HF  H2O, H2 S, H2Se, H2Te  HF, HCl, HBr, HI
 Cis-chloropropene, Trans-chloropropene  InCl3, GaCl3, AlCl3  BF3, BCl3, BBr3, BI3
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17) Basic Character (Increasing order)  I2, Br2, Cl2, F2
 LiOH, NaOH, KOH, RbOH, CsOH  Zn+2, Fe+2, Pb+2, Cu2+, Ag+
 Be(OH)2, Mg(OH)2, Ca(OH)2, Ba(OH)2 22) Reducing Power (Increasing order)
 BeO, MgO, CaO, SrO  PbCl2, SnCl2, GeCl2  HF, HCl, HBr, HI
 CO2, B2O3, BeO, Li2O  Ag, Cu, Pb, Fe, Zn  HNO3, H2SO3, H2 S
 SiO2, Al2O3, MgO, Na2O  H3PO4, H3PO3, H3PO2
 SbH3, AsH3, PH3, NH3 23) Reactivity with water (Increasing order)
 F–, OH–, NH 2 , CH3  Li, Na, K, Rb, Cs  Be, Mg, Ca, Sr, Ba
 NiO, MgO, SrO, K2O, Cs2O 24) Extent of Hydrolysis (Increasing order)
18) Bond Angle (Increasing order)  CCl4, MgCl2, AlCl3, SiCl4, PCl5
 CH4, C2 H4, C2H2  H2O, NH3, CH4, CO2  BiCl3, SbCl3, AsCl3, PCl3, NCl3
25) Hydration Energy (Increasing order)
 H2O, NH3, CH4, BH3  NO 2 , NO 2 ,NO 2
 Ba+2, Sr+2, Ca+2, Mg+2, Be+2
 H2Se, H2S, H2 O  AsH3, PH3, NH3
 Cs+, Rb+, K+, Na+, Li+
 PF3, PCl3, PBr3, PI3  NF3, NH3, NCl3
 Na+, Mg+2, Al+3
 OF2, H2O, Cl2O
26) Thermal Stability (Increasing order)
19) Bond Length (Increasing order)
 Li2 CO3 , Na2CO3, K2CO3, Rb2CO3, Cs2 CO3
 N2, O2, F2, Cl2  N  N, C  N, C  C
 BeCO3, MgCO3, CaCO3, BaCO3
\ |
 CO, C = O, – C–O–  NO+, NO, NO–  Be  OH 2 , Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2
/ | Polarisation
 LiOH, NaOH, KOH, RbOH, CaOH

 O2, O3, H2O2 (O–O bond length)
 BeSO4, MgSO4, CaSO4  SbH3, AsH3, PH3, NH3
 CO, CO2, CO32–  N2, N2–, N2–2
 H2Te, H2Se, H2S, H2 O  HI, HBr, HCl, HF
 O2+2 , O2, O2 –, O2–2  HF, HCl, HBr, HI
27) Solubility (Increasing order)
20) Bond Strength (Increasing order)
 BaCO3, SrCO3, CaCO3, MgCO3, BeCO3
 HI, HBr, HCl, HF
 Be(OH)2, Mg(OH)2, Ca(OH)2, Ba(OH)2
\ \ \ \
 – C – I, – C – Br,, – C – Cl, – C – F  BaSO4 , SrSO4 , CaSO4, MgSO4, BeSO4
/ / / /  Li2 CO3 , Na2CO3, K2CO3, Rb2CO3, Cs2 CO3
 N – N, N = N, N  N
 As – H, Sb – H, P – H, N – H  LiF, LICl, LiBR, LiI
 LiF, NaF, KF, RbF, CsF
 N 22  , N 2 ,N 2 , N 2  O22–, O2–, O2, O2+, O22+
 CaF2, CaCl2, CaBr2, CaI2
 LiI, LiBr, LiCl, LiF  CsCl, RbCl, KCl, NaCl
AgI, AgBr, AgCl, AgF 1
 BaO, SrO, CaO, MgO  F2, H2, O2, N2  solubility 
PbO2, CdI2, RbI Covalentchar.
 NO–, NO, NO+  I2, F2, Br2, Cl2
28) Reactivity with Hydrogen (Increasing order)
 O – O, S – S  NaI, NaBr, NaCl, NaF
 Cs, Rb, K, Na, Li
 F – F, O – O, N – N, C – C, H – H
 Ba, Sr, Ca, Mg, Be
21) Oxidizing Power (Increasing order)
29) Reactivity Towards Air (Increasing order)
 Cr2 O7 2– , MnO4 –  MnO22– , MnO4 –
 Be, Mg, Cs, Sr, Ba
 WO3, MoO3, CrO3  GeCl4, SnCl4, PbCl4
Atoms  highly unstable  due to their electronic configuration & high amount of energy
In the process to decrease their energy and to attain the stability Atoms undergo bond formation
Which leads to formation of chemicals
3 known as
If Octet of Central atom incomplete then 1
there will be ADAPTATIONS for survival Chemical Bond
H = –ve (Always exothermic)
*Mainly in the compounds of B, Be, Al.
2 B ased on Octet Rule
Primary Bond (in general)
Back Bonding Can be of two types mainly

Required for the existence of
Presence of Vacant orbital on Central/Peripheral
Can b e of fo ur ty pes
molecules & Compounds.
atom.
Involvement of electrons occurs in
Lone pair on Central/Peripheral atom. the formation of primary bond
Eg. BF 3, BCl3 , BBr3 , BI3 & Boric Acid –1
(L.P. on Peripheral atom, Peripheral to center back bonding). Bond energy = 200 – 400 kJ/mol
–
Eg. O(SiH 3)2, N(SiH 3)3, OCl 2, CCl 3 Secondary bonds cannot exist
(L.P. on Central atom, Center to peripheral back bonding). without primary bonds
Bridge Bonding Ionic Bond
Size of central atom should be Large than B. Transfer of electron/s.

Size of Be & Al > B. In between metal and non-metal.
Due to large size lesser Steric Hindrance. Formation of Ionic Bond, via Electrostatic force
Be & Al can Arrange 4 Peripheral atom. of attraction.
Eg. BeCl 2 (Dimer), BeCl 2 (Polymer), Non directional in nature.
AlCl 3 (Dimer), AlCl3 (Polymer) Covalent Bond
Banana Bonding Sharing of electron/s.
Peripheral atom must be Hydrogen. In between non-metal and non-metal.
– Nuclear-electron attraction in more than nuclear-
3 C – 2e bond.
nuclear and electron- electron repulsion.
Eg. Diborane (B2 H6), BeH 2 (Dimer).
Directional in nature.
Metallic Bond
Co-ordinate Bond
Metal ions are dipped in sea of electrons.
First transfer then sharing of electron/s.
In between metal and metal.
Formed between lewis base and lewis acid.
Exception : Mercurous ion (Hg 22+ ), has covalent
+ + Also known as Co-ionic, semi-polar or Dative bond.
bond in between [Hg – Hg ].
Both electrons come from single atom/molecule.
Metallic bonds have free electrons which conduct
electricity.
Strength  no. of unpaired electrons
in metal atom.
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Cannot exist without the
formation of Primary Bond. 4
Secondary Bond
Super Trick
Secondary bonds lack the I.D.  1
involvement of Electrons. I.I.D.  4
14366 D.D.  3
Based on Electrostatic force D.I.D.  6
of attraction. Trick to remember distance London  6
dependence of molecular forces
Bond energy = 2 - 40 kJ/mol–1
Hydrogen Bonding Molecular Forces

Hydrogen must be connected with F/O/N. Ion dipole. 
It is stronger version of dipole-dipole interaction. Responsible for solubility of ionic
E.N. of atom Non compound in water.
Strength of hydrogen bond 
Size of atom Vanderwaal’s Responsible for the hydrated radius
forces of the ions.
Intra-molecular hydrogen bonding
Mainly of two types
Ion induced dipole. 

Hydrogen bond within the molecule.
Found in Ortho substituted, Phenols, Aldehydes,
Amines & Carboxylic Acids by OH, NO2, dipole-dipole 
F etc. groups. Vanderwaal’s dipole induced dipole 
B.P., V.P. , Viscosity , Solubility 
forces
Inter-molecular hydrogen bonding London force of attraction. 
Hydrogen bond in between two same or different molecule. London force of molecular mass
Found in HF, H2O, NH 3, and Para substituted attraction  branching
Phenols, Aldehydes, Amines & Carboxylic acids
by OH, NO 2, F etc. groups Responsible for physical adsorption,
B.P., V.P. , Viscosity , Solubility  Determining the B.P. of molecules
and nobel gases.
H2S is gas but H2O is liquid due to hydrogen
bonding. Strength of molecular forces :
B.P. of H 2O is greater than HF due to more no. Ion dipole > dipole-dipole >
of hydrogen bonds in H2O. ion-induced dipole >
dipole - induced dipole >
H2O is liquid while H2S is gas. london forces
HF is liquid while HCl is gas.
Viscosity & Special type of Hydrogen Bonding
Surface tension  Glycerol > Ethylene glycol > Methanol H
Cl O Chloral hydrate is stable only on
Cl – C – C – H account of intra molecular
Cl O hydrogen bonding.
H
Chloral hydrate
+ –
KHF 2 is possible but not K [F --- H –– F]
KHCl 2 it is due to ion type
H-bond
Order of Boiling Point
HF > HI > HBr > HCl
H2O > H2Te > H 2Se > H2S
PH3 < AsH3 < NH3 < SbH3 < BiH3

Covalent Bond
1
Lewis dot structures
Electron of outermost shell are shared to complete octet of central atom to achieve noble gas like configuration.
Formal charge is the by-product of octet rule in which
Lewis dot structures are based on Octet Rule. specific charge is assigned to Lewis dot structure to
complete the octet.
Lewis dot structures Failed to Explain
Existence of molecules having Existence of molecules having Species having odd electron.
incomplete octet of central atom. super octet/expanded octet of Central atom : Has odd electron
–
No. of electron < 8 central atom. NO, NO 2, ClO 2, ClO 3, O 2
BeH2, BF 3, BCl 3, BBr 3, No. of electron > 8
BI3 , AlCl3, AlI3 PCl3 , IF 7, XeF 6, XeF 2, SF 4
Lewis theory was not able to explain the process of sharing of electrons between two atoms
2 How Electron are shared

V.B.T. (Valence Bond Theory) was explained by V.B.T.
Electrons are shared via orbital overlapping
Requirement of Orbital Overlapping Factors affecting overlapping

according to V.B.T.
Strength of covalent bond  extent of overlapping
Orbitals of outermost shell participate in
overlapping. Orbitals undergoing overlapping Shape of Orbitals (p-p > s-p > s-s)
must be half-filled. Directional orbitals form stronger bond
If electron in the orbitals undergoing Size of Orbitals (2p-2p > 2p-3p > 2p-4p > 2p-5p)
overlapping are paired then promotional
Same size better fitting for overlapping
energy is used to unpair.
: :
: :
Insufficient promotional energy causes l.p.-l.p. repulsion –C–C–> :N–N: > :O–O: > :F – F:
:
:
inert pair effect in heavy p-block elements

Presence of l.p. decreases overlapping
Hybrid orbital undergoes stronger overlapping
than pure atomic orbitals
sp < sp2 < sp3 < sp3 d < sp3 d2 < sp3d3
more the directional properties
more the overlapping
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Overlapping can be of two types
Based on electron density Angle of Approach

 = 180°  = 0°
Positive Negative Axial overlapping Partial/parallel Lateral Overlapping
Overlapping Overlapping  bond formation  bond /  bond formation
Head to Head Head to Tail Internuclear
s-s overlapping
Tail to Tail Tail to Head p-p
axis
overlapping p-p
Zero pi-bond
No. Overlapping s-p overlapping
p-d p-p 
p-p overlapping overlapping pi-bond
d-d d-d
overlapping pi-bond
also known
as  bond
V.B.T. Fails to Explain
V.B.T. Could not explain In CH 4 molecule 3 bonds are formed V.B.T. Could not explain
the shape of molecule by s-p overlapping while one by p-p magnetic behavior of molecule
overlapping. Besides these bonds have V.B.T. Could not explain existence
same bond energy however it couldn’t and non-existence of various
Explained be explained by V.B.T. molecules and bond order as well.
by
Explained Explained
–
Valence shell e pair by by
repulsion theory Hybridization Molecular Orbital Theory
(V.S.E.P.R.T.) (mixing of atomic orbitals) M.O.T.
Hybridization (Mixing of Atomic Orbitals)

Salient features of hybridization : Hybridization involving d-orbital
The main features of hybridization are as under : Type of ‘d’ orbital involved
3
• In CH4 molecule 3 bonds are formed by s-p sp d
overlapping while one by p-p overlapping.
sp3 d2
Besides these bonds have same bond energy
however it couldn’t be explained by V.B.T. sp3 d3
• The number of hybrid orbitals is equal to the
dsp2
number of the atomic orbitals that get hybridised.
• The hybridized orbitals are always equivalent in Important conditions for hybridization :
energy and shape. • The orbitals present in the valence shell of the
• The hybrid orbitals are more effective in forming atom are hybridized.
stable bonds than the pure atomic orbitals. • The orbitals undergoing hybridization should
• These hybrid orbitals are directed in space in have almost equal energy.
some preferred direction to have minimum • Promotion of electron is not essential condition
repulsion between electron pairs and thus a prior to hybridization.
stable arrangment is obtained. Therefore, the • It is the orbital that undergoes hybridization and
type of hybridization indicates the geometry of not the electrons.
the molecules.
Sr. No. Type of Orbital No. of hybrid orbital Geometry Example
1. One s + one p 2; sp Linear BeH2, BeCl2
2
2. One s + two p 3; sp Triangular BCl3, BF3
3
3. One s + trhee p 4; sp Tetrahedral CH4, CCl4
4. One s + three p + one d 5; sp3d Triangular bipyramidal PCl 5
3 2
5. One s + three p + two d 6; sp d Octahedral SF 6
3 3
6. One s + three p + three d 7; sp d Pentagonal bipyramidal IF7
Valence shell Electron pair Repulsion Theory (VSEPRT)

• The shape of a molecule depends upon the number of valence shell electron pairs (bonded or nonbonded)
around the central atom.
• Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.
• These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise
distance between them.
• The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum
distance from one another.
• A multiple bond is treated as if it is a single electron pair in VSEPR.
• lone pair - lone pair > Lone pair bond pair > bond pair - bond pair (order of repulsion)
Type of No.of No.of Shape Example
Hybridisation B.P. L.P.
sp-hybridisation 2 - Linear BeF2, CO2, CS2, BeCl2, HgCl2
a) sp2 hybridisation 3 - Trigonal planar BF3, AlCl3, BeF3–
b) sp2 hybridisation 2 1 V-shape, Angular NO2 ,SO2 ,O 3
a) sp3 hybridisation 4 0 Tetrahedral CH4 ,CCl4 ,PCl 4 ,ClO4 ,NH4 ,BF41 ,SO42 ,AlCl4
b) sp3 hybridisation 3 1 Pyramidal NH 3 ,PF3 ,ClO 3 ,H 3O  ,PCl 3 ,XeO 3 ,N(CH 3 ) 3 ,CH 3
c) sp3 hybridisation 2 2 V Shape H 2 O,H 2 S, NH 2
Angular OF2 ,Cl 2 O,SF2 ,I 3
a) sp3d-hybridisation 5 - Trigonal bipyramidal PCl5, SOF4, AsF5
b) sp3d-hybridisation 4 1 See Saw SF4 ,PF4 ,XeO 2F2
c) sp3d-hybridisation 3 2 Almost T shape ClF3, ICl3
d) sp3d-hybridisation 2 3 Linear I 3 , Br3 ,ICl 2 ,XeF2
a) sp3d2 hybridisation 6 - Square bipyramidal/ PCl 6 ,SF6

octahedral
3 2
b) sp d hybridisation 5 1 Square pyramidal XeOF4, ClF5, SF5–, XeF5+
c) sp3d2 hybridisation 4 2 Square planar XeF4
a) sp3d3 hybridisation 7 - Pentagonal bipyramidal IF7
b) sp3d3 hybridisation 6 1 distortedoctahedral XeF6
Super Note : In finding geometry both l.p. and b.p. are added but to find shape only b.p. are considered.
Geometry  Tetrahedral Geometry  Triangular bipyramidal Geometry  Octahedral
NH3 = SF4 = XeF4 =
Shape  Pyramidal Shape  see saw shape Shape  Square Planar
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Bonding Parameter Molecular Orbital Theory (MOT)
(bond length, bond angle & factors affecting) • M.O.T. explained existence and non-existence of
1. Bond Length various molecules, ions their bond order and
Internuclear distance magnetic behaviour.
Factor affecting Bond length Super Note : According to M.O.T. electrons are
considered in wave form
• Atomic size ; bond length  size [No. of shell]
Atomic orbitals  electron waves  interference
• EN, Bond length  1/EN
d AB  (rA  rB  0.09  EN)Å Constructive Destructive

interference interference
1 
• Bond order : Bond length  
B.O. Anti-Bonding
Bonding Molecular
• Hybridisation : Molecular Orbital
Orbital (BMO)
1 (ABMO)
Bond length  • Just as electrons of any atom are present in
% s  charater
various atomic orbitals, electrons of the molecule
Note : are present in various molecular orbitals.
Regular geometry/same hybridisation/ Bond • Molecular orbitals are formed by the
angle same BF3 = BCl3 = BBr3 = BI3 combination of atomic orbitals of comparable
1 energies and proper symmetry.
B.A. 
E.N. of size atoms • An electron in an atomic orbital is influenced by
one nucleus, while in a molecular orbital it is
1 influenced by two or more nuclei depending
B.A.  EN  B.O. 
size of atoms upon the number of the atoms in the molecule.
Thus an atomic orbital is monocentric while a
2. Bond Angle
molecular orbital is polycentric.
Angle between two adjacent bond is known as
• The number of molecular orbitals formed is equal
bond angle.
to the number of combining atomic orbitals.
Factor Affecting Bond angle When two atomic orbitals combine, two molecular
• Hybridisation orbitals called bonding molecular orbital and anti-
Bond angle  % s-character bonding molecular orbital are formed.
• The bonding molecular orbital has lower energy
C C C C and hence greater stability than the
corresponding antibonding molecular orbital.
3 2
sp sp sp • Just as the electron probability distribution
around anucleus in an atom is given by an atomic
109°28' 120° 180° orbital, the electron probability distribution
• No. of lp/bp around a group of nuclei in a molecule is given
[when hybridization is same] by molecular orbital.
• The molecular orbitals like the atomic orbitals
1   are filled in accordance with the Aufba principle
Bond angle  Eg. : CH  N H  H O :
lp 4 3 2 obeying the Pauli’s Exclusion principle and the
Hund’s Rule of Maximum Multiplicity. But the
• Type of central atom, Apply when :
filling order of these molecular orbitals is always
* hybridization same *No. of lp/bp same experimentally decided, there is no rule like
Bond angle  EN of central atom (n + l) rule was in case of atomic orbitals.
Eg. NH3 > PH3 > AsH3 > SbH3

Super Note : Super Note :
Same orbitals undergo LCAO or interference If two molecule or ions have same bond order than
according to M.O.T., s with s and p with p orbital molecule or ion with more electrons in A.B.M.O.
there is no mixing of orbitals according to M.O.T. is lesser stable for example N2– and H2– are lesser
like hybridisation. stable than N2+ and H2+ respectively.
Internuclear axis = Z
Energy level of 1s < *1s < 2s < *2s < (2p x = 2py ) < 2pz < ( *2px =  *2py) < *2pz Total Electrons < 14
molecular orbitals 1s < *1s < 2s < *2s < 2pz < ( 2px =  2py) < ( *2px =  *2pz) < *2pz Total Electrons > 14
Bond Order and Magnetic Behaviour • Species with 11, 13, 15, 16, 17, 19 electrons are
Bond order : paramegnetic.
No. of bonds present between two atoms. Isoelectronic species (CN– , NO+, C2, O2+ )
• Stability of molecules  B.O. • Same bond order  same magnetic properties.
• Bond Strength  B.O. N b  Na • In case of same bond order, stability depends
B.O. 
2 upon no. of anti-bonding electron/s
• Bond length  1/B.O.
• Bonding electron (Nb)  No. of electrons present 1
• Stability 
in BMO no. of anti bonding e 
• Anti-bonding electron (Na)  No. of electrons • Stability order = N2 > N2+ > N2–, N2 > H2+ > H2–
present in ABMO. • The bond order CO+ is 3.5 which is an exception.
Magnetic Nature : • In C2 molecule both the bonds are  and it is
• Species with 12, 14, 18, 20 electrons are diamagnetic.
dimegnetic.
Bond Order and Magnetic Behaviour
S.No. No. of electron BMO ABMO B.O. Paramagnetic/diamagnetic
1 1 1 0 0.5 Pramagnetic
2 2 2 0 1 Diamagnetic
3 3 2 1 0.5 Paramagnetic
4 4 2 2 0 Does not exist
10 10 6 4 1 Paramagnetic
14 14 10 4 3 Dimagnetic
16 16 10 6 2 Paramagnetic
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Dipole Moment • Differentiation between cis and trans alkenes.
• It is vector quantity and is defined as the product H CH3 H CH3
of the magnitude of charge on any of the atom C C
and the distance between the atoms. It is
represented by. C C
H CH3 CH 3 H
• Magnitude of dipole moment µ  0 µ 0
|µ|= q × r • Predict shape and polarity of molecule.

(charge in esu) (Distance in Å)
• The direction of dipole moment is from positive • Identification of Polar or Non-polar molecule.
to negative end. • Non-polar molecule : Symmetrical distribution
• Dipole moment is usually expressed in Debye of electron cloud H2, F2, Cl2, N2 etc.
units (D). 1 Debye = 1 × 10–18 e.s.u. cm. • Polar molecule : Unsymmetrical distribution of
• 1D = 3.33564 × 10 –30
C m, where C is coulomb electron cloud HF > HCl > HBr > HI
and m is meter.
E.N.
• Calculation of µ for Polyatomic Molecule : • µ 
bond angle
µ R  µ12  µ 22  2µ1µ 2 cos  • Molecules with regular geometry and same

peripheral atoms have zero dipole moment.
µR  Vector sum of bond moment
For Example : CO2 , BF 3 , CCl 4, PCl 5 , SF 6 , IF 7
Important Orders of Dipole Moment (Regular geometry = l.p. absent on central atom)
1) NH3 > NI3 > NBr3 > NCl3 > NF3
• In general molecule with lone-pair on central
2) CH3Cl > CH3F > CH3Br > CH3I atom have non-zero dipole moment.
3) CH3Cl > CH2Cl2 > CHCl3 > CCl4 For example : NH3, H2O, SO2, SF4
4) H2O > H2 S Super Note : Critical temperature and surface
5) CD3Cl > CH3Cl tension represent attraction between the molecules.
6) SO2 > CO2 . • Some molecules enven with lone-pair on central
atom have zero dipole moment.
Application of Dipole Moment
• % Ionic character of a covalent bond = For example : XeF4, XeF2
• Molecule with higher dipole moment have
Experimental dipole moment greater critical temperature and surface tension.
 100
Theoretical dipole moment assuming
• A symmetrical molecule is non-polar even
100% ionic character
though it contains polar bonds.
• Orientation of substituent groups on benzene For example : Carbon dioxide, methane and
ring carbon tetrachloride, being symmetrical
molecules, have zero dipole moments.
Cl  Cl Cl
Cl  Super Note : Bond moment - It defines polarity in
 a bond.
> >
Cl Dipole moment it defines polarity (ionic character)
Cl in a molecule.
Orthodichloro metadichloro paradichloro
benzene benzene benzene

Ionic Bond • Greater the distortion of anion, greater will be
• Transfer of electron/s. polarisation as a result of which covalent
character increases.
• In other words extreme polar covalent bond is charge of cation
an ionic bond. • Polorizing power of cation ()
size of cation
(Al+3 > Mg+2 > Li+ > Na+)
• In between metal non-metal.
• Polarisability of anion  charge of anion
• Formation of Ionic Bond, via Electrostatic force
of attraction. (F– < Cl– < Br– < I–), (F– < O–2 > N–3)
• Non directional in nature. Factors Affecting Polarisation
• Eg. NaCl, KF • Polarisation  charge of cation or anion.
2 3 6
Properties of Ionic Salt • CrO  Cr 2 O3  Cr O3 Covalent character
• Hard, Solid, Brittle (Strong electrostatic force of 2 4 6
attraction between ions) • SF 2  SF 4  SF 6 Covalent character
1 2 3
• Non directional nature (ionic compound do not • Li F  Li 2 O  Li 3 N Covalent character
exhibit stereoisomerism)
(anion charge)
• Higher Melting Point/Boiling Point.
• Isomorphism : size of anion
• Polarisation 
MgSO4 7H2O; ZnSO47H2 O; FeSO47H2 O. size of cation
Energetics of Ionic Bond Anion size 
• LiF > LiCl > LiBr > LiI Polarisability of anion 
Hf + – Covalent character
M(s) + X2(g) M X (s)
H(sub) H(dies) Cation size 

• BeCl 2>MgCl 2>CaCl 2>SrCl 2>BaCl 2 Polarisability of cation 
M(g) X(g) Covalent character
–
–e IE
–
+e Heg Application of Fajan’s Rule
+ –
• Variation of M.P. [M.P. of covalent < M.P. of
M (g) X (g) ionic] BeCl2 < MgCl2 < CaCl2 < SrCl2 < BaCl2
HL.E.
• Ag2S is less soluble than Ag2O in H2O because
Hf = heat of formation M+X–
Ag2S is more covalent due to bigger S2– ion.
H(sub) = heat of sublimation of M
• Solubility order
Hi = ionisation energy of M
H(diss) = heat of dissociation of X2 Na2S > ZnS > CuS (Zn2+(r) > Cu2+(r)),
Heg = electron gain enthalpy of X polarizing power of Cu2+ is greater than Zn3+.
ULE = Lattice energy of M+X–. • Fe(OH)3 easily form precipitate in water than
So according to Hess’ law. Fe(OH)2 .
Hf = H(sub) + Hi + H(diss) + Heg + HLE • The colour of some compound can be explained
Fajan’s Rule on the basis of polarization of their bigger
negative ions.
• Fajan’s Rule explained covalent character in ionic
compound. • For example : AgCl is colour less but AgBr and
AgI are yellow deu to large size of Br– and I–.
• According to Fajan’s rule no compound is 100% ionic.
Concept of Solubility
• Even most ionic compound CsF has 9% covalent
characters. • Solubility of S-block salts is determined on the
basis of hydration enthalpy and lattice enthalpy.
• Fajans pointed out that greater the polarization
• Solubility of p & d-block salts is determined on
of anion in a molecule, greater is the covalent
the basis of Fajan’s rule.
character in it.
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Lattice Energy (U) or HLE Trick to find Solubility
• The lattice energy of an ionic solid is the amount
Solubility of s-block salts depends on
of energy relesed during the formation of one
mole of ionic solid from gaseous constituent ions. lattice and hydration enthalpy
• If common ion smaller, L.E. decides solubility
Factors Affecting Lattice Energy of An Ionic
Compound : IA –2 – – –2 –2
O , OH , F , SO 4, CO 3
Solubility   size
O –2, OH –, F –
Z , Z IIA
• Lattice energy 
(r   r  ) • If common ion is larger, H.E. decides solubility
IA
Br–, I– , ClO4–
• + –
(r + r ) = Inter-ionic distance. Solubility HE
Co3 –2
, SO4–2, NO3,– Br –, I –, S –2, Cl–
IIA
• Z+/Z–  charge on cation and anion respectively.
• Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
• Lattice energy  coordination number (C.N.) I
• Common ion smaller (CO3–2), solubility 
• Lattice energy should be less than hydration LE
energy for solubility of ionic compound. BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3
Common ion larger (CO3–2), solubility  HE
• Lattice energy decides solubility of s-block salts
having small common ion. Solubility of p & d-block salts depends
on Fajan’s Rule
Hydration Energy
• PbF2 > PbCl2 > PbBr2 > PbI2
• Hydration enthalpy is the amount of energy
released when one mole of gaeous ions combine (Anion size , cov. Char. , Solubility )
with water to form hydrated ions. • Fe(OH)2 > Fe (OH)3
(+) charge , PP, CC, solubility
charge • ZnCl2 > CdCl2 > HgCl2
• Hydration  2
 size  Zeff, PP, CC, solubility
• AgF > AgCl > AgBr > AgI
• More the hydration more is hydrated radius.
Anionic size, PP, CC, solubility
• More the hydrated radius lesser the ionic • NaCl > CuCl
mobility. PP, CC, solubility
• Li+
>Na +
>K + +
>Rb (aq)>Cs +
(hydrated radius) P.P. = Polarity Power
(aq) (aq) (aq) (aq)
C.C. = Covalent Character
• Li+(aq)<Na+(aq)<K+(aq)<Rb+(aq)<Cs+(aq) (ionic radius) Co-ordinate Bond (Dative Bond)
• Lithium is strongest reducing agent due to high • First transfer then sharing of electron/s.
hydration enthalpy.
• In ionic bond electrons are transferred, in
• Fluorine is strongest oxidizing agent also due to covalent bond electrons are shared, but in co-
high hydration enthalpy. ordinate bond electrons first transfer then shared.
• Hydration Energy determines solubility of • Also known as Co-ionic, semi-polar or Dative

s-block for large common Anions. bond.
• Both electrons come from single atom/molecule.
• Example : NH4+, O3, H2SO4, HNO3, H3O+, N2O,
[Cu(NH3 )4 ]2+
• Formed between lewis base and lewis acid.

Physicsl Properties Comparison between IA & IIA
IA IIA
Order of metallic CS > Rb > K > Na > Li Ba > Br > Ca > Mg > Be
Or Ionic radii
Reason up to down size increases up to down size increases
Order of density Cs > Rb > Na > K > Li Ba  Sr  Be  Mg > Ca
Reason due to empty d orbital in k due to empty d orbital density of

density of K < Na Ca < Mg and due to small size
of Be density of Be > Mg
Order of MP & BP Li > Na > K > Rb > Cs Be > Ca > Sr > Ba > Mg
Reason On increasing size packing efficiency decreases
Order of hydration Li > Na+ > K+ > Rb+ > Cs+
+
Be+2 > Mg+2 > Ca+2 > Sr+2 > Ba+2
in cation
Reason Up to down size increases and charge density decreases hydration  charge density
Order of conductivity Cs+ > Rb+ > K+ > Na+ > Li+ Ba+2 > Sr+2 > Ca+2 > Mg+2 > Be+2
of cation in polar
solvent like water
Reason Up to down size of hydrated ion decreases
Order of conductivity Li > Na > K+ > Rb+ > Cs+
+ +
Be+2 > Mg+2 > Ca+2 > Sr+2 > Ba+2
Chemical Properties Comparison between IA & IIA
IA IIA
Reactivity towards O2
M H 2O
M2O  CO 2
 MOH  M2CO3
O2
MMO   M OH  
H 2O CO 2
 MCO3
2
moist air
Reason Li when heated in air it also Be when heated in air it also
forms nitride forms nitride
Reacitivty towards Li-Normal oxide, Na-peroxide, Be-Normal oxide, Mg-Normal oxide
Oxygen K-Super oxide, Rb-Super oxide, Ca-Peroxide, Sr-peroxide, Ba-Peroxide
Cs-Super oxide
Reason Up to down size increases so affinity towards oxygen increses.
Reactivity towards H2O Li < Na < K < Rb < Cs Be < Ca < Sr < Ba < Mg
Reducing Power Li is strongest reducing due to Be is weakest reducing agent due to
high heat of hydration high heat of Atomization
Affinity towards H2 2M + H2  2MH M + H2  MH2
Stability of Hydride LiH > NaH > KH > RbH > CsH BeH2 > MgH2 > CaH2 > SrH2 > BaH2
Reaction with
M + (X + Y)NH3  M + (NH3 )x +e   NH3 y M + (X + Y)NH3  M 2+ (NH3 )x +2e   NH 3  y
liquid NH3
Ammoniated electrons Ammoniated electrons
Due to ammoniated electrons solution become deep blue and with respect to time this blue colour
fades due to formation of metal amide.
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• Be and Mg salts do not impart colour to flame.
Diagonal Relationship
• Be does not form peroxide like other alkaline
earth metals.
Li shows resemblance Be shows resemblace • It salts can never have more than four molecules
with Al, an element of of water of crystallization as it has only four
with Mg, an element
group 13th available orbitals in its valence shell.
of group 2 nd.
• Beryllium carbide reacts with water to give
Group 1 st Group 2 nd Group 13th methane whereas magnesium carbide and
Li Be B calcium carbide give propyne and acetylene
respectively.
Na Mg Al
Type of Hydride
Abnormal Properties of Lithium • Ionic/salt like/saline
• Due to its small size and high charge density *form ionic bond* give H– in H2O
(atom and ion.) Eg. s, p-block metal
• LiOH, Li2CO3, LiNO3 behave differently than BeH2 and LiH are more covalent
other alkali corresponding salts towards heating
• Covalent/molecular
2LiOH  Li2O + H2O;
Form covalent bond give H+ in H2O
Li2CO3  Li2O + CO2 ; Eg. p-block non-metal
4LiNO3  2Li2O + 4NO2 + O2 • Interstitial hydride
Hydroxides and carbonates of other alkali metals Do not form strong bond, do not give H+ and H–
are stable. The nitrates of other metals decompose in H2O
to give only oxygen. Eg. d and f-block metal
• Lithium directly combines with nitrogen
Comparison of Properties of Beryllium
6Li + N2  2Li3N. with other elements of the group
• LiHCO3 is known only in solution but not in Beryllium
solid state.
• Forms covalent compounds.
• Li2SO4 does not form double salt.
• High melting and boiling point.
• LiF, Li 3 PO 4 , Li 2 C 2 O 4 , Li 2 CO 3 are sparingly
• Does not react with water even at elevated
soluble in water.
temperature.
Abnormal Properties of Beryllium
• Does not combine directly with hydrogen.
• Due to its small size and high charge density • Does not combine directly with halogens. Halides
(atom and ion.)
are covalent.
• Be is lightest alkaline earth metal. Order of Thermal Stability
• Be possesses higher m.pt. and b.pt than other • Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
group members.
• LiH > NaH > KH > RbH > CsH
• BeO is amphoteric in nature whereas oxides of
other group members are strong base. • BeH2 > MgH2 > CaH2 > SrH2 > BaH2
• BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3
• It is not easily effected by dry air and does not
decompose water at ordinary temperature. • BeSO4 < MgSO4 < CaSO4 < SrSO4 < BaSO4
• BeSO4 is soluble in water. • Instability of BeCO3 & BeSO4 is due to small size
of Be2+ ion which is unable to stabilize the bigger
• Be and Mg carbonates are not precipitated by
CO3 2– & SO4 2– .
(NH4)2CO3 in presence of NH4Cl.
Other elements of the family Salt of Oxo-acids
• Form ionic compounds. • The alkali metals are highly electropositive,
therefore their hydroxides are very strong bases
• Low melting and boiling point.
and thus they form salts with all oxoacids and
• React with water. hydracids.
• Combine directly with hydrogen. • They are generally soluble in water and stable
• Combine directly with halogens Halides are towards heat. The carbonates (M2CO3) of alkali
electrovalent. metals are remarkably stable upto 1273K, above
which they first melt and then eventually
Order of Solubility
decompose to form oxides.
• Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
• Li2CO3, however is considerably less stable and
• LiOH < NaOH < KOH < RbOH < CsOH decomposes readily.
• Be(OH) 2 < Mg(OH) 2 < Ca(OH) 2 < Sr(OH) 2 < Li2CO3  Li2O + CO2
Ba(OH)2
• This is due to large size difference between Li+
• BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3 and CO 3 2– which makes the crystal lattice
• BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4 unstable.
• For carbonates and sulphates of IIA increase in • The stability of the carbonates increases in the order:
lattice energy down the group which
Cs2CO3 > Rb2CO3 > K2CO3 > Na2CO3 > Li2CO3
predominates over hydration energy so that
solubility decreases down the group. • Being strongly basic, alkali metals also form solid
bicarbonates.
General Characteristics of The Compounds
of The Alkali Metal • Lithium, however does not form solid
bicarbonates though it exist in solution.
Oxides and Hydroxides
• Aqueous solutions of carbnates and bicarbonates
• The oxides and the peroxides are colourless when
are basic in nature due to anionic hydrolysis.
pure, but the superoxides are yellow or orange
in colour and paramagnetic due to presence of Some Important Compounds of Sodium
unpaired electron in superoxide ion.
Sodium Carbonate (Washing soda, Na2CO3.10H2O
Eg. KO 2 Orange
• Sodium carbonate is generally prepared by
RbO 2 Brown
Solvay Process and Leblanc process.
• Sodium peroxide is used as oxidising agent in
• Due to low solubility of sodium hydrogen
purifying air because it release oxygen reacts with
carbonate, it gets precipitated in the reaction of
carbon dioxide.
sodium chloride with ammonium hydrogen
2Na2O2 + 2CO2  2Na2CO3 + O2 carbonate. (NH4 HCO3 )
• The oxides are easily hydrolysed by water to form 2NH3 + H2O + CO2  (NH4)2 CO3
the hydroxides.
(NH4)2CO3 + H2O + CO2  2NH4+ + 2HCO3–
M2O + H2 O  2MOH
NH4HCO3 + NaCl  NH4Cl + NaHCO3
M2O2 + 2H2O  2MOH + H2O2
• In the process NH3 is recoverd when the solution
2MO2 + 2H2 O  2MOH + H2O2 + O2
containing NH 4 Cl is treated with Ca(OH) 2 .
• The alkali metal hydroxides are strongest of all Calcium chloride is obtained as a by-product.
bases and dissolve in water with evolution of heat
due to high enthalpy of hydration. 2NH4Cl + Ca(OH)2  2NH3 + CaCl2 + H2O
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Super Note : General Characteristics of The Compounds of
• Solvay process cannot be extended to the The Alkaline Earth Metal
manufacture of potassium carbonate because Oxides and hydroxides
potassium hydrogencarbonate is too soluble to
• The alkaline earth metal oxides, MO are prepared
be precipitated by the addition of ammonium
either by heating the metals in oxygen
hydrogencarbonate to a saturated solution of
potassium chloride. 2Ca + O2 
heat
 2CaO
Properties :
CaCO3 
heat
 CaO + CO2
• This is also called washing soda. It is readily
soluble in water. On heating, the decahydrate • Except BeO(Wurtzite sturcture) all the alkaline
loses its water of crystallisation to form earth oxides are ionic in which doubly ions are
monohydrate. packed in a NaCl type of lattice (6 : 6) leading to
their high crystal lattice energy and thus high
• Above 373 K, the anhydrous and monohydrate stability.
changes to becomes a white powder called soda
ash. • However beryllium oxide is covalent due to small
size and relatively large charge the beryllium ion.
Na2 CO 310H2 O 
375K
 Na2 CO 3.H 2 O + 9H2 O MO + H2O  M(OH)2 + Heat;
N2CO3 H2 O 
above 373K Na2 CO3 + H2 O • The solubility of hydroxides of alkaline earth
metals in water increases on moving down the
Sodium Hydroxide (Caustic Soda), NaOH
group. The increasing solubility of the
• It is generally prepared by electolysis of sodium hydroxides on moving doen the group is evident
chloride in Castner-kellner cell. A brine solution from their solubility products.
is electrolyzed using mercury cathode and
• Due to the small size, high electronegativity and
carbon anode.
high ionisation energy of beryllium, the oxides
• Reaction at Cathode - NaCl  Na+ + Cl– and hydroxides of beryllium are more covalent
Na+ + e– + Hg  Na – Hg than ionic and thus are amphoteric.
Be(OH)2 + 2HCl  BeCl2 + 2H2 O
1
• Reactions at anode - Cl–  Cl2 + e– Be(OH)2 + 2NaOH  Na2BeO2 + 2H2 O
2
• On the other hand, the oxides and hydroxides
• The amalgam is treated with water to give sodium of the other metals are basic in charater and their
hydoxide and hydrogen gas basicity increases on moving down the group.
2NaHg + 2H2O  2NaOH + 2Hg + H2 Be(OH)2<Mg(OH)2<Ca(OH)2<Sr(OH)2<Ba(OH)2
Uses : Salt of Oxo-acids
• It is used in the manufacture of soap, paper,
i) Carbonates
artificial silk and a number chemicals,
• The carbonates dissolve in water in the presence
• Sodium hydrogencarbonate (Baking Soda), NaHCO3
of carbon dioxide to give bicarbonates.
Na2CO3 + H2O + CO2  2NaHCO3
CaCO3 + H2O + CO2  Ca(HCO3)2
• It is mild antiseptic for skn infections.
Calcium Calcium
Biological Importance Sodium and Potassium
Carbonate Bicarbonate
• Na+ and K + are present ins doium Pump.
• This process is responsible for maintaing large
excess of Na+ outside the cell and large excess of
K+ ions the inside of cell.

ii) Sulphates Some Important Componds of Calcium
• These can be prepared by dissolving the metal
Calcium Oxide, CaO
oxide in H2SO4.
• CaO is known as quick lime.
MgO + H2SO4  MgSO4 + H2O
• One calcination of lime stone (CaCO3), CaO is
iii) Nitrates formed.
• Magnesium nitrate crystallises with six molecules 1070K
CaCO3   CaO + CO2 
of water, whereas barium nitrate crystallises as 
the anhydrous salt. • Reverse reaction is suppresed by removing CO2

• This again shows a decreasing tendency to form lim lime kilns by calcining lime stone in an open
hydrates with increasing size and decreasing vessel.
hydration enthalpy.
• CaC2 + N2  CaCN2 + C
All of them decompose on heating to give the
• CaCN2 + C - Nitrolium.
respective oxide.
2M(NO3)2  2MO + 4MNO2 + O2 • As limestone contains clay as impurity it reacts
at high temperature with CaO to form a fusible
(M = Be, Mg, Ca, Sr, Ba) slag (CaSiO3).
Halides CaO + SiO2  CaSiO3
M + 2HX  MX2 + H2
6CaO + P4P10  2Ca3(PO4)2
M(OH)2 + 2HX  MX2 + H2O
Calcium Hydroxide (Slaked lime), Ca(OH)2
MCO3 + 2HX  MX2 + CO2 + H2O
• Calcium hydroxide in prepared by adding water
• Beryllium halides are covalent compounds due to quick lime, CaO.
to small size and relatively high charge on Be2+
ion causing high polarising power. CaO + H2O  Ca(OH)2
• Due to covalent bonding, beryllium chloride, a • The aqueous solution is known as lime water and
typical member of beryllium halides, shows a suspension of slaked lime in water is known as
following anomalous characteristics. milk of lime.
• It does not conduct electricity in the fused state. • CO2 is passed through lime water and forms
calcium carbnate (White ppt.)
• Beryllium chloride reacts with lithium aluminium
hydride to form the following products. Ca(OH)2 + CO2  CaCO3 + H2 O
2BeCl2 + LiAlH4  2BeH2 + AlCl3 + LiCl CaCO3 + CO2 + H2 O  Ca(HCO3)2
• Hygroscopic nature of beryllium halides is due • Milk of lime reacts with chlorine to form
to the fact that Be2+ ion has value of hydration bleaching powder Ca(OCl)2
energy and therefore has strong tendency to form
hydrates. 2Ca(OH)2 + 2Cl2  CaCl2 + Ca(OCl)2 + 2H2O
• It is electron-deficient and behaves as Lewis acid. Calcium Sulphate

Beryllium chloride exhibits different structure in • Calcium sulphate is formed when lime stone
the vapour and in the solid states, as shown (CaCO3) is treated with dilute H2SO4
below:
CaCO3 + H2SO4  CaSO4 + H2 O + CO2
Cl – Be – Cl monomeric
• On concentrating and crystallising calcium
Cl sulphate dihydrate (CaSO4.2H2O) separates out.
Cl – Be Be – Cl Dimeric
Cl
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Super Note : • The composition of the portland cement :
• CaSO4.2H2O is called as gypsum. CaO 50–60%
• CaSO4.2H2O, is heated to 393 K. to form plaster SiO 2 20–50%
of paris. Al 2O3 5–10%
• 2(CaSO4.2H2 O)  2(CaSO4)H2 O + 3H2 O MgO 2–3%
• Above 393 K, no water of crystallisation is left Fe2O 3 1-2%
and anhydrous calcium sulphate, CaSO 4 is
formed. This is known as ‘dead burnt plaster’. SO 3 1–2%
• Plaster of paris is CaSO4.½H2O (or) 2CaSO4.H2O • Portland cement contains the important
ingredients as
• Plaster of paris is thus hemihydrate (or)
semihydrate of calcium sulphate. Dicalcium silicate (Ca2.SiO4) 26%
• It is prepared by heating gypsum at 1200 – 1300°C. Tricalcium silicate (Ca3SiO5) 51%

Tricalcium aluminate (Ca3Al2O6) 11%
390 K 1 3
CaSO4  2H2O   CaSO4 H2O + H2 O Biological Importance Of Mg2+ And Ca2+
2 2
Mg2+ in Biology
Cement
• Mg2+ is a constituent of chlorophyll, the green
• It is important building material. It was
pigment in plants and Mg2+ is complexed with
introduced by Joseph Aspdin. It resembles with
ATP.
natural limestone so it is also called as power plant
cement. Ca2+ in Biology
• Cement is a dirty greyish heavy powder • Ca 2+ ions are necessary for blood clotting,
containing calcium aluminates and silicates. maintain heart beating, muscles contraction.
General Difference Between IA & IIA

Alkali Metals Versus Alkaline Earth Metals
• Alkali metals are soft • Alkaline earth metal are hard
• Each alkali metal has single electron • Each alkaline earth metal has two electrons.
• Have low melting points. • Have relatively high melting points.
• Hydroxides are strongly basic. • Hydroxides are relatively less basic.
• Carbonates do not decompose • Carbonates decompose to form oxide when
heated to this temperature.
• Nitrates give corresponding nitrates and • Nitrates give corresponding oxides, nitrogen
oxygen as products dioxide and oxygen as products
• Bicarbonates exist in solid form at room • Bicarbonates exist in solution form at room
temperature. temperature.
• Lithium, sodium, potassium, rubidium, • Beryllium, magnesium, calcium, strontium,
cesium and fracium are examples. barium and radium are examples.

p-Block Elements Extent of back bonding :
Conceptual Part BF  BCl 3  BBr3  BI3
3
2p 2p 2p 3p 2p 4p 2p 5p
Back Bonding Allotropes
Inert pair effect Silicate/Silicones Lewis acid strength :
Hydrolysis Bleaching Agent BF3 < BCl3 < BBr3 < BI4
Oxyacids Few more examples of back bonding :
Compound of p-block 1. Shape of trimethyl amine pyramidal while shape
13 group - Borax, H3BO3, B2H6 Alum of trisillyl amine is triangular planar.
14 group - CO, CO2, carbides
15 group - N2, NH3, oxides, HNO3, PH3, PCl3 , pyramidal SiH 3
PCl5 oxides N
CH3 CH 3 N Back bond
16 group - O2, O3, H2S, SO2, H2SO4 CH3 SiH 3 SiH 3
17 group - X2, Cl2, HCl, CaOCl2 No back bonding due to Trigonal Planar
no vacant orbital in carbon
18 group - Xenon fluorides.
Back Bonding 2. Lewis base strength
• Coordinate type  bond. N(CH3)3 > N(SiH3)3

• If coordinate type  bond get form between lp involve in
back bonding
central atom & bonded atom of a molecule it is
known as back bonding. 3. Bond angle of (CH3)2O is very less than (SiH3)2O
Condition for formation of back bonding
• One species must have lone pair.
O O
• Another species must have vacant orbital. CH3
CH 3 SiH3 SiH3
• Size of atom should be small. No back bonding back bond effect of lp
C : No vacant orbital bond angle 
Eg.1 Back bonding in Boron Trihalide
Inert Pair Effect
X
P – P X = F, Cl, Br, I
• Some heavy metallic elements of P-block exhibit
back X  Contain lp - donar
B bonding higher stability in lower oxidation state in
B  Contain vacant
X X comparisons of their group oxidation state it is
orbital - acceptor
due to inert pair effect.
Eg.2 Exhibit resonance in back bond • Tl+1 > Tl+3, Pb+2 > Pb+4, Bi +3 > Bi+5
X X X X Electron pair of s-subshell of valence shell is

 reluctant to participate during chemical
B B B B combination, it is known as inert pair & this effect
X X X X X X X X is known as inert pair effect.
Resonance
hybrid
• It is due to higher amount of energy required
for this electron pair removal which is not
compensated by bond formation energy.
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• Generally in oxide & fluorides inert pair effect 15th Group Halides
becomes non-effective (due to higher bond
ordinary
energy) • N F3 + HOH 
conditions
 No hydrolysis
Due to inert pair effect : • NCl3 + HOH  NH3 + 3HOCl
TlCl exist but not TlCl3 • PCl3 + HOH  H3PO3 + 3HCl
PbI2 exist but not PbI4 • AsCl3 + HOH  As(OH)3 + 3HCl
BiCl3 exist but not BiCl5 • SbCl3 + HOH  SbOCl  2HCl
( partial hydrolysis)
Order of stability of oxidation state :
B+3 > Al+3 > Ga+3 > In+3 > Tl+3 • BiCl3 + HOH  BiOCl  2HCl
(partial hydrolysis)
+ + + + +
B < Al < Ga < In < Tl
• PCl5 + HOH  POCl 3  H 3PO 4
C2+ < Si2+ < Gu2+ < Sn2+ < Pb2+ partial completely
Hydrolysis (Hydro - Waterlysis - break down) Hydrolysis of higher covalent character

Break down of a molecule through water and containing slat
formation of new product is known as
• Be2C + 4HOH  2Be(OH)2 + CH4
hydrolysis.
• Mg2C3 + 4HOH  2Mg(OH)2 + C3H4
• It is nucleophilic substitution reaction.
• CaC2 + 2HOH  Ca(OH)2 + C2H2
• HOH + MX H–O---M–X M–OH + HX • Al4C3 + 12HOH  4Al(OH)3 + 3CH4

H • Mg3N2 + 6HOH  3Mg(OH)2 + 2NH3
molecule Intermediate Product
• AlN + 3HOH  Al(OH)3 + NH3
Extent of hydrolysis  covalent character. • Ca3P2 + 6HOH  3Ca(OH)2 + 2Ph3
• BeCl2 + 2HOH  Be(OH)2 + 2HCl • LiH + HOH  LiOH + H2
• BCl3 + 3HOH  B(OH)3 + 3HCl • CaH2 + 2HOH  Ca(OH)2 + H2
• AlCl3 + 3HOH  Al(OH)3 + 3HCl Hydrolysis of Interhalogen Compounds
• SiCl4 + 4HOH  Si(OH)4 + 4HCl HX Hydrohalic acid HOA, HAO2, HAO3, HAO4
oxyacid of halogen.
• SF6 + H2O  No hydrolysis due to crowding
• AX + HOH  HX + HOA
ordinary
• CCl4 + HOH  No hydrolysis
conditions • AX3 + HOH  3HX + HAO2
• Carbon  No vacant orbital. • AX5 + HOH  5HX HAO3

• AX7 + HOH  7HX + HAO4
• BF3 + 3HOH  B(OH)3 + 3HF
Some specific hydrolysis
• 3BF3 + 3HF  3H+ [BF4]–
HOH
• 4BF3 + 3H2O  3H[BF4] • XeF
2  Xe + 2HF + O2
(partially hydrolysis) • HOH

6XeF
4  4Xe + 2XeO3 + 24HF + 3O2
Similarly XeOF4 HOH 2HF +
HOH
• XeF
6  2HF + partial

• SiF4 + 4HOH  Si(OH)4 + 4HF
• 2SiF4 + 4HF  H2+[SiF6]2– XeO 2 F2 HOH 2HF + XeO3
partial
 complete
hydrolysis followed by Lewis acid-base reaction.

Oxy-Acids Oxyacids of Sulphur :
• Mainly oxy-acids are hydroxide of Non-metal • Sulphurous acid - H2SO3
oxides. • Sulphuric acid - H2SO4
• No. of H+ in furnish by an oxyacid is known as • Thiosulphuric acid - H2S2O3
their basicity. Oxyacid obtained by dissolving
• Peroxymonosulphuric (Caro’s acid) - H 2 SO 5
non-metal oxide in water.
(Peroxide bond)
Eg. CO2 + HOH  H2CO3 or OC(OH)2
• Peroxydisulphuric acid (Marshal’s acid) - H2S2O8
Here : CO2  Non metal oxide - Anhydride of - (Peroxide bond)
carbonic acid • Pyrosulphurous acid - H2S2O5 - (S-S linakge)
OC(OH)2  Oxyacid • Pyrosulphuric acid - H2S2O7 (S-O-S linkage)
• NO2  Mixed anhydride • Thionus acid - H2S2O4
• it gives  HNO2 & HNO3 • Thionic acid - H2S2O6
OxideAcid • Polythionus acid - H2(S)nO4 (S-S linkage)
• N2O3  HNO2 – Nitrous acid • Polythionic acid - H2(S)nO6 (S-S linkage)
• N2O5  HNO3 – Nitric acid Oxyacids of Halogen (Cl)
• P4O10  H3PO4 – Phosphoric acid • Hypochlorous acid - HClO
• SO2  H2SO3 – Sulphurous acid • Chlorous acid - HClO2
• SO3  H2SO4 – Sulphuric acid • Chloric acid - HClO3
• Cl2O7  HClO4 – Perchloric acid • Perchloric acid - HClO4
• Oxyacids of different elements Order of acidic strength
Order of acidic strength
• HClO < HClO2 < HClO3 < HClO4
H3PO2 > H3PO3 > H3 PO4
Oxidising nature
Reducing Nature
• HClO > HClO2 > HClO3 > HClO4
H3PO2 > H3PO3 > H3PO4
Allotropy
Element Oxide Oxyacid Basicity
• Those substance which are made up of same
1 Boron B2 O 3 B(OH)3 Not protonic acid
boric acid monobasic elements but having different bonding
2 Carbon CO 2 H2 CO 3 Two arrangement are known as allotropes & this
3. Nitrogen H2 N2 O 2 phenomenon known as allotropy.
Hyponitrous acid • Those elements which exhibit higher tendency
HNO2 of catenation exhibit higher tendency of allotropy.
Nitrous acid
• Therefore carbon, phosphorus & sulphur exhibit
HNO3
maximum allotropy.
Nitric acid
HNO4 Allotropes of Carbon
Pernitric acid Diamond :
4. Phosphorus H3 PO 2 • C-sp3, tetrahedral structure
Hypophosphorus acid • C-C bond length 1.54 Å
H3 PO 3
• Compact 3 dimensional structure
Phosphorus acid
H3 PO 4 • Hardest substance
Ortho phosphoric acid • Very high mp (~3400°C)
HPO3 • Very high density.
Meta phosphoric acid
• Non conductor.
H4 P 2 O 5
Pyrophosphorus acid
• Very high refractive index
H4 P 2 O 6 • Exhibit total internal reflection
Hypophosphoric acid • Shines brighty in light
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Grapite : Hexagonal layer structure • Contain pentangon & hexagonal structure
• All sp2 hybrid carbon Unhybrid orbital electron • C60 : Buckminster fullerence soccer ball (football)
form -bond. This -bond exhibit resonance and or bucky ball.
due to resonance there is mobility of electrons • C60 : 20 hexagon rings
and it becomes conductor of electricity. • 12pentangon rings.
Fullerene : Latest discovered allotrope of • Purest form of carbon
carbon it is found in chimney sooty particle. • No dagling bond.
• It contain C60–C320; C : sp2 hybrid
Allotropes of Phosphorous
a) White phsophorous b) Red phsophorous c) Black phsophorous
White phsophorous Red phsophorous
Waxy solid Brittle powder
Poisonous Non poisonous
Soluble in CS2, Insoluble in water Insoluble in water & CS2
Monomer of P4 Polymer of P4
Highly reactive due to bond angle strain More stable than white phosphorous
It glows in dark due to slow oxidation (phosphorescence) It does not glow in dark
It gives phosphine (PH3) on reaction with NaOH It gives hypo phosphoric acid on
reaction with NaOH
Order of stability of MP or density  white < red < black
803K
Red Phosphorous -Black Phosphorous
high P
inert
573K
medium
473K
White Phosphorous -Black Phosphorous
high P
Allotropes of Sulphur
S
Crystalline Amorphous
Phombic sulphur (-S) Milk of sulphur
most stable form Plastic sulphur (-S)
Monoclinic sulphur (-S) Colloidal sulphur
>95.6°C
-S -S H2S + 2HNO3 Redox S + 2NO2 + 2H2O
<95°, 6°C RA OA
a) density of S > S
b) Both are puckered crown shape having S8 units.
c) S2 is paramagnetic sulphur which exist in vapour form at high temperature.
d) S6 is chair form of S
Effect of 95.5°C 119°C 130-200°C Viscosity of >200°C Viscosity
S 8() S8() S(liq)
Temperature liquid increase decrease
13th Group : Boron Family
Periodic Trends and Chemical 1) Reaction with Air
Reactivity of elements 4B+3O2  2B2O3
1. Atomic radius : 4Al+3O2  2Al2O3
B < Ga < Al < In < Tl 2B+N2  2BN
2. Ionisation Potential (IP) 2Al+N2  2AlN
IP1  B > Tl > Ga > Al > In
Note :
IP2  B > Ga > Tl > In > Al
B2O3(Acidic), Al2O3, Ga2O3 are amphoteric,
IP3  B > Ga > Tl > Al > In
In2O3, Tl2O are basic
Overall :
2) With Acids and Alkalies
B > Tl > Ga > Al > In
• Since Al is amphoteric it react with both acids and
3. Density :
bases
B < Al < Ga < In < Tl
4. MP : B > Al > Tl > In > Ga 2 Al( s )  6HCl( aq )  2 Al(3aq )  6Cl(aq )  3H 2( g )
5. BP : B > Al > Ga > In > Tl
Al(s)+Con. HNO3  Passive due to (Al2O3 layer)
6. EN : B > Tl > In > Ga > Al
2 Al( s )  2 NaOH(aq )  6H 2O(l )  2 Na [ Al (OH )4 ](aq )  3H 2( g )
7. Chemical Reactivity Sodiumtetra hydroxo alu min ate ( III )
• Boron forms an oxide and a nitride when burnt in • Reactivity Towards Halogens
air. But Al does not undergo any change and remains
unreact because it forms an oxide layer 2 E( s )  3 X 2( g )  2 EX 3( s ) ( X  F , Cl , Br , I )
• At high temperature Al gives its nitride. E = B, Al, Ga, In, Tl
Note : TlI3 not formed directly (due to inert pair effect)
Compounds of Boron
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Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

14th Group : Carbon Family
Periodic Trends of Elements and 8. Reacitivity Towards water :
their Compound • C, Si, Ge are unaffected by water.
1. Atomic radius : • Sn reac ts with steam to give SnO 2 and H 2.
C < Si < Ge < Sn < Pb 

Sn+2H 2 O   SnO2  2 H 2
2. Ionisation Potential (IP) • Pb is not effected by water due to an oxide layer on
IP1  C > Si > Ge > Sn > Pb the surface.
IP2  C > Si > Ge > Pb > Sn 9. Reactivity Towards Halogens :
IP3  C > Ge > Si > Pb > Sn • The members of the group form two types of halides.
3. Density : Pb > Sn > Ge > C > Si They are dihalides (MX2) and tetra halides (MX4 )
except PbBr4 and PbI4.
4. MP : C > Si > Ge > Pb > Sn
• The thermal stability of tetrahalides decreases in the
5. BP : C > Ge > Sn > Si > Pb order
6. EN : C > Pb > Si = Ge = Sn CX4 > SiX4 >GeX4 >SnX4 >PbX4
7. Dioxides 10. Catenation :
• CO2,SiO2 and GeO2 are acidic, SnO2 and PbO2 are • The order of catenating power in 14th group
amphoteric in nature.
elements is C  Si  Ge  Sn .
• Acidic nature of : CO 2>SiO2 >GeO2 >SnO2 > PbO2
• Lead does not show catenation.
Compounds of Carbon
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Study of SiO2 and Silicones Step 1 :
Silicon Dioxide (SiO2) : Cu

2 RCl  Si   R2 SiCl2
570 k
• Sand is one form of crude silica.
Step 2 :
Allotropes of silica: Cl+H OH OH
R R
• a) Crystalline Allotropes -1HCl
Si Si
quartz, tridymite and crystobalite.
R Cl+H OH R OH
b) Amorphous Allotropes
Step 3 :
agate, jaspar and Onyx.
R| R| R| R|
• Quartz is pure form of silica and it is also known as  H 2O
HO  Si  OH  HO  Si  OH   HO  Si  O  Si  OH
rock crystal. R
| |
R
|
R
|
R
• Pure quartz is colourless and transparent. • The chain length of silicones can be controlled by
• When impurities are present, quartz is coloured. adding (CH3)3 SiCl which blocks the ends Structure.
• Siliceous rock composed of minute sea organisms is • Hydrolysis of RSiCl3 gives crosslinked silicone.
called Kiesulguhr. • Commercial silicone polymers are usually methyl
derivatives and to a lesser extent phenyl derivatives.
Properties of Silica :
• Silica is almost non reactive because of very Study of Slicates
high Si-O-bond enthalphy even at elevated Silicates
temperatures. • Silicates are metal derivatives of silicic acid.
 Silica is insoluble in all acids except HF.
eg: feldspar, zeolites, mica and asbestos.
• Silica dissolves in HF and gives SiF4.
• The Si-O bonds in silicates are very strong.
SiO2 + 4HF SiF4 + 2H2O
(H2SiF6 may also formed). • Silicates do not dissolve in common solvents.
SiF4 + 2HF H2SiF6 • The Silicates are mainly divided into six types
depending on the manner in which different
Silicones
• Silicones are organo silicon polymers containing Si – SiO 4 4  units are linked together..
O – Si bonds.
• Silicates are formed by heating metal oxide or metal
• Silicones are formed by the hydrolysis of alkyl or aryl carbonates with sand.
substituted chloro silicates and their subsequent
polymerization. Na 2 CO3 fused
 with
 Si
 Na 2 SiO3  CO 2
• Silicones contain R2 SiO repeating unit.
• The basic structural unit of silicates is SiO44– in which
• The empirical formula of silicone R2SiO is analogous silicon atom is bonded to 4 oxygen atoms in
to that of ketone (R2CO) and hence are named silicones. tetrahedral fashion as shown in fig.
• Alkyl or Aryl substituted chlorosilanes are prepared
by the reaction of R – Cl with silicon in the presence of
metallic copper as a catalyst

Zeolites :
Silocon
• Aluminium silicates are called Zeolites.
Oxygen
Si eg. Na2Al2Si2O8x H2O

(sodium aluminium orthosilicate)
• If aluminium atoms replace few silicon atoms in 3-D
• When silicate units are linked together form chain, net work of silica (SiO2) the overall structure known
ring, sheet structures. as alumino silicate is formed and it acquires negative
charge.
• If all the four corners are shared with other tetra
hedral units, 3 dimensional network silicates are • Cations such as Na+, K+, Ca2+ etc. balance the negative
formed. charge.
• The minerals having silicate chains are collectively • These have honey comb like structure and have the
called pyroxene. general formula
• Glass and Cement are man - made silicates. Mx/n (AlO2)x (SiO2)y .H2O
(M = Na+, K+ or Ca2+)
(n = charge on metal ion)
No. of General Structure Example

Silicate shared O
per unit formula
O–
–4
Ortho silicates 0 SiO 4 – Zircon ZrSiO4
– –
O O
– –
O O Hemi morphile
–6
Pyro silicate 1 Si2O –
O –
7
–
Zn 3SiO7 .Zn(OH)2 .2H 2 O
–
O O
O– O–
– –
Single chain 2 (SiO3–2)n LiAlSi2O6 Spodumene
O O –
O O
silicate
O–
O–
–
Cyclic silicate 2 (SiO ) 3

–2
n
O O Beryl (Be3Al2Si6O18)
– –
–
O O O–
O–
–
– –
Sheet silicate 3 (Si2O ) 5
–2
n
O – O O – O Talc Mg3(OH)2(Si2O5)2
O O
– –
– –
O O –
O O
O–
–
O –
3-D silicate 4 (SiO2)n O Si Silica (SiO2)
Si
O
–
–
O– –
O O–
O
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Group - 15 (Nitroen Family)
Reachinvity Towards Oxygen
E.N B.P and size
N
P N2 O3 N 2O5
As P2 O3 Acidic P 2O5
Sb As2 O3 strength As2 O5
Bi Sb2 O3 decreases Sb 2O5
Decreases Increases
Bi2 O3 Bi2O5
• Exception :
M.P. – N < P < As > Sb > Bi 3 5
• Acidic strength of E 2 O3  E 2 O 5
N < P < Bi < Sb < As increases
N 2O3 P2O3 As2O3 Sb2O3 Bi2O 3
• Oxidation Stat : +5 and +3
Acidic Amphoteric Basic
Stability of +5 O.S.  from top to bottom and
stability of +3 O.S.  from top to botoom due to Reactivity Towards halogen
inert pair effect.
+3 +5
As+ 5 > As3 EX3 and EX5
+5 +3
Sb > Sb Stability order Covalent Character Order 
+5 +3
Bi < Bl
NCl3 > PCl3 > AsCl3 > SbCl3 > BiCl3
Chemical Properties 5 3
Reactivity Towards Hydrogen Covalent Character Order  E X  E X
5 3
• EH3 Reactivity Towards Metal

Bond energy EH 3  NH3 M3E2 - Oxidation State
and Thermal PH 3 Ca3 N2 - Calcum Nitride
AsH3
Stability and Ca3P2 - Calcium Phospide
SbH3
lewis baisc
BiH3 Some Important Compound of Nitrogen
strength and
Bond angle Dinitrogen (N2)
Decreases 1. NH4Cl + NaNO2  NaCl + NH4NO2
• Exception : NH4 NO2 

 2H2O + N2
Inter molecular
H-bonding
2. (NH4 )2 Cr2O7 

 4H2O + Cr2 O3 + N2
B.P  PH3 < AsH3 < NH3 < SbH3 < BiH3 3. From azide pure N2 is prepared
NaN3 

 Na + N2
M.P  PH3 < AsH3 < SbH 3 < BiH3 < NH3
Ba(N3)2 

 Ba + N2
• Hybridization :
  
NH3 PH3, SbH3 , AsH3 , BiH3 N3  N  N  N

SP 3 No-Hybridization
due to drago’s rule

Properties of N2 2. Ostwal Process
1. At is inert due to high bond energy NN.
Pt/Rh
2. Reaction with N2 4NH3 + SO2 500K, 9 bar NO + H 2O
O2
M + N2 

 Metal Nitride
NO2
Mg + N2 

 Mg3N2 NO2
HNO2 + HNO3
Li + M2 

 Li3N 
NO + HNO3
3. Habber process
N2 + 3H2 2NH3 + Heat
3. Birkland Eyde Process
Favourable Condition
High pressure and Low Temp. N2 + O2 2NO
O2
4. Berkland Eyde Process
NO2
Heat + N2 + O2 2NO H 2O
Favourbale condition : HNO2 + HNO3


High Temp. and No effect of Pressure. NO + HNO3
Ammonia  NH3
Properties :
1. Prom urea
1. Reaction with Non-metal
NH2 CONH2 + 2H2O (NH4 )2CO3 


I2 
Conc HNO 3
 HIO3 + NO2 + H2O
NH3 + CO2 + H2 O
P4 
Conc HNO 3
 H3PO4 + NO2 + H2O
2. NH4Cl + NaOH  NaCl + NH 4 OH
(aq NH 3 )
S8 
Conc HNO 3
 H2SO4 + NO2 + H2O
Properties of N2
C 
Conc HNO 3
 CO2 + NO2 + H2O
1. Colourless gas, pungent smelling.
2. Reaction with metal
2. Reaction wtih salt
a) Metal Nitrate + NH3 + H2 O
a) ZnSO4+NH4OH  Zn(OH) + (NH4)2SO4
White very dil HNO 3
dil HNO 3
M [Highly reactive] Metal Nitrate + N2 O + H2 O
b) FeCl3 + NH4OH  Fe 2 O 3 .XH2O + NH4Cl Con. HNO 3
Brown
Metal Nitrate + NO2 + H2 O
3. Complex formation Tollens reagent
a) AgCl  NH 4OH  [Ag(NH)2 ]Cl b) Metal Nitrate + NO2 + H2O

White Colourless
Con HNO 3
b) CuSO 4  NH 4 OH  [Cu(NH3 )]SO 4 M [Less reactive]

Blue Deep blue
dil HNO 3
Nitric acid (HNO3) Metal Nitrate + NO + H2O

H2SO4
1. NaNO3/KNO
3  HNO3 + NaHSO4/KHSO4
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3. Brown ring complex Phosphorous
Fe+2 + NO3– + H+  Fe+3 + NO + H2O White Phosphorous :
• White waxy solid. P 60°
[Fe(H2O)6 ]+2 
No
 [Fe(H2O)5 NO] + H2 O
• Insoluble in H2O but P P
4. Aqua regia [Con HNO3 + Con HCl] soluble in CS2. P
3
1 : 3 • Glow in dark. SP
HNO3 + HCl  NaCl + H2O + [Cl] Monomer
• Kept under water.
Oxide of Nitrogen Red Phosphorous :
(+4) NO2 Angular Acidic Parama- Brown gas P
• Non poqsoures
gnetic P P
• Does not glow indark.
(+2)NO Linear Metal P Colourless P
• Insoluble in H2O and CS2 3
gas SP
White P4 
300 C
 Red P4 Linear Polymer
(+3)N2 O 3 Planer Acidic D Blue liquid
• Reactivity W > R > B
(+1)N2 O Linear Neutral D Colourless
• Stability W < R < B
gas
(+4)N2 O 4 Planer Acidic D Colourless Black Phosphorous :
solid
(+5)N2 O 5 Planer Acidic D Colourless P P
solid P P P

a) NH4NO3   H2O + H2O P P P
P P
b) NaNO2 + FeSO4 + H2SO4  Fe2(SO4)3
3
+ Na2SO4 + NO SP
c) NO + H2O4  N2O3 Hexaonal Polymer
d) Pb(NO3)2 

 PbO + NO2 + O2
530°

Cool
 Red P4 -Black [Rhombic]
e) 2NO2 
Heat
 N2O4
200°
f) HNO3 + P4O10  HNO3 + N2O5
- Black
NO  N = O
[Monoclinic]
+
N 2 O  N  N  O  N  N  O  N = N = O
Oxide of Phosphorous
O O Limited
1. P4  O 2   P4O 6
N–N
N2O3  air
O
2. P4  O 2 
 P4 O10
excess
O O
N 2O4  N–N P
O O O P-O-P bond = 6
O
O  -bond = 0
P O P Lone pair = 16
O O
N 2O5  O Sigma bond = 12
N N O
P
O O O

O • Cl – PCl3 – Cl
 RCl + POCl3 + HCl
+
P Sigma bond = 16
O R–O–H
O -bond = 4
O Hybridization = sp
3
O=P O P=O Cl Cl 3
P-P bond = 4 T.B.P  Sp d
O O Lone Pair = 20 P
P
Cl Cl
O
Cl
Phosphine [PH3]
Ca3P 2 + H2 O Ca(OH)2 + PH3 PCl5(s)  PCl4 . PCl6

3 3 2
HCl Sp Sp d
CaCl2 + PH3 Some Important point of Nitrogen Family

1. Disproportionation
• Lab method :
3

P  NaOH  H 2 O  Inert
 PH + NaH PO H 3 PO 3   H 3 PO 4  PH 3
4 atm
White 3 2 2
2. Hydrolysis of Trichlorice
Properties :
Cl+ OH – H
1. Colourless gas +
• N Cl OH – H  NH3 + 3HOCl
2. Poisonous nature –1
Cl OH – H
3. Basic in nature
4. Rotten fish smell Cl H–OH
5. Non inflammable • P Cl H–OH  H3PO3 + HCl
6. No hybridizatin Acc Cl H–OH
to drago’s rule H – P – H Cl H–OH

90° • As Cl H–OH  As2 O3 + HCl
H
Cl H–OH
Halide of phosphorous
• PCl5  Mop – • SbCl3 + H2O  SbOCl + HCl
• BiCl3 + H2O  BiOCl + HCl
1. P4 + 10CL2 
dry 4PCl5
3. Nitrolim [CaC2 + N2]
2. P4 + SO2Cl2  PCl5 + SO2
Properties - Yellowish Powder •
CaC2  N 2  CaCN 2  C
Carbide Calcium cyanamide
• PCl5 
 PCl3 + Cl2

• CaCN2 
H 2O
 Ca(OH)2 + NH3
Ag
• PCl5  PCl3 + AgCl
 4. Solid PCl5  PCl4 PCl6
Sn
• PCl5 
 PCl3 + SnCl4 5. Solid PBr5  PBr4 Br
Cl – PCl3 – Cl
6. Solid N2O5  NO2 NO3
•  POCl3 + HCl Sp Sp3
H –– O –– H
7. Holmes signal (CaC2 + Ca3P2)
• Cl – PCl3 – Cl
 RCOCl + POCl3 + HCl
+
RCO – O – H
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8. Str. of (HPO3)3 17. R3P = O exist but R3N = O does not exist due to
non availability of d-orbital.
O 18. N show catenation less than P due to lon pair
OH
P-O-P  3 repulsion.
P
-bond = 3
O O 19. PCl5 + H2O  H3PO4 + HCl
P-O bond = 9
O= P P=O p – p = 3 Oxo acid of Phosphorous
OH O OH
POP = 3
H3 PO4  H3PO3  H3PO2
9. Reaction of NH3 with Cl2 Orthophosphoric Ortho Hybo
acid phosphorous phosphorous
NH 3  Cl 2  NCl 3  HCl acid acid
excess
–H 2O
H3PO4 HPO3
NH3  Cl 2  NH 4 Cl  N2 Meta
excess ×2
phosphoric
acid
10. Anhydride of acid H6 P2 O8
–H 2O –H2 O

2HNO3  H2N2O6 –H 2 O N 2O5
H4 P2 O7 H4P2O 6
Anhydride
 Pyrophosphoric Hypophosphoric
2HNO3  H2N2O4 –H 2 O N 2O3 acid acid
H3PO3
HNO3 + HNO2  H2O + N 2 O4 [2NO 2 ] ×2
mixe dnhydride
–H 2O
H6 P2 O6 H4P2O 5
11. N- does not form petahalide due to unavailability Pyrophosphoric
of d-orbtial. acid
12. All trihalide of N except NF3 are unstable.

13. All trihalide except BiF3 are lovalent BiF3  Ionic
14. BiCl5 does not exist due to inert pair effect. Oxo acid of N
15. Cr and Al do not react with HNO 3 due to HNO3 
 HNO 2 
 H 2 N2 O 2
formation of passive film of oxide Cr2O3 and Nitric acid Nitrous acid Hyponitrous acid
Al2 O3 .
16. Acidic strength order
H 3PO2 > H3PO3 > H3 PO4
due to cross conjugation

2. Reactivity towards oxygen
Group - 16
EO 2 and EO3
Oxygen Family O3, SO2, SeO2, TeO2, PoO2
1. Chalcogen Oxidisin g power
  SO3, SeO3, TeO3, PbO3
Size O
and S E.N. 3. Reactivity towards halogen
m.p. & b.p. Se and
and Te I.E. EX 4 and EX 6
4 6
density Po
Increases Decreases Covalent character EX6 > EX4
Act to Fajan’s rule
• Electron affinity
Small cation at large anion
S > Se > Te > Po > O
 due to compact nature of oxygen
Some Important Compound of Oxygen
1. Dioxygen [O2]
4 6
a. Method of Preparation
 
Stability  and Stability  
from O  Po from O  Po  MnO3   M2O + NO2 + O2
M = Li, Mg, Ca, Sr, Ba etc.
Se+6 > Se+4 and Fe+6 > Te+4, Po+4 > Po+6
M  Na, K, Rb, Cs
• Oxidation no. of oxygen.

O–2  oxide –2 b. KClO3   KCl + O2
O2–2  peroxide = –1 
c. KMnO 4   K 2 MnO4 + MnO2 + O2
Purple Green Brown
1
O2–1  Superoxide 
2 
d. K 2 Cr2 O7   K 2 CrO4 + Cr2 O 3 + O2
red orange Yellow Green
1
+1
O2 [AsF6] –1
 
2 
Pb 3O 4   PbO  O 2
e. litharage
red lead
1
KO 3   f. 
H2O2   H2O + O2
3
OF 2  +2 g. 
Ag2O   Ag + O2
O2 F 2  +1
O2 O
h. 4OH  2H2O + O2 + 4e–

electrolysis of H2O at anode
• Properties
1. Reaction with Hydrogen Properties
B.E. and T.S. and bond angle  decreases 1. Reaction of oxygen
H2O, H2S, H2Se, H2Te, H2Po
PbO, PbO 2,

Increases
 Pb3O4
Acidic strength and Reducing nature and B.L. Ag2 O
Ag
Pb ZnO
Exception O2
Zn
Al ZnS
M.P. and B.P.  H2S < H2Se < H2Te < H2 Po < Al2O3 CH4 ZnO + SO2
H2 O
Due to Intermolecular H-bonding. CO 2 + H2O
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2. O2 is colourless and paramagnetic gas. S
3. Ozone [O3]
S S Chair form
S6 

Method of Preparation  3O2  
 2O2
Electric
S S
discharg e
S SP 3
Properties  i. at is pale blue gas.
3. SO2 (Sulphur dioxide)
ii. dark pale blue liquid
Chemical Reaction
iii. Violet black solid.
O2
SO2   SO3
4. Structure VO 2 5
+
Fe
O
2
O
+
x
+1
O y
SO 2 
HO
 Fe +2 + SO 42 + H +
  2
1 3 0 – 0 –1
O O O O O O H2S
SO 2   S + H2 O
Bond length X = Bond length Y
NaOH
SO 2   Na 2SO 3
3
Bond Order = = 1.5 Cl 2 P4 H2 O
2 SO2  SO 2 Cl 2   SO 2 + PCl 5   H3PO 4
Formal charge is 0, +1, –1 KMnO 4
SO2   MnSO4 + H2SO4 + K 2SO 4
HO 2
5. Chemical Reaction of O3 :
K 2 C 2 O7
It is a powerful O.A. SO 2   K 2SO 4 + H 2O + Cr2 (SO 4 )3
 SO2 act as bleaching agent
O2 + [O]
Coloured
Matter
PbSO4 + O 2 SO2 + H2O  H2SO4 + [H]  Colourless
Pb NO2+O2
S
NO Reductive bleaching
O O3 SO2
H2 Temporory effect
KOH KI Pb SO 3 + O2
+ I 2 + O2
1
PbO + O 2
S O S
O O O
Allotropes of Sulphur
B.O. = 1.5
1. -sulphur
bentshape
2. -sulphur
4. H2SO4  King of chemical
-Sulphur is formed by evapourity
i. Contact process
Transition Temp.
H2 O
SO2+O
2
V2O5 SO
 3
H2SO4
 H2S2O7   H2SO4
 96° oleum 98%pure
(S8) 
Rhombic Monoclinic ii. Lead chamber process
Yellow Colourless SO2 + O2  SO3 
NO H 2O
 H2 SO4
i. at 96° c both are stable Chemical reaction of H2SO4
ii. T < 96° -stable
POCl3 + SO2Cl2 + HCl MHSO4 + HX
iii. T > 96° -stable
PCl5 MX
S
S S 3
SP S MX 2
S S SO2 + H 2O H2 SO4 M 2SO4 + HCl
S8  S
KI C 12H 22 O 11  Charing of sugar
C
S S
I2 + SO2 + H2 O 12C + 11H2 O
CO 2 + SO2 + H2 O
5. Na2S2O3  Sodium thiosulphate 6. Distrubance of Miniscus of Hg (Tailing of Hg)
Na2S2O3.5H2O  Hypo solution by passing ozone.
i. S + Na2SO3  Na2S2O3 Hg + O3  Hg2O + O2
ii. S + NaOH  Na2S + Na2S2O3 7. Estimation of ozone.
iii. I2 + Na2S + Na2SO3  NaI + Na2S2O3 KI + H2O + O3  I2 + KOH + O2
Properties : I2 + Na2S2O3  NaI + Na2S4O6
Structure 8. SO2 turns lime watermilky
SO2 + Ca(OH)2  CaSO 3

O milky
NaO S S
CaSO 3  SO2  H 2 O  CO(HSO 3 )2
SP
3 +6 excess solub le
ONa
10. H2O is liq while H2S is gas due to H-bonding.
Chemical Reaction :
Oxo acid of S
Thiosulphate
 –O –O
Sodium Argento H2SO 4 H 2SO 3 H2SO 2
AgBr Sulphuric Sulphurous Hybosulphurous
i. Na2S2 O3 NaBr + Na 3 [Ag(C 2O3) 2]
acid acid acid
Fixer in photography
AgNO3 +O –O
ii. Na2S2O3 Ag2S 2O 3 + NaNO3 H2SO5 H2 SO4 +S H2S2O3
Peroxy Th ionic acid
H2O sulph uric acid ×2 or
(Caro’s acid) th iosulph uric acid
Ag2S + H2SO 4
Black H4S2O 8
–H2 O –H2O2
iii. Na2 S2O3  –H2
I2
 NaI + Na2S4 O6 Pyrosulph uric Dithionic acid
acid or
H2 O H4S2O 8 Dith iosulphuric
iv. Na2S2 O3 
Cl2
 NaHSO4 + HCl acid
Marshal acid
Some important point of oxygen family

1. OF6 does not exist due to absence of d-orbital. H2SO3
2. All hexahalide of S are unstable except SF6 X2
3. SF6 does not hydrolose H4S 2O6
–H 2O –H2 O2
4. Se 2 Cl 2  SeCl 4  Se H2S2O5 H2S2 O4
disproporationation
Pyrosulphurous Dithionous
acid acid
5. S2 is parimagnetic at look just like O2.
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Group 17 (Halogen)
Size and BP and MP and Density 3. Reactivity towards Halogen
F Cl Br I Increases Inter Halogen compound
I.E and E.N Decreases XX1, XX13, XX15, XX17
Exception : X  Bigger size / small E.N.

X1  Small size / more E.N.
Electron gain Enthalpy
Interhalogen compounds are usually more
due to vaccant d-orbital reactive than Halogen compound
Cl > F > Br > I
XX1 > X2
 Order
reactivity order
F 2 - Yellow gas
Some Important compound of Cl
Cl2 - Greenish yellow gas
1. Cl 2
Br 2 - Redish brown liquid
Method of Properation  From pyrolusite
I2 - Violet black solid
a. MnO2 + HCl  MnCl2 + Cl2 + H2O
Oxidising power : b. MnO2 + NaCl + H2SO4
1. F2 > Cl2 > Br2 > I2  MnCl2 + Cl2 + H2O + NaHSO4
2. B.D.E. [Exception] c. Decon’s process
Cl2 > Br2> F2 > I2 CuCl2
HCl + O2 
723K
 Cl2 + H2O
 due to lone pair repulsion
d. Electrolysis of Molten NaCl
Chemical Properties :

 1 
1. Reaction with hydrogen at anode : Cl  Cl 2  1e
2
Acidic strength & Reducing power & Bond length at cathode : Na+ + 1e–  Na
HF HCl HBr HI Increases
Chemical Reaction
B.D.E. and T.S. and Stability decreases Decreases
S + HCl HCl
Exception : HIO 3 + HCl
S2Cl2
H2S
B.P.  HCl < HBr < HI < HF

I2
H2
H2
H2SO4 +HCl SO S8
O
2 +H PCl3/PCl5
M.P.  HCl < HBr < HF < HI 2 O P4
Na2SO3
2. Reactivity towards metal Na2SO4 + HCl H2O
Cl2 Na
NaCl
O4
MX, MX2 and MX3 ........ H2S H) 2 Fe
(O
2
Ca
CH=CH
CH
Covalent Character  MX2 > MX

RT
4
FeCl 3
SO
h
4
Ca(OCl) 2+CaCl2 + H2O

2
Fe
Covalent Character  LiF < LiCl < LiBr < LiI Cl

| CH3Cl
Covalent Character  LiF>NaF>KF > RbF > CsF Fe 2(SO4)3 + HCl CH 2–CH2
|
Cl
Solubility order of silver Halide
AgF  AgCl  AgBr  AgI

Solub le White Pale yellow yellow
ppt ppt ppt

2. Reaction with NH3 Oxoacid of chlorine
HClO +1 Hypochlorous acid Cl–OH
a. NH3 + Cl 2 
 NCl 3 + HCl
excess explosive
HClO2 +3 Chlorous acid O = Cl – OH
b. NH 3 + Cl2 
 NH4Cl + N2 O
excess ||
HClO3 +5 Chloric acid O  Cl  OH
3. Reaction with alkali
a. X2 + NaOH  NaX + NaOX + H2O O

cold/ dil. ||
HClO4 +7 Perchloric acid O  Cl  OH
b. X2 + NaOH  NaX + NaXO3 + H2O ||
Hot / conc. O
X = Cl, Br, I
Some Important Points of Halogen
A. Bleaching Properties of Cl2
1. Occurance
Cl2 + H2O  HCl + HOCl  HCl + [O]
Coloured matter
  Colourless 3Ca3(PO4 )2.CaF 2
Fluoroapatite
i. Oxidative bleaching F Fluorspar CaF2
ii. Permanent effect Cryolite
B. HCl Na 3AlF 6
Method of Preparation
420K 2Ca3 (PO4) 2.CaCl 2
i. NaCl + H2SO4   NaHSO4 + HCl
Chloroapatite
823K
ii. NaCl + NaHSO4   Na2SO4 + HCl Cl Common salt NaCl
Carnallite
Properties KCl.MgCl2.6H2O
1. NH3 + HCl  NH 4 Cl
White fumes
Br - Sea water
2. Na2CO3 + HCl  NaCl + CO2 + H2O I - Calche (NaNO3 + NaIO3)
3. NaHCO3 + HCl  NaCl + H2O + CO2 2. Non-metal Displacement Reaction
4. Na2SO3 + HCl  NaCl + H2O + SO2
KI
I2 + KF
5. Reaction of Au of Pt with Aqua regia KBr
F2 Br2 + KF
[HNO 3 : HCl] KCl Cl2 + KF
1 : 3
KF
3 ×
Au + HNO3 + HCl  H Au Cl 4 + NO + H2O KCl I2 + KI  KI3
Br2 ×
4 KI I2 + KBr
Pt + HNO3 + HCl  H 2 Pt Cl 6 + NO + H2O
6. Reaction of Fe with HCl KF
×
KBr
Fe + HCl  FeCl2 + H2 Cl2 Br2 + KCl

KI I2 + KCl
Inhibitor
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KF 10. Reaction of Cl2O6 with HF
×
KCl Cl2O6 + HF  [ClO2] + F– + HClO4
I2 ×
KBr × 11. Purification of Br2
3. Reaction of F2 with alkali Br2 + Na2CO3  NaBr + NaBrO3 + CO2

Impure H 2SO 4
F2  NaOH  NaF  OF2  H 2 O
Cold/ Dil Br2
(pure)
F2  NaOH  NaF  O 2  H 2 O
Hot/Lon 12. Structure
4. Reaction of F2 and Cl2 with H2O a) KI3  K+ + I3–1 [I – I – I]–1
Cl2 + H2O  HCl + HOCl x
b) KHF2  K+ [F– –– y
H –– F]
F2 + H2O  HF + O2 + O3 Bond Length [x = y]
5. NH3 + NaOCl  Cl2 + NaOH + NH2–NH2 c) CsBr3  Cs+, Br–, Br2
6. Reaction of Cl2 with H2O2 d) CsI3  Cs+, I3–1
Cl2 + H2O2  2HCl + O2 e) I4O9  I+3 + 3IO3–1
7. Reaction of HF with SiO2 f) I2O4  IO+, IO3–1
HF  SiO 2  H2 SiF6 Cl Cl Cl
excess
g) ICl3 dimer I I
8. Heating of HClO3
Cl Cl Cl
HClO3 
 ClO2 + O2 + H2O
T 375K
9. Reaction of I2O5 with CO HClO4 Oxidizing power

A.S
HClO3
of
I2O5 + CO  I2 + CO2 
Na 2 S 2O 3
 NaI + Na2S4O6 HClO2
T.S
HClO
Decreases Increases

Group - 18
Inert Gas Properties
IE & EN  decreases Hydrolysis :
He Ne Ar Kr Xe Rn Unstable
Size/BP/MP/density  Increases 1. Xe F2 + H2 O 2HF + XeO

• Electron gain enthalpy Heg = +ve Xe + O2
for all noble gas Fin al
product 2HF + Xe + O2
order of Heg is  Partial
2. XeF6 + H2O XeOF4 + 2HF
Ne > Ar > Kr > Xe > Rn > He Hdrolysis
• 1st compound of Noble gas Partial

H2O
Hdrolysis
1
Xe  [PtF6 ]1 on the basis of O 21 PtF6  XeO3 + 2HF
H 2O
XeOF2 + 2 HF
Red
Complete
Red
Hydrolysis
bcz 1st I.E. of O2  I.E1 of Xe XeF6 + 3H2O

Complete
XeF3 + 6HF
Hdrolysis
• KrF2 and RnF2 also exist.
 6
Fulorides of Xenone 3. XeF4  H 2O 
Disproportionation
 Xe  O 2  HF  XeO 3
400 C
1. Xe(g)  F2(g) 
Lbar
 XeF2(s) Reaction of Xenon Rluoride with PSs, SbFs and
excess 1 MF
600 C
Xe  2F2   XeF4(s) XeF2 + PF5  [XeF]+ [PF6]–
2. 7 bar
(1 : 5) XeF4 + SbF5  [XeF3]+ [SbF6]–
300 C
XeF6 + MF  M+ [XeF7]–1
3. Xe  3F2 
6070bar
 XeF6(s)
(1 : 20) M = Na, k, Rb, C5
M  Li
Some Important Point of Noble Gas
1. Reaction of XeF4 with O2F2 XeF4 + O2F2  XeF6 + O2
2. He and Ne do not form clatherates due to small size.
3. Solubility in water  from Top to bottom.
4. Ar used in Arc welding.
226
5. Decay of 88
Ra 222
86
Rn + 42 He
6. O.N. Com.of Hybridization Geometry Shape L.Pon Total
Xenon Xenon Lone pair
+2 XeF2 Sp3d [2BP + 3 L.P.] TBP Linear 3 9
+4 XeF4 sp3d2 [4BP + 2 L.P.] Octahedral Octahedral 2 14
+4 XeF3+1 Sp3d [3BP + 2 L.P.] TBP T-shape 2 11
+6 XeO2F 2 Sp3d[4BP + 1 L.P.] TBP See-saw 1 11
+6 XeO3 Sp3[3BP + 1 L.P.] Tetrahedral Trigonal pyramidal 1 7
+6 XeF4 Sp3d2 [SBP + 1 L.P.] Octahedral Square pyramidal 1 15
7. Inert gas are least reactive due to high I.E., fully filled configuration.
8. Inert gas can be separated by adsorption or desorption on charcoal.
9. Half life of Rn is very small.
10. he have low solubility in blood. Hence used in scuba diving.
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d-Block Elements (Transition Elements) Melting Point : s-block metals < d-block metals
• Incomplete n and n-1 shell in atomic or in ionic • In a series on increasing number of unpaired e–
state – Transition Element. M.pt. increases upto Cr then decreases.
• *Zn, Cd & Hg - are d-block nontransition
element. •
General Electronic Configuration

• ns0-2 (n-1) d1-10
Zn > Cd > Hg
Cr = 4s1 3d 5 • Melting Point (data based)
,Pd = 5s 0 4d10 Cu > Au  Ag
• Exceptions  1 10
Cu = 4s 3d
Atomic Radius
• Left to Right
3d series
Sc > Ti > V > Cr > Mn > Fe  Co  Ni < Cu < Zn
• In a Group :
3d to 4d series increase but 4d and 5d series nearly
same due to poor shielding of f electron.
(Lanthanide contraction)
Oxidation State
• 3d < 4d  5d • Transition element exhibit variable oxidation state
due to small energy difference of ns and (n-1) d
Smallest  Ni electrons.
• Eg. Ti < Zr  Hf
Larg est radius  La • Sc(+3) and Zn(+2)  Only one oxidation state.
• Common oxidation state is +2.
• 3d sereis  +7 (Mn) (high oxidation state).
• In d-block  [highest oxidation state is +8 (Os,
Ru)].
• In carbonyl compound oxidation state of metals
is zero due to Synergic effect/back bonding.
• Their higher oxidation states are more stable in
fluorides and oxides.
• Higher oxidation state in oxides are normally
more stable than fluorides due to capability of
oxygen to form multiple bonds.
Super Note : Most stable oxidation state of Mn is
+2 while for Cr, it is +3.
• In +3 Oxidation state Mn acts as oxidizing agent,
while Cr in +2 acts as reducing agent.
Element Outer Oxidation states Ionisation Potentials
– n
e conf .
• First Ionization Potentials : 1st I.P. values for
Sc 3d1 4s2 +3 the first four 3d block elements (Sc, Ti, V and
Ti 3d2 4s2 (+2), +3, +4 Cr) differ only slightly from one another. The
V 3d3 4s2 (+2),(+3), +4, +5 value of 1st I.P. for Zn is considerably higher. This
Cr 3d 4s5 1
+1,(+2),+3, (+4), (+5), +6 is due to the extra-stability of 3d10 level which is
5 2 completely filled in Z-atom.
Mn 3d 4s +2,+3,(+4),(+5), (+6),+7
Fe 3d 4s6 2
+2, +3, +4, (+6) • Second Ionisation Potentials : The vlaue of 2nd
IP for Cr and Cu are higher than those of their
Co 3d7 4s2 +2, +3, (+4)
neighbours. This is due to the fact that the
8 2
Ni 3d 4s +2, +3, (+4) electronic configurations of Cr+ and Cu+ ions
10 1
Cu 3d 4s +1, +2 have extra stable 3d5 and 3d10 levels. There is a
Zn 3d10 4s 2 +2’ sudden fall in the values of ionisation potentials
Transition Series is goving from II B (Zn-group elements) to IIIA
sub-group.
1st 3d series Sc 21 –Zn 30 9+1 = 10
Magnetic Property
2nd 4d series Y39 – Cd48 9+1 = 10
3 rd 5d series La57, Hf72 – Hg90 9+1 = 10 • All transition elements are paramagnetic due to
presence of unpaired electrons. They attract when
4 th 6d series Ac89, Rf104 – Cn112 9+1 = 10 magnetic field is applied. Magnetic moment of
Density unapired electron is due to spin and orbital
angular momentum.
• s-block metal < d-block metals.
• “Spin only” magnetic moment can be calculated
• Density in a period
• Sc < Ti < V < Cr < Mn < Fe < Co  Ni < Cu > Zn by using formula µ = n  n + 2  Bohr magneton.
• The density vary inversely with the atomic radii. (n is number of unpaired e–)
As we move in a period, the density increases (as • If
the radii decreases). The density increases while
n = 1, µ = 1.73 BM n is 2, µ = 2.84 BM
descending a group.
n is 3, µ = 3.87 BM n is 4, µ = 4.90 BM
• Density in a group : 3d < 4d << 5d.
n is 5, µ = 5.92 BM
Metallic Character • Substance that are not attracted by applied
• They are solid, hard, ductile, malleable, good magnetic field are diamagnetic, they have all the
conductor of heat and electricity and exhibit electron paired. d-block element and ions having
metallic lusture, high tensile strength. d0 and d10 configuration are diamagnetic.
• **Hg is liquid Colour
• ** Greater the number of unpaired of d-electron, • Colour in transition metal ions is associated with
greater is the number of bonds and therefore d-d transition of unpaired electron from t2g to eg
greater is the strength of these bond, so hardness set of energies.
and enthalpy of atomization increases with
• This is achieved by absorption of light in the
increase in number of unpaired electron.
visible spectrum, rest of the light is not longer
white.
• Colourless – Sc3+, Ti4+, Zn2+ etc.
• Coloured – Fe3+ yellow, Fe2+ green, Cu2+ blue,
Co3+ blue etc.
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Alloys • Super Note :
• Solid mixture of metals in a definite ratio. K2Cr2O7 is preferred over Na2Cr2O7 as a primary
• (15% difference in metallic radius) standard in volumetric estimation because
Na2Cr2O7 is hygroscopic in nature but K2Cr2O7
• They are hard and having high melting point.
in not.
• Eg. Brass (Cu + Zn)
• Chemical :
• Bronze (Cu + Sn) etc.
3
• Hg when mix with other metals form semisolid 2K2 Cr2O7  
 2K2 CrO4 + Cr2O3 + 2 O2
amalgam except Fe, Co, Ni, Li.
K2 Cr2O7 + 2KOH  2K2CrO4 + H2 O
Complex Formation
• Transition elements show tendency to form Cr2O72- + 2OH  2CrO42  H2O
complex compounds due to. Small size and high Orange Yellow
effective nuclear charge. (colour change in basic med.)

• Availability of low lying vacant d-orbitals which
can accept lone pair of electrons donated by a 2Cr2O2-4 + 2H  CrO72  H2 O
Yellow Orange
ligand.
• Complex forming tendency  charge on metal/ (colour change in acidic med.)
size of metal. • CrO42– and Cr2O72– exist in equilibrium and are
Interstitial Compounds interconvertable by altering the pH of solution
• When less reactive nonmetals of small size eg. H, 2CrO24 + 2H +  2HCrO 4  Cr2O72 + H 2O
B, N, C, Trapped in the interstitial space of transition
metals, interstitial compounds are formed. • It acts as a powerful oxidising agent in acidic
• e.g. TiC, Mn4N, Fe3H etc. medium (dilute H2SO4 )
• They are nonstoichiometric compounds. 2CrO27  + 14H +  6e   2CrO 3+ + 7H2O

• They have high melting point and density than
Potassium Dichromate [K2Cr2O7]
pure metals.
• They are chemically inert, (Due to lack of free Preparation
space for electron movement.) • Commercially it is prepared by fusion of MnO2
Potassium Dichromate [K2Cr2O7] with KOH followed by electrolytic oxidation of
manganate.
Properties
• Physical : MnO24 
 MnO4 + e 
 green   purple 
2–
O Properties
a) Physical :
Tetrahedral
Cr
Yellow colour
O O O O
Tetrahedal Tetrahedal
O
manganate permanganate
Chromate ion Mn Mn (purple) ion
(green) ion
2– O O
O O O O
pm O
Orange colour
O O
Tetrahedral
9
17 0
126
O Cr Cr O b) Chemical :
16
3
O O • Effect of heating
pm
751K
Dichromate ion 2KMnO4   K2 MnO4 + MnO2 + O2 .
• In alkaline & neutral medium : f-Block Element
2KMnO4 + 2KOH  2K 2MnO4 + H2 O + [O] Inner Transition Elements
(conc.) manganate
The f-block elements are known as inner
If solution is dilute transition elements because they involve the
filling for inner sub-shells (4f or 5f)
2K2MnO4 + 2H2O  2MNO2 + 4KOH + 2[O]
(Brown ppt)
a) Lanthanides
• This type of behaviour is shown by KMnO4 itself It consists of elements that follows lanthanum
in neutral medium and involve the filling of 4f subshell.
3e  + 2H2 O + MnO 4  MnO 2 + 4OH  Electronic Configuration :
• Inn alkaline or neutral medium KMnO4 shows [Xe] 4fn+1 5d06s2 or [Xe] 4fn5d16s2
oxidising properties. • Colouration :
• In acidic medium (in presence of dilute H2SO4)
Many of the lanthanides ions are coloured in solid
MnO 4 + 5Fe 2+ + 8H +  5Fe 3+ + Mn 2+ + 4H 2O state as well as in solutions. The colour is due to
Green Yellow
the f-f transition since they have partly filled f-
orbitals.
2MnO 4 + 5SO2 + 2H 2O  5SO 42 + 2Mn 2+ + 4H +
• Lanthanide Contraction :
Some Important Reagents and Catalyst
The steady decrease in the size of lanthanide ions
• Ziegler Natta catalyst : TiCI4 + (C2H5)3AI (M3+) with the increase in atomic no. is called
lanthanide contraction.
• Lindlar’s catalyst : Pd / BaSO4
• Wilkinson’s catalyst : (Ph3P)3RhCI • Causes :
• Adam’s catalyst : Pt / PtO As we move from left to right in a lanthanide

series, the atomic no. increases and for every
• Brown’s catalyst or P-2 catalyst : Nickel boride. proton in the nucleus the extra electron goes to
• Baeyer’s reagent Dilute alkaline KMnO4 used to 4f orbital. The 4f orbital is too diffused to shield
test the presence of unsaturation. the nucleus effectively, thus there is a gradual
increase in the effective nuclear charge
• Tollen’s reagent Ammoniacal solution AgNO3 ,
experienced by the outer electrons.
i.e., [Ag(NH3 )2]OH. used to test the aldehyde
Consequently, the attraction of the nucleus for
group.
the electrons in the outermost shell increases with
• Nesseler’s reagent Alkaline solution of K2HgI4(g) the increase of atomic number, thus size
and NH3 . decreases.
• Benedict’s solution CuSO4 solution + sodium • Separation of Lanthanides:
citrate + Na 2 CO 3, used to test the aldehyde
Due to the similar sizes of the lanthanides, it is
group.
difficult to separate them but due to lanthanide
• Lucas reagent HCl (cone.) + anhydrous ZnCl2, contraction their properties slightly vary (such
used to distinguish between 1°, 2° and 3° as ability to form complexes). The variation in
alcohols. the properties is utilized to separate them.
• Basic Strength of Hydroxide
Due to the lanthanide contraction, size of M3+
ions decreases and there is increase in covalent
character in M–OH and hence basic character
decreases.
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• Similarity of second and third transition series b) Actnides
The atomic radii of second row transition It consists of elements that follow Actinium and
elements are almost similar to those of the third involve the filling of 5f subshell. These are
row transition elements because the increase in radioactive substances. 7s2 is stable configuration
size on moving down the group from second to for actinides. Show +3, +4, +5, +6 & +7 oxidation
third transition elements is cancelled by the state.
decrease in size due to the lanthanide contraction.
Difference between Lanthanides and Actinides

Lanthanides Actinides
1. In lanthanide the filling of 4f orbitals take place 1. In actinide the filling of 5f orbitals take place
2. This series includes atomic number 57 to 71. 2. This series includes atomic number 89 to 103.
3. These elements are non-radioactive except 3. All the elements of this series are radioactive.
promethium. 4. Binding energy of 5f orbitals is higher.
4. Binding energy of 4f orbitals is higher. 5. Besides +3 oxidation number it also shows +4,
5. Besides +3 oxidation number it also shows +2 and +5 and +7 oxidation state in few compounds.
+4 oxidation state in few compounds. 6. Most of the actinides ions are deeply coloured.
6. Lanthanides have a bright and silvery 7. Actinides have stronger tandency towards
appearance. complex formation.
7. Lanthanides have less tandency towards complex 8. Oxides and hydroxides of actinides are more
formation. basic.
8. Oxides and hydroxides of lanthanides are less
basic.
Mischmetall
• It is a well-known alloy which consists of a
lanthanoid metal (–95%) and iron (–5%) and
traces of S, C, Ca and Al.
• A good deal of mischmetall is used in Mg-based
alloy to produce bullets, shell and lighter flint.

Double Salts
Lose their identity in solutions
ADDITION OF COMPOUNDS FeSO4, (NH4) 2.6H 2O (Mohr’s Salt)
(Two or more simple salts are mixed)
Co-ordination Compounds
The concept of co-ordination compounds arises from the
complex formation tendency of transition elements.
Retain their identity (i.e. dosen’t lose their identity) in solution
K4[Fe(CN)6], K[Ag(CN)2]
Central Metal Atom (CMA) +4 + x + 6 (–1) = 0

Accept l.p./e– from ligands to form co-ordinate +4 + x – 6 = 0
e– bond. x=+2
Oxidation Number Co-ordination No.
“Charge present on central metal atom.” Co-ordination = No. of ligand × denticity
e.g. K4[Fe(CN)6]
Complex Compound
Representation of co-ordination compound
K4 [Fe(CN) 6] C.N.
(Co-ordination no.)
Ionisation sphere/Counter Ion

Co-ordination sphere/Entity
Central metal atom/ion
Ligand
Ambidentate Cation Ligand

Ligand
They can change there donar +
Eg. : N  O , NH2–NH3
+
atom but not denticity.

2
– – – –
Eg. : SCN , NO , CN , NCO
Other On the basis
Flexidentate type of charge Natural Ligand
Variable Denticity. Eg. : H 2O, NH3 , Pyridine,
2–
Eg. : EDTA, SO 4 On the basis CO, NO
of Denticity
 acid ligand Anionic Ligand
Eg. : CO – –
Eg. : X , OH , NH2
–
Monodentate Bidentate Polydentate

– 2–
Eg. : NH 3, H2 O, X , P(PH) 3 Eg. : C 2O4 , [Oxalate ion [Ox] Eg. : Diethylentriamin (dien) [Tri-dentate]
Glycinate ion (Gly) Ethylene diamine tetra acetato [EDTA]
Dimethylglyoximato [DMG] [Hexadentate]
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Chelating Ligand
• These are the polydentate ligands which bind to the central metal to form a puckered ring structure.
• Chelation leads to extra stability.
For Eg : All bidentate or polydentate ligand
Except : Hydrazine (NH2NH2)
Due to formation of three membered ring angle strain is there.
Question for Concept
Question - Explain [Fe(en)3]3+ is less stable than [Fe(EDTA)]–?
Solution - [Fe(en)3]3+ has three five membered rings in the structure.
On the other hand [Fe(EDTA)]– has five, six membered ring in the structure.
3+ –
O
CH 2–CH 2
C
NH 2 NH2
O
O
C
CH2–N–CH2
O O
3+
Fe NH
H2 2 –CH Fe
–N NH 2
C
O
CH 2
H2 2– CH O CH 2 N–CH2
–2 N 2
CH C
CH 2
O
Effective Atomic Number Rule Given by Sidgwick
Effective Atomic Number (EAN) = No. of electron present on the metal atom/ion + No. of electrons
donated by ligands to it.
Bonding in Co-ordination Chemistry
Werner Theory
Metal in a complex shows two type of valences – Primary & Secondary
Primary Valency Secondary Valency
• It is oxidation no, of metal • It is co-ordination number.
• It is variable • It is non variable.
• Satisfied by anions (present in co-ordination or • Satisfied by ligands (present in co-ordination
ionisable sphere) sphere)
• Ionisable. • Non-ionisable
• Ionic : Nondirectional. • Directional : Decide geometry of complex ion.
• Represented by dotted line in Werner structure. • Represented by solid lines in Werner Structure.
H2 O
H 2O H2 O
Cl Co Cl
CoCl3.5H2O, [CoCl(H2O)5]Cl2
Cl H2 O
H2 O

Valence Bond Theory
Central metal atom/ion & ligand come close to Type of Orbitals participating in intermixing
each other, ligand donate lone pair & CMA depend upon two factors.
provide vacant orbital. There is hybridization of a) Availability of orbtials
atomic orbitals provided by central atom to
b) Nature of ligand
ligands.
Co-ordination Type of
Shape of complex Co-ordination no. 4 - Example
Number of metal hybridisation
4 sp 3 Tetrahedral [NiCl4 ]2– sp3 --- Tetrahedral
4 dsp2 Square planer [NiCn)4]2– dsp2 --- Square Planar
3
5 sp d Trigonal bipyramidal [Ni(CO)4 ] sp3 --- Tetrahedral
3 2
6 sp d Octahedral (High Spin) [Zn(NH3)4 ]2+ sp3 --- Tetrahedral
2 3
6 d sp Octahedral (Low Spin) [Cu(NH3 )4 ]2+ dsp3 --- Square Planar
Co-ordination No. 6 : Examples
[Fe(CN)6]4– d2sp 3
[Fe(CN)6]3– d2sp 3
[Co(NH3 )6]3– d2sp 3
[Ni(H2 O)6]2+ sp 3d2
• If the complex is formed by the use of inner d- Crystal Field Theory

orbitals for hybridization (d2sp3), it is called inner • The splitting of five degnerate d-orbital of the
orbital orbital complex. metal into different sets of orbitals having
• If the complex is formed by the use of outer d- different energies in the presence of electrostatic
orbital for hybridization (sp3d2), it is called an field of ligands is called crystal field splitting.
outer orbital complex. Such complex is also called egset :- dx2 – y2, dz2 t2gset :- dxy, dyz,
as high spin complex e.g. [CoF6]3–. dxz.
• Unpaired electron present  High spin complex. • Crystal field splitting energy, (0 for tetrahedral
• Unpaired electron absent  Low spin complex. structure and t = 4/9 0 octahedral structure) is
the difference between the various sets of energy
Magnetic Moment  µ  n  n  2  (n = no. of level formed by crystal field splitting.
• Weak field ligands which cause a small degree of
unpaired electron)
crystal field splitting
• It couldn’t explain why pairing occurs in S.F.L.
e.g. I–, Br–, Cl–, F–, OH–, C2O42–, H2O etc.
and no pairing in W.F.L.
• Strong field ligands are those ligands which cause
• It couldn’t explain colour of compound.
a high degree of splitting e.g. CO, CN, NO. etc.
• It doesn’t distinguish between strong and weak
• Spectrochemical series
ligands.
I– < Br– < SCN– < Cl– < S2– < N3– < F < OH– < ox2–
< H2O < NCS– < EDTA4– < NH3 < py~en < dipy <
o-phen < N2– < CN– < CO.
(O) and N donar act as SFL except N3–)
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Z Energy correspond
Energy Y
dx – y,dz
2 2 2 to absorption
eg
3/5 0 or + 0.6 0 Average
+6L 0 energy
X 2/5 0 or – 0.4 0
level
Metal Average energy t 2g
d orbitals of ‘d’ orbitals in dxy,dxz,dyz
spherical Energy corresponds to
crystal field evolution of energy.
Crystal field splitting
Free metal ion for octahedral complex
Crystal field splitting in octahedral complex
t = (4/9)0
Energy dxy,dxz ,dyz

t2g
+ 3/5 t = + 0.4 t
+ 4L t
– 3/5 t = – 0.6 t
Average energy of ‘d’ eg
orbitals in spherical dx – y,dz2 2 2
crystal field
Free metal ion
Crystal field splitting in tetrahedral complex
dx – y
2 2
dx – y2 2
1
dxydyzdzx dx – y dz
2 2 2
(t2g + eg)
(t2g) +0.4Dt –0.6 = +6 q (eg) dz 2
dxy sp
Dt = 0.45D0 dxydyzdzxdx –y dz
2 2
0 = 10 q 2
–0.6Dt Five degenerate d-orbitals
–0.4 = –4q
on the central metal cation dxy dz 2
dx – y dz
2 2 2 dxy dyz dzx
(eg) (t2g) dxy dzx 3
Tetrahedral Octahedral Tetragonal
dzy dyz
Crystal field splitting in square planar complex
Square planar

sp = 1.3 0.
Jahn-Teller Distortion Limitations of C.F.T.
• Only for octahedral complexes. 1. It considers only the metal ion d-orbitals and
• If the d-orbitals are asymmetrically filled, they gives no consideration at all to other metal
will repel some ligands in the complex more than orbitals (suchh as s, px, py and pz orbitals).
the others. This results in distortion of octahedral 2. It is unable to account satisfactorily for the
complexes. relative strengths of ligands. For example it gives
• Distortion caused by asymmetric filled of t2g is no explanation as to why H2O is a stronger ligand
too small to measure. than OH– in the spectrochemical series.
• d4 (high spin), d7 (low spin) and d9 configuration 3. According to this theory, the bond between the
show Jahn Teller distortion. metal and ligands are purely ionic. It gives no
Colour In Co-ordination Compounds account on the partly covalent nature of the
According to the crystal field theory the colour metal ligand bonds.
is due to the d-d transition of electron under the 4. The CFT cannot account for the -bonding in
influence of ligands. We know that the colour of complexes.
a substance is due to the absorption of light at a
specific wavelength in the visible part of the
electromagnetic spectrum (400 to 700 nm) and
transmission or reflection of the rest of the
wavelengths.
Isomerism
Structural Stereo
Ionisation Hydrate Linkage Co-ordination Geometrical Optical
Structural
a) Ionisation Isomerism c) Hydrate/solvent Isomerism
Same molecular formula but gives different Same molecular formula but different number
ionisable species. (only anionic) of water molecules associated with central metal.
Eg. Co(NH3)5BrSO4 Eg. CrCl 3.6H2O
b) Linkage Isomerism d) Co-ordination Isomerism

Ligand should be ambidentate Isomers having both anion and cation as
Eg. (NO2–, CSN–, CN–, CNO– etc) complex entity. Can inter change position of
ligands as well as metal.
[Co(NH3)6][Cr(SCN)6] and
[Cr(NH3)4(SCN)2][Co(NH3)2(SCN)4]
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Stereoisomerism
Geometrical Isomerism (GI) Square Planar complex with symmetrical
bidentate ligand
CN = 4 CN = 6 Eg. No GI
Octahedral [M(AA)a4] and [M(AA)3]
Square Mabcdef – 15 GI Type of complex can not exhibit G.I.
Tetrahedral
planar Ma 2bcde – 9 GI
Ma 2b2 cd – 6 GI [M(AA)2a2] type of complex have two GI
cannot show Ma4 – NO GI Ma 2b2 c2 – 5 GI (Cis & trans)
G.I. because Ma 3bcd – 4 G
Ma2 b – NO GI Ma 3b2 c – 3 GI *[M(AA)2a2] type of complex gives three stereo
all 4 position
are equivalent Ma2 b2 – 2GI (cis & trans) Ma 3b3 – 2 (Fac-Mer) isomer:
in tetrahedral Ma 4bc – 2 (cis-trans)
Ma2 bc – 2GI (cis & trans) 1) cis, 2) trans, 3) mirror image of cis
Ma 4b2 – 2 (cis-trans)
geometry
Mabcd – 3 GI Ma 5b – NO GI Compounds containing bidentate ligand and
Ma 6 – NO GI
unidenate ligands.
I) M(AA)a3b – Two geometrical isomers are
possible.
II) M(AA)a2b2 – Three geometrical isomers are
possible.
III) M(AA)2a2 – Two geometrical isomers are
possible.
Optical Isomerism
A coordination compound which can rotate the III) Octahedral complex
plane of polarized light is set to be optically Optical isomerism is common in octahedral
active. complexes involving bidentate ligands. For
I) Square planar complex example, [Co(en)3]3+ had d and l forms as given
Square planar complexes are rarely found to below.
show the optical isomerism. The plane formed
by the four ligating atoms and the metal ion is
considered to be a mirror plane and thus prevents
the possibility of chirality. en en
3+ 3+
II) Tetrahedral complex en Co Co en
Optical isomerism is expected in tetrahedral
complexes of the type [Mabcd] analogous to dextro en en
tetrahedral carbon atom. laevo
a a mirror
3+
d and l of [Co(en)3]
M M
d b b d
c c
Mirror plane

Organometallic Compounds
Metal Carbonyl Sigma ( ) bonded pie () bonded
Metal with CO as a ligand Eg : Metal with alkenes, alkynes,
1) Grigard Reagent Bezene ring and other rings.
R-MgX Eg :
Monomeric Polymeric 2) (CH3)4Sn 1) Zeise’s Salt
2
Contain only one metal Contain two or more than two 3) (C2 H5)4Pb K [PtCl(3  -C2 H4]
atom per molecule. metal atoms per molecule. 4) Al2 (CH3 )6 2) Ferroscene
Eg : [Ni(CO)4 ], [Fe(CO)5 ] They have Metal-Metal bond. 5) Al2 (C2H 5) 6 5
[Fe( -C5 H5)2]
Eg: Mn2(CO)10 (CO)9 3) Bis(Benzene) chromium
6
[Cr( -C6 H6)2]
Back Bonding
• M–C  bond - Donation of l.p. of e– from metal d. orbitals *
 A.B.M.O. (P. orbitals)
to vacant *A.B.M.O. of CO.

Co acts as a 
• (1)  donar (CO  M) 
M C O
• (2)  acceptor (CO  M)

Back Bonding CO is  acid

(Synergic Bonding) Ligand
Extent of Back Bonding IUPAC nomenclature of complex compounds

No of d-orbitals'e–. A) For ani oni c compl ex (l i k e K 4[Fe(CN)6]
–
• If e increase then extent of back bonding Common name of normal cation (without
increase CO bond length decrease then CO bond numeral prefix) + Name of ligands (with
order decrease. numeral prefix) + latin name of CMI along with
If No. of d orbitals e – are same then Back suffix ate + Ox. St (in roman number.)
Bonding depends on Charge of Metal ion. Eg. Potassiumhexacyanoferrate (II)
B) For cationic complex like [Cu(NH3)4]SO4
Name of ligands (with numberal prefix) +
+Ve charge –Ve charge
common name of CMI + Ox. St (In roman
number) + Name of anion (without numeral
prefix)
Eg. Tetraammine copper (II) sulphate.
Due to back bonding C) For neutral complex like [Fe(CO)5]
th e ca r bon ox ygen
Name of ligands (with numeral prefix) +
bond length is increase
common name of CMI + Ox. St.
by 0.01Å –0.1Å.
(in roman number)
Eg. Pentacarbonyliron
D) Rule same just apply alphabatical order when
write the name of ligands
Eg. [Pt(NH3)2Cl2]
Diamminedihloroplatinum (II)
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• Super Note : The ultimate target of every metallurgical step is to increase the concentration of metal.
• Metal : The element which tends to form positive ion is called a metal.
• Minerals : The various compounds of metals which occur in the earth’s crust and are obtained by
mining are called minerals. In earth crust order of abundance of elements is. O > Si > Al > Fe.
A mineral may be single compound or a mixture.
• Ore : The mineral from which a metal can be extracted profitably and easily is called an ore.
Type of Ores
(I) Combined Ore : Metal placed above H in electrochemical series are generally reactive i.e., why they
generally found in combined state.
a) Halide ore / Sulphate ore / Oxy ore : Metal are highly reactive (Li  Mg)
b) Oxide ore : Reactive metal (Al to Sn)
c) Sulphide ore : Metal placed near H or below H. (Pb, Hg, Cu, Ag)
(II) Native Ore : Metal placed below H in electrochemical series are generally found in native state. (Ag, Au,
Cu, Pt etc.)
Gangue or matrix : The undesirable impurities present in an ore are called gangue.

Type of Metallurgy
Pyrometallurgy Hydrometallurgy Electro metallurgy
Temp. in involved Hydrometallurgy Electro metallurgy
For heavy metals According to E.C.S. IA, IIA, Al
Fe, Zn, Cu, Hg, Sn etc For metals placed below H
Cu, Ag, Au
Metallurgical Process Chemical Process
1. Mining : Ore obtain in big lumps (less reactive) Leaching
2. Crushing/grinding/pulverization : Big lumps • Leaching is often used if the ore is soluble in some
convert into powder (more reactive) suitable solvent.
3. Concentration : To remove matrix/gangue • E.g. acids, bases and suitable chemical
(major impurities) from ore to increase the reagents.
concentration of ore particle in ore sample. • Baeyer’s process, Hall’s process and Cyanide
Extraction of Crude Metal from Impure Ore process are example of leaching.
Step - I - Concentration of Ore a) Alumina from bauxite : Al2 O3 .2H2O + Fe2 O3
Physical Process (Major impurity)
a) Gravity separatin / Hydraulic washing / i) Baeyer’s process : NaOH is used.
Levigation : Al2O3 + NaOH  NaAlO2
• Based on difference in the densities of the gangue excess
  Al(OH)3 + NaOH
H2 O
and ore particles.
• Generally use the concentration of oxide Fe (Basic) + NaOH  insoluble
carbonate ores and native ores. ii) Hall’s process : Na2CO3 is used.
b) Electromagnetic Separation : HOH
Al2 O3 + Na2CO3  2NaAlO2 
CO 2

• Based on differences in magnetic properties of
the ore compounts. Al(OH)3 + Na2 CO3
• Chr omi te ore (FeO.Cr2 O3 ) is separated from b) Cyanide Process :
non-magnetic silicious impurities and Cassiterite 4M(s) + 8CN– (aq) + 2H2O(aq) + O2(g) 
ore(SnO2) is separated from magnetic Wolframite 4[M(CN)2 ]– (aq) + 4OH– (aq)
(FeWO4 + MnWO4). 2[M(CN2 ]– (aq) + Zn(s)  [Zn(CN)4]2–(aq) + 2M(s)
c) Froath floatation :
where (M = Ag or Au)
• Based on the fact that gangue and ore particles
Step II - Conversion of Ore to Oxide
have different degree of wettability with water
(Oxides are easy to reduce to metal)
and pine oil;
Calcination
• The gangue particles are preferentially wetted by
water while the ore particles are wetted by oil. In the absence of air
• Generally used for concentration of Sulphide ore. For carbonate/Hydroxide/Oxide ore
• Frother – Pine oil, Floating agent – Sodium ethyl • The carbonate ore gets decomposed to form the
xanthate depressant -NaCN, Froth stabilisers oxide of the metal MCO3  MO + CO2.
– cresol, aniline etc.
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• Water of crystallisation present in the hydrated III. Metal displacement reduction
oxide ore gets lost as moisture • Metal placed below H. In E.C.S.
M(OH)2  MO + H2O
• Organic matter, if present in the ore, gets expelled Ag, Au, Cu
and the ore becomes porous. Volatile impurities
are removed. i) Cyano complex or Mac Arthur process
Roasting
4Au(s)+ 8CN– (aq)+ 2H2 O(l)+ O2(g)
• It is a process of heating the concentrated ore
4[Au(CN)2]–(aq) + 4OH–(aq)
strongly in the excess of air or O 2 below its
melting point. ii) Reduction to free metal
• For sulphides ore : 2Na[Ag(CN)2 ]– + Zn  Na2[Zn(CN)4] + 2Ag
Impurity of S, P, As, SO2 to be removed 2K[Au(CN)2] + Zn  K2 [Zn(CN)4] + 2Au
MS + O2  MO + SO2  IV. Electrolytic Reduction
Step III - Reduction of Oxides to Metal In aqueous solution :
I. Chemical reduction
• Electrolysis can be carried out conveniently and
cheaply in aqueous solution that the products
do not react with water Copper and zinc are
(a) by C (smelting) (b) by Al obtained by electrolysis of aqueous solution of
their sulphates.
MO + C + Flux Cr 2O3 + 2Al Al2O3 + 2Cr
In other solvents :
 M + CO2  + Slag Mn 2O3 + 2Al Al2O3 + 2Mn
• Electrolysis can be carried out in solvents other
Flux – Substance to convert non-fusible than water.
impurities to fusible one. • Fluorine reacts violently with water and it is
Flux produced by electrolysis of KHF2 dissolved in
anhydrous HF.
Acidic Flux Basic Flux In fused metls :

• Elements that react with water are often extracted
Remove basic Remove acidic from fused melts melts of their ionic salts.
impurities impurities
• Aluminum is obtained by electrolysis of a fused
mixture of Al2O3 and cryolite Na3[AlF6].
Non metallic Metallic oxide
oxide (SiO2) (CaO) • Both sodium and chlorine are obtained from the
Imp. Point – electrolysis of fused NaCl.
• At high temp. C is reducing agent. Hall Heroult Process
• At low temp. CO is reducing agent. • This process is used for extraction of Al from
II. Self reduction alumina. The extraction of Al for Al2O3 is quite
• Compounds of certain metals are reduced to difficult because.
metal without using any additional reducing • Fusion temperature of Alumina is quite high
agent. ores of Cu, Pb, Hg etc. (2050°C). Even more than boiling point of Al
• Their sulphide ores are partially roasted to give (1150°C)
some oxide. This oxide is now reduced to the • It is a bad conductor of electricity. To overcome
metal by the remaining sulphide ore at elevated these difficulties we mix some amount of neutral
temperatures in the absence of air. flux [Na2AlF6 + CaF2].
• The process is known as self reduction. • Neutral flux provides free ions to the solution
2Cu2 S + 3O2  2Cu2O + 2SO2 which decreases the fusion temperature of
2Cu2O + Cu2S  6Cu + SO2 Alumina from 2050°C to 950°C.
i) From cryolite : AlF3  Al+3 + 3F–
At cathode : Al+3 + 3e–  Al (reduction)
3
At anode : 2F– – 3e–  F
2 2
3
F2 reacts with Al2O3 3F2 + Al2O3  2AlF3 + O • According to Ellingham diagram, the metal
2 2
below can reduce the oxide of metal above it in
So at anode O2 gas is liberated which on reaction
the curve, as affinity of metal below for oxygen
with graphite anode convert into CO2 & destroy
is more.
the anode C + O2  CO2.
Ex. Al Metal can reduce Cr2O3 but can not reduce
ii) From Al2 O3
MgO & CaO.
At cathode : Al+3 + 3e–  Al (reduction)
At very high T after 'A' Point 'Al' mental can
At anode : C(s) + 2O–2  CO2(g) + 4e– reduce MgO because formation of MgO contains
The main drawback of this process it that anode less –ve DG.
should be changed frequently.
Thermodynamics of Extraction :
Ellingham Ellingham Diagram II)
CO 2(
• It is explanation of feasibility of pyrometallurgical 2
process by using gibbs equation + O2
2CO
2C + 2O 2  2CO 2(I)
ΔG = ΔH  TΔS G°
2C
+ O
• If G = –ve Process is stable or Spontaneous 2 
2C
G = +ve or Less –ve then process is Unstable O(
III
)
or non-Spontaneous
• When pryometallurgical process contains more
than one type of reaction then stability of reaction 710° T
can be explain by Ellingham diagram. Super Note :
• According to diagram at high T(710° OR above
• Ellingham diagram contains plot ΔG vs T 710°C) Oxidation of C contains more –G so at
high T'C' is good Reducing agent.
400
• At Low T(below 710°C) Oxidation of CO
300
contains more –ve G so at Low, T, CO is good
200
Reducing agent.
100
0 O 3
Step IV - Refining : To obtain metal (99.98%)
 Cr 2
–300 /2 O 2 I) Physical Process
r +3
–500 2C
O3
–700  Al 2 A
G° 2O 2
–800 l+ 3 / O
2A g
–900 2M

+O
2
–1000 g Ca O
2M O 2
+ 2
–1100 2 Ca
–1200
0 400 800 1200 1600 2000
T
Prof.Motegaonkar
S.R.M.Sc.Chem.Gold
DRDO,TIFRqualified
qualified Page:
Page: 61
61
II) Chemical Process Important Ores
Oxide Ore
Al 2O3 .2H2 O Bauxite
Fe2O 3 Haematite
ZnO(Philosopher’s Wool) Zincite
SnO 2 Cassitertie (Tin stone)
Carbonate Ore
CaCO3 Lime stone
MgCO3.CaCO3 Dolomite
ZnCO3 (Smithosonite) Calamine
PbCO 3 Cerrusite
III) Thermal decomposition
FeCO3 Siderite
CuCO3 .Cu(OH)2 Malachite
2CuCO3 .Cu(OH)2 Azurite
Sulphate Ore
MgSO 4 .7H2 O Epsomite or
Epsom salt
Sulphide Ore
ZnS Zinc Blende
(Sphalerite)
IV) Electrolytic Refining
HgS Cinnabar
• Anode – made up of impure metal
PbS Galena
• Cathode – made up of pure metal (pure metal
FeS 2 Iron pyrities
deposit)
(Fool’s gold)
• Impurity deposited below anode as anode mud.
CuFeS2 , CuS.FeS Copper pyrites
(Chalcopyrities)
Cu2S (Copper glance) Chalcocite
Halide Ore
AgCl Horn Silver
CaF2 Flourspar
AlF3.3NaF Cryolite
KCl.MgCl 2.6H2 O Carnelite

Flow Chart
Prof.Motegaonkar
Zinc Iron Aluminium Copper (Cu)
ZnS i) Purification of bauxite CuFeS2
Haematite
n
Al2O3.2H2O
Fe2O3
n
Baeyers (For red bauxite + Fe2O3) FFP
Halls (Fe2O3+SiO2)
S.R.M.Sc.Chem.Gold
Gravity seperation Serpercks (SiO2)
Concn 2CuFeS 2
n
c no C)i
Al2 O3 .2H2 O
ZnS
O2
ae R
(Hall & Heroult’s process)
c no C )i
smelting
1200 K
Reverberatory furnance Na3AlF6 3NaF + AlF3
i) Zone of combustion (2000K)
AlF3 Al3+ + 3 Cu2S + 2FeS + SO2 
+3 –
** RCC * *RCC
 ** RCC * *RCC ** * *RCC RCC * *RCCAt
** Cathode
RCC * *RCCAl** RCC + 3e* *RCC
Al**(l)RCC * *RCC ** RCC
2FeS *+*RCC
3O2 **2FeO
RCC+*2SO* 2
si s yl ort c el E )ii
RCC ZnO + SO 2
RCCH
C +RCCO*2 *RCC **CO = – 220
** kJ
(CO acts as both as At anode  FeO + SiO 2
 FeSiO 3
(slag)
a fuel & reducing
g nit s ao R)ii
C(s) + O2– (melt) CO(g) + 2e–
Coke = 60% & 40% ZnO 2CO 2C + O 2 agent)
1673 K,
g nit s a o R )ii
ii) Zone of redn (900 K) C(s) + 2O2– (melt) CO2(g) + 4e– Matte (Cu2S + FeS)
Fe2O3 + 3CO 2Fe (spongy) + 3CO2 2Al2O3 + 6F2 4AlF3 + 3O2
2Cu2S + 3O2 2Cu2O+2SO2
spelter Zn + CO 
Fe2O3 + 3C 2Fe + 3CO F2 + 2e– 2Cu2O + Cu2S  6Cu + SO2
For 1 kg Al 0.5 kg Carbon rod eaten away.. (Auto redn)
g nitl e mS)iii
iii) Zone of slag formn (1200–1500K)

iii) Refining (Hoopes process)
g nitl e mS )iii
CaCO3 CaO + CO2 Blister copper (99%Cu)
DRDO,TIFRqualified
(Ag + Au + Fe, Ni, Zn)
qualified
CaO + SiO2 CaSiO3 (slag) Cathode(–) Pure Al
Na 3AlF6 + BaF2
iv) Zone of fusion (1500 K) Anode (+) Impure Al
Fe + C, Si, Mn, P, S Molten Pig Ruby (red)         Al2O3 + Cr2O3
Fe. Sapphire (blue)  Al2O3, Fe2O3 + TiO2
Emerald (green)  Silicates of Ca, Cr & Al
(spongy) Anode – Impure Cu
si s yl ort c el E) vi
Cathode – Pure Cu
Electrolyte – CuSO4 + H2SO4
Page:
g ni ni f e nRo)itvazi r a mess e B) vi
Page: 63
63
SOME COMMON ELEMENTS WITH
THEIR NATURE OF OCCURRENCE
Iron (Fe) Calcium (Ca)
Haematite : Fe 2 O 3 Limestone (calcite) : CaCO 3
Magnetite : Fe3O 4 Gypsum : CaSO 4 .2H 2 O
Limonite : Fe 2 O 3 .3H 2 O Fluorspar : CaF 2
Iron pyrites or Fool’s gold : FeS2 Dolomite : CaCO 3 .MgCO 3
Spathic iron or Siderite : FeCO 3 Magnesium (Mg)
Copper (Cu) Magnesite : MgCO 3
Cuprite (Ruby copper) : Cu 2 O Carnallite : KCl.MgCl2 .6H 2 O

Epsom salt : MgSO 4 .7H 2 O
Copper glance (Chalcocite) : Cu 2 S
Malachite : CuCO3.Cu(OH)2
Lead (Pb)
Galena : PbS
Azurite : 2CuCO 3 .Cu(OH) 2
Anglesite : PbSO4
Copper pyrites (Chalco pyrites) : CuFeS2
Cerrusite : PbCO 3
Zinc (Zn)
Mercury (Hg)
Zinc blende or Sphalerite : ZnS
Cinnabar : HgS
Zincite or Red zinc : ZnO
Silver (Ag)
(philosopher’s wool)
Argentite (Silver glance) : Ag 2 S
Calamine or Zinc spar : ZnCO 3
Hornsilver : AgCl
Franklinite : ZnO.Fe 2 O 3
Tin (Sn)
Willemite : Zn 2 SiO 4
Cassiterite : SnO 2
Aluminium (Al)
Bauxite : Al 2 O 3 .2H 2 O
Kaolinite ( a form of clay) : [Al2 (OH) 4 Si 2 O 5 ]
Cryolite : Na 3 AlF 6
Feldspar : KAlSi 3 O 8
Corundum : Al 2 O 3
Diaspore : Al 2 O 3 .H 2 O
Mica : K 2 O.3Al 2 O 3 .
6SiO 2 .2H 2 O
Pyrolusite : MnO 2

Types of Ores 4. Sulphate Ore :
1. Carbonate Ore : 1. BaSO4  Barytes
1. MgCO3  Magnesite 2. PbSO4  Anglisite
2. CaCO3  Lime stone 3. CaSO4 2H 2 O  Gypsum
3. MgCO3 .CaCO3  Dolomite 4. MgSO4 .7H2 O  Eypsomite
4. ZnCO3  Calamine 5. SrSO4  Celestine
5. PbCO3  Cerusite 6. K2 SO4 .Al2 (SO4 )3 24H2 O  Alum
6. FeCO3  Siderite 5. Silicate Ore :
7. CuCO3 . Cu(OH)2  Malachite 1. LiA(SiO3)2  Spodumene
8. 2CuCO3 .Cu(OH) 2  Azurite 2. KAl Si3O8  Felsper
9. SrCO3  Strontianite 3. Al2 O3 .2SiO3 .2H2 O  Caolin (or China-
2. Sulphide Ore : clay)
1. ZnS  Zinc Blande 4. 3BeO.Al2 O3.6SiO2  Beryl
2. HgS  Cinabar 5. CaO.3MgO.4SiO2  Asbestus
3. PbS  Galena 6. K2O.3Al2O 3.6SiO2 .  Mica
4. Ag2S  Argentine or Silver glance 2H2O KH2 .Al3 .(SiO3)4
5. FeS2  Iron pyrites 6. Nitrate Ore :
6. CuFeS2 .  Copper pyrites 1. NaNO3  Chilli - Salt peter
CuS.FeS 2. KNO3  Salt peter
7. Cu2 S.Ag 2 S  Copper silver glance 7. Phosphate Ore :
8. Ag2S.Sb2S3  Pyrargirite, Rubisilver 1. Ca3(PO4 )2  Rock Phosphate
9. Ag5.SbS4  Stifenite 2. Fe3 (PO4 )2 .8H2 O  Vivianite
3. Oxide Ore : 3. AlPO4 .Al(OH)3 H2 O  Terguoise
1. ZnO   Zincite 8. Halide Ore :
2. MnO2   Pyrolusite 1. NaCl  Rock Salt
3. SnO2   Cassiterite 2. AgCl  Horn Silver
4. Cu2 O   Cuprite 3. CaF 2  Flour Spar
5. Fe2O3   Hematite 4. AlF 3 .3NaF  Cyrolite
6. Al2 O3 2H 2 O   Bauxite 5. KCl.MgCl2 .6H2 O  Carnelite
7. FeO, Cr2O3   Chromite

8. Fe3O4   Magnetite
9. Fe2O3 .3H2 O   Limonite
10. 3BeO,Al2O3 .6SiO2   Beryl
Prof.Motegaonkar
S.R.M.Sc.Chem.Gold
DRDO,TIFRqualified
qualified Page:
Page: 65
65
HYDROGEN 2. Allotropes :
1. Occurence • Ortho : Spin of P+ in same direction.
• First lightest element (non-metal) in the P.T. • Para : Spin of P+ in opposite direction.
• It exist as diatomic gas (H2)
– –
e e– e e–
• Most abundant element in universe and human
body.
P P P P
• Main constituent of H2O.
Ortho Hydrogen Para Hydrogen
2. Historical back ground
(H2) (H2)
• Henry Cavendish : first prepared and named
it as inflammable air. • Ordinary hydrogen consists of 75% Ortho and
• Lavoisier : Named as Hydrogen (Hydra = water 25% para forms at 25°C (O : P = 3 : 1 at room
genus-maker) = water maker. temperature).
• Humphry Davy : • At 20 K 99.82% Para and only 0.18% Ortho is

present.
Established it as an element.
• Ortho H2 is more stable than Para H2.
• Unique features :
• Ortho exist at high tempearture.
- It is a clean fuel.
3. Reactivity
- Giant planets such as Jupiter and Saturn
contain mostly Hydrogen. • Atomic hydrogen : Obtained from H2 on a hot
filament of W or Pt.
- Sun and other stars mostly contain
Hydrogen. • Very reactive form than ordinary hydrogen its
life span is 0.3 second.
- It i s only element that exi st without
neutrons. • Nascent hydrogen : Liberated as a result of
chemical reaction. It is powerful reducing
FORMS OF HYDROGEN agent.
1. Isotopes • Molecular Hydrogen : Exist as H2
• Hydrogen (Protium) : • Reactivity order -
1
H1 or H (e– = 1, P+ = 1, n = 0) Atomic > Nascent > Molecular Hydrogen
Abundance - 99.98% - Stable PREPARATION OF HYDROGEN
• Deuterium (Heavy hydrogen) : • Zn + H2SO4 (dil.)  ZnSO4 + H2(Lab method)
2 2 – +
1
H or 1D (e = 1, P = 1, n = 1)
1023K  1073K
• 3Fe + 4H2O(steam)   Fe3O4 + 4H 2
Abundance - 0.016% - Stable
(Lane’s Process)
• Tritium :
1
H3 or 1T3 (e– = 1, P+ = 1, n = 2) • 2Al + 2KOH + 2H2O 
 2KAlO2 + 3H2 
• In ordinary hydrogen, the ratio of protium to (Uyeno’s Method)

deuterium is 6400 : 1.

CHEMICAL PROPERTIES Compounds of Hydrogen [H2O, D2O, H2O2]
1. H2O
5000C
• H 2 (g) 
95.5%
 2H(g)
Dihydrogen Atomic H. • Structure :
Ni ,Pt ,Pd H2O is angular or bent inshape
• Alkene / Alkyne 
473K
 Alkane
Hyb. = sp3, b.p. = 2, l.p. = 2,  0
Ni
• Aldehyde/Ketone 
 Alcohol O
H 104.5° H
Ni
• Vegetable oil (liquid) + H 2

473K 
In gaseous state
As discrete molecule
• Exists
Vegetable Fats (Vegetable ghee) (Solid) In Solid and
liquid state By H-bonding
[Hydrogenation]
• Properties :
HYDRIDES OF HYDROGEN
2H2O  2H2 + O2 [Decomposition]
General formula - MHX

where M = Element, X = Number of H. H2O(l) + H2O(l)  H3O+(aq) + O H (aq)
1. Ionic/Saline/Salt like [Self ionization]

Acts as catalyst in redox reaction and amphoteric
• Formed by s-block elements. Except Be and Mg
in nature.
form covalent hydrides.
Salient features :
• High bp, mp, heat of formation and density.
• Most plentiful and readily available of all
• Powerful reducing agent.
chemicals.
• Always Stoichiometric. • 3/4th of the earth surface, 1/3rd of human body
2. Molecular/Covalent is water.
• Formed by p-block and some s-block elements • Natural forms are - rain, sea and surface water.
• Volumetric and gravimetric composition of
• Low b.p. and m.p.
water is 2 : 1 and 1 : 8 (H : O) respectively.
• Hydrides of
• It is a universal solvent.
Group 13 - Called electron defficient (BH3, AlH3
Hardness of Water
etc.)
• Soft water produces sufficient lather with soap.
Group 14 - Called electron exact (CH4, SiH3 etc.)
• Hard water forms an insoluble scum before it
Group 15 - Called electron rich (NH3, PH3 etc.) forms lather with soap.
3. Metallic / Interstitial : Types of Hardness
• Formed by d and f block element. i. Temporary Hardness :
• Non-stoichiometric (LaH2.8%, TlH1.5–1.8%) Due presence of bicarbonate of Mg and Ca.
• Due to interstitial hydrides, metals adsorb large e.g. Mg(HCO3 )2, Ca(HCO3)2
volume of hydrogen (occlusion).
• Removal by boiling and Clarks’ Process.
• Order is Pd > Pt > Au > Ni. ii. Permanent Hardness :
• Due to presence of sulphate and chlorides of Mg
and Ca.
e.g. MgSO4, MgCl2, CaSO4, CaCl2
Prof.Motegaonkar
S.R.M.Sc.Chem.Gold
DRDO,TIFRqualified
qualified Page:
Page: 67
67
• Can not be removed by boiling and clark’s Uses :
method.
• In control pollution.
• Removal by treatment with Na 2 CO3 , Zeolite
• As an antiseptic (as perhydrol)
(Permutit method), by ion exchange method etc.
• For restoring colour of old paintings.
iii. Degree of Hardness :
• As antichlor, bleaching agent for wool, hair.
• The number of parts of CaCO3 or equivalent to
various Ca and Mg salts present in 106 parts of • As a fuel for rocket, submarine etc.
water by mass. • Strength of H2O2 :
• Hardness in generally estimated by using EDTA (i) As percentage
solution and Erichrome black-T.
(ii) As number volume
Ca+2 and Mg+2 ions form complex with EDTA.
e.g. 10 Volume H2O2 means – 1ml H2O produces
Heavy Water [D2O] by Urey 10 ml O2 on complete decomposition of H2O2 at
• Colourless, odourless and tasteless liquid. NTP.
• Obtained by water on prolonged electrolysis • Direct conversion of concentration term :

• Chemically similar but reacts more slowly than 17
H 2 O. (i) % strength = × Volume Strength
56
• Molecular mass is 20 u.
(ii) Volume strength = 5.6 × Normality
Uses (iii) Volume strength = 11.2 × Molarity
• As neutron moderator.
• Chemical properties of H2O2
• As a tracer compound.
Stability :
• Preparation of deuterium.
Unstable liquid, decompose on standing and
Hydrogen peroxide or Oxygenated water.
heating (Auto oxi. and red. - Disproportionation)
H2O2 by Thenard. H
 2H 2 O + O 2
2H 2 O 2 
Structure : O O.S. (  1) ( 2) (0)
1.48 Å
97°
- Open book like
Catalyzers :
0.97°
- Non-planar O
H 98° MnO2, carbon, finaly divided metals (like – Au,
- Hyb-sp 3 Pt, Ag etc.)
Preparation : Retarders :
BaO2 + CO2 + H2O 
 BaCO3  + H2O2 Acids (like H3PO4) acetanilide, alcohol basic acid.
[Merck’s process] Acidic nature :
Autooxidation
2-butyl anthra-quinol + O2(air)   Pure H2O2 is weak dibasic acid turns blue litmus
to red but aq. solution of H2 O 2 is neutral
Pd
2-butylanthraquinone 
H
 towards limus
2
2-butylanthraquinol + H2O2 Oxidising and reducing both nature

Most recent [Industrial method] e.g. PbS + 4H2O2  PbSO4 + 4H2O
2HCHO + H2O2   2HCOOH + H2
[H2O2 as O.A.]
H2O2 + O3   H2O + 2O2
Ag2O + H2O2   2Ag + H2O + O2
[H2O2 as R.A.]

-: Note :-
-: Note :-
-: Note :-

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Inorganic Chemistry

8. Hydrogen and It’s Compounds 66

3. Newland’s Law of Octave a) He was unable to include all elements into

Eka 'B' Scandium (Sc) B.Sc. 89

Page: 2 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

A(g) + e–  A(g ) ; + xKJ, Heg = –x ii. EA  Zeff

G-17 Cl  F > Br > I > At

Si P S Cl d) Bridge element : Mg & Ca

Atomic radius Increases Decreases

Ionisation potential Decreases Increases

Electronegativity Decreases Increases

Electron affinity Decreases Increases

Covalent character Decreases Increases

Metallic nature Increases Decreases

Oxidising nature Decreases Increases

Reducing nature Increases Decreases

Screening effect Increases Increases

Effective nuclear charge (Zeff) Constant Increases

Valency w.r.t. oxygen Constant Increases

Basic character (Metals) Decreases

Basic character of oxides (Non metal) Decreases Decreases

Basic character of Increases Decreases

Strenth of oxy acids Decreases Increases

Thermal stability of sulphate Increases Decreases

Thermal stability of carbonates Increases Decreases

Thermal stability of nitrates Increases Decreases

Thermal stability of hydroxide Increases Decreases

Density Increases First increass then decreases

Electro positivity Increases Decreases

 LiOH, NaOH, KOH, RbOH, CaOH

Back Bonding Can be of two types mainly

Size of central atom should be Large than B. Transfer of electron/s.

Hydrogen Bonding Molecular Forces

Ion induced dipole. 

Page: 10 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

Lewis dot structures Failed to Explain

2 How Electron are shared

Requirement of Orbital Overlapping Factors affecting overlapping

inert pair effect in heavy p-block elements

Based on electron density Angle of Approach

Hybridization (Mixing of Atomic Orbitals)

Valence shell Electron pair Repulsion Theory (VSEPRT)

a) sp3d2 hybridisation 6 - Square bipyramidal/ PCl 6 ,SF6

d AB  (rA  rB  0.09  EN)Å Constructive Destructive

Page: 14 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

|µ|= q × r • Predict shape and polarity of molecule.

µ R  µ12  µ 22  2µ1µ 2 cos  • Molecules with regular geometry and same

Page: 16 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

H(sub) H(dies) Cation size 

• Hydration Energy determines solubility of • Also known as Co-ionic, semi-polar or Dative

Page: 18 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

Order of density Cs > Rb > Na > K > Li Ba  Sr  Be  Mg > Ca

Reason due to empty d orbital in k due to empty d orbital density of

Page: 22 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified

the anhydrous salt. • Reverse reaction is suppresed by removing CO2

• It is electron-deficient and behaves as Lewis acid. Calcium Sulphate

• It is prepared by heating gypsum at 1200 – 1300°C. Tricalcium silicate (Ca3SiO5) 51%

General Difference Between IA & IIA

Page: 24 Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified