CHEMICAL BONDING AND MOLECULAR STRUCTURE

IONIC BOND
Valence Bond Theory
Gave the concept of Hybridisation
Hybridisation Atomic orbitals

sp, sp², sp³ s + any p

Properties of ionic comopounds
Hard & Brittle with High Boiling and Melting Points. dsp² s+ pₓ+ pᵧ+ dₓ²-ᵧ²
Soluble in Polar Solvents (Hydration>Lattice enthalpy)
Conductivity : Aqueous > Fused > Solid State sp³d s+ pₓ+ pᵧ + pz + dz²
Solubility∝ ∝ ∝
Dieletric constant 1/Polarisation Diff.
in size of cations and anions s + pₓ+ pᵧ + pz +
sp³d²
dₓ²-ᵧ² + dz²
Other types : Covalent Bond & Coordinate Bond
s + pₓ+ pᵧ + pz +
sp³d³
MP and BP : Ionic > Coordinate > Covalent dₓ + dᵧ + dz

FORMAL CHARGE
OCTET RULE
(Total Valence e⁻ (No. of electron (Shared pair
Stable arrangement of atoms when surrounded by 8 e⁻
in a neutral atom) in Lone Pair) of electrons)
(owned or by sharing)
-1 Incomplete or Expanded or Odd e⁻
Hypovalent Hypervalent molecules
AlCl₃, BF₃, BeF₂ PF₅, SF₆, H₄SO₄, IF₇ O₂⁻, NO, ClO₂
+1 Octet rule doesn't tell about energy of molecules
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 VALENCE SHELL ELECTRON REPULSION THEORY (VSEPR)
Repulsions : Lone Pair - Lone Pair (LP-LP) > Lone Pair - Bond Pair (LP-BP) > Bond Pair - Bond Pair (BP-BP)
Strength of Orbital overlap
𝜎 bond : s-s > s-p > p-p | π bond : 2pπ-2pπ > 2pπ-3pπ > 3pπ-3pπ

Mol. Geometry Shape S.N. Hyb Examples

AB₂ Linear Linear 2 sp BeCl₂, Alkyne, CO₂, HgCl₂
AB₃ Trigonal planar Trigonal planar 3 sp² AlCl₃, BF₃, Alkene
AB₂L Triagonl Planar Bent 3 sp² NO₂⁻, SO₂, O₃
AB₄ Tetrahedral Tetrahedral 4 sp³ CH₄, SiH₄, ClO₄⁻, PO₄³⁻, SO₄²⁻
AB₃L Tetrahedral Pyramidal 4 sp³ NH₃, PCl₃, ClO₃⁻, CH₃⁻, NF₃
AB₂L₂ Tetrahedral Bent 4 sp³ H₂O, PbCl₂, OF₂, NH₂⁻, ClO₂⁻
AB₄ Square planar Square planar 4 dsp² PtCl₄²⁻, Cu(NH₃)₄²⁺, Ni(CN)₄²⁻
AB₅ T.B.P. T.B.P. 5 sp³d PCl₅, SbCl₅, PF₂Cl₃
AB₄L TBP See Saw 5 sp³d SF₄, PCl₄⁻, XeO₂F₂
AB₃L₂ TBP T-Shape 5 sp³d IF₃, ClF₃, XeOF₂
AB₂L₃ TBP Linear 5 sp³d I₃⁻, XeF₂
AB₆ Octahedral Octahedral 6 sp³d² SF₆, PF₆⁻, SnCl₆⁻²
AB₅L Octahedral Square Pyramidal 6 sp³d² IF₅, BrF₅, ICl₅, XeOF₄
AB₄L₂ Octahedral Square Planar 6 sp³d² XeF₄, ICl₄⁻
AB₇ P.B.P P.B.P 7 sp³d³ IF₇
AB₆L P.B.P Distorted Octahedral 7 sp³d³ XeF₆
AB₅L₂ P.B.P Pentagonal Planar 7 sp³d³ XeF₅⁻ 6
 Total Bond Unpaired Magentic HOMONUECLEAR M.O.T
Species
e⁻ order e⁻ character
Be₂, Li₂-2 , B₂²⁺ 8 0 0 Diamagnetic n e⁻ < 14
B₂⁺, Be₂⁻ 9 0.5 1 Paramagnetic
B₂, Be₂²⁻ , C₂²⁺ 10 1 2 Paramagnetic
n e⁻ > 14
C₂⁺ , Be₂⁻ 11 1.5 1 Paramagnetic
B₂²⁻, C₂, N₂²⁺, BN, CN⁺ 12 2 0 Diamagnetic
C₂⁻ N₂⁺, CN 13 2.5 1 Paramagnetic Bond order = 1/2 (Nb - Na)
N₂, O₂²⁺, C₂²⁻, CO, If B.O. = 0, Molecule doesn't exist
NO⁺, CN⁻
14 3 0 Diamagnetic
Bond order ∝ ∝
Bond Strength Bond
N₂⁻, O₂⁺, NO 15 2.5 '1 Paramagnetic
∝
Stability 1/Bond length

N₂⁻², O₂, NO⁻, F₂²⁺ 16 2 2 Paramagnetic Bond order in resonating strucrtures

O₂⁻, F₂⁺ 17 1.5 1 Paramagnetic = Total number of bonds between atoms
Total number of resonating structures
O₂⁻², F₂, Ne₂²⁺ 18 1 0 Diamagnetic
F₂⁻, Ne₂⁺ 19 0.5 1 Paramagnetic CO₃²⁻ = 1.33 ; O₃ = 1.5
Examples
F₂⁻², Ne₂ 20 0 0 Diamagnetic SO₄²⁻ = 1.5 ; ClO₄⁻ = 1.75

DIPOLE MOMENT T NF₃ < NH₃ ; H₂O > F₂O µ = 0 for non polar & symmetric molecules
R Trans C₂H₂Cl₂ < Cis C₂H₂Cl₂ e.g. BeCl₂, CH₄, SbF₅, Trans C₂H₂Cl₂
% ionic Character
E Exception :
Trans N₂F₂ < Cis N₂F₂ Hydroquinone
N Lone pair not involved
D CH₃Cl > CH₂Cl₂ > CHCl₃ > CCl₄ in resonance
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 Back Bonding - Factors and Consequences Hydrogen Bonding (Consequences)
Hydrogen
Connected to E.N.
element forming non
bonding interaction.
Trend Property Backbonding B/w

PF₃ > PH₃ Bond Angle P-F (F Donor) Strength : HF > H₂O > NH₃ (depends on E.N.)

PH₃ > PF₃ Bond length P-F ( F Donor ) 1. NH₃ & H₂O have highest M.P. and B.P. in their gps.
2. Lower alcohols and NH₃ are soluble in water
BF₄⁻ > BF₃ Bond Length B-F ( F Donor ) 3. Viscosity Increases with H-Bonding
4. Volatility of compounds Decreases
Cl₂O > H₂O > F₂O Bond Angle Cl-O ( O Donor)
5. ( H-Bond strength ) Ice > Water > Impure water
B(OH)₄⁻ > B(OH)₃ Bond Length B-O ( O Donor )
Bridged Compounds
(SiH₃)₂O > (CH₃)₂O Bond Angle Si-O ( O Donor)
B₂H₆ Al₂Cl₆ Al₂I₆ Al₂(CH₃)₆
(SiH₃)₂O > Cl₂O Bond Angle Si-O ( O Donor)
3c-2e⁻ 3c-4e⁻ 3c-4e⁻ 3c-2e⁻
R₃SiOH > R₃COH Acidic Nature Si-O ( O Donor)

R₃NO > R₃PO Dipole Moment P-O ( O Donor) Bent's Rule

More electronegative
N(CH₃)₃ & P(SiH₃)₃ are Pyramidal in nature whereas
element occupies the axial
N(SiH₃)₃ & N(GeH₃)₃ are Planar in nature due to B.B.
position ( % p is more)
Less electronegative/lone
CH₃NCS and CH₃NCO are bent in nature pairs occupies equatorial
SiH₃NCS and SiH₃NCO are Linear in nature due to B.B. position ( % s is more )
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 INORGANIC SALT ANALYSIS
ANIONS OBSERVATIONS CONFIRMATORY TESTS
IONS Dil. H₂SO₄ Carbonate (CO₃²¯)
Brisk effervescence, colorless, odorless gas Salt + dil. H₂SO₄ brisk efferv.(CO₂)
Carbonate (CO₃²¯)
(CO₂)- turns lime water milky. CO₂ + lime water Milky solution
Milky lime water + excess CO₂ colorless
Colorless gas, rotten egg like smell (H₂S)- turns
Sulphide (S²¯)
lead acetate paper black. Reactions-
Na₂CO₃ + H₂SO₄ Na₂SO₄ + H₂O +CO₂
Brown fumes (NO₂)- turn acidified KI solution
Nitrite (NO₂¯) Ca(OH)₂ + CO₂ CaCO₃ + H₂O
containing starch solution blue.
CaCO₃ + CO₂ + H₂O Ca (HCO₃)₂
IONS Conc. H₂SO₄
*Ca (HCO₃)₂ is soluble in water.
colorless gas, pungent smell (HCl)- gives dense
Sulphide (S²¯)
Chloride (Cl¯) fumes when rod dipped in NH₄OH is brought
near the mouth of test tube. Water extract + NH₄OH Alkaline
Alkaline extract + sodium nitroprusside
Reddish brown gas, pungent odor (Br₂ vapors)-
Bromide (Br¯)
intensity of red increases on adding solid MnO₂
Blue/Violet
Violet vapors (I₂)- turn starch paper blue, Fumes
Iodide (I¯) Reactions-
become dense on adding MnO₂
Na₂S + Na₂ [Fe(CN)₅NO]
Brown fumes (NO₂)- become dense on heating, Na₄ [Fe(CN)₅NOS]
Nitrate (NO₃¯)
Cu solution when added make solution blue.
*anions which react with dil. acid don’t react with conc. acid and vice
versa
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 Nitrite (NO₂¯) Test-2 for Cl¯
Salt solution + AgNO₃ White ppt
Water extract + acetic acid + sulphanilic acid +
(soluble in NH₄OH)
1-naphthylamine reagent= formation of Red color dye
Reaction- (Test 2)
Reactions- 2NH₄OH
NaCl + AgNO₃ NaNO₃ + AgCl [Ag(NH₃)₂]Cl
NO₂¯ + CH₃COOH HNO₂ + CH₃COO¯
Test-3 for Cl¯- Chromyl chloride test
Salt + solid K₂Cr₂O₇ + conc. H₂SO₄ +heat Gas(CrO₂Cl₂)
Gas + NaOH Yellow solution
1st Part 2nd Part
Blue
Yellow Acetic acid + Dil. H₂SO₄ + amyl organic
ppt lead acetate alcohol + H₂O₂ layer
Reactions-
RED AZO-DYE
NaCl + K₂Cr₂O₇ + H₂SO₄ KHSO₄ + CrO₂Cl₂ + NaHSO₄ +
H₂O
CrO₂Cl₂ + NaOH Na₂CrO₄ + NaCl + H₂O
(CH₃COO)₂Pb + Na₂CrO₄ PbCrO₄ + CH₃COONa
CrO₄²¯ + 2H⁺ + 2H₂O₂ CrO₅ + 3H₂O

Chloride (Cl¯) Structure of Chromium pentoxide

(CrO₅)
Salt + conc. H₂SO₄ + MnO₂ green- yellow gas
[Dissolves in amyl
Reaction- (Test 1) alcohol to give
heat
MnO₂+ NaCl+ H₂SO₄ Na₂SO₄+ MnSO₄+ Cl₂+ H₂O BLUE color]

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 Bromide (Br¯) Nitrate (NO₃¯)
Test 1- Na₂CO₃ + dil. HCl + Salt Salt solution Aq. sol. of salt+ conc. H₂SO₄+ cool+ FeSO₄ Brown
CCl₄/CHCl₃+ Cl₂ water(excess) +salt sol. Orange- Ring
brown
organic layer Reactions-
Reactions- NaNO₃ + H₂SO₄ NaHSO₄ + HNO₃
2NaBr + Cl₂ 2NaCl + Br₂ FeSO₄+ H₂SO₄+ HNO₃ Fe₂(SO₄)₃+ H₂O+ NO
FeSO₄ + NO [Fe (H₂O)₅(NO)]SO₄ (brown)
Test 2- Na₂CO₃ extract + dil. HNO₃ Solution
Solution + AgNO₃ pale- yellow ppt Sulphate (SO₄²¯ )
NH₄OH
dissolves with difficulty
Water extract + dil. HCl + BaCl₂ White ppt
Reactions-
Note- ppt is insoluble in conc. HCl/ conc. HNO₃
NaBr + AgNO₃ NaNO₃ + AgBr (ppt)
Reaction (Test 1)-
Iodide (I¯)
Na₂SO₄ + BaCl₂ BaSO₄ (ppt) + NaCl
Test 1- Na₂CO₃ + dil. HCl + Salt Salt solution
Test 2-
CCl₄/CHCl₃+ Cl₂ water(excess) +salt sol. Voilet
Sodium carbonate + lead acetate + acetic acid
organic layer
White ppt
Reactions-
Reaction (Test-2)-
2NaI + Cl₂ 2NaCl + I₂
Na₂SO₄ + (CH₃COO)₂Pb PbSO₄ (ppt)+ 2CH₃COONa
Test 2- Na₂CO₃ extract + dil. HNO₃ Solution
Solution + AgNO₃ yellow ppt NH₄OH Insoluble

Reaction- NaI + AgNO₃ NaNO₃ + AgI (ppt)

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 CATIONS
PRELIMINARY TESTS
SALT COLOUR TEST FLAME TEST
COLOURS CATIONS Make tiny loop of Pt wire Dip in conc. HCl
Light green, Yellow, Brown Fe(III), Fe(II) Hold in non- luminous flame (till it imparts NO Color)
Salt (in watch glass) + conc. HCl
Blue Cu(II) Dip Pt loop in the paste- bring in non- luminous flame.
Bright green Ni(II) COLOUR CATION
Blue, Red, Violet, Pink Co(II) Green flame; blue center Cu(II)
Light Pink Mn(II) Crimson red Sr(II)
DRY HEATING TEST Apple green Ba(II)
Dry salt in test tube + Heat Brick red Ca(II)
COLOUR CATION BORAX BEAD TEST
White Cu(II) Loop of Pt wire heat Red- hot wire
Dirty white/ Yellow Fe(II) Red- hot loop + borax powder heat colorless bead
Colorless bead + dry salt heat observe color (bead)
Yellow Zn(II)
Note- Ensure bead is colorless before dipping in dry salt.
Blue Co(II) In case the bead is colored- clean the Pt wire and make
Note- The observed colors are when the salt is hot and the the bead again.
color changes when it gets cold.

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