Organ ic Chem istry - •Some Basic Princi ples

and Techn iq,,.;._es:

12
Chapter
G) CLASSIFICATION OF ORGANIC COMPOUNDS (d) For branched alkyl groups, the carbon atom of the 0
branch that attaches to the root alkane is numbered (1 ) II
Organic Compouncls CH 3 C- CH 2
such as
- - CH 2 - CH 2 - COOH
l 6 5 4 '.l 2 1
-& ~ 4 3 2
CH 3 - CH - CH 2 -
1
CH - (1 , 3-Dimethylbutyl ) -
5-0xohexanoic acid
Acyclic or o~n chain Cyclic or closed chain I I OH
5 4 3 2 1
CH 3 CH3
(>-.A) ~
CH2 = CH - CH 2 - CH - CH 3
{,
Alicyclic compounds
,I
1
Aromatic compounds

(e) While writing the names of the substituent s in

alphabetical order, the prefixes iso and neo are
considered to be the part of fundamental name of alkyl
group but sec- and tert- are not considered to be the
Pent-4-en-2-ol
:) NQmenc;lature of 1Jubstltuted

I
OH U :i Cyclohex-2-en- '\-ol
N02
partoffundamen tal name, ben:tene compounds -..::::
"'~ :;i. (f) If two chains are of equal size then that chain is to be
a
Homocyclic Heterocyclic Benzenoid Non-benzenoid CI
or carbocyclic compounds compounds selected which contains more number of side chains Cl
compounds ~
compounds (non-aromatic) 2 10 \ CH,
3~ 5 ).___7 .Jl.9 O2N
(o.r5') (9) 3 NO 2 2-Chloro-'\-met hyl
(V.0) (0) 1-Chloro-2, 4--<iinitrobenzen e
OMe
-4-nitrobenzene
NH2 CH3
¢t ¢t
CI
Heterocyclic aromatic
compounds 5-(2-Ethylbutyl) -3, 3-dimethyldeca ne .
3
Q Nomenclature of Cyclic Compounds
(0-9)
4 4
~2 (Alphabetic order of numbering)
CH 3
2-Chloro-4-meth ylanisole
C-iHs
4-Ethyl-2-methy laniline
~ 1-Methyl-3-prop ylcyclohexane
3
@ NOMENCLATURI: o Nomencloturo of organic compo\mda h ovlng functional @ ISOMERISM
~ Abbreviati on for alkyl groups groupa(s)
(a)Structural Isomerism
CH 3 (a) The functional group present in the molecule is identified
I CH 3 Compounds having the same molecular fonnula but
which determines the choice of appropriate suffoc
CH3 -CH- CH 3 - CH 2 - CH -
I ,
H
/'-. (b) The longest chain of carbon atoms containing the
different structures are classified as structural isomers.
(i) Chain isomerism: Example, C 5H, 2 represents three
CH 3 3C CH 2 - functional group is numbered in such a way that the
lsopropyl - sec-Butyl - functional group is attached at the carbon atom chain isomers
lsobutyl-
possessing lowest possible number in the chain.
~
CH 3 CH 3
I I (c) The order of decreasing priority for some functional ~
H3C - C - CH 3 - C - CH 2 - Pentane
I I groups: 2-Methylbutane
CH 3
tert-Butyl -
CH 3
Neopentyl -
-COOH, -S0 3H, -COOR, -COCI, -CONH 2 , -CN, -J- (2, 2-Dimethylprop ane)
I;) Nomenclature of B ranched Chain Alkanes: (Rules)
(a) Longest carbon chain is identified
(b) Numbering is done so that branched carbon atoms get
-HC ' =0, -OH, -NH ,/C
=0,/C ' =C....._.
/ -C = C-2
(ii) Position .isomerism: Example, C 3 H80 represents
two alcohols
the lowest possible numbers O 0
II II OH
(c) Fortwo substituents present at equivalent positions, the CH 3 - CH 2 - C - CH 2 - C - CH 3 ~ OH
lower number is given to the one coming first in
alphabetical listing
6 5 4 3 2 1 ~
Hexane-2, 4-dione Propan-1-ol Propan-2-ol
 ··- --.-;;;.~
11 1
Organic Chemistry - Some Basic Principles and Techniqu
es
~
~
(iii)Functlonal group isomerism: Example , (ii) Homolytic cleavage: One of the electrons of
r ~
the (iii) Resonance effect -
C3H60 represents an aldehyde and a ketone shared pair in a covalent bond goes with each of o It is a permanent effect
0 bonded atoms resulting iry formation of free radicals.
o It operates through rc-bond(s)
~ /'-.. CHO
o Free radicals : Stability order
o It Is of two types
propanone propanal CHJ < cHi H2 < (CH 3 JiCH < (CHJ ):i C +R effect : Halogens, -OH, -OR,--Oco,f
(iv)Metamerism:
(b) Nucleophiles and Electrophiles - R effect : - COOH , - CHO, -CN,-Nol~
It arises due to different alkyl chains on either
o Nucleophlles: A reagent that brings an electron pa ir (iv )Electromerlc effect
side of the functional group . to
lhe reactiv e site is ca lled a nucJeoph/le (Nu :) u It is a temporary effect
Example : CHpC JH7 and C HsOC H are metamers.
2 2 5 Exam ples: H2 0 , NHJ. CHJ> . SH u Organic compounds having multiple bmi~
(b) Stereolsomerism
0 Electrophlle : A reagent that lakes away an electr or triple bond) show this effect In p
The compounds that have the same on •
attacking reagent
1
consti tution pair from reactive srte. rs called electrophlle (E)
and seque nce of covalent bonds but differ
in u It is of two types
relative positions of their atoms or groups in space Example AJCJ, . [Link] . CI
are called stereoisomers. They are classified as 1 Positive electromeric effect (+E effect)
(c) Electron Ol splacomon·I Effects In Coval ent
(I) Geometrical Isomerism Bond s
P) Indu [Link] 1rrf11 c l ' A, , ., /
(II) Optical Isomerism
, When coval-On t bond rs formed
C'f/C.+H - >C - C
betw een atoms of / \ / I\
drl'hiront [Link] livrty. the electro n densi ty H
0 Is
FUNDAMENTAL CONCEPTS IN ORGANIC
REACTION MECHANISM
Altnc:ldng
rc'1gcnt

\
I ,
'°""""01tls lho moro olocironega tive atom .
ITl()(ti
fl opo,n( as lhrtx.19h r.•bon ds
, Tho 1MlvCI No offoc1 Is rola ted lo tho ability of /

\f)tfc_ ,_/
Negalive electromerlc effect (- Eeffect)
C = C + CN -
\
>C- C
/ I\
Organic mole cule ----"- -+ [Intermediate !
-► Byproduct(s) ~tttv .onl(s } to orthor wtthdr aw or dona te electro CN
(Substrate) ,i n
duru,ry to tho 011.o1chod carbon atom (v) Hyporcon}ugatlon
Produ ct(s) , It is n pcrm.:incn t offoct ', II Invo lves d elocal lsatlon of a electro nsofC- H
'. a) Fission of Coval ent bond
(I) Hetorolytlc cloavage and (II) Homolytlc cleavage
.J It rs of ""'°
ryp~ o f an alkyl group directly attached to an all)",
(I) Heterolytlc cleavago • I l!t:Od o g - CH,. - CH CH olc unsa turate d sys tem or to an atom with an u
1 1
In heterolytlc cleava ge , the bond braaks In - 1atf0e1 o g - N0 1 • -C N. -CHO . - COOH olc. porbita l
such a
fashion thot the shored P81r or electrons remain fb) Re,[Link] anco s lruct.u nts
s w,lh H H H' H H H ~
one or the fragments I I I
., 8-enze ne can be repre sented by energ I I ,
,} Carbocatton s: etlca/ly H- C- C+ H H - C = C f-► H ' C = C H H- C·
• A species having a carbon atom posse d enticaJ structures (I) and (II ) called resonance I I I I I I
ssing stn..'[Link] H H H H H H H'
sexte t or electrons and a positive charge is called
cnrbocation.
• All,.)'1 groups directly attached to Iha positiv
charged carbon stablhs a the carbocations due
Inductive and hypen:onjugation effects.
ely
to
•os
2/
l
(I)

6
A • 101~
2 -::,...
)

t
•
Ir
', II la a perma nent effect.
@ METHODS OF PURIFICATION OF
ORGANIC COMPOUNDS
• S ta bilityo rder. (11) The common techn iques used for purification:
. . . ~ Actual structu re (1) Su blimation
(CH1 b C > (CH1 h CH > C~Cl- b > CH is resona nce hybnd of (I) and (11 ) (ii) Crystallisation
1
:i The resonance strudlJ (Ill) Dist/I/at/on : It Is used to separate
• Carbanlons : res (canon ical strucw res) are (a) Volatile //quids fro m non-vo latile Impurit ies .
• A carbon species carrying a negau w charge hypothetical and incfMdually do not rep resent
on real mc:1'[Link]. an y (b) The I/quids having suffld on t difference In bolling
cartion po1f1!i
atom is called c:arbanion. e g. mixture of chloroform (b .p 334 K) and
anl'rnt
• caroon in caroanioo is generaI/y s:p l hybncftSed ., The energy af actual structu re af the molecu
le Is / {b.p. 457 K) Is separa ted by rh is melh?d·
and [ts structure is distorted tetrahe dral low'erthan that of any of the canon ical structu (c ) Dlstllla tlon can be achie ved by three drfferen
res . t ways
, FractJonal Dl•tllla tlon : This Is appllca ble
• Srabili,y oroar: The differe nce tn er:, ergy betw een the actual 1! ~
/ points of two liquids Is no t much. e g lfu.s
ctt 3 > ctt1 ~.2 <c~ }[Link] > (c~ ~c strudlJTe and the lowest energy resona nce structu
is called the resonance energy.
re app//ca bte to separa te differen t fracrl = of Cf\JOa
u
i:JJli
lnpccroleum_!__n~ ~- _ ~
- Orga n ic C hemlstnJ - Som e Basic F'ri_nci_~les and Techni q u es
NCERT Maes
.:, ~ m Olstlllatfon: This technlque 1s applied to (A) Test for nitrogen Let. [Link] of orgarnc compound = m g
r
separate substances which are steam volatile and Volume of HzSO I of molarity M netlded for neutralisation
6CN + Fe • ➔ fFe( CN~
2
are immiscible with water. of ammonia produced = V ml
&,ample: Anmne is separated by this technique 3[Fe(C N)J,._ + 4Fel+ ~¥ • Fe 4 (Fe(C'N)J 3 )d,{,;O
from aniline w a ter mixture . (P ruS9ian blue) \/ < 2M < td
-> D lstlllat l on unde r reduced pressure : Th i s % o'f nitrogen ~ m
(B) Test of Sulphur
method is used to purify liquids having very high
(i) S - + Pb2. ➔ PbS (black)
2
boll ing points and those , which decompose at or 1
~ Kjeldahl's method IS not applicable to compounds
below their boiling points. (ii) s 2 - + [Fe(CN )5 N0]2 - ➔ [Fe(CN)5 NOS}..._ contain ing nitrogen m rntro and azo groups a nd nitrogen
Example: Glycerol can be separated from spent-lye Nltn>pruss ld e Yl o i.t present in ring (e .g. pyridine).
in soap industry by using this technique .
In case, nitrogen and sulphur both are present. sodlum (B ) Halogens
(iv) Differential Extraction: Carius method:
thiocyanate is formed
.:, When an organic compound is present in an aqueous
medium , it is separated by shaking it with an organic Na+ C + N + S ➔ NaSCN
3+ - 2+ Organic compound p _,...'"? >'><O:i_, AgX 1
solvent in which it is more soluble than in water. Fe + SCN ➔ [Fe(SCN)] (Blood red) "9~-'
o The organic solvent and the aqueous solution should be
immiscible with each other. (C) Test of Halogen Let mass of compound =mg
o They form distinct layer which can be separated by X+Ag• ➔ AgX
Mass of AgX formed = m, g
separatory funnel. o A white precipitate , soluble in NH 4 OH shows presence of
::i The compound is obtained by evaporating the organic
chlorine. atomic mass of X " m 1 "' 100 0 ,
solvent o A yellowish precipitate soluble , sparingly soluble in % o f h a Iogen ~ ----------~ - - ,.,
mole cular mass of Ag X x m
(v) Chromatography: It is an important technique extensively
used to separate mixtures into their components .
NH 4 OH shows presence of Br
Based on the principle involved it is classified into two main o A yellow precipitate insoluble in NH 4 OH shows presence (C ) Sulphur
categories. of Iodine Carius method:
(a) Adsorption chromatography and (0) Test of Phosphorus
(b) Partition chromatography Organic N.a-io, aaci:z ,
Na O HNO compound ) [Link] 4 - -~-> BaSO 4 ...
(a) Adsorption Chromatography: It Is based on the fact Compound ~ Na 3 PO 4 _ _ , ,,. H PO
3 4
that different compounds are adsorbed on an
adsorbent to different degrees . Commonly used
(NH4),P04 . 12 Moo,. (NH.>:, Moo.I Let mass of compound = m g
(Yellow ppt) M ass of BaSO 4 = m, g
adsorbents are silica gel and alumina . It is of two types.
·• Column chromatography
• Thin layer chromatography (J) QUANTITATIVE ANALYSIS 32-X-m,
,o o f sup
0/ I h ur = ~ X 1 00 0 /
- - ,o
(b) Partition Chromatography: It is based on continuous (A) Nitrogen Is estimated by Dumas and ~eldahl's method 233 x m
differential partitioning of components of a mixture
(I) Dumas method
between stationary and mobile phases . Paper (D ) Phosphorus
chromatography is a type of partition chromatography. Let volume of nitrogen at STP = V ml
Mass of organic compound = m g Organic Fuming (NH.),Mo0 4 1
compound HN03
H3 PO 4 ----➔ (NH.),PO, · 12Mo03 +
@ QUALITATIVE ANALYSIS OF
ORGANIC COMPOUNDS 28 x V x 100
Percentage of nitrogen = xm Let mass of compound = m g
Nitrogen, sulphur, halogens and phosphorus present in an 22400
organic compound are detected by Lassaigne's test. The Mass of (NH 4 }i PO 4 · 12MoO3 = m 1 g
elements present in the compound are converted from co.v alent (ii) KJeldahl's Method
I form into the ionic form by fusing compound with sodium metal. Organic compound+ H 2 SO 4 ➔ (NH 4 ) 2 SO 4
Molar mass of (NH 4 hPO 4 • 12MoO3 = 1877 g
4
I
Na+ C + N~NaCN
· l NaOH
H,so. % of P = 31 x m 1 x 100 %
2Na + S~Na2S; Na+ X~NaX (X = Cl, Br or I) (NH 4 )iSO 4 ~ NH 3 1877 x m
 Hydrocarbons
13
Chapter
G)
AlKANES 0 Physical Properties (vii) Pyroly~sis C H + H •;) Preparation
6 12 2
o General formula (CnH2;,. 2) Isomeric alkanes having more branching 773 K CH (i) From alkynes
CaH1• C4Ha+ 2 s R R'
o Alkanes show structural isomerism
has lower boiling point.
C H + C H + CH 4
\ I
3 6 2 2 (a) RC=CR' Pd/C C=C (cis)
o Chemical properties o Conformations : I \
o C6 H 14 has got five structural isomers (i) Substitution reaction Alkanes show conformational isomerism H H
whereas G_}i , 6 has nine. due to C - C bond rotation as is seen in
CH + Cl ~ CH CI + HCI
4 2 3 H R'
ethane. Na \ I
o Pre paratio n
o Rate of reaction of alkanes with halogens is a Ethane molecule (C H ) contains a carbon-
2 6
(b) RC=CR' . C = C' (trans)
Uq.NH3 / \
(i) Hydrogenation carbon single bond.
F2 > Cl 2 > Br2 > 12 R H
o C - C bond results into infinite number of (ii) From alkyl halides
CH = CH + H Pt,'Pd!Ni ) CH - CH
2 2 2 o Rate of replacement of hydrogens of alkanes is :
3 3 spatial arrangements of hydrogen atoms CH 3 - CH 2 - Cl alcJKOH CH 2-- CH 2
30> 20> 10 t.
(ii) From alkyl haf!des attached to one carbon atom with respect to
(a) Reduction of alkyl halides (ii) Combustion the hydrogen atoms attached to the other .J The reaction is called f3--eliminatio'n
Zn CH.(g) + 20i{g) ➔ COi{g)+ 2H 2 0(I) carbon atom. y It is observed that for halogens, the rate
CH 3 - a + ~ ~ C H4 o These are called conformational isomers is : iodine > bromine> chlorine
(b) Wurtz reaction H
2C~Br + 2Na drt e!tier CH 3 - CH 3
3
CnH2n.2 + [ n/ ]02
1
➔
nC02 + (n + 1)H 2 0
o One such conformation in which hydrogen
atoms attached to two carbons are as '-J The rate for alkyl groups is : tert >
closed together as possible is called secondary > primary
It is used for the preparation of higher eclipsed conformation. (iii) From vicinal dihafides
alkanes containing even number of (iii) Controlled oxidation v The conformation in which hydrogens are
carbon atoms. 523 Zn
(a) 2CH 4
+ 0 Cu/
2 100 aim
K 2CH 3
OH as far apart as possible is known as CH 2 - CH 2 - C H 2 CH 2 =
(iii) From carboxylicacids
Mo2O3
staggered conformation . I I
(b) CH4 + 0 2 t. CH 30H + H20 o Any other intermediate conformation is Br Br
(a) Decarboxylation
called skew conformation .
- • Soda lime • >J Chemical Pr operties
CH 3COO Na t. CH4 + N~C03 (c) 2CH3CH3 + 302 (CH3COO)iMn
(b) Ko/be's electrolytic method
2CH 3COOH + 2Hp

HyqH H
H
H
H
7-1
HH
~ H
H
(I) Addition ofdihydrogen
RCH =CH 2-+
Pd
R - CH 2 - CH3
2CH3COO-Na •(aq) Electrolysis , CH3 - CH3 H2
(i) Eclipsed form (ii) Staggered form (ii) Addition of halogens
(d) (CH 3)3CH KMnO◄ (CH 3hCOH
o Reaction at anode: @ All(ENES Br2
CH 2 = CH 2 ~ CH 2 - CH 2
·O 0 (iv) lsomerisation • I I
II - -2e- II • u General formula (CnH 20 ) Br Br
2CH3- C- 0 - 2 C H3- C - O:
~ +~
CH3 - CH3 -

l ..
2CH3 + 2C02 t
C anhy./AlCI, •
HCI
(v) Aromatisation

,1 Alkenes show structural isomerism

CH 2 = CH -
(i)
CH 2 - CH 3 CH 2 = C - CH
I
3

o The reddish orange colour of bromine

solution in CCl4 is discharged when Br2
adds to unsaturation site. this is test for
unsaturation.
Q Reaction at cathode:
0 CH 3 - CH = CH - CH 3 (~)H 3
H20 + e - --OH + i:J C Cr2 O3 or V2OG or Mo2 O3
773 K; 10-20 aim V
(ii) Ill
,) Alken es show geometrical isomerism
H

(iii) Addition of hydrogen halides

(a) Markovnikov's reaction
2H-H2f R - CH = CH HBr R - CH- C~
(vi) Reaction with steam
NI
)=( cls-But-2-ene & )=( trans-But-2-ene 2 2 I
, Methane cannot the prepared by this CH4 + H20 1273 K' CO+ 3H 2 H H H Br
method are geometrical isomers (Major)
-- NCERT Maes Hydrocarbons .Mi: ~
~
(b) Anti Markovnikov addition o Chemical Properties o Chemical Properties
(i) Acidic character o Electrophilic substitution reaction
CH3 - CH = CH2 cc.H~g;l,O, CH 3 CH 2 C_ H 2Br
(Major) = - + j_H
CH 3 - C CH + Na ➔ CH 3 - C C Na +. 2 2 = (i) Halogenation (ii) Nitration
Cl NOz
Acidity order of some hydrocarbons :
anhyd. , 13"
Peroxide effect is not observed in addition of HCI and HI
0
(iv) Addition of H 2SO4
HC = CH > CH 2 = CH 2 > CH 3 - CH 3
=
HC ,,,; CH > CH 3 - C CH >> CH 3 - C C - CH 3 =
(
a
) 0 + Cl 2
V AIC1 3 l8J
A.
V
Cone. HN0 3
Cone. H,so. @
I CH 3 -CH = CH 2
(v) Addition of H2 O

H 2 SO•
CH 3 -CH-CH 3
SO H
I
3

(ii) Adc;lition reactions

(a) Addition of dihydrogen
R - C = CH + 2H 2 .....E!L. RCH 2CH 3
{b) Q+
---, anh. C *"'C I
6Cl2Aici7 Cl I.,,: Cl
dark, cold

Cl
Cl
I A'-:::: + H O
2
H+
-------+ ,X-: 2-methylpropan-2-ol
(b) Addition of halogens
CH 3 -C = CH~CH
Br
Br Br
I I
(iii) Sulphonation
SO 3H
(iv) Friedel-Crafts alkylation
C2Hs
a~~:- 6
2
-C-CH
(vi) Oxidation reaction .

OH (Major) 3
Br Br
I I A 6.A
v+ H2so4'so3)~ v + H0 2 0 + C 2H 5 CI
Reddish orange colour of the solution of bromine in fuming 6
- ' dil KMno.
(a) CH 2 - CH 2 273 K • CH 2 - CH 2 CCl 4 is decolourised . COCH
! (v) Friedel-Crafts acylation
I I (c) Addition of hydrogen halides 3
I OH OH
7 A
v+ CH 3COCI 0
v \
I
anhyd .
Cold, dilute, aqueous solution of KMnO 4 is called AlCl,
CH = C H ~ [CH 2 = CH - Br] 6 \
Baeyer's reagent
CH 3 - CHBr2 o Mechanism of electrophilic substitution reaction
Decolorisatiori of KMnO 4 solution is used as a test of {d) Addition of water
Halogenation \
\jnsaturation. Step-I Step-II HOCI l·
CH 3 C = CH
H20
CH 3-C=CH 2
,..- Tautomerism ® ~ ® \
(b) CH 3CH = CHCH 3 KMno. 2CH 3 COOH
~
It ♦ Hg /H
2• •
I -JI Cl - Cl + AICl 3 - Cl + [AICIJ- ~T~T ➔ I....-: (cr Complex)
(e) Polymerisation O- H CH 3 -C- CH 3 Step-111
(vii) Ozonolysis II
0 ~~ --~
0
)= (i)03 )= 3CH = CH
Red hot
Fe tube 873 K V
(ii) Zn/H20 0 + HCHO
V V
(vii) Polymerisation © AROMATIC HYDROCARBON Addition reactions \
0.
a Cl
High T/P
nCH2 = CH 2 Catalyst
-f CH 2 - CH21n
Polythene
.l...
o Species which is cyclic, planar having delocalised n
electrons and fellow's Huckel's (4n + 2)n rule is
aromatic. n is an integer (n = 0, 1, 2 ... )
(l)o~~: o (ii) + 3 Cl2
UV
500 K
Cl◊CI
Cl Cl

I
\
o General formula (CnH 2,,_2)

(D ALKYNES
0
'-.:
00,~- 00 CCCl _...._.... '-.:'-.:'-.:
a Combustion
C 6H 6 +
15 0
2 2➔ 6CO 2+3Hp
Cl (BHC)
Preparation
(i) CaC 2 + 2H 2 O ➔ C 2 H 2 + Ca(OHh

(i) (ii)
are aromatic species

(iii) (iv) (v)

CxHy + t ++J 0 2 2+
➔ xCO ~ H O 2
(ii} yH2- 9H2 alc./K0H
CH 2 = CH-Br
o Preparation of benzene
COONa OH
o Directive influence of function group towards EAS reaction:
o/p directing groups : - OH, - NH 2~ - NHR, - NHCOCH 3 , - OCH 3
Br Br Li
iNaNH 2
CH=CH
(i)@ + NaOH c1° 0 (ii)@+O -CH 3 , - C 2H 5 etc.
Meta directing groups : - NO 2, - CN, - CHO , - COR. - com-
-COOR, - SO 3H etc.
)
 15
Chapter
G) CLA~SIFICATION BASED ON CRYSTAL LATTICE
Crystalline Solids -( @ CRYSTAL LATTICE AND UNIT CELL J Amorphous So ftds
o Pseudo solids or super cooled fiquids
o True solids
♦
o Short range order
o Long range order ♦
o Do not have a definite pattern of arrangement of
o Have definite pattern of arrangement of particles
Primitive Unit Cells Non•Prlmltlve Unit Cells particles
- o Arusotropic
o eg. Naa, Solid s0 2 o Constituent particles are present o Constituent particles are present o Isotropic
o Are categorised accortfmg to intermolecular forces, only at the comer of unit cell at comer as well as body-centre or Q eg. rubber, glass
into Ionic, Metallic, Molecular and Covalent solids o 7 types of Primitive unit cells with face centre.
14 Bravis lattices
~ @ CUBIC SYSTEM
1 . ZM
IDensity = -NAa
- - I @
•
~ 3 NON-STOIC OMETRIC DEFECTS
o Metal excess defect :
Type Position of z CN Relation of Packing (i) Arises due to anionic vacancies, leaving a I le which is occupied by an electrons thus maintaining
J
atoms r, d, a efficiency electrical neutrality. The anionic sites, occu1 ied by unpaired electrons known as F-centre and impart
colour to the crystal. eg : NaCl with Na vap impart yellow colour.
Simple 6 d a
r =-=- 52.4% ➔ (ii) Arises due to presence of extra cations at i1 rstitial sites. e.g. on heating ZnO loses [Link] and
Comer 8 X ..!... = 1
cubic 8 2 2 2+
excess Zn move to interstitial sties.
d ,13a 0 Metal deficiency defect : Arises when metal sh ows variable valency. The defect occurs due to missing
BCC Comer and 1 8 r= - = - - 68%
Sx-+1=2 4 a cation from its lattice site and the loss of pos e charge is made up by the presence of the cation having
Body centre 8 2
higher charge in the adjacent lattice site eg. FEis found with composition of Fe0 _95O
FCC Comer and a x..!...+ sx..!... =4 12 · d a 74%
r= - = -
face centre 8 2 2 2-./2 RITY DEFEC-TS
- (!) TYPE OF DEFECTS 1
(;:)@ (;:)@
r 0 r
SrCl 2 is crystallised,
Q

some sites of Na ... are occupied by sr2+ . Each sr2• replaces two Na+ ions.
Another similar example is the solid solution of CaCl and AgCI.
@0@<;,
(f) STOICHIOMETRIC DEFECTS 2
(Intrinsic or thermodynamic defect) O@~@I
@ SCHOTTKY DEFECT
@ FRENKEL DEFECT
o It is due to equal number of cations and anions are missing from lattice sites.
0000 Q Due to dislocation of ions (usually cations) from the lattice sites
and occupy interstitial sites. 0808
o It results in decrease of density of crystal 0000 9 Has no effect on density
G~O
o It is found in crystals having almost similar size of cation and a~ion eg. NaCl, KCI, AgBr etc. 0000 o Found in crystals with large difference in size of ions.
0~0
Q eg: AgCI, ZnS, AgBr etc.
.NCERTMaps The Solid State -
@) CLOSE PACKING
0
In one aunension : Co-ol'dination number (CN) = 2 o In fee unit cell, two tetrahedra l voids are present on each body diagonal and
0
In two dimenSion : (a) AAA type : Square dose packing have CN = 4 octahedra l voids are present on body centre and on each edge centres.
(b) ABAB type: hexagona l dose packing have CN = 6
lo three dimenSion :(a) AAA type : simple cubic lattice have CN = 6 Voids in fee lattice : if N atoms in lattice
0
(b) ABAB type : hep lattice have CN = 12 o Tetrahedra l voids = 2N
(c) ABCABC type : fee lattice have CN = 12
o Octahedral voids = N
(, @ CLASSIFICATION OF SOLIDS )
@ · Based ~n Eiectrl~al Properties 14--_ _ _ _ _ _ __.__ _ _ _ _ _ __..,( @ Based on Magnetic Propertie s )
i
o Conducto rs: Conductiv ity 104-107 ohm-1 m-1
o Insulators : Conductiv ity 10-20 - 10-10 ohm-1 m-1 o Paramagn etic substance :. Which are weakly attracted by external magnetic field
o Semicond uctors : Conductiv ity 1O~ ·- 104 ohm-1. m :-:--1 '·
0
• _eg.: 0 2, Cu2+ etc.
o Diamagne tic substance s : Which are weakly repelled by external magnetic field :
-----l Semicond uctors .: When the energy gap between the valence band eg.: NaCl , H 20 etc.
and conduction band is S"'!_all eg.: Si, Ge
o Ferromag netic substance s : substance which show permanen t magnetism even
in the absence of external magnetic field . eg Ni, Fe, Co, Cr0 etc.
2
n-type semicond uctor : When Si i:'> dopped with P or As.
CfXD1XD1)
a Antiferrom agnetic substance s, which have zero net dipole moment even
though they have large number of unpaired electrons eg. MnO
( p--type semicond uctors : When Si is dopped B or Al. }
o Ferrimagn etic substance s : Which posses very small net magnetic moment even
• Diode is a combinati on of n-type and p-type semicodu ctors
through they have very large number of unpaired electrons eg. Fe 0 , MgFe 0 .
and used as a _rectifier. 3 4 2 4
• VO, V02 , V0 3 and li03 show metallic or insulating properties These substance lose ferrimagn etism on heating and become paramagn etic.
depending on temperatu re.
 16
Chapter
G) EXPRESSING CONCENlRATION OF soumoNS @ RAOULTS LAW @ ·coWGATIVE PROPERTIES
0
o For non-volatile solute in volatile solvent P1 -P1
. . of a •component
..... (w/w} = Mass
Mass [Link] x 100
0 ... 0 o Relative lowering of vapour pressure : o = x.,..
PS0L11ian = PS0MJl'II >C_.. P1
0 •
o For volatile liquids:
Volume of a component x
100
o Elevation in boiling point ATb =Tb - Tb =Ki,m
o Volume percentage (v/v} - Total volume of solution P- = P, + P2 = P:X, + P;X-i = P~ + (p~ - P~)-X-i
o Mole fraction of any component in vapour phase:
Where, Ki,
RX M, X T!
_ Mass of solute x Y, = p,Jp- 1000 x A.,.pH
a Mass by volume percentage (w/v) - Volume of solution 100
0
@ TYPE OF SOLUTIONS o Depression in freezing point AT,= T, - T, = Kirn
Mass of solute x 6
o Ideal solutions : A - 8 interactions are of same
o Parts per million (ppm) 10 RxM 1 xi
Mass of solution Where, K, = r
magnitude as A - A and 8 - 8 interactions. tN mix = 0 and 1000 x Ar-.H
Mole of a component ti.H,_ = 0
o Mole fraction (X) = Total moles of all components o Osmotic pressure:x =CRT=(:) RT
eg .: n- hexane and n-heptane , bromoethane and
Moles of solute chloroethane. o Osmotic pressure method is widely used to dete
o Molarity (M) - Volume of solution (I) o Non-ideal solutions: A - 8 interactions are of different molar mass of proteins, polymers.
Mass of solute magnitude than A - A and 8 - 8 interactions. AVmix *0 o Isotonic solution have same osmotic pressure.
o Osmotic pressure associated with the fluid inside
o Molafrty (m) Mass of solvent (kg) and [Link] * O.
blood cell is equivalent to 0.9% (mass/vol) of NaCl solution.
o (+)ve deviations : A - 8 interactions are weaker than
o Solubifrty of a substance is its maximum amount that can be
dissolved in a specified amount oT solvent at a specified
A-Aand 8 - 8 interactions. {J) van't Hoff FACTOR AND 'ITS SIGNFlCANCE
temperature. . Observed value of colligative property
• Afi,,...>0, AVrrn >0 , Pot>s>Pca1 1
= Calculated value of colligative property
@ SOLUB1UTY OF A SOLID IN A UQUID I • eg: acetone+ ethanol ,
Normal molar mass
= ------------
Io Significantly affected by temperature change. o (-)ve deviations: A - 8 interactions are stronger than I Abnormal molar mass
o Pressure does not have any significant effecl A-Aand 8-8 interactions. a For normal solute (i = 1)
• [Link] <0, AVrm <0 , Pot>s <P ca1 -o For association,i< 1
1
@ SOUJS JUTY OF A GAS IN A LIQUID eg: nitric acid + water, chloroform + acetone
o For dissociation, i > 1
o Henry's law: p = ~
•
/o\--=========---===----======~ J
(~::=::-=~
o Azeotropes : constant boiling m i xtures whose ~ IIODIAED COUJGATJVE PROPERTIES
o Decreases with increase in temperature. composition does not change on distillation.
0
P, - P1 in 2
0
o lnaeases with increase in pressure. 0 --
o Minimum boiling azeotrope: 95% C2H5 0H and 5% P1 n,
o The air tanks of scuba divers are diluted with He to avoid
bends. HiO by volume o ATb = il<i,m
;:) To inaease the solubility of CO2 in soft drinks and soda water, o Maximum boiling azeotrope: 68% HN03 and 32% H2 0 o AT1 = ilyn
the bottle ls sealed under high pressure. o 1t = ICRT
 17
Chapter
· G) lYPE OF [Link] @
,r
NERNST EQUATION ~ B..ECTROCHB IICA SERIES
I
,
j

O SedJocltAlliCal cell : Device used to convert chemical

er,ergJ d a redox reaction into eledrical energy. It is also
knCJWOasgalvanicceII.

o For the reaction : M.,. + ne- ~ M

E =E°- RT In [M]

I 0
o A negative E means that the redox couple is stronger
reducing agent than the W~ couple.
o A positive E means that the redox couple is a weaker
0
nF [M"+]
0 Bedlotftic cell : Device ~ uses electricity to bring
I reducing agent than thew~ couple.
aoouta non-spontaneous redox reaction. E = E° _ 0.0591 _1_ Oxidised form Reduced form E0 N
109
n [M"+] • Fz(g)+ 2e- ➔ 2F 2.87
Co3++e- ➔ Dr' 1.81
@ DANIELL~ o For the reaction : aA + bB~cC + dD
Clz(g)+2e- ➔ 20- 1.36
o Cell reaction: Zn(s) + Cu2+(aq.)~Zn2+ (aq.) + Cu(s)
o When external opposite potential is applied to the cell in
E
ceu
=Eo
cell
_ RT In [Ct[Ot
nF [A]a[B)b
-
C
•Cl

O2(g)+ 4W + 4e-
Br2 +2e-
➔ 2H.z0
➔ 2Br-
1.23
1.09
,ct
standard state Ag·+ e- ➔ Ag(s) 0.80
o For a reaction at equilibrium, E..,. = 0. Cl
C Fel++e-
iii ➔ Fe2+ 0.77
(a) E. = 1.1 V, no flow of electrons. ;; 0 2(9) + 2H• + 2e- ➔ H.iO2 0.68
0 Eoce11-_ 2.303 RT Iog Kc -_ 0.0591 1og K c
F >C -
(b) E_> 1.1 V, electrons flow from Cu rod to Zn rod.
(c) E._<1 .1 V,electronsflowf romZn rod to Cu rod.

n
@
n
GIBBS ENERGY
I -
0
0
-
~
t ll

12+2e-
Cu2++2e-
2H"+2e-

➔ 21
➔ Cu(s)
➔ HJg)

0.54
0.34
0.00
o It is the reversible work done by the galvanic cell. C
-e
Pb2++2e- ➔ Pb(s) --0.13
@ CELL POTENTIAL o i\G = -nFEc:e11 c,) sn2++2e- ➔ Sn(s) --0.14
o Electrode potential : It is the potential difference developed 0
o i\G = -nF E~ tll Cr3>+3e- ➔ Cr(s) --0.74
•f•
C
between the electrode and the electrolyte. When the o i\G0 =-RTlnK=-2.30 3RTlogK Zn2++2e- ➔ Zn(s) --0.76
concentration of all the species involved is unity it is known I
u [Link]+2e- ➔ H2(g) + 2O~(aq) --0.83
as standard electrode potential. Cf) [Link] OF ELECTROlfflC SOLUTIONS ~ Na• +e- ➔Na(s) -2.71
° Cell potential : The difference between the electrode ca2++2e- ➔ ca(s) -2.87
potentials (reduction potentials) of the cathode and anode. o Resistance : R = p£ unit = ohm
A' t<>+e- ➔ K(s) -2.93
0
E~F of cell : The cell potential when no current is drawn u • +e-
RA ➔Li(s) -3.05
through the cell. o Resistivity : p = -e- · unit = ohm-cm
o Ece1=E'9'1- Eteit . @ OlLUTlON EFFECT OH [Link]
o Conductance : G =~ = IC~ . unit = ohm - 1 or S o Conductivity always decreases with decrease in
o E;_..=~- E~ R £
0 concentration (means on dilution) both for weak and strong
lnagalvaniccell :
(a) Anode has negative potential w.r.t solution .
° Cell constant : G* = !:...A'
unit=cm - 1 electrolytes.
o For weak electrolytes. molar conductivity increases steeply
(b) Cathode has positive potential w.r.t solution . on dilution.
o Conductivity : IC = Gl unit = ohm - 1 cm- 1
,o Standard hydrogen electrode : A' £> For strong electrolytes, molar conductivity increases slowly
W(aq.)+e- ~ .!~(g) with dilution.
\ (11,1} 2 •
E° -
-
oVolt (Assumed) o Molar conductivity : A = 1C x 1000 unit = s cm 2 mor1
m t,A ' o Forstrongelectrolyte : A __ = A - AJc .
0
 - Electroche mi~try
®
KOHLRAUSCH LAW OF INDEPENDE NT @ BATTERIES o Secondar) batteries: Which can be recharged
[Link] OF JONS o Primary Batteries : Which cannot b~ reused . (1) Lead storage battery :
o Limiting molar conductivity of an electrolyte can be
(1) Dry cell : (Leclanche cell)
represented as the sum of the individual contributions of the
2+
Pb(s) + Pb0 2 (s) + 2J-fi50 4 (aq.) ~~
anion and cation of the eJectrofyte at infinite dilution. Anode : Zn(s) - - . Zn + 2e-
o If an electrolyte on dissociation given v. cations and v_anions Cathode : Mn02 + NH; + e- ~ MnO(OH) + NH 3
2PbSO ,.(s) + 2J\i
(2) Nickel cadmium cell : It has longer life than
then~ =V,_A: + V_A:
storage cell :
• ~ : t<">Ca2->M if'>t<'>Na• Carbon rod
(cat!lode) Cd(s)+ 2Ni(OH1(s) ➔ CdO(s) + 2Ni(OHh(s)+ HiO(~
• "-
0
m: ot-r > so2-
4
> Br-> er> c~
''3 coo- o Fuel cells : Galvanic cell that converts the energy p1
• Fora weak electrolyte : a= A,,/A",r, during combustion offuel directty into electrical energy
2
Ca 2 CA e.g: ~-02 fuel cell
• For acetic acid : K =- - m
a 1-a ~(A:-Am) Anode : ~(g)+20H -(aq.)~2~ 0(l)+2e-
Cathode : Oi{g) + 2t½O(l ) + 4e- --+40H-(aq .)
@ FARADAY'S LAW OF ELECTROLY SIS
The cell was used in Apollo space programme
a First law :w = za =Zit= _E_ x It
96500 7/ Anode-
W1 E, Zinc cup Mn02 +
o Seeondla w:-=-
W2 E2 (anode) carbon black Aqueous electrolyte
+ NH4 CI paste NaOH
o 1F = Charge on 1 '!IOI electron= 96487 C = 96500 C,
Fig. A commercial dry cell consists of
a graphite (carbon) cathode in a zinc
@ PRODUCTS OF ELECTROLYSIS container; the latter acts as the anode. H2 ➔ +-02
o Molten NaCl : Anode : Cl2 , Cathode : Na (2) Mercury cell : Cell potential(= 1.35 V) remains constant
o Aqueous NaCl : Anode : Cl 2 , Cathode : H2 during its life
o Dilute H2S04 : Anode: 0 2 , Cathode: H2 Anode : Zn(Hg) + 20H- ~ ZnO(s) + H20 + 2e-
1 o Concentrated H2S04 : Anode: S20:- , Cathode: H2 Cathode : HgO + H2 0 + 2e- ~ Hg(l ) + 20H-
I • Fi,g . Fuel ceU using H2 and 0 2 produces electricity
@) CORROSION
o It slowly coats the surfaces of metallic objects with oxides or other salts of metal.
o Corrosion of iron is called rusting. It is an electrochemical phenomenon .
o Rust is Fe2 0 3 • xH 2 0 .
o Prevention of rusting can be done by
(i) Covering the surface with paint or by chemicals (e.g. bisphenol) Oxidation : Fe(s) .➔ fe 2•(aq) + 2e-
(ii) Coverthesur facebyother metals(Sn,Z netc.) Reduction: 0 2(9) + 4W(aq) + 4e- ➔ 2HP(I)
(iii) Provide a sacrificial electrode of other metal (Mg, Zn etc.) Atmos~heric oxidation : .2Fe2•(aq) + 2H2 0(I) + 1/20i{g) ➔ Fe20 3 + 4tr
~JQ. Corrosion of iron in atmosphere
 Chemical Kinetics
18
Chapter
---- CD RATE OF REACTION
/
I\
1 @ INTEGRATED RATE EQUATION ANO HALF LIFE r ® TEMPERA1'1JRE DEPl!NQ£NC RAT!! o,
! o, ..,.~~
! k> For a readion, aA + b8 ➔ xX + yY Zero order reaction:
REACiltlN
-1 ~AJ - 1 c(B] 1 <V<J - a For a chemicaJ reaction with rise in temperature by 1o•,
1
I 1~
rate- . ---- - -- - Rate == --<(R] == k[Rr
I a dt b dt x dt y dt dt the rate of reaction is nearty doubled
l ~
., l,)11 d rate of I eactiol I : [R] = kt
[R] 0 - a Antienius equation · k = Ae ~
-4 -1
t, = -[RJo
t URJ I
I
I
(i) rrd L s 0
2 2k
~ 1 ~ tercept = lnA
\
-l
(i) atm s
o Average rate = -A{RJ = -([R 2 J- [R,1) o l,00% == lRJo
~ slope+
at t 2 -t,
k
First order reaction :
0 ,-
0 1/T _ ',
tnstantaneous rate = - ~J = ~I o Rate = -d[R] == k[R]1
1
fQ
I
@ OROER
dt dt
O
q k == 2.303

dt
In [R] =In [RJ0 - kt
[RJo
l Lk,gl~J ~
2.303R
[TT TT
2 -
1 2

1
=
o Fa a rate law equation : rate k{A]" [8]1order of t
109
[R] ~ 9 The energy required to form the reaction intermediate,,
=
reaction X + y "'"h
~ I called activated complex, is known as activation energy (E.)
o Order of reaction can be O, 1, 2, 3 and even a fraction. Q k = 2.303 log [R)1 oi
o Order of reaction is an experimental quantity.
(t 2 - t 1) lRh .Q
0
,__.
------- + o Threshold energy= Activation energy
+ energy possessed by
o Order is applk:able to elementary as well as complex Q t1 = 0.693 reacting species.
reaction. 2
k
. ~
g For complex reaction, order is given by slowest step. th o Forbiomolecularreaction. Rate= pz"8eRT
g For n order reaction , t 1 oc [R0 )1- n
@ MOLECULARITY 2
~==========================================~. . . \. where, Pis stericfactor and ZAfl is Collision frequency. )
It is the number of atoms, ions are molecules that must ® PSE!UDO FIRST ORDER REACTIONS
l ® EFJ;ECT OF CATALYST
<;>
collide simultaneously with one another to result into a Q Hydrolysis of ethyl acetate in acidic medium
chemical reaction
q Inversion of cane sugar in acidic medium q Catalyst increases the rate of reaction by reducing the
o It cannot be zero or a non-integer activation energy of reaction. \\
(f) ORDER OF SOME Rl!ACTION6
Q It is applicable only for elementary reactions Q A small amount of the catalyst can catalyse a large amount
Reaction Order
of reactants 1
1130 K
© Reaction order, Unit of rate constant 2NH3(g) D♦ ,.,,.,,1.. c♦) N2(9) + 3H2(9) Zero
Q ,\catalyst does not alter Gibbs energy, ~G of a reaction.
1
mot L- s-
1 2Hl(g) Gold sAurface) H2(9) + 12(9) Zero constant of a ,\
Zero o Catalyst does not change the equilibrium
-1 Radioactive decay First reaction
First s
- 1
1 1 N20 5(g)
6.
> 2N02 + ~02 First Q ,\catalyst can catalyse the spontaneous reactions only.
Second moi- Ls-
 ..
19
Surface Chemistry · Chapter
@) CATALYSIS
CD
ADSORPTION o Substance, which accelerate the rate ·of a cherrucal reaction
0 The accumulation of molecular species at the surface rather than in the bulk of a soud
or liquid is termed adsorption. themselves remain c hemically and quantitatively unchanged after
0 The molecular species or substance, which concentrates or accumulates at the surface is termed adsorbate and the reaction, are known a s catalyst
material on the surface of which the adsorption takes place is called adsorbent a Promoters are su bs ta nce that e n hances the activity of catalyst
o In adsorbtion the concentration of the adsorbate increases only at the surface of the adsorbent. while in absorbtion o Poisons decrease the activity of a catalyst
the concentration is uniform throughout the bulk of solid. a When the reactants, products a nd the catalyst are i n same phase,
Mechanism of adsorption process is said to be homogeneous catalysis
o The extent of adsorption increases with the increase of surface area per unit mass of the adsorbent at a given a The catalytic process in which the reactants and the catalyst are
temperature and pressure. different phases is known as heterogeneous catalysis ·
o Another important factor featuring adsorption is the heat of adsorption during adsofption , there is decrease in surface
energy which appears as heat therefore adsorption is an exothennic process. In other words, 6 H of adsorption is I I I Adsorption of I I I
- 0- 0 - 0 - A B reacting molecules ) - 0 - 0 - 0-
always negative. When a gas is adsorbed, the freedom of movement of its mo,ea..iles becOme restricted. This 1 I I
amounts to decrease in the entropy of the gas after adsorption i.e .. 6 S is negative fo< a process to be spontaneous .
I I I + +
- 0 - 0 - 0 - Reacting
- 0 - 0 - 0-
6G must be negative at constant pressure and temperature .
I I I molecules 1 I I
o As the adsorption proceeds 6H becomes less and less negative ultim at eJy /\H bea,i 1,es equal to T L\S and 6 G
Ads
becomes zero. At this state equilibrium ls attained
Typn o f • dscrptlon
C a talyst surface having
free valencies l of readi'ti
molecuaa
Physlsorptlon
C horn is-0-rptJ on
I I I Desorption of
I I I
1. II Is caused by chemK:al bond formation. - 0 - 0 - 0 - - 0 -0-0-
1. It arises because of van der Waals' forces . product molecules
2 . It Is not specific In nature.
3 . It Is reversible in nature.
2.
3.
II fs highly specific r.n nature
It is irreversible
II a lso depends on lhe nalure o f gas . Gases wh ich
-
1
? _
I
? _
I
? _
+A - B
Product
_ ?_?_?_
1 I I
4 . fl depends on lhe nature of gas. More easily 4 .
llquefiable gases are adsorbed readily. can read WTth the adsorbent show d1em [Link] . Cataly st
1 1
5. Enthalpy of adsorption Is low (20-40 kJ mor ) 5. Enthalpy of adsorption tS high ( 80-24-0 lcJ mol ) .
6. Low temperature is favourable for adsorption . It 6 . High tem pe ratu re ts favourable for adsorption . o The activity o f a catalys t d e pends upon the strength of chemisorption
decreases with Increase of temperature. II increases with the increase of temperature. a large extent
7. No apprecia ble activation energy is needed. 7. High adJvat1on energy is sometimes needed .. o The selectiv ity of a ca talyst is its abil ity to d irect a reaction to yiekj
8 . ft depends on the surface area. It Increases wi th 8, II also depends on the surface ar ea .. It too increases particular product selectively, when under the same reaction condi
an Increase of surfa ce area . with an increase of surface area.. many products a re possi ble
9 . It results into multim olecular layers on adsorben t 9. It results into un i~ layer.
surfa ce under high pressure. o The catalytic re a ction that depend s u pon the pore s tructur e of
ca-talyst and the size of the reacta nt a nd p roduct is called s
selective catalysis e .g . z eolites .
'\...21 ADSORPTlOH tSO THERMS (FlltEUHOUCH AOSORPTJOIH lSOTHERII)
I a ~ = "-P Ln(n > 1)
m
y
j
I
I o Numerous re actions tha t occu r in bodies of a n imals and plants
cataJysed by enzymes termed as b iochemical catalyst
~"I
. x = mass of gas adsorbed. m = mass of adsorbent t 1
Slope = ;,-
o Characteristics of enzyme ca ta lysis
(i) M ost h ig h ly efficient
p = [Link] of gas. K. n = constants depend on naiure of adsorbent and gas
a t a p.:irocu!ar temperature log ~ (ij) Hj ghly specific na ture
m (iii) H ig h ly active u nde r o p timu m tem perature
) 1o iJ ' - k>gK • 1 k>gP
,,.., n } logk = rnter cept (iv) Highly active und er optJmu m pH
l
n I..::; ~zwecn OtD 1 (probabte range O , to 0.5) 0 log p ~
X
(v) Increasing actJVrty tn presence o f acuvators :lnd ...-::::>--~,-....-~~~~
J (v f) Influ e nce o f inhibrtors a nd [Link]~ -
NCERT Maps
,,...
SOME !EN2YMATIC REACTION (iii) Classlflcation based on type of particles of dispersed phase

Surface Chemistry
(a) Multimolecular colloids contains a large number of atoms or smaller molecules of a

-
Enzyme Source Enzymatic reaction
substance aggregate together to form species having size in the colloidal range. e.g., Gold
lnvertase Yeast Sucrose ➔ Glucose and fructose sol, sulphur sol
(b) Macromolecular colloids - Macromolecules in suitable solvents form solutions in which
Zymase Yeast Glucose ➔ Ethyl alcohol and carbon dioxide
the size of the macromolecule may be in colloidal range e.g., starch, protein etc.
Diastase Malt Starch ➔ Maltose (c) Associated colloids (Micelles) : At low concentrations behave as normal strong
Maltase Yeast Maltose ➔ Glucose electrolyte, but at higher concentrations exhibit colloidal behaviour due to formation of
aggregates (micelles) Micelles formation takes place above a particular temperature called
Urease Soyabean Urea ➔ Ammonia and carbon dioxide
Kraft temperature (T.J and above a particular concentration called critical micelle
Pepsin Stomach Proteins ➔ Amino acids concentration (CMC) e.g. soaps and synthetic detergents
@ COLLOIDS
@ IP1ijf:PA'.~T~O.N O.F COJ..[Link]
J Chemical methods
0 A collold Is a Heterogeneous system in which one substance is dispersed
Double decomposiUon
(dispersed phase) as very fine particles in another substance called dispersion As 20 3 + 3H 2S - - - - ' - - - + As 2S3 (sol) + 3H 20
medium
Oxidation
0 The range of diameters of colloidal particles is between 1 to 1000 nm S0 2 + 2H 2S - - - 3S(sol) + 2H 20
o Classlflcatlon of colloids
(I) Classification based on physical state of dispersed phase and dispersion Reduction
2AuCl3 + 3HCHO + 3H 20 - - - 2Au(Sol) + 3HCOOH + 6HCI
medium
Hydrolysis
Dispersed Dispersion Type of FeCl3 + 3H 20 - - - Fe(OH!J(sol) + 3HCI
Examples
phase medium colloid
> Electrical disintegration or Bredig's Arc method - In this method, electric arc is struck between
Solid Solid Solid sol Some coloured glasses and gem stones electrodes of metal immersed in dispersion medium . The intense heat produced vapourises the
Solid Liquid Sol Paints, cell fluids metal, which then condenses to form particles of colloidal size. Colloidal sols of metals such as gold,
Solid Gas Aerosol Smoke, dust silver, platinum etc. can be prepared by this method.
Liquid Solid Gel Cheese. jellies ') Peptization - Process of converting a precipitate into colloidal sol by shaking it with dispersion
Liquid Liquid Emulsion Milk, hair cream, butter medium in the presence of a small amount of electrolyte. The electrolyte used for this purpose is
Liquid Gas Aeros-01 Fog, mist, cloud, insecticide sprays called peptizing agent
Gas Solid Solid sol Pumice stone, foam rubber
Gas Liquid Foam Froth, whipped cream, soap lather
@ [Link].10.N Of ..COl,..!..[Link].. SO.!..!.JTlONS
(li) Classification based on nature of Interaction between dispersed phase The process used for reducing the amount of impurities to a requisite minimum is known as purification
and dispersion medium of colloidal solution.
(a) Lyoph lllc colloids directly formed by mixing substances like gum, 0 Dialysis : Process of removing a dissolved substance from a colloidal solution by means of
gelann, starch , rubber eic wnh a suitable liquid. These sols are diffusion lhrough a suitable membrane.
1 ') Electro~iatysis : Ordinarily, the process of dialysis is quite slow. It can be made faster by applying
revers ible 1n nature
an electric field if lhe dissolved substance in the impure colloidal solution is only an electrolyte
(b) Lyophoblc coll oids can be prepared onty by special methods. These
J Ultrafiltration is the process of separating the colloidal particles from the solvent and solubla.
sols are read ,ly coagulated on additJon of small amount of electrolyte by
solutes present in the colloidal solution by specially prepared filters which are penneabla to .:111 ,
he.'.lting or by shakmg and hence are not stable. These sols are
su bstance except the colloidal particles.
trreverslble in nature
 \I) PROPERTIES OF COLLOIDAL SOLUTIONS HARDY-SCHUUE RULE
the numbe r of particle s in a
;o\\iga tive properties : Colloid al particle s being bigger aggreg ates, Greate r the valence of the flocculating ion added, greate r is its
power to
the true solution hence colligative
colloid al solutio n i s compa rativel y small as compa red to
cause precipitation.
prope rties are of small order as compa red to true solutio ns.
For -ve colloids flocculating power is in th~ order : At > sa2•> Na•
in all directions in space which
Tynda ll effect is due to the fact that colloidal -particles scatter light
>
illumin ates the path of beam. The bright cone of light is known
as Tyndall cone. For +ve colloids flocculating power is in the order : [Fe(CN)J4-
~ 2- -
ngth depends on size and PO4 > SO4 > Cl
Colou r : Depen ds on the wavele ngth of light scattered . The wavele
s with the manne r in which the
nature of the particle s . The colour of colloidal solution also change
in
observ er receive s the light 0 Coagulating value : The minimum. concentration of an electrolyte
hours. The
s and depends on the size of millimoles per litre required to cause precipitation of a sol in two
Brownian movement: Zig-zag continuous motion of colloidal particle
of an
smalle r the quantity needed, the higher will be the coagulating power
particl es and viscosi ty of solution .
ion.
~ Charge on colloidal particles:
Positively charged sols· I Negatively charged sols .
® EMliJJlSl,ONS
Hydrat ed metalli c oxides, e.g., Al2O3,XH2O, Metals , e.g., copper, silver, gold sols.
These are liquid-liquid colloidal systems. These are of two types
Cr03.xH2O and Fe2O3.xH2O. etc. Metallic sulphides, e.g.,As2S3, Sb2S 3 , CdS sols.
Acid dye stuffs, e.g., eosin. congo red sols. o Oil dispersed in water (O/W type) e.g., : milk and vanishing cream.
•Basic dye stuffs. e.g., methylene blue sol.
Haemoglobin (blood) Sols of starch, gum, gelatin , clay, charcoal, etc. o Water dispersed in oil (W/O type) e.g., butter and cream
Oxides , e.g., no2sol.
@ C,Ot!.J:.OtDS;ARO.l!J,NO; U,S
diffused layer of opposite
o Zeta potential : The potential drfference between the fixed layer and coagulation of
o The styptic action of alum and ferric chloride solution is due to the
charges is called electrokinetic potential or zeta potential.
potential. blood forming a clot which stops further bleeding
o Electrophoresis: Movement of colloidal particles under an applied electric t in sea water
by some suitable means , it is o When river water meets the sea water, the electrolyte presen
o When electrophoresis i.e., movement of particles is prevented ion with the
field. This phenomenon is coagulate the colloidal solution of day resulting in the deposit
observ ed that the dispersion medium begins to move in an electric
formation of delta.
termed electroosmosis.
o Coagulation or precipitation o Argyrol is a silver sol used as eye lotion.
lyophob ic sols can be carried out
The proces s of settling of colloidal particles. The coagulation of o Colloidal antimony is used in curing kalaazar.
by o Colloidal gold is used for intramuscular injection.
(a) Electrophores is o Milk of magnesia is used for stomach disorders.
(b) By mixing two oppositely charged sols in hardening of
o Animal hides are colloidal in nature when soaked in tannin results
(C) By boiling used in place d
lather. This process is known as tanning . Chromium salts are also
(d ) By persistent dialysis tannin.
,, A v ;::irlrlition of electrolytes
r 23
Coor dinat ion Comp ound s Chapte r
CD WERNER'S THEORY © STRUCTURAL ISOMERISM
Isomers give different ion in solution eg . fCo(NH, ). SOJBr and (Co(NH,).Br]SO•·
o In coordination compounds metals posses two type of valences : primary o Ionisation isomerism
and secondary : Different number of solvent molecule bonded to meta l eg . (Cr(H,O).]C13 a
o Solvate Is omerism
o The primary valences are normally ionisable and are satisfied by [Cr(H, O)0 CIJCl2 • H,0
negative ions . : The ligands are interchanged in bolh lhe cationic and anionic ions. eg . [Co(NH
o Seconda ry valences are non-ionisabl e and satisfied by neutral o Coordlna·tlon Isomerism '
{Cr(CN)J and (Cr(NH, ) 0 ] (Co(CN)0 J
molecul_El_s o_,-_neg_atlve ions.
II is due lo presence of ambidentale ligand eg . (Co(NH 3 ) 5 ON O]CI, a
o Linkage Isomerism
0 SOME IMPORTANT TERMS
{Co(NH, )0 NOJ Cl2 •
o Double salts : Which are stable in solid stale but broken down into
indivldual constituents when dissolved in waler eg. Mohr's sall , [FeSO. •
0 STEREOISO MERISM
(NH.) 2 SO, . 6H 2 O) and potash alum fKAl(SO.) 2 • 12H,OJ o Geometr [Link] Isomers : Common In heteroleptic o Optical Isomers : These are mirror images
comp/exes w ith in CN = 4 (square planar) and CN = 6 . cannot be superimpos ed on one another.
o Coordinatio n compounds : Which retain lhe/r Identity in solid stale as
well as in solution eg K. (Fe(CN)J (i ) Square planar comp/ex : [MX.,L.,J (2 isomers), (i) (Co(en), ]3' have d and l isomer
fMABXL) (3 isomers) show els-trans Isomerism . 3+ ~
Ligands : Species which are dlreclly linked with lhe central metal In
I (rJ 7
o
"--o7
complex. These are Lewis base. (II) Octahedral comp/ex [MX.,(L - L )J, [Ma 3 b 3 ] (fac-
er, H, O, NH, mer isomers).
(a) Unldentate ligand
NH3 NH3
(b) Didenlate ligand NH,CH,CH,N H, , C 2 0;- I co( Jn
EDTA '-
O2N~ / NH3 H3N ' I / N02 e 'L..,-Co ' )
(c) Hexadenlatel /gand : 1,co, Co
(_en en j
(d) Ambldenlale llgand : No,-.scw 0 2 N"-•-~ NH3 02N / I "'-Naz
N0 1 NH3 dex tro Mirror laevo
o Coordination number : The number of atoms of the ligands thal are 2
directly bound to the central metal Fae Mer (ii) Cis-[PtCl 2 (en)J " show optical activity
=
eg. [Fe(C, O,)J>--, here CN 6, [N i(NH,)J'', here, CN 4=
o Homoleptlc complex : Only one kind of ligands are present eg.
[Co(NH,)J,.
® IMPORTANT COMPLEXES
Complei Coordination number [Link] Shape Nature Unpaired electrons
Heteroleptlc complex : More than one kind of ligands are present eg. fCo(NHJ. j 6 d's/1' Octahedral Diamagnetic Zero
[Co(NH,),CI.,T
fCoF. j 6 s{1'd' Octahedral Paramagnetic Four
~,a.j 4 sp' Tetrahedral Paramagnetic
G) NAMING OF COORDINATION CO MPOUNDS , I [Ni(CO)J 4 sp' Tetrahedral Diamagnetic
Two
Zero
[Cr(NH,),(H,O )JCI, Triamminetria quachrom ium(II I) chloride / [Ni(CNJ.r 4 dsp'
1 Sequare planar Diamagnetic Zero
1 ' (Mn(CN). j 6 d'sp'
o K,IZn(OH)J Potassium tetrahydroxid ozincate(f/) Octahedral Paramagnetic Two
[Mn~ 6 sp' d'
J {Nf(CO)J Tetracarbony l nidce/(0) Octahedral Paramagnetic Four
{Fe(CN).i 6 d'sp' Octahedral Paramagnetic One
, {CoCll en),f Dichloridobis (ethane- 1.2-diamine)cobalt.(III) ion. fFeF. j 6 s{1'd' Octahedral
-' [Pt{[Link] 1 CJ(NO,)} Diamminedllo ndonitJito-N-Pla tinum(I/) ___ _ O,).J'"'
[Co(C, 6 ~ Paramagnetic Five
d'so' Octahedral Diamagnetic Zero
:;ERT Maps
Coordination Compounds II!
(j)
CRYSTAL FIELD THEORY (CFT)
According to CFT, under the influence of ligand field, degeneracy of d-orbitals is destroyed and they split into two or more energy levels. The extent of spilliting depends upon the strength of ligand.
OCTAHEDRAL COMPLEXES
1
TETRAHEDRAL COMPLEXES
dxy, dvz, d.,
I. J~ dx2 - y2' dz2 ....-":'l eg
5-1
i ...···
...•····
5
3
6
°
l::
....... 9
~
::·········~·'}'~~tre
Ene,gy1
1··· ·~·~~·····1~, ····............. ......1·········~············1.10
-5 60
··•...
d ••.
xv• dyz, dx;·..
·.::1
[ =========]e
d X 2- y 2,d,
r
Metal d orbitals ~g
d orbitals free Ion ·erage energy of the Splittlng of d orbitals dxy, dyz, d., Average energy of the Splitting of d orbitals
dx2 - / ' dz2 d orbitals in spherical in octahedral crystal
d orbitals In spherical In tetrahedral crystal
crystal field field Free metal Ion crystal field field
© SPECTROCHEMICAL SERIES ® COLOUR OF COMPLEXES @ METAL CARBONYLS
Arrangement of lig~nds in order of increasing field strength . 0 Colour of complex can be explained by d-dtransition Q The metal-carbon bond in metal carbonyls possess both cr and
r < Br- < sew < c1- < s 2- < F- < ow < c 2 0~- < H2 O 10 1t character.
0 Metal atom/ion of cf or d configuration do not show d-
< NCS- < edta 4 - < NH 3 < en < CW < CO Q The M - C cr bond is formed by the donation of lone pair of
d transition . electrons on the carbonyl carbon into a vacant orbital ·of the
0 If 6o < P, complex is high spin and ligand is weak field ligand
o The colour of the complex is complementry to that metal.
0 If 6o > P, complex is low spin and ligand is strong field ligand
which is absorbed. Q The M - C 1t bond is formed by the donation of a pair of
0 l\ = (4/9)6<> electrons from a filled d orbital of metal into the vacant
Complex Colour
antibonding 1t* orbital of carbon monoxide.
@ APPLICATIONS OF COORDINATION COMPOUIN DS [Ti(H 2O)J:i. Violet 0 Metal to ligand bonding is known as synergic effect.
7t*
"'8
[Cu(HP)J,. Blue
Hardness of water is estimated by titration with Na2EDTA
- M: C0~
P
[Co(NH 3) ~ Yellow orange
lo [(Ph ,P), RhCI], Wilkinson catalyst is used for the
hydrogenation of alkenes.
[CoCl(NH 3).j Violet {J)_
CuSO, · 5H.p Blue
, lo Excess of Cu and Fe are removed by the chelating ligands D- Synergic bonding
[Co(CN)er P~leyellow 0
i penicillamine and desfenioxirne B. eg : eg : II
[Ni(HP)J,. Green 9~co 9~co oc, / c ,/co
~ EDTA is used in the treatment of lead poisoning OC - Mn Mn- CO OC- Co - Co - CO
° [Ni(~OMen)r Pale blue oc/ 1 oc/ 1 oc/ '-c / '-co
1 Cis-platin effictively inhibit the growth of tumors. co co II
[Ni(~Oh{en}J· Blue/Purple 0
; , In photography, hypo (N8iS.,O:J solution on reaction with [Mn 2(CO)1J [CoJ(CO)J
I AgBr form (Ag(S.,O,},)~ ion. (Ni(en):J· Violet Decacarbonyldimanganese(0) Octacarbonyldicobalt( 0)
'-
 J
24
-
. ",)
Haloalkanes and Haloar:en·es - ';_/ # - :: .,. !~; . .
-
@ CHEMICAL REACTIONS
G) CLASSIFICATION
M ;,;:;:;:,iliosub,til,t~CH, ~ · REACTION OF HALOALKANF;
~ ~
(a) On the basis of number of halogen atoms (A) Nucleophllic substitution reaction
C2H5X CH2-CH2
I I
CH2-CH- CH2
I I I
lSJ Fe~:ark ) X + o+ 6-
Nu +)c- X~ )c- Nu+ X
-
Monohaloalkanes I I
X X X X X X
Dlhaloalkane Trihaloalkane • Fluoro compounds are not prepared by this method Mechanism : This reaction has been found to
process by two different mechanism.
due to high reactivity of fluorine.
(b) Compounds containing sp3 C- X b?nd : (i) Substitution nucleophlllc blmolecular (SN2) :
(i) Alkyl halides or haloalkanes (R - X) (iii) Sandmeyer's reaction G> _ ©X • The reaction between CH3CI and OH ion to yield
Primary (1 °)
(ii) Allyllc halides

Secondary (2') Tertiary (3°)

(iii} Benzylic halides
(n'T
~
NH2
NaN0 2 + HX )
273 - 278K
6Y
L-8)
N2X
Cu2X2 )
[X=Cl, Br]
0 + N 2i
methanol follows a second order kinetics,
depends upon the concentration of both reactants.
i.e. the
~x ©(x - H
~
H le
~ J<
H,,,H -
(c) Compounds containing sp2 C - X bond:

~v) From alkenes

• Addition of halogen halides

OH + H ,,,,.,1
Hl'-CI
t HO···)~-- Cl
H H
(T.S.)
HO H
+ Ci
AxOX
(I) Vlnylic halides :
crx
(ii) Aryl halides :
~ +H - l ~
• Addrtion of halogen:

I
A + ./"'--.../
Major Minor
1
• Transition state (T.S.) is formed
• Reaction is generally carried out In acetone
polar aprotic solvents
Addition of Br 2 in CCl 4 to an alkene results in (ii) Substitution nucleophlllc unlmolecular (SN1) :
@ METHOD OF PREPARATION
discharge of reddish brovm colour of Br 2 • It occurs in two steps
(a) From alcohols ~ Br2 ~
ZnCl2 ,, ~ ~ r ; Ho- + (CH3)3C - B r ~ (CH3)3 C- 0H+
• R - OH + HCI ~ R - Cl + Hi() CCl4 Br
H,504
Br Step- I lffi B -
• R - OH + NaBr ) R - Br + NaHS04 + Hi() vic-dibromide (CH3)3CBr < > ~ + r
(c) Halogen Exchange Slow
• 3R - OH + PX 3 ~ 3R - X + H3P03 (X = a . St)
~
• Finkelstein reaction : - Step- II
• R - OH + PCls ~ R - Cl+ POCl3 + Ha @ + OH
Fast
> (CH3):iCOH
R - X + Nal - R - I + NaX [X, Cl, Br]
• R - OH Red P/X2 • Swarts reaction :
R- X • Greater the stability of carbocatlon greater is
X2 = Br2, 12
CH3 - Br+ ~F - CH 3 - F + ~Br.!.
rate of reaction
• R - OH + SOCl 2 ~ R - Cl+ S02 + Ha
• SN 1 and S~ order can be generalised as
I (b) From [Link]>ons @ PHYSICAL PROPERTIES
(i) Free radical halogenation • Boiling point of alkyl halide decrease in the order. For S ~ reaction
Cb/UV fight
- Rl > RBr > RCI > RCI > RF Tertiary halide, secondary halide, primary tialidlll
/""'.../
or heat
~ + ---y • Boiling point of 1SOmeric haloalkanes decrease with
Cl Cl
increase in branching For SN 1 reaction
-
~
4
1~ r tJ ,{ :l~t1 c,r'I-
~ r,r,· 1nr1'n.• .. ~ •... .,... ~"-~~.,...-.
.., .....,. .. ._ ·1 ~ •111 ' l ·1
:!.1 ·~~~ ~., •-=~~ l •O •P'_1_S_!f'-..1,. l\,!!l.~! •~J~;•~ L~t!i ! •~'.!'!
• ;-,r:t:-r1:~~~,.,. ~~ ~ ~~ • ~ J ~ . . . ~vr rr---= ,-,:.-
•
i.'. _ ·• -'- =: P· ~ &. C .. f c.,H , t°'.. ii •~ C,,Ji-,
.
i;
.;
,... _1· y
l'
~ l ~ ;
i{ il) ~ ent~ felll ~ o1 "'1,c~ .. IJ il: r ~.-., r +-- - \ ,. •i
l
1 ,I:.~ ~,1, !
.._
wutsfftuttor1 ....._~ w lC ~. ' \
I •
~ •!
1) I
~ ftTmO"'tlm'I co~
~
ly • ~,i,""r ,·f tH ..ff"~ ,-'!°':""1l }WT~ ~ --~~, p
HI o,,ticfll ~Y'ltf
A • 8
-~~~w'"" ,,,..,-..~;. ~ ' M , ~ti ~~;Yi!"-:f ~ ~ .t-i'"'"1 ~ ~t
-,v,- eorn;rov~ ~ ~[Link]~ ol11:-t.. oola<t~ ~ 50- . _.,...
t.e.,1 ~ opticafl\ ad!vt> (~f"•4.-:[Link]•n l
/. ~ >► I i.,i ; t I( , ~
• fl .;i [Link],poJ,O rota~· Pffi~ pol3 •1..oo hghl in ( B ) EJff\1!11a:,,o,, reacoor.s
I) •I
doek~ d..-aci,cn " n. caltoo c:[Link] Br ........,_,, "">,
~ ~~ ~
Ne.
3'\d f' 11 rotat~ •., a-,IJ cloctl W I ~ d1r0ct1011 ft la ~ ~ KOH.\ KO ,"t' ' .,i_... '41t~
callee ~vorotat'ory \4ap' ~t ~: , BlJ;•t,oOf'[Link] .._,,,_.m,,liof\. ~~-o-,,_
(tJ ~ i . r ..-ymmetry, Chlral lty [Link] •[Link] : Saytteff product [Link] l9f'- ,, r,dOH;{> •W f t t A K ~ -:)d£•_• "''• ,I f',>
• rt' t~ spat.31 ;:r-~m~~'"ll o! tour dtfforon1 group~ '-.-0.:'lff>t} I lfl \) HIC') »• n.-.l(){r-.H••~-<-><'. •,O ¼MK>•'
(C) Roaic::uon w,u, motaf
around tti6 060Val cwoo., ,s tot:rsh<tdral then tho ,u!QhO<\uhOfi , 11\(1 ffit')ds>l • ,-,,i,. ;c,.·,.'
~ Pr-tt(lGllJl,on -<i,.t{'
C81'tK>"l IS caHod • . - Y ~C carbon Clry 1\lt\1 Of
/ ' - . . / 81 .. Mg ~ / ' - . . / ~ t o n , ...... ~
~ The compounds """1 ,ch sre ,o., ~...1punmpo:.ablo on
Or1on.:ir<.1 ruuuw11 (ll Wv,tt- rnllq ' dc:ICtlOI>
t!leir m,rror 1m.-;,9es .sre Ch lnil snd an.:1 called
( OrgJ nofrlu!utllc .. .wipu~a'kl j \
e-iBntio mers
~ ~}[~·~
lQi
;::"'->r
RMgX • H,O ~ Rt-I • MlJ (Ot>H,-.. ~ Nu r ·v ( - ->
,, Tne S1erao1s omer-s having no mirror 1ma9a ► l •t cJfOL .... C.,, l
re lationsh ip ar:e called d l••[Link]& I• c.., q i,- -1 c, I tt • 1· ••• ,., • ( 11) FttuO 1.-[Link]
• A m [Link] contammg tw o enanUOfnSf'S tn equal (A ) N uc ..ophll l4. &ube utu iloo J\ryl " " 11uu.. v,m,,11nt1ly
'
, 11 0
proport,on s w ul have [Link] opoca.l [Link] Such
rru,:wre is lm own as racem lc mixture
l&S8 reactt'\/~ loAJ{ U;:, nu1.l1Joph1l1 1.; ~ubi:,OlUlttJn f oQ<.,II0111b
due to folfio'wt'1Q [Link] ..
2 (Q) . 2 N.. t:Jf\ut, ~ (QJL01
(c) Retentio n : In genera l, 1f dunn g a reaction , n o (1) R~ U tftjCt Lll1lc;I l)Jlf or chlorin.; It, Ill 0 1pncflyl
bond to the [Link] tre 1s b roke n , the [Link] is conJU9a1Joo w1lh b,;[Link].a [Link] ung 1n doublt3 bond ' v i,; II,,i .. •] y " , r" iJ•H ll I t i ·,
hy
said to proceed w ith retention o f configurauon character o l C - C l bond As a resul t bono cleavage ol -,
fH 3 CH3
in haloa1ene 1~ d 1ffieult
2CHCt, ~ 2coc1.i
... ~ ..., ~ 2H C t
i /:1 f (11) Di fferenc e 111 [Link] o f carbon atom in C- X bond
H j - CH 2 - 0H + H CI ~ H - , - C i-i 2 - C l • H .-0
CH~
(ii i) Ins tabili ty of phenyl c allon
CH2
I I (1v) Repu lston be twe en haloarene and appro d c h ing
CH 3 C H3
( + )- 1-ch loro-2-m e thylbutane nuc leoph1 le
H -2-rnethylbutan- 1-ol
 25
C hap ter
Alc oh ols , Ph en ols an d Eth ers
,. @ PREPA RATIO N OF PHENO LS l• A cidity of alcoho ls : A cid ic streng th o rder ==- ~
R"-.
CD PREPARATION OF ALCOH OLS R
R-CH, OH >R)CH OH > RR""CO H
(i) From alkene s (a) From haloare nes OH
Cl ONa ' l~
(a ) By acid catatys ed hydrati on :
➔o
Acidity of pheno ls P he no ls are more acidic. than alcoho
CH,CH =CH,,+ HcO
H+
»CH,-y H-CH,(Maj or)
V
A + NaOH 623 K
300atm
➔V
0 ____!:i9
~ 0 0
ise.t
conju_llate base of ph eno l (p h eno xide io n ) is resona nce stabir
O- o::,
(b) By hydrob orat:ion - oxidati on OH
CH,-CH =CH_+ (H-SHJ, ➔ CH,-C H -CH2-BH2
1
~CH,CH =CH2

(b) From benzen e sulpho nic acid

SO,H
~
A , (i) NaOH A ,

OH
~ u -Q7- cQ--O-O
0
Oleum
. _ .9H,CH =CH 2 ,
(CH,C H ~ C H,CH2CHJ 2 BH
2
➔ v(ii)H' ➔ v (ii) Esterif ication : H+
Ar/R-0 -H + R 'COOH ~ Ar/ ROCO R' + H2 0
H,0!3H ,0/ 0 H
3CH,C H,CH,O H + B(OH),
• The alcohol formed looks as if it has been fomied
by the ad<frtion of water to [Link] in a way opposite ( ) HCI
NH, NaNO,
>
o~Cr
(c) From diazon ium salts+
H,O ➔o
OH
A oH
V
COOH
+ (CH,C 0)20

Ester
H
+
>
A
V
COOH
ococH,
+ CH, COOH
to MarkovrnlcoV's ruJe. 273-27 8 K b
(ii} From carbon yl compounds (d) From cumen e Salicyl ic acid (Asprn n)
H,C-
(a} By reduction of aldehydes and ketone s : CH(CH3)2 Hl C __.......C-0- 0H OH (b) Reacti ons involvi ng cleava ge o f C - 0 bond in alcoho
ls
RCHO + H2~
RCOR' NaBH,
>
RCH,O H
R-CH- R'
I VA O, > 0
V H'
H,O
➔0 + CH3COCH,
V
(i) Reacti on w ith h yd rogen halide s : (Lucas test)
•
ROH + HX ➔ R- X + H 2 0
Lucas reagen t (Cone. HCI and ZnCl2)
OH Cumen e
Cumen e •Tertiar y alcoho l produc e turbidity w ith Lucas reagen t imm
hydrop eroxide twa
•Primar y alcoho ls do not produc e turbidi ty at room tempera
(b) By reduction of carboxy1ic acids and esters :
(
@ PHYSICAL PROP ERTIES (ii)Reaction w ith phosp horus trihalid es :
(i) LiAJH,
> RCH,OH 3R- OH + PX3 ➔ 3R- X + H 3 P03 (X = C l, Br)
RCOOH (ii) H,O • High boiling points of alcoho ls are mainly due to the
presen ce of intermo lecular hydrog en bondin g in them . (Iii) Dehydration : C 2 H 5 0H ~;~ > CH2 = CH2 + H2 0
RCOOH ~?H > RCOOR' p~' > RCH, OH Solubil ity of alcoho ls and phenol s in water Is due to their
Relativ e ease of dehyd ration : Tertiar y > Secon dary > Pri
•
/ / (iii) From Grignard reagent + R'OH ability to form hydrog en bonds with w ater. .J (iv) Oxidat ion
HO
HCHO + RMgX ➔ RCH, OMgX ~CH,O H CrO3
@ CHEMICAL REAC TIONS : • RCH,O H > RCHO
1° alcoho l
(Al Reaction of alcoho ls PCC
• CH,-C H=CH -CH2 0H > CH,-C H=CH -CHO
RCHO + R'MgX ➔ R - yH - OMgX H,O .:J., l(a) Reactio ns involvin g cleava ge of 0 -H bond CrO3
R' R - 9H - OH
(i) Acidity of alcoho ls and phenol s • R- CH-R ' > R-C-R '
• Reactio n with metals _ + I 11
OH 0
R' 2° alcoho l 2R-O- H + 2Na ➔ 2R0Na + H 2
R • Pheno l reacts with aqueou s NaOH • RCH OH 2
Cu
.,..,.,. ,,.> RCHO • R-CH -R' Cu >R-C--R'
I H, O I 573 K I
RCOR + R'MgX ➔ R - C - OMgX OH ONa 0
C H, OH
O•NaOH---➔ O•H,O
I R .:J.,
R' I I Cu ·
R-9- oH • C H J-C-OH >CH -C=C H
3 2
I . 573 K I
<>frnhnl R' C H, CH.
NCERT Maes Alcohols, Phenols and Ethers NJN
?!
[Bl Reaction phenols. : . @ PREPARATION OF COMMERCIAL LY IMPORTANT ALCOHOLS Mechanism :
o~
(a) Electroph1hc aromatic substitution CH3
. Zn0-Cr2 0 3
(i) Nitration : Methanol : CO + 2H,---_.;..-" --~ CH,OH C + CH3 OH
OH OH 200-300 atm C H , ~ H; Slow > (CH)3 3
6
573-673 K Stable carbonium ion
6 2 CH,
lnvertase
•
Dilute ) N0
+ Ethanol : C 12H 220 11 + H, O > C 0 H 120 8 + C 0 H 120 0
(CH3)3C + r FaS
t > (CH3)3C - I
HN03 ~ Glucose Fructose
Zymase
> 2C,H,OH ·+ 2CO, (ii) Electrophllic substitution
OH
02N◊N0
OH
2
N02
c . H ,,o .
• Ethanol is made unfit for drinking by mixing in it some copper
(a) Halogenation
OH,
•
6 OH

C
H~~- >
3
I
OH

~
NO (Poor yield)
2 OH

(Picric acid)
sull)hate and pyridine. II is known as denaturation of alcohol.
Preparation of ethers
@ ETHERS
(a) Dehydration of alcohols : CH 3CH, OH
H so
4
~ ~
3
> C 2 H, OC2 H 0
6-.?
OCH3
Br in
Elh~no;c ac;d >
Br

O H3
I
~
,<" + I
~
,<"
M ino r

Br
ON◊NO
.() Cone. >
H 2SO,
Q S03H
Cone.
HN03 ➔

2
I
A

--..;: 2
(b) Williamson synthesis : R-X + R' - ON~
• A lkyl halide is primary

5 2
H > R-0-R' + NaX
• Al koxide ion can be primary, secondary or tertiary.

M ajor
(b) Friedel-Crafts reaction :
• Alkyla tio n
l NO, CH 3 .-----------_
I.=+~/!.
~ CH 3
I
@}
OCH,
CH,CI anh~':,~1c1,,
~ H,
0
Q
(Ii) Hoalogenation OH OH CH,-C-ONa + CH,-Br-->- CH,-C-0-CH,
I I
Br2 inCS 2 ➔ ~
-.::::: -.::::: Br CH, CH 3
• If tertiary alkyl halide is used, then only alkene is formed . H3
•
273K ~
+
V CH 3
I - +
Major
+
r (Minor) CH,-C-Br + CH,-ONa --->- CH 3-C=CH,
(M ajor) I
CH,
Chemical reactions :
I
CH 3
@J 0
CH3
•O :6 OH
'
➔
B v c :B r
I (White ppt)
~

(i) Cleavage of C-0 bond in ether : R-0-R + HX ➔ RX + R-OH

• The order of reactivity of halogen halides HI> HBr > HCI
• Cleavage of ether takes place with concentrated H I or HBr
• Acylatio n M in o r
H,
@
OCH 3
r at high temperature.
(b) Kolbe's reaction : 2, 4 , 6-Tribromophen ol Example 1 : Excess anhyd>
1 1 @ • C H,COCI A ICI,
CH 3-Q-C 2 H, HI ) CH,-1 + C, H,1
O OH OONa OOH COOH
NaOH) I --=::: Q_) C?1➔ ~ I - ~ A_.,,_ H - 0 CH,
~ (11) H ~
S tep-1 : CH, -2--CH2 CH, + H-1 ~ CH,-9--CH,CH 3 + I Maj or
j -
+
(Salicylic acid) ~ H SN2
(c) Reimer-Tiemann reaction
OH - a+
ON ONa+ OH
S tep-2: f + CH3~ H2CH 3 ~ CH,-1 + CH,CH 20H
AA_
lSJ
~ ~ >~
-CH3
6
CHC HO CHO
CHCI,
aq. NaO V NaO~
v- H.
V Ste p<3:CH, CH2 ~Jr E > CH3CH ~H + I
2 2
(c) Nitration : M inor
Step-4: ~
0 Q
+ S 2 OCH, H, 11
o
(d) Reaction with Zinc dust and chromic acid [Link]
T + yH2~ H2 ~ CH 3CH 2-I + H20
0 OH.
A
V H,SO,
➔
NO,
I
-.:::::
~ ~
0
CH, CH +
Na, Cr,0 7 3 HNO, o I
I
H, SO, V +ZnO I
Example 2 : CH,-C-0-CH, + H I ~
I
S 1
CH,OH + (CH,)3C-I Minor NG,
~L1jor
l
0 CH.1
LB~nzoqu,none)
 26
Aldehydes, Ketones and Carboxylic Acids Chapter
ALDEHYDES ANO KETONES (ii) From nitriles
>=o•C:
NMgBr R 0
G) PREPARATION OF ALDEHYDES
(i) From acyl chlorides (Rosenmund reduction) CH 3CH 2C = N
PhMgBr
Ether
II
•CH 3CH 2- C - Ph
HClgas
<... dilHCI
,
X 0
J+H20
XO H30 ·
0
II
R
Ketone
R
Ketal
u
~I H2
Pd-BaS0 4 llJ
A
0
II

~ H 3CH 2- C - Ph
(iii) From aromatic hydrocarbons o
anhyd. )=o+H,N=Z ~~ (:J>C=N-Z+H,O
o
(ii) From Nitriles and Esters
Stephen reaction
V +R - C - CI AJCl3
H30 + (d) Addition of ammonia and its derivative
RCN + SnCl 2 + HCI --+RCH = N H - RCHO
G) CHEMICAL REACTIONS Z = alkyl , aryl , - OH , - NH 2 , C 6 H 5NH etc
(Reduction by DIBAL-H (i) Nucleophilic addition reactions
~ (i) DIBAL-H ~ _ Reagent Carbonyl derivative Product name
(a) Addition of hydrogen cyan ide (HCN)
CN (ii) H20
'&-~ f,' /J- ~ f,' JJH
• ' - 'CHO
f. =O+ N~ ~ Ammonia lmine
~
~ O C2H 5 (i) DIBAL-H >=NH
O (ii) H20 CN CN
0 Cyanohydrin Schiff's base
(b) Addition of NaHS0 3 Amine >=NR
(iii) From Hydrocarbons
a Etard reaction \_., \. j303H
+ NaHS03 ~/ \ _ Hydroxylamine >=N - OH Oxime
1
x0
CH 3 . CHO
ONa
6 + Cr0 2Cl 2
~
·

2
I ...-::
(Chromium
Complex)

3 · o
..,_ CH(OCrOHCl2)2 ~
s ..,_
I ...-:: Proton
transfer
OH

3Na Hydrazine >=N - NH 2

Hydrazone
N0 2
o Gattennan-Koch reaction (Crysta lline)
CHO a Bisulphite addition product is crystalline 2,4-DNP >=N - NH - @ - N02 2, 4- Dinitroph
~ CO, HCI o It is water soluble and converted back to orig inal carbonyl
hydrazone
V [Link] CuCI compound by treating it with acid or alkali
0
II
Semicarbazide >=N- NH -C-NH 2 Semicarbazone
a It is useful for separation and purification of aldehydes .
G) PREPARATION OF KETONES (c) Addition of alcohols :
(i) From acyl chlorides (ii) Reduction
OR' OR' (a) Reduction to alcohols. : Aldehydes and ketones
2R - Mg - X + CdCl 2- R2 Cd + 2 Mg(X)CI R'OH 'R - CH / ~ /
RCHO s:--;-;:_, ~,~ "-oH ~ " - CH reduced to primary and secondary alcohols respe
0 0 H "-
OH
II 11 by NaBH 4 or LiAIH 4
Ald ehyde Hemiacetal Acetal
2R' - C - Cl + R, Cd ---+2R' - C - R + CdCl 2 {b) Reduction to hydrocarbons
-
NCERTMaps
-

Aldehy_des, Ketones and Carboxylic A cids

E
,-
>=o 2
~ ~ 1H
9 • )+ H O (Clemmensen reduction)
2
(ii) Cross-aldol condenstation (c ) From nitrites and amides
0
II • -
.-, CHO 0 R- CN H·or o-H R- C- NH H orO H RCOOH
•>= ©•®+®-CH= CH J-@
KOH/ OH OH t . ~o 2 ~
NH, -NH2
>= Q HCI N - NH 2
(Wolff-Kishner reduction)
6 >+ N2 I
CONH 2 COOH
(iii) Oxidation Other reactions @ H:o• @ + N H3
0
Aldehydes are oxidised to carboxylic acids on treatment (v) Ca1:mlzzaro reaction o
with common oxidising agents like HNO3 , KMnO 4 , (d) From Grignard reagents
2HCHO Cone~ KOH CH OH + H -
3
~- O_K+ 0
K2Cr20 7 etc. Dry II - +
Mild oxidising agents (Tests of aldehydes) R - Mg - X + 0 = C = 0 ~ R - C - 0 Mgx
0 CHO CH 2 OH COO- Na+
,Tollen's test : Silver mirror is formed on warming
ai dehyde with freshly prepared ammon iaca l ,@=o,-•OH @+@ . (e) _ From acyl halides and anhydrides

Hc,o· R - COOH
AgNO3 solution (Toi/en 's reagent)
(vi) Electrophilic substitution reaction
RCHO + 2 [Ag(NH 3 )i( + 30H ➔ RCOO- + 2Ag RCOCI~ R - COOH + Cl-
CHO CHO HO
2H 2 O + 4NH 3 (C6 H 5 CO)iO...:..=.+ 2C 6 O 5 COOH
6 .HNO,IH,so.
Fehllng's Test:
o On heating aldehyde with Fehling's reagent, a reddish
l2J 273-283K
®NO, (f) From esters
COC 2H 5 COOH
@~@+c,H,OH
brown precipitate is obtained.
1
R - CHO + 2cu2+ + SOH➔RCOO-+ Cu 20 ,I..+ 3H 2 O G) CARBOXYLIC ACIDS
(red-brown ppt)
o Methods of Preparation
o Aromatic aldehydes do not respond to this test 0
(a) From primary alcohols
Haloform reaction :
Oxidation of methyl ketones
0 0
RCH 2 OH
(i) alkaline KMn0 4
(ii)H,0
• RCOOH

~ /'.... NaOH
Ethyl
0
butanoate
~ CH 3 CH 2 CH 2 COO- Na + C 2 H 6 OH
tH 30•
\
II X2 II _ +
CH (CH ) CH OH cro3 - H,so.
R - C - CH _ _.___ R - C - 0 Na + 3 2 6Jones reagent
2 CH3(CH2)sCOOH CH 3 CH 2 CH 2COOH
3 NaOH
CHXiX = Cl, Br, I) Butanoic acid
(b) From alkylbenzenes
o lodoforrn reaction with lifNaOH is used for detection of
CH 3 CO or ~H 3 CH(OH) groups
CH 3CHO group on oxidation.
which produces CH 3
@KMoO,-KOH
COOK
01~@
COOH
o
I

@ PHYSICAL PROPERT\ES
Due to extensive association by intermolecular
H-bonding carboxylic acids have higher boiling point than
'
(iv) Reaction due to a-hydrogen
aldehydes, ketones a n d a lcohols of comparable
(i) Aldol condensation reaction :
A COOK COOH
@H,0• @
molecular mass.
2CH3 - CHO =====~
NaOH '> dil.
CH 3 - CH - CH 2
I
- CHO
LSJ KM•Or KOH o In vapour phase or in aprotic solvent most carboxy\ic
\
OH
~ CH 3 - CH = CH - CHO 1 acids exist as dimer
- H2 0 \
 ).
.'-
Aldehydes, Ketones and Carboxylic Acids NCERTlJ.
--._;_;__ "I,
(c) Reactions Involving - COOH group
@ CHEMICAL REACTIONS (b) Reaction involving cleavage of C-OH bond
(i) Reduction
Reactions involving cleavage of O - H bond (i) Formation of anhydrides
(1) LiAJH,/ether or B2H6
(Acidity) RCOOH • RCH20H
(ii)H30
2RCOOH + 2Na ➔ 2RCOO-Na• + H2 0 0
//
CH 3 - C +
\
\\
C - CH 3
I
~·:6 -1<} 0
(ii) Decarboxylation
RCOOH + NaOH ➔ RCOO-Na• + H20 P 0 ,/6
2
Elhanoic anhydride
OH HO RCOONa NaOH & Cao R - H + N8 CO
6 2 J
RCOOH + NaHC03 ➔ RCOO-Na ++Hp+ CO 2 i
(ii) Esterification (d) Substitution reactions in the hydrocarbon part
arboxylic acids evolve CO 2 gas on reaction with NaHC03.
RCOOH + R'OH ~ RCOOR' + H20 (i) Halogenation (Hell - Volhard-Zelinsky reaction)
'his is used to detect the presence of carboxyl group in an
X
>rganic compound . (iii) Reaction with PCl 5, and SOCl2 (i) X/ Red P I
RCH 2 - COOH (ii) HiO R - CH - COOH
:::arboxy\ic acids dissociate in water to give resonance X = Cl, Br
RCOOH + PCl5 ➔ RCOCI + POCl3 + HCI
stabilised carboxylate anions and hydronium ion
RCOOH + SOCl 2 ➔ RCOCI + S0 2 + HCI (ii) Ring substitution
R-COOH + H20 ~ Hp+ R-C.-.R-CI\
+ tr! /tii }?
= R - C( -
(iv) Reaction with ammonia o Aromatic carboxylic acids undergo electrophil~
tb (o 'a - + CONH 2 substitution reaction
> Effect of substituents on the acidity of carboxylic acids : O
COOH
+ NH _.
3 .,-

OCOONH~
I
Ammonium
benzoate

/.
6
~ ,.... I
-H,O :-....
Benzamlde

o They do not undergo Friedel-Crafts reaction because

the carboxyl group is deactivating and calalysi
aluminum chloride gets bonded to carboxyl group
O Electron withdrawing group (EWG )
@§)-/4: stabilises carboxylate anion and increases
O acidic stength COOH
-+ ·
©rCOONH4
,, Nitration
(Phthalic acid) + NH3 === Q _ +
© r COOH COON~ COOH COOH
0 Electron donating group (EOG) destablises
~4 the carboxylate anion and decreases
O acidic strength

Ammonium
phthalate
A
~
Conc. HNOi
Cone. H2SO,
N02
o Acidic strength order of some carboxylic acid
CF,COOH > CCl,COOH > CHCl,COOH > NO,CH,COOH>
0 +-"',OJ o Bromination m-nirtobenzolc acid
NCCH,COOH > FCH,COOH > CICH,COOH > BrCH, COOH >
(Phthalimide)~ --: NH ~ Q CONH2 COOH COOH
~~~~~~
HCOOH > CICH,CH,COOH > C,H,COOH> C,H,CH,COOH >
6~
/, . - ~
heating CONH2
CH,COOH> CH,CH,COOH O Ph thalamide
Br
Direct attachment of groups such as phenyl or vinyl to the cartxixylic
m-bromobenzolc add
acid increases the acidity of corresponding cart>oxylic acid,
Contrary ID the decrease expected due to resonance effect
J
 27
Chapter
Amines
G) CLASSIFICATION (Ill) Reduction of [Link]
@ CHEMICAL REACTIONS
- --·--1
(I) Basic character of amines
R R ..._ R- C N llAIH , R - CH 2 - NH 2
,., Order of basclty of amines in gaseous phase: l
RNH 2 'N - H N - R" Ot H ,INI or N;1{Hg)IC 2 H~OH
R' .., R',... tertiary amine> secondary amine> primary amine > NH 3
-7~
(Iv) Reduction of amides
Primary Socon d ary Te rtIary
0 <> Basic nature of amines In aqueous medium :
(1 " ) (2 " ) (3 °) LI (l)UAJH ,
s are said to be simple wh en all th e alkyl groups are R - C - NH 2 f•J H,o R - CH2 - NH2 (a) (C 2 H 6 hNH > (C 2 H 5 hN > C 2 H 5 NH 2 > NH 3
0 I e
Amn ,
samo ond mlxod whon they are dilloron t. (v) Gabrle l phthallmldo Synthosl.s
(b) (CH 3 )iNH > CH 3 NH 2 > (CH 3 hN > NH 3
@ NOMENCLATU RC:
CI o=)-
0 ...,._ 0 0 o Aryl amines are less basic than alkylamlnes because in
arylaf'lllne the lone pair on nitrogen is Involved in
NH, NH -~.. (1 ~ y-"-'+ R
resonance .
A CH ~ NH - CH7C H , I ti' \
I
Propon-2-omlno N -mothytathonomine O O O (II) Alkylatlon
N (CH , ),
I.
~ .- COO R- NH7 ._J Nom1(oq) R - NH 2 + CH 3 - Br - RNH - CH 3 + HBr I
l
~ NH ,
Propon -2-cn·- 1-on11nu N . N -D i mou, yl l)():1\2 enomina
l
1 pnmruy amine

ll COO + ( 1 • -a m \n e)
~ [Link] mothod is useful in the prep aration of aliphatic
r:::; ( NH.i

(Ill) Acylatlon
C H NH 2 + CH 3
2 6
••
-
O
II
C - Cl
Ba
~ C2 H 5 - NH - C - CH 3 + HCI
II
0

I
I
(I} PREPARATIO N OF AMINE6 ., Atoma tic primary amine \ ~ is not prepared by (Iv) Carbylamlne reaction (chemical teat)
(I) Red·u ctlon of [Link] [Link]·s
th i s method bec au se a rylh a li de donot undergo R - NH 2 + CHCl 3 +3KOH ~ R - NC + 3KCI + 3H 2 0 \
H,""1 [Link] reactio n . It is used as a test for primary amines
o. PhNO, ~ P h NH ;
(vf) [Link] brnmamlde di:!grad.a-tlon reaction (v) Reaction with nitrous acid (With primary aliphatic amine) · '
51\hiO 0
b PhNO , ---♦ PhN H . I
• ""F~ •HICI • R - NH 2+ HN02 NaNO?,. lR - ~ 2cq H,o,. ROH+ N 2+ HCI
R - C - NH.i + Br2 + 4N aOH _ . R - NH2 + Na2 C0 3 HCI
(U) M\monotyals of Alkyl H aHdecs + 2NaBr + 2H 2 0
.:"'\. ~ . (vi) Reaction with arylaulphonyl chloride
.._,._--..., , Primary [Link] formed contains one carbon less than that
~'H,~"'R - X - - RNH .,X - - - R,",/r._ (Hlnsberg's reagent)
. presert n the amide .
,., Reaction with primary amine
R., '-i R, N.X
. ~ R !'~ H R., R ,N l'h Q u a • ~•
, •• , - {'r\ - - (3') - -~-- - , © PHYSICAL PROPERTIES PhS02CI+ C 2H 5NH2- PhS02NHC, H 5
· ammonA-ITI Sa.1.
, ~ and other arytamines are usually colourless but lSoluble In all<aft)
-\.~ . . . _ . has ~an-:age al )'elc.'°9 a mtX:ture al gei caour on swrage due to atmosp he ric oxidation ) Reaction with secondary amine
~ - ~ ~ [Link] and a:.s.o qua~emary , Lower aliphatic amines are soluble in water because they
~~~ PhS0 2 CI+ (C , H 5 ) 2 NH-- PhS0 2 N (C,H ~}:
torm hydrogen bonds with w a te r molecules .
(1nsolube, In a,'nl,")
r.'~-a;,..T- -., a ~ as map p,,ocue1 ~ 3ki.-,g large , ()rde( ot [Link] poinis o f isomeric amines: P ri mary >
, Tertiary amines do n ot rea c t w ith banz-ansul~'t1c,, \,, '
....
~ , 01 ~.-;"', ' Secoc Ida y > Tertiaf'/
chlorides .
d:I Biomolecules
NCER~
- - - - - - - - - - - - -~
@ POLYSACC:[Link] @ VITAMINS
@ DJSACCHARJOES These~
Amylase ( 15-20% of starch) (i) Fat soluble vitamins: vitamins are soluble in fat
, Two monosaccha rides are joined together by an oxide (i) Starch - { vitaminsA, D, E and K.
linkage formed by loss of water molecule forming a . Amylopectin (80-85% of starch)
(ii) Water soluble vitamins: 8 group vitamins and vitamin
disaccharide. Such a linkage between two monosaccha ride -o Amylose is water soluble component . It is long are water soluble vitamins.
units through oxygen atom is called glycosidic linkage.
unbranched chain with 200-1000 a-D-(+) glucose units. Deficiency Diseases
(i) Sucrose Name of Vitamin
o Amylopectin is water insoluble component. It is branched Xerophthalm ia
1 1. VitaminA
HOH2 C chain polymer of a-D-glucose units.
2. Vitamin 8 1 (Thiamine) Beriberi
0 (ii) Cellulose
5 0 It is a straight chain polysacchar ide 3. Vitamin 8 2 (Riboflavin) Cheilosis
4 1
o It is composed of P-D-glucose units 4. Vitamin 8 12 Pemici9us anaemia
Glycosidic 4
(iii) Glycogen 5. Vitamin C (Ascorbic acid) Scurvy
H OH linkage 'J It is called animal starch. 6. Vitamin D Rickets (in children)
OH H osteomalac ia (in adults)
o Its structure is similar to amylopectin and is rather more
a-O-glucose P-0-fructose
_____ _____
highly branched . _____________ ) 7. Vitamin K Increased blood clotting time
<> It is dextrorotatory
o It is non reducing sugar @ PROTEINS @ [Link] ACfDS
(ii) Maltose o All proteins are polymers of a-amino acid o Complete hydrolysis of DNA (or RNA) yields a pentos
6 ~ The amino acids which can be synthesised_in the body, sugar, phosphoric acid and nitrogen containing
6
CHpH CH2 0H
are known as non-essential amino acids. heterocyclic compound (called bases)
o The amino acids which cannot be synthesised in the body o In DNA molecule, the sugar moiety is t}-D-2-deoxyribose
and must be obtained through diet are known as essential whereas in RNA molecules, it is t}-D-ribose
0 amino acids. 5 5
o In aqueous solution, the carboxyl group can lose a proton HOH24 C0 w~H HOH24 C0 w~H
H H OH and amino group can accept a proton, giving rise to a
H H H H
a-D-glucose a -D-glucose dipolar ion known as zwitter ion H H H H
0 0 3 2 2
o It is dextrorotatory II 11
o It is reducing sugar R - CH - C - OH ~ R - CH - C - 0 -
OH OH OH H
o It gives positive test with Tollen's reagent and Fehling's ~H ~H (Zwitter ion)
2 e J /3-D-ribose tJ-D-2-deoxynbose
solution
(iii) Lactose Structure of Proteins o Bases in DNA: Adenine (A), guanine (G), Cytosine (C)
and thymine (T)
o Proteins can be classified into two types on the oasis of
6 6
CH 2 OH CH 2 OH
their molecular shape o Bases in RNA: Adenine (A), guanine (G), cytosine (C)and
(a) Fibrous proteins: uracil (U) 0
5•
n s·
0 o The polypeptide chains run parallel and held together by
HO-H2C w oBase -o - r_-O - H2CwoB'~se,
hydrogen and disulphides bonds giving fibre like structure
o They are insoluble in water e.g. keratin, myosin
4' 1' 0 HH
H OH H OH (b) Globular proteins: H H H H
!3-D-galactose P-D-glucose 3' 1
o In this case polypeptide chains coil around to give a
It is dextrorotatory and is a reducing sugar spherical shape
HO OH HO OH
It reduces Tollen's reagent and Fehling's solution o They are soluble in water e.g. insulin, globulin nucleoside nucleotide