Chemistry
Chemistry
1
1. SOME BASIC CONCEPTS OF CHEMISTRY
W(g) NA
(1). Number of molecules in W(g) of substance
GMM
VNA
(3). Number of molecules in V litre of gas at S.T.P.
22.4
W(g)
(4). Number of gram atoms = (GAM gram atomic mass)
GAM
W(g)
(5). Number of gram molecules =
Gram molecular mass
% 10 d
Molarity
GMM
(12). Mass % of an element in a compound Mass of that element in 1 mole of the compound 100
Molar mass of the compount
Mass of solute
(13). Mass percent 100
Mass of solution
2
XB molality MA
(14). where MA - mass of solvent
1 XB 1000
9 o
(17). T(o F) T( C) 32
5
No. of moles of A
(19). Mole fraction of A
No. of moles of solution
2. STRUCTURE OF ATOM
h
mv
h
p
h
2Em
Radial nodes = n – l – 1
Angular nodes = l
E hv
(6). 1
hv hv 0 me v 2
2
1 1 1
v 109677 cm1 where v is wave number and v .
n 2
n2
1 2
Where n1 1, 2,.....
n2 n1 1, n1 2, .....
E
(a) Frequency of radiation absorbed or emitted during transition ; v
h
E2 E1
v
h
n2
(d) Radii of the stationary states/orbits rn 52.9 pm
Z
4
1 1
(9). Energy gap between the two orbits E R H
n 2
n2f
i
18
Where RH 2.18 10
nf final orbit
h h
x p ; x m v
4 4
(12). Speed of light is equal to the product of frequency and wavelength of light
c v
3. STATE OF MATTER
an2
(1). Van der Waals Equation : P (V nb) nRT
V2
P1 V1 P2 V2
(2). Combined Gas Equation : ; (n, R constant)
T1 T2
V1 V2
(5) Charles’s La : (at constant P and n)
T1 T2
PV
(9). Compressibility factor Z (for 1 mole of Gas)
RT
4. THERMODYNAMICS
Enthalpy of reaction
H iHo (products) iHo (reactants)
By convention heat of formation of every element in its standard state is arbitrarily assumed to
be zero.
subHo fusHo vapHo
q
Heat Capacity Specific heat capacity cs
m T
q q
C molar heat capacity cm
T nT
6
Enthalpy
H U pV
Cp Cv R
qrev
S
T
G H TS
Go RT In K
Atomicity Cp Cv
Monoatomic 5/3 5R/2 3R/2
Diatomic 7/5 7R/2 5R/2
Triatomic non linear 4/3 4R 3R
5. EQUILIBRIUM
(1). K w Ka Kb
(2). Ki [A ][B ]
[AB]
[A ][H3 O ]
(5). K a
[HA]
[B ][OH ]
Kb
[BOH]
7
(6). K w H OH 1016 at 25o C
(7). pH log [H ]
(9). Kp K c (RT)n
1
pH [pK w pK b log c]
2
1
pH [pK w pK a log c]
2
1
pH [pK w pK a pK b ]
2
Ka
(11). Equilibrium constant, K eq
Kb
(12). K a or K b c
2
[C]c [D]d
(13). Concentration quotient, Q
[A]a [B]b
8
6. SOLID STATE
Z M
(or d) g.cm3
a NA
3
NA Avogadro's Number
a edge length
(3).
Crystal Radius of atom (r) No. of atoms per unit cell p.f.
Simple cubic a 1 52.4 %
2
F.C.C. a 2 74 %
2 2
B.C.C 3 2 68 %
a
4
(4). Packing Fraction (p.f.) = Volume occupied by particles (per unit cell)
Volume of unit cell
1
Contribution of each atom present on the corner =
8
1
Contribution of each atom present on the centre of face =
2
9
1
Contribution of each atom present on the edge centre =
4
(a) Cubic : 90 , a b c
o
(b) Tetragonal : 90 , a b c
o
(c) Orthorhombic : 90 ; a b c
o
(d) Monoclinic : 90 ; 90 ; a b c
o o
(e) Hexagonal : 90 ; 90 ; a b c
o o
(g) Triclinic : 90 ; a b c
o
7. SOLUTIONS
RT02 MART02
Kf
1000 Ifusion 1000 Hfusion
1 (n 1)
i { = degree of dissociation}
1
10
PAo X A PB0 XB
(3). Psol
0
Raoult's law
(PB PA )XB PA
0 0
CRT
1 Y Y
(5) A B
Psol Po Po
A B
PAo P
B { B = mole fraction of solute}
PAo
PA PB
(7) YA ; YB
PT PT
RT02 MA RT02
Kb
100 I vapour 1000 Hvapour
Where, m = molality
(9).
11
Normality (N) = Number of gram equivalent of solute g equiv / L
Volume of solution (L)
PAB P (i nB )
PAB (i nB ) nA
Tb i Kb m
Tf i Kf m
iCRT
(1 )
i n
{ = degree of association}
1
(12). He ry’s La
12
8. ELECTROCHEMISTRY
(1). Oh ’s la V RI
R
a
V = Potential difference
R = Resistance
I = Current
= Specific resistance (resistivity)
= length of conductor
1
(2). Conductance G
R
G.
1000
(4). Molar conductance M (or C ) {C = concentration of electrolyte in terms of
C (or M)
molarity}
1000
(5). Equivalent conductance M (or AC ) {C = concentration (normality)}
C (or N)
M N (n factor)
13
For strong electrolyte, C 0 B(C)
1/2
{B = constant}
AxBy xA y yBx
x o o
Ionic velocity
Potential gradient
M C( M / 0 )2
Degree of dissociation, , Keq
0 1 ( M / 0 )
2 2
Cell representation Zn | Zn (aq.) || Cu (aq.) | Cu
Anode( ) Cathode( )
14
(12). G nFEcell
=-W
Go nFEcell
o
2.303 RT
Ecell Eocell log Q
nF
0.0591
Nernst ' s equation Ecell Ecell
o
log Q
n
0.0591 P
Ecell log 1 (P = Pressure)
2 P2
For electrolyte concentration cell (Cu | Cu2 (C1 ) || Cu2 (C2 ) | Cu)
anode( ) cathode( )
0.0591 C
Ecell log 2
2 C1
H
Ecell T.(T.C.)
nF
15
T.C. 0 Cell-reaction is endothermic and vice-versa.
6 . Fa ada s st
law of electrolysis
m = Zit
Z = electrochemical equivalent
i = current
t = time
Atomic mass
Z
nF
Fa ada s nd
law of electrolysis
m1 E1
(E = equivalent weight)
m2 E2
2.303
Eox Eox
o
log [Mn ]
nF
2.303 RT
Ered Ered
o
log[Mn ]
nF
16
mA nB products
dx
Theoretical rate k[A]rm [B]n
dt
dx
Rate k[A]m [B]n
dt
d[A]
Rate k[A]B k (cons tan t)
dt
[A0 ] [A]
K
K
d[A]
Rate k[A]
dt
[A]0
(7). For a zero order reaction, t1/2
2k
0.693
For a first order reaction, t1/2
k
1
For an nth order reaction, t1/2 (for n 2)
[A]n01
17
d[A]
(k1 k 2 )[A]
dt
(9). For a first order reaction : A B C , a reagent reacts with all A, B and C
2.303 V V0
k log10
V V
{V = vol. of reagent}
t t
k
T 10o C
(10). Temperature coefficient =
kT
Ea /RT
Arrhenius equation, k Ae
k2 Ea T2 T1
log10
k1 (2.303 R) T2 T1
E0
log10 k log10 A
2.303RT
E0
log10 k log10 A
2.303 RT
t
(14). In a radioactive decay, Nt N0 e
18
n
1
N N0
2
t
(15). Activity, A t A0 e , A N
K 'PA
1 KPA
x aP m 1 b
Or, or
m 1 bP x aP a
1
x
(3) KC n ; C Concentration of solute in solution.
m
4
(4). Zeta potential, Z
D
19
11. HYDROGEN
= Normality 5.6
(1). In general metallic character, electropositive character, atomic radii, basic character, reducing
character decreases on moving left to right in a period and increases down the group.
21
14. COORDINATION COMPOUND
(2) 0 (CFSE) 4 n 6 n Dq
e e
(t2g )
(eg )
(3). t (CFSE) 4 n 6 n Dq
e e
(t2g )
(eg )
4
(4). t
9 0
[ML 4 ]
(5). For the reaction : M 4L ML 4 , overall stability constant of complex (ML4) is 4
[M][L]4
2 Mass of H2 O formed
% of H 100
18 Mass of the compound
28 Volume of N2 at NTP
% of N 100
(Dumas's method) 22400 Mass of compound
22
At. mass of X Mass of AgX formed
% of X (Halogens) 100
(108 At. mass of X) Mass of the compound
||
CH3 C H
2. Two different types One type of similar H- 3 3 6
of dissimilar H- atoms
atoms CH3 CH2 CHO
CH3 COCH2 CH3
3 Two different types Two different types of 4 4 8
of dissimilar H- dissimilar H-atoms
atoms PhCH2 CO CH2 CH3
CH3CO CH2 CH3
Structure of Alcohols :
Preparation of Alcohols
(b) By hydroboration-oxidation
24
B H ,H O /OH
CH3 CH CH2 (H BH2 )2
2 6 2 2 CH3CH2CH2OH B(OH)3
NaBH
RCOR '
4 R CH R '
|
OH
H
2 RCH OH R ' OH
RCOOR ' 2
Catalyst
Reduction of aldehyde, ketones and esters with No alcohol is called Bouveault-blanc reduction.
R X KOH(aq) ROH KX
Ease of hydrolysis of alkyl halides RI > RBr > RCI > and 3o > 2o > 1o alkyl halides.
H SO
R O R H2 O
2 4 2ROH
25
Methylamine does not give methyl alcohol when treated with HNO2. It gives CH3OCH3 and CH3ONO.
Zymase
C6H12 O6 2C2H5OH 2CO2(g)
glucose and fructose ethyl alcohol
Preparation of Phenols
26
Alcohols react as nucleophiles :
2R O H 2Na 2R O Na H2
Sodium alkoxide
H
RO H R ' COOH ROCOR ' H2 O
Alcohol
H
RO H (R ' CO2 )O ROCOR ' R ' COOH
Alcohol
Pyridine
RO H R'COCl R OCOR ' HCl
Alcohol
P/Br
3ROH PBr3
2 3RBr H3PO3
P/I
3ROH PI3
2 3RI H PO
3 3
Cu, 573k
Or
CrO3
Or
PCC
(i) Pr imary Alchol Aldehyde
Cu, 573k
Or
CrO3
(ii) Secondary Alcohol Ketone
Cu, 573k
Or
KMnO 4
(iii) Tertiary Alcohol Alkene
27
Phenols
H
Ar OH R' COOH Ar OCOR' H2O
Phenol
H
Ar OH (R'CO)2 O Ar OCOR' R'COOH
Phenol
Pyridine
Ar OH R ' COCl ArOCOR ' HCl
Phenol
(a) Halogenation
28
(b) Sulphonation
(c) Nitration
29
(d) Reimer-Tiemann reaction
30
iii) Reaction with zinc dust
(iv) Oxidation
Ethers
Structure of Ethers
31
Preparation of Ethers
H SO (conc.)
2CH3 CH2 OH
2 4 CH3 CH2 O CH2 CH3 H2 O
excess 418K
Willia so ’s Sy thesis Only primary alkyl halides when react with sodium alkoxide give ether while
tertiary alkyl halides give alkene due to steric hindrance.
CH3 CH2Br CH3 CH2 ONa CH3 CH2 OCH2 CH3 NaBr
(ii) Halogenation
Cl
CH3CH2OCH2CH3
2 CH CHClOCH CH
3 2 3
Dark ( monochloro diethyl ether)
h
C2H5OC2H5 10Cl2 C2Cl5OC2Cl5 10HCl
(excess) (light) (perchlorodiethyl ether)
32
(iv) Reaction with CO
BF /150o C
ROR CO
3 RCOOR
500 atm
33
Other conversion reactions :
(a) Phenol to salicylaldehyde
34
(b) Phenol to benzene diazonium chloride
35
17. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
Aldehydes and ketones are generally prepared by oxidation of primary and secondary alcohols,
respectively.
CrO
RCH2 OH
3 RCHO
CrO
R CH R '
3 R C R '
| ||
OH O
By dehydrogenation of alcohols
Cu
R CH R ' 573 K R C R '
| ||
OH O
HgSO
R C CH H2O
4 R CO CH
3
H2SO4 ketone
36
Preparation of Aldehydes
H O
RCN SnCl2 HCl RCH NH
3 RCHO
Alternatively, nitriles are selectively reduced by diisobutylaluminium hydride, [DiBAL-H] to imines which
on hydrolysis give aldehydes.
(i) AlH(iBu)
RCN
2 RCHO
(ii) H2O
(i) DiBAL H
CH3 (CH2 )3 COOC2H5 CH3 (CH2 )3 CHO
(ii) H2O
Using chromium oxide (CrO3) : Toluene or substituted toluene is converted to benzaldehyde in presence
of chromic oxide in acetic anhydride.
37
(iv) Side chain halogenation is followed by hydrolysis of toluene
Preparation of Ketones
38
(ii) From nitriles
39
(ii) Addition of sodium hydrogen sulphite
40
Z Reagent name Carbonyl derivative Product Name
-R Amine C NR Substituted imine
| S hiff s ase
Phenyl- Phenylhydrazone
hydrazine
2, 4- 2, 4-dinitrophenyl
dinitrophenyl hydrazone
hydrazine
Semi- Semi-carbazone
carbazide
Reduction
(3). Oxidation
(i) Aldehydes are oxidized to acids in presence of mild oxidizing agents HNO3 , K2Cr2O7 , KMnO4
[O]
R CHO R COOH
(ii) Ketones are oxidized under drastic conditions i.e. with powerful oxidizing agents like
HNO3 , K2Cr2O7 / H2SO4 , KMnO4 / H2SO4 at higher temperature.
41
1 2 3
[O]
R CH2 CO CH2 R ' R COOH R ' CH2COOH R CH2COOH R ' COOH
(By cleavage of C1C2 bond) (By cleavage of C 2 C1 bond)
Base catalysed crossed aldol condensation between an aromatic aldehyde and an aliphatic aldehyde or
ketone is called Claisen-Schmidt condensation or Claisen reaction.
42
Cannizzaro reaction
Ketones do not form silver mirror and hence do not give this test.
Fehli g’s test : When an aldehyde is heated ith Fehli g s reagent it forms reddish brown
precipitates of cuprous oxide.
Fehli g s eage t : Fehli g solutio A a ueous solutio of CuSO4) + Fehling solution B (alkaline solution
of sodium potassium tartarate)
Carboxylic Acids
Methods of Preparation of carboxylic Acids
CrO H SO
(b) RCH2OH
3 2 4 RCOOH
43
From aldehydes
(a) RCHOH 2[Ag(NH3 )2 ] 3OH RCOO 2Ag 2H2O 4N
2
(b) R CHO 2Cu 5OH RCOO Cu2O 3H2O
All acid derivatives like amides (RCONH2 , a id halides ‘COCl , este s ‘COO‘ , a id a h d ides ‘CO-O-
COR) on hydrolysis give carboxylic acids. All acid derivatives break from RCO+.
Dil. HCl
RCOZ
RCOOH
or dil. NaOH
From alkenes
Suitably substituted alkenes are oxidized to carboxylic acids on oxidation with acidic potassium
permanganate or acidic potassium dichromate.
KMnO /H
(a) R CH CH R
4 2R COOH
KMnO 4 /H
(b) R CH CH R1 R COOH R1 COOH
44
By heating germinal dicarboxylic acids
From alkynes
(i) O (ii), H O or
R C C R
3 2 2 2RCOOH
KMnO4 /OH ,
Formation of anhydride
Esterification
H
RCOOH R'OH RCOOR' H2O
Carboxylic acids react with ammonia to give ammonium salt which on further heating at high
temperature gives amides.
45
/ H O
(a) CH3COOH NH3 CH3COONH4
2 CH CONH
3 2
Ammonium acetate Acetamide
(b)
(a) Reduction
(i) LiAlH /ether
RCOOH
4 R CH2 OH
or B2H6 (ii) H3O
(b) Decarboxylation
NaOH, CaO (Ratio 3:1)
RCOONa
R H Na2CO3
Hell-Volhard-Zelinsky reaction
X /Re d Phosphorus/H O
R CH2 COOH
2 2 R CH COOH
|
X
X Cl, Br
Halocarboxylic acid
Arndt-Eistert reaction
PCl CH N
HOH
RCOOH
5 RCOCl
2 2 RCOCHN
2 RCH2COOH
diazo ketone
Reducing property
HCOOH HgCl2 Hg 2HCl CO2
46
18. AMINES
Nitro compounds can be catalytically reduced by passing hydrogen gas in presence of Raney Ni, finely
divided Pt or Pd as catalyst at room temperature.
Ni, Pt or pd
(a) R NO2 3H2 R NH2 2H2O
47
Ni, Pt or pd
(b) Ar NO2 3H2 Ar NH2 2H2O
Nitro compounds can also be reduced with active metals such as Fe, Sn, Zn etc. with conc. HCl.
Sn/HCl or Fe/HCl
(a) R NO2 3H2
R NH2 2H2O
Sn/HCl or Fe/HCl
(b) Ar NO2 3H2
Ar NH2 2H2O
The free amine can be obtained from the ammonium salt by treatment with a strong base :
(a) NH3 RX RNH X NaOH
RNH2 H2O Na X
3
(1o amine)
48
(vi) Hofmann bromamide degradation reaction
Reactions of Amines
(i) Alkylation
(ii) Acylation
49
(iii) Benzoylation
Pyridine
CH3NH2 C6H5COCl CH3NHCOC6H5 HCl
Heat
R NH2 CHCl3 3KOH R N C 3KCl 3H2O
isocyanide
(a bad smalling compound)
Methyl isocyanate gas (CH3 N C O) was responsible for Bhopal gas tragedy in December 1984.
50
Reaction with aldehydes
Nitration
(a) Under strongly acidic medium aniline gets protonated to form anilinium ion, which is deactivating
group and is meta directing. Hence m-nitroaniline is also formed in 47 % along with ortho and para
products.
51
Aromatic amines cannot be nitrated directly because HNO3 being a strong oxidizing agent oxidizes it
forming black mass.
(b) Nitration by protecting the –NH2 group by acetylation reaction with acetic anhydride :
(c) Sulphonation On sulphonation, aniline gives sulphanilic acid, as the major product.
Oxidation
Benzene Diazonium Chloride (C6H5N2 ; Cl )
53
Azo coupling reactions
Alkyl Cyanides
Methods of Preparation
100 C o
RX KCN(alc) RCN RNC
(major)
(i) Hydrolysis
H O H O
RCN
2 RCONH2
2 RCOOH NH
3
Alk H2O2 amide H carboxylic acid
(partiial hydrolysis)
(ii) Reduction
Na C H OH
RCN 4[H]
2 5 RCH2NH2
LiAlH
RCN 4[H]
4 RCH NH
2 2 (Mendius reduction)
SnCl /HCl H O
2 R CH NH HCl
RCN 2 RCHO NH Cl
4
imine hydrochloride aldehyde
R' R'
| |
Ether
RCN R 'MgX R C NMgX
2H2O R C O
54
Alkyl isocyanides
Methods of Preparation
Hydrolysis
H
R N C 2H2O RNH2 HCOOH
(ii) Reduction
Na/C H OH
RN C 4[H]
2 5 RNHCH3
or Ni or Pt
2o amine
Due to the presence of unshared pair of electrons on C atom, alkyl isocyanides give addition reaction.
RNC S RNCS
RNC O3 RNCO
55
Nitro Compounds
Methods of Preparation
Reduction
If neutral reducing agent like Zn dust + NH4Cl is used, hydroxylamines are obtained as major product.
ZnNH Cl
RNO2 4[H]
4 R NHOH H O
2
N alkylhydroxylamine
Nitrobenzene gives different products with different reagents and in different mediums.
Action of HNO2
1o nitroalkane gives nitrolic acid which gives red colour with NaOH.
HNO NaOH
RCH2NH2
2 RC(NO ) NOH
2 RC(NO2 ) NONa
H2O nitrolic acid (red)
|
NO2
Pseudonitrol
50% H SO
2 4 R CH O
NaOH
R CH2NO2 R CH N O Na aldehyde
|
O
Nucleophilic substitution reaction -NO2 group activates the ring towards nucleophilic substitution.
57
19. HALOALKANES AND HALOARENES
From Alcohols
58
Free Radical Halogenation of Alkanes
Cl
CH3CH2CH2CH3
2 CH3CH2CH2CH2Cl CH3CH2CHCH3
UV light or Heat
|
Cl
| | | |
C C C HBr CCC
| | | | |
Br
2bromopropane
| | | |
Organic peroxide
C C C HBr
C C C Br
| | | | |
Hunsdiecker Reaction
Preparation of haloarenes :
(a) By electrophilic substitution reaction :
59
(c) Gattermann reaction :
60
2. Elimination Reactions
Dehydrohalogenation is a -elimination reaction in which halogen is from -carbon atom
and the hydrogen from the -carbon according to Saytzeff rule, e.g.
Br
|
Alc. KOH
CH3 CH2 CH CH3 CH3 CH CH CH3 CH3CH2CH CH2
KBr, H2O but 2 ene butene 1 (minor)
(major)
Reduction
Ni, 575 K
C2H5 Br H2 C2H6 HBr
Red P, 420 K
C2H5I HI
C2H6 I2
61
Reaction with Metals
Dry ether
RX 2Na XR
R R(alkane) 2NaX
Isomerisation
Cl
|
573 K
CH3CH2CH2 Cl CH3 CH CH3
or anhy. AlCl5
a Do ’s Pro ess
62
(c) With conc. sulphuric acid and nitric acid
63
(i) Other conversions :
R X KCN R CN KX
Na, C H OH or LiAH or Ni/H
HONO
R CN
2 5 4 2 R CH NH
2 2 RCH2OH
H O NH
R CN
3 R COOH
3 R CONH
2
LiAlH
R COOH
4 RCH OH
2
Dry ether
R X Mg
RMgX
20. HYDROCARBONS
64
Alkanes
Preparation of Alkanes
Frankland reaction
RX Zn Rx R R ZnX2
Sabatier-Senderens reduction
Ni/
R CH CH2 H2 R CH2 CH3
Ni/
R C CH H2 R CH2 CH3
Decarboxylation –
Reactions
Combustion :-
CH4 2O2 CO2 2H2O, H 217.0 K cal / mole
Oxidation :-
65
Cu
CH4 O2 2CH3OH
573 K
Mo O
CH4 O2
2 3 HCHO H O
2
Methanal
Substitution :-
Halogenation :-
UV
CH4 Cl2 CH3Cl HCl
UV UV UV
CH3Cl CH2Cl2 CHCl3 CCl4
Cl
CH3CH2CH2CH3
2 CH CH CH CH Cl CH CH ClCHCH
3 2 2 2 3 2 3
nButane hv
Nitration
450 C o
CH3CH2CH3 CH3CH2CH2NO2 CH3CHNO2CH3 CH3CH2NO2 CH3NO2
Conc. HNO3
25 % 40 % 10 % 25 %
66
Aromatization :-
(6) Thermal decomposition or Pyrolysis or cracking or Fragmentation : - when higher alkanes are heated
at high temp (about 700 – 800 K) in the presence of alumina or silica catalysts, the alkanes break down
to lower alkenes and alkanes.
CH3 CH2 CH3 CH3 CH CH2 CH3 CH3 C2H4 CH4
1000 C o
CH4 H2O(Steam) CO 3H2
Isomerization
Alkenes
Preparation :
1. From Alkynes : - Alkynes on partial reduction with partially deactivated palladised charcoal known as
Li dla s atal st gi e alk es.
Pd/C
CH CH H2 CH2 CH2
Ethyne Ethene
67
3. From Dihaloalkanes :- Dehalogenation
Al O
CH3CH2CH2CH2OH
2 3 CH CH CH CH
3 2 2
300o C
Reactions of Alkenes
1. Addition of Hydrogen :-
H /Ni
RCH CH2
2 RCH2CH3
2. Addition of Halogens :-
CCl
CH2 CH2 Br2
4 BrCH CH Br
2 2
Solvent
H O
CH2 CH2 Br2
2 Br CH CH OH HBr
2 2
Solvent (Colourless)
(Brown colour)
Addition reaction of HBr to unsymmetrical alkenes takes place according to Markovnikov Rule
68
Markownikov rule :- negative part of the addendum (adding molecule) gets attached to that carbon
atom which possesses lesser number of hydrogen atoms. E.g.
Pe o ide effe t o Kha as h A ti Ma ko ikoff s additio :- In 1933 Kharasch and Mayo observed that
when HBr is added to an unsymmetrical double bond in the presence of organic peroxide, the reaction
take places opposite to the markovnikov rule.
HBr
CH3 CH CH2 CH3 CH2 CH2Br
Peroxide Pr opyl bromide
2. Oxidation :-
2. Hydrocarboration-oxidation:- Alkenes react with diborane to form trialkyl boranes which on oxidation
with alkaline H2O2 give alcohols.
BH H O /OH
3CH2 CH2
3 CH CH
3 2 B 3CH3CH2OH
2 2
Triethylborane Ethyl alcohol
3. Oxymercuration-demercuration :-
Hg(OAC) NaBH
H2C CH2
2 OH CH CH Hg OAc
2 2
4 CH CH OH Hg
3 2
THF, H2O OH
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2KMnO4 H2O 2KOH 2MnO2 3[O]
Bayer’s Test
(i) Alk. KMnO
CH3 CH CH2
4 CH COOH CO H O
3 2 2
(ii) H
Alkynes
Preparation :-
Reactions
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Birch Reduction
2. Addition of Halogens :-
2Br
HC CH
2 Br HC CHBr
2 2
5. Polymerisation –
(a) Linear polymerization : of ethyne gives polyacetylene or polyethyne which is a high molecular weight
polyene containing repeating units of (CH = CH – CH = CH) and can be represented as – (CH = CH – CH=
CH)n-
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Aromatic Hydrocarbon
Preparation of Benzene
(ii) Reduction of phenol: Phenol is reduced to benzene by passing its vapours over heated zinc dust
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Benzene on treatment with excess of chlorine in the presence of anhydrous AlCl3 in dark yields
hexachlorobenzene (C6Cl6)
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Directive influence of a functional group in monosubstituted benzene :-
2. Meta directing group and deactivating :- NO2 , CN, CHO, COR, COOH, COOR, SO3H ,
3. Ortho and para directing groups and deactivating – Halogens because of their strong – I effect, overall
electron density on benzene ring decreases. However due to resonance the electron density on o- and
p- position is greater than that at the m-position. Hence, they are also o- and p- directing groups.
21. POLYMERS
Polyolefins
1. Polythene
Polymer of ethylene or ethene.
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333343k /6 7 atm zieglar Natta catalyst
nCH2 CH2 (CH2 CH2 )n
Ethene Polythene
(d) Polyacrylonitrile
Polymerisation/Peroxide catalyst
nCH2 CHCN (CH2 CN CN)n
Acrylonitrile Polyacrylonitrile
2. Polystyrene (Styrone)
3. Polyvinylchloride (PVC)
4. Polypropylene (PP)
5. Polytetrafluoroethene (Teflon)
catalyst/High pressure
nCF2 CF2 (CF2 CF2 )n
Tetrafluorethene Teflon
6. Polyacrylonitrile
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Condensation polymers
Polyamides
H H O O
| | || ||
[N (CH2 )6 N C(CH2 )4 C]n
553 K /High pressure
nHOOC(CH2 )4 COOH nH2N(CH2 )6 NH2
Nylon 6,6
Polyesters
(a) Terylene or Dacron : It is manufactured by heating a mixture of ethylene glycol and terephtalic acid
at 420 to 460 K in the presence of zinc acetate-antimony trioxide catalyst.
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2. Glyptal
Polymethylmethacrylate (PMMA)
The polymer is known by several commercial names such as lucite, acrylite, plexiglass and perspex.
Resins
1. Phenol-Formaldehyde Polymer
These polymers are obtained by the condensation reaction of phenol with formaldehyde in the presence
of either acid or a base catalyst. The reaction involves the formation of methylene bridge at ortho, para
or both ortho and para positions. A linear or cross linked material is obtained depending upon the
condition of reaction.
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(b) Novolac on heating with formaldehyde forms Bakelite
2. Urea-Formaldehyde Resin
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4. Natural Rubber
CH3
|
CH2 C CH CH2
isoprene
(a) Natural rubber : Natural rubber is a linear polymer of isoprene (2-methyl-1, 3-butadiene) and is also
called as cis-1, 4-polyisoprene.
Vulcanisation of Rubber
The properties of natural rubber can be modified by introducing -S-S- polysulphide crosslinks in its
structure.
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The process of heating a mixture of raw rubber with sulphur and an appropriate addictive in a
temperature range between 373 K to 415 K to improve upon physical properties like elasticity, strength
etc.
Synthetic rubber
Cl Cl
| |
nCH2 C CH CH2 [CH2 C CH CH2 ]n
Polymerisation
(B) Buna – N
CN CN
| |
[CH2 CH CH CH2 CH2 CH]n
Copolymerisation
nCH2 CH CH CH2 nCH2 CN
Acrylanitrile BunaN
1,3butaline
(C) Buna – S
C6H5
|
nCH2 CH CH CH2 nC6H5CH CH2 [CH2 CH CH CH2 CH2 CH]n
Styreme Butadine styreme copolymer
1,3butadine (BunaS)
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(b) Nylon 2-nylon 6 : It is an alternating polyamide copolymer of glycine (H2N CH2 COOH) and amino
caproic acid (H2N(CH2 )5 COOH)
O O
|| ||
nH2N CH2 COOH nH 2 N (CH2 )5 COOH (HN CH2 C HN (CH2 )5 C)n
Glycine A mino expronic acid
Some polymers:
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