E°(M^3+ /M^2+ ) values shows that Mn^3+ & Co^3+ ions are strongest oxidising agents in aqueous solutions among 3d series

The ions are strong reducing agents Ti^2+, V^2+ &cr^2+
among 3d series and will liberate H from dilute acid

TiO is used in pigment industry
2. MnO2 is used in dry battery cells
3. TiCl4 & Al(CH3 )3 , Ziegler catalyst is used to manufacture polyethene
4. PdCl2 is used as catalyst in Wacker process
5. AgBr is used in photographic industry.

(a) Unidentate ligand : Cl, H20 & NH3
(b) Didentate ligand : NH2CH2CH2NH2 , C2O4^2-
(c) Hexadentate ligand : EDTA^4-
(d) Ambidentate ligand : NO2^-, SCN^-

Nucleophilic substitution : Aryl halides are extremely
less reactive towards nucleophilic substitution reactions due to following reasons

(i) Resonance effect : Lone pair of chlorine is in
conjugation with benzene resulting in double bond
character of C — Cl bond. As a result bond cleavage in haloarene is difficult.

(ii) Difference in hybridization of carbon atom in C– X bond

(iii) Instability of phenyl cation

(iv) Repulsion between haloarene & approaching
nucleophile

HCHO GR 1° alcohol
RCHO 2•
RCOR 3°

Acidity of phenols : Phenols are more acidic than alcohol because
conjugate base of phenol (phenoxide ion) is resonance stabilised.

[B] Reaction of phenols :
(a) Electrophilic aromatic substitution

(i) Nitration dil/HNO3 mono
Conc/HNO3 picric acid

(II) Halogenation
Br2/cs2 mono
Br2/H20 2,4,6 tribromophenol ( white ppt)

(b) Kolbe’s reaction
(Salicylic acid)

(c) Reimer-Tiemann reaction
Salicylaldehyde

(D) Na2cr2O7/h2so4 : (Benzoquinone)
Zn : Benzene

PREPARATION OF ALDEHYDES

(i) From acyl chlorides (Rosenmund reduction)
H2/pd-Baso4

(ii) From Nitriles and Esters
Reduction by DIBAL-H

(iii) From Hydrocarbons
Etard reaction
Toluene + cro2cl2 (Chromium
Complex) = CHO

Gatterman-Koch reaction

Benzene + co +HCL/Anhyd.AlCl /CuCl

2 PREPARATION OF KETONE

acyl chlorides + R2CD

From nitriles + phmgbr/ether

Benzene + acyl chloride

(ii) Reduction
Nabh2 & lialh4


(b) Reduction to hydrocarbons

Zn-Hg/Hcl (Clemmensen reduction)

Nh2-Nh2/ Hcl (Wolff-Kishner reduction)

4 CARBOXYLIC ACIDS

Methods of Preparation
(a) From primary alcohols

alkaline KMnO4/h30^+
Cro3-h2so4 Jones reagen

(b) From alkylbenzenes
Kmno4-koh /heat water

(c) From nitriles and amides

d) From Grignard reagents

R-mg + O=C=O /dry ether

CHEMICAL REACTIONS

(a) Reactions involving cleavage of C- O H bond
(Acidity)

2ch3cooh + p2p5 = Ethanoic anhydride

(iv) Reaction with ammonia

+ Ammonium Benzamide /-h20 = Benzamide

(Phthalic acid) +Nh3 = .... ..(Phthalimide)

c) Reactions involving –

(1) Reducsn COOH group

Lialh4/ether or b2h6 /h30^+
RCH2OH

(ii) Decarboxylation
NaOH & CaO/heat = R-H + na2co3

d) Substitution reactions in the hydrocarbon par

NaOH & CaO/heat =R-H+ na2co3

PREPARATION OF AMINES

Phno2 .. H2/pd ethanol
Sn/hcl Or fe+ hcl PhNH2

(ii) Ammonolysis of Alkyl Halides
Quaternary
ammonium salt

(iii) Reduction of Nitrites


(iv) Reduction of amides

(v) Gabriel phthalimide Synthesis


(vi) Hoffmann bromamide degradation reaction


Br2 + 4NaOH = R-Nh2 + na2co3+2nabr + 2h20

Primary amine formed contains one carbon less than that
present in the amide

Biomolecules.

(a) Glucose (c6h12o6) : It is an aldohexose

+ HI = N hexane
suggesting carbons are linked in straight chain.


Presence of carbonyl group is confirmed by the following
reactions.
HCN & NH2OH

Carbonyl group present is an aldehyde is confirmed by
the given reaction
Br2/H20 = (Gluconic acid)

Acetylation of glucose gives glucose pentaacetate which
confirms presence of five OH groups

Glucose and gluconic acid is oxidised to saccharic acid
by nitric acid. This indicates presence of primary –OH
group

Cyclic Structure of Glucose

The given observations could not explain chain structure
of glucose
(i) It does not react with NaHSO3 or Schiff's reagent

(ii) Pentaacetate of glucose does not react with NH2OH.
(iii) Glucose exist in two different crystalline forms, a and b forms

.

#_4marks #_chem

Acidic: CO₂, SO₂, SO₃, P₂O₅, SiO₂
Basic: Li₂O, Na₂O, K₂O, MgO, CaO, BaO
Amphoteric: BeO, Al₂O₃, ZnO, Cr₂O₃, SnO/SnO₂, PbO/PbO₂
Neutral: CO, NO, N₂O ,H2O
#_chem #_4marks