1-~ I I I

.....nlc Chemistry : Some Basic Principia and Techniqun

90,.-

. ffect are of two types • Greater the number of alkyl groups attached to a positively
rice
,..AtOf1'1e this effect, the 1t-electrons of the multiple charged carbon atom, the greater is the hyperconjugati on
I
1
ir effect nnsferred to that atom to which the reagent
• -t dare tra
interaction and stabilisation of the cation.

i,o'1 ttached.
gets a •, Cc/ + H+ --+ '-c+-c✓ Marks Maximizer
• /c '
(Attacking
/ I'
reagent) H • No. of hyperconjugation structure s No. of alpha hydrogen +1
• Species that behave as an electrophile as well as nucleophiles
eet In this effect the 1t-electrons of the multiple are known as ambiphiles (ambidents) .
..E eff transferred to that atom which is attacked by e.g.
• dare
i,on mical reagent.
...eche
v• 'c ('>le( + cN- --+ ~c-c( ;5
,··=ot
'-.Nuc:Jeoph1le

/ (Attacking I Electrophile
CN
.. ..
reagent)
• Charged : Hp•
..
n inductive and electromeric effects operate in
,.ate :::osite directions, the electromeric effect predominates. .. -
•Neutral: ROH,HOHand RNH2

·H perconjugation Types of Organic Reactions and Mechanisms

Y.
It invo
Ives delocalisaiton of cr-electrons of C-H bond of Organic reactions can be classified into the following categories
• lkyl group directly attached to an atom of
• Substitution reactions
an aturated system or to an atom with an unshared
unsa • Addition reactions
p-0rbital.
• Elimination reactions
• It is a permanent effect. .
• Rearrangement reactions
. also called no bond resonance.
• It IS •

Methods of Purification of Organic Compounds

•=
The common techniques used for purification are as follows
.Me;hods

erystallisation
-- • ;rinciple •

It is based on the difference in the

• , Process

• In this method, a hot

concentrated solution
Applications

Sugar having common salt as impurity

can be crystallised through hot .
,. j

solubilities of the compound and

the impurities in the suitable of the compound is ethanol as it is soluble in hot ethanol
solvent. prepared. but common salt does not
• This gives the crystals of the
pure compound upon filteration
and cooling.

This process is employed to In this process, the impure solid Impure samples of naphthalene,
Sublimation
separate sublimable compounds is taken into China dish and on anthracene, camphor, benzoic acid,
from non-sublimable impurities. heating, the solid changes to NH4CI, dry ice, salicylic acid can be
vapour without converting purified by this process.
into liquid phase and the
vapours upon cooling give back
the solid.
 Mlll8flflF.IIIICI
. - -
J,rVQ"81illtij ll
--~ II

r-M_;; s
- -- ------- ------
Applfcatfons -....,
Prlnclple
Distillation • In this process, vapours of • Separation of mixture of he.a,, • •
• It is based upon the large
difference in the boiling points of . liquids in the mixture formed (b.pt. 342 K) and toluene (b. Pt ~
3
two liquids or two components. separately on reaching at their ~-
. boiling points.
• It is generally used if an organic • The vapours on cooling • Separation of mixture of chlo
liquid contains a non-volatile , . , condense to give back the (b.~t. 334 K) and aniline (b.pt,r~~orrn 7
• • ' ' original liquid in its pure form. . • ~-
... .. .. -
• impurity.
..... - .. . . .... --- - .... -
·- - .. ·- - ....... --•-·····-- ---· - --- ......-- • • .. - .................. __
Fractional distillation • This method is based upon the • The distillation is carried out • A mixture of acetone and
separation of two liquids having • with the help of specially • ' . methyl alcohol is separated by th'
nearly equal boiling points. designed fractionating columns. process. is
• Vapour of the liquid with higher • Chemical compounds are • Separate different fractions of
boiling point condense before the separated by heating them to a oil i~ petroleum industry. Cl'lJcfe

vapours of the liquid with lower temperature at which one or

boiling point. more fractions of the mixture
will vaporise.
Distillation under • ••• i~.i~·~s;d·f~~ ~h~s;·iiq~ids.~hi~h ••••• u~-d~·r r~d~~;d-~~~;~~~~:·th~··-····-;;·;2 m;;;Hg p;;~;~~;:·~~~;;,--.
reduced pressure have very high boiling poin~ and .'. liquid will boil at low boils at 453 K without decomposition
decompose at or below their temperature. and can be separated from spent-lye
boiling point. . in soap industry•
.. ___.._,.. ______ .,______ .,~-- ............. ..:... -·--- -- ' .............................................__ , - .... ~......... -........ - . _.... -· .... - --------·· ···----------- --------·---- ------- ---- ------·-·-------·-------.... _
5team distillation It is used for steam volatile • Compound is distilled with A~iline is separated from aniline water~·-
substances which are immiscible steam under reduced pressure mixture. •
with water. - at a ter:nperature below 373 K.
• Pure compound comes out with
• •, . i , •. '. , steam and separates on cooling.
Diff~~~~;i~,·~~;~~i~·~·· ·······T~o-·i~;;i~-~ib1~·jj~~;d;·h~~;····:,••••••••••Th~-;~·~;;io~-~f~ ;;~;~;~-···-···· ··s;nz~i;~;d-~·;p~~~~ fr~;·;a~; ~
different solubility in a solvent compound from its aqueous using benzene.
forms different layer. solution can be carried out by
shaking it with an organic solvent
in which the compound is
• • insoluble.
• - It is based ~pon the principle of • In this process, the stationary •For~;p~r~ti~~~f s~~;~ and·;;ino ___
• Chromatography
distribution of components of a • . phase can either be solid or acids.
given organic mixture between two liquid supported over a solid. A
phases, i.e. stationary phase and pure solvent a mixture of
mobile phase. solvents or a gas is allowed to
move slowly over the stationary
phase. The moving phase is
called mobile phase.

Adsorption chromatography • Differential adsorption of the . • Mobile phase is allowed to • Silica gel, cellulose microcrystalline
various components of a mixture move over a stationary etc.
on a suitable adsorbent such as phase (absorbent) the
silica gel or alumina. ' components of the
mixture move by varying
distance over the
statio~ary phase.
Column chromatography • The mixture is passed ~hrough • It consists of a stationary • Mixture of naphthalene and
adsorbent packed in glass tube. solid phase that adsorbs benzophenone.
and separates the
compounds passing
through it
 , I 1 I I I I I I I I I

-- - .
• The mixture ls passed over • Amino acids can be detected by
~
•
1 ... -"'
• • ,,,, ...
•• ·iography
1
adsorbent on a thin glass plate
(about 0.2 mm). •
• The stationary phase is
applied on the surfac e of spraying the plate with nlnhydrln
I i,'I" thin glass plate then pour solution.
~ t~e mobile phase into the • The relative adsorption of each
TLC. component of the mixture ls
expressed In terms of Its retardation
factor. ..... -
1 ■ - .. .. - .. ... .. ... - ...... ■ . . . - • - 4 .. ■• .. - • • - • ..

: . • to9raphy • lt_is based on ~o~ti~~ou~· • •• • It mainly includes paper • For separation of sugar s and amino
_1~11. ,t1ro'!'1 • differential partitioning of.
components of a mixture
chromatography in which a acids
,... . strip of chromatographic • For separating a coloured ink
between stationary and mobile paper is spotted with the
phases. solution mixture suspended
)
d in a suitable solvent which
acts as mobil-e...phase UIHl4 t4)
- ·- ..... -- ... ........ .... .. .... .. ------- --- -·-
..--········ • -· ·····;·---·· ........ ···--•····--···--·.....................-...... -- ....- ...

->: Orgariic c0fflpounds

litative Analysis ofcomp - _
OU8 d tection and percentage ositio f I in an organic co~pound. These are as follows
I/Owes th:_ :- ___ ___ ___ ·-·~ --_~ :_:_ men ~ present ical"■~--·_·. .,.'~,... Chem
_Method/Detectlo~ge!'t . Procedure • • -· ••• •H

•ri ~
+ Ca(OH2) --+C aC?3 J, +H2O
• CO2 reacts with lime water which develops • CO2
, . ar,d t,y<trogen • Heat the co~p ound with ms carbo n. (lime water> <Milkiness>
toppe r (II) oxide • turbidity and confir
c,rt,a11
C + 2CuO ~ Cu + CO2 • H2O reacts with • SH2O+ cuso.. ~u so... SH20
6
2 anfiyd. CuSO.... and
! • (White> (Blue>
l
• 2H + CuO ~ Cu+ H2o develops blue colour confirms hydrogen.
j
__ -·-------- ------ ---· ·-- ..... -·-
t -------······•·••• ••••••• • • -~----"'-···----.-· ··-·········-··-------------.... ·----- ------ ------ - .. -----.......... ______ 2
extract (LE) with FeSO.- • 6NaCN+ Fe •--+ [Fe{CN) 6]'4-
..--1---·· • Lassaigne's extract (NaCN) • Boil Lassaigne's .wHzO
r,rogen
Na+ C + N ~Na CN and then acidify with cone. H2SO.-. Fe3+
r • 3[Fe(C N)6y4 - + 4
• Formation of prussian blue colou
t Fe4[fe(CN)6h•xH2O
f ,. , ' •confirms, nitrogen. • •, (Prussian blue)
----- - - .
._
.... ___,:____._ ____ __ ____ ......- ........-··· ....
··-·.··--- - - - --· -----
--····· -· ······••••••••• •• - •• -- •--·· -· -··· --•••••• ---
f •···-·· ··-······ -· ·-- .. ·····--·
~ 2 2+ --+P bSJ.
-:-· • Lassaigne's extract (Na 2S) • Add acetic acid and lead acetate to • 5 - + Pb
(Blade)
5111phur Lassaigne's extract to get a black
• 2Na + S~N a 2S (LE) 2
).
precipitate. • 52- + [Fe{CN)5NO] ---+
' _ ; [Fe(CN)5NOS)4-
• Add sodium nitroprusside to Lassaigne's - (VIOiet)
extract to get violet colour confirms
sulphur.
.... -···--· ........ ··----· ··----- ·--·--- ··-···- -·--
••. ··-· ·•·•·•· .••.. -----· -----·-······. ·------- ..... ·-·· ·-··· .... ····-
-, --··· ......... -······ .....•• -- - + NaSCW --+ [Fe{5CN)J:1 2
LE with acetic acid and lead acetate. • FeCl 3
Ntrogen and sulphur • Lassaigne's extract (N_aSCN) • Boil Blood red UIHI.J•fJj • NaCl
• Na .+ .+ N ~ c • Formation of blood red colour and no
s --!..+ NaSCN
together , •
prussian blue colour. ----------· ·------ -······-···-········--- . ----·-· -----·-··---
---. ·•·· --
:t
;··----··--··· ........ --- .... ·- ........... ---· ·······-···· - ......... -- ·-·· ....• -......... ....... ······- ........ ----·-- ·
,••··

• Acidify lassaigne's extract with HN03 and •

+Ag •--+ ~ x-
Halogen • Lassaigne's extract (NaX)
•
• Na+ X ~N aX then add AgNO 3. A white ppt soluble in
i NH.-OH shows presence of chlorine. • CX represents a halogen Cl, Br or I)
I
' · • • Yellow ppt. sparingly soluble in NH.-OH
1
shows presence of bromine.
'
• A yellow ppt. insoluble in NH 4OH shows
! presence of iodine.
j
·:·s~i~ti~~·~- ~ii~-~ith-~it~i~-~~ld-~~d.th~~- ·: ---N;~PO~-~ iHNO~-~-H~PO~------·-·····-
~~ ••••• - • • Heat the comp ound with
treated with ammonium molybdate. • HlO. - + 12(NH 4 hMo 0 4 + 21HNO 3 - .
(oxidising agent) sodium
' Anvncnium mal'jbdlte
peroxide. • Formation of yellow colouration or ppt
indicate the presence of phosp horus. (NH,. h~O,. ·12Mo03 +21 NH4NO3+12Hz0
Nl 2o 2. Boil Amr nor un~ te
•P- --N a 3PO, b'llawPP'-)
"
 .....__,, II

Quantitative Analysis . ..
The percentage co .. . . . . ·
follow·ing . . mpos,t,on of elements present in an organic compound ,s determined by the methods based
principles • on the

Procedure with formulas

Carbon and Hydrogen
Uebig's combustion method
(C and H)
• A known mass of an ~rganic compound is burnt in presence of excess of 0 2 and CuO.
C)i 1 +(x+ :)02~~02 + ~Hp •

• CO 2 evolved· is absorbed by cone. solution of KOH •HP produced is absorbed by anhydrous CaCl2.
• Increase in masses of these absorbing compounds gives the masses of CO2 and H2O produced.

• %of C= _g_ x Mass ofCO2formed x 100 %of H= I_ x Mass ofH20 formed x 100
. - . . .. - . ,_
_
·44 Mass of compound ' 18 Mass.of compound .
. Nitrogen (N) ····--- ... •••••••• ·,;~;~;~· ;~~h~d··· .......... ···-··--·····--··· ··········-·-·········---···-·· ... · ·~·-- ·- - --··--- --··· ,..... ---·- -· --. - ·

• Nitrogen.containing organic compound is heated with CuO in an atmosphere of CO2.

. .,
.C)i N. ,+ (2x,+ Y2rL--uo --+ xC0 +~HP+ fNz +(2x + ; rL--u
1 1 2
I
•

• N2 evolved gets collected over cone. KOH solution which absorbs CO2.
• % of N = ~ x Volume of N2 gas at STP xlOO , .
~--····-·--··· 22400 ~ Mass of compound . . _ .
i ·- ...........~;jd;hl~~·~ethod - ····-··....... ----·-······-·--····-····-···--·-···· --····-· ...

-
• Organic compound +H~0 2NaOH en • 2NH 2Hf'I - ••
4(co~c.) ...:...+(NH4)zS0 4---Na2-"-'4 + 3+ 'Z'-'
L .
•
r
2NH + H~0 ~ (NH )zS0
3
'

4 4 4
_.

... ,!, ' ' ' ',

• % of N = 1.4 x Molarity of add x Vol. of acid used x Basicity of acid

Mass of compound
• ·% of N :::;: 1.4 x Normality of acid x Vol. of acid used i
Mass of compound , ,
Limitation Kjeldahl's method is not applicable to ,co~pounds containing nitrogen in nitro and azo groups and
: nitrogen present in the ring _lik~ ~yridine. • .
I ' 4 , ., -~ , ""' ..>.. , _ ___ - - - - - - - -.......___ ...___: - - - - - - - -

!Halogen (X) Carius method • • ;

i _[X = Cl, Br, I] • ~.~logen in organic compo~n<;I is precipitated as silver halide by boiling with cone. HNO3 ~n~~~n a~~ing~ !
: % f Cl 35.5 x Mass of AgCI % f 80 x Mass of AgBr , • -,· • ;
• o = x 100 • o 8r = - - - - - - = - - x 100 1

I
143.5 xMass of Compound 188 xMass of Compound
• % of 1= 127 x Mass of Agl x
100
. 235 x Mass ofCompound
~ ---- ............-------------------------·-------------- ............................. ---------- . .......... '" ............ - .....................................________ .................................." ....................................____ --
l Sulphur (S) • Carius method •' ' •
Sulphur in organic compound is oxidised to H2SO4 by boiling with Na2O2 or cone. HNO3 and is precipitated as
BaSO4 by adding excess of BaCl 2 solution in water.
. • S O)HN03,~ BaSO4 ,!, • %·of 5 = 32 x Mass of BaSO4formed x 100
'I Qi) BaCI 2 White ppt 233 Mass of compound
:--· -------- ------ ...................................... ---- .... ---- -......... --------- --- -........ -- ..... . . .. .... -- . -~ ..... -- .. -. .. . . ... -- -........ -.. -......... -- ....... -....................... ---- ...... -- ......... ----. -- --....... -- .. --------- .. --- ..............---·-·
) Phosphorus (P) Ignition method • ,. '•- , - ...
HN03
• p ---+ HiO4 • HlO4 + Mg 2 + + NH4CI ~ MgNHlO4 +HCI
(Phosphorus) ~ (Phosphoric acid) (Magnesium arrvnonun
phosphate (White ppl)

-. % of P= 62 x Mass of MgzP2O7 'x 100

222 Mass of compound
 ygen is given by iodine Or
ntitative analysis of ox
= 5 x 16 x mass of 12 formed 100
ftle qua ou nd taken ,c
ma ss of comp
~ (11ethod·
entage of oxygen = 10
0 - (Sum of the 2.x ~27 .
r elements).
, pe~ ntages of all othe ~ th ~ eS ti~ation of elements in an or
ganic
,,erce Or • Presen ~ly es of
r- t by using microquantiti
compou nd is earned ou hniques. •
A
02 + other gaseous pr
o~ucts c experimental tec
, organic.comp ound ~ subStance and automati
n present in a
n, hydrogen and nitroge
02 + 2( 11?0oc) 2( 0 • The elements carbo own as CHN
ned by an apparatus kn
compound are determi ry small
+ SCO 2 aly ser. Th e an alyser requires only a ve
5CO + 120 5 -- -- -+ 12_ eleme nta l an the values
ce (1-3 mg) and displays
32 x mass of CO2 amount of the substan
x 100 ort time.
O- und taken on a screen within a sh
% 0 f - 88 x mass of compo

e ca .
a tro gro
nitrogeri bf comp·m ounds having; n1 1.t~ !9 -p
• 'nt ·n·ng ~,fr-n .~- "
~itrn nen prese~ •. \ .... ..,-> ,i ., ""
:¾ir•!'f'l~
.,._ ~:
-1
n ,u~ . • , ..

rism,_._hyperconjug
-~
~ .,,,.,.,,_
\'')o,,:i,.

If resonance, me5:0me
:

•
•• and ctromeri · ..
ele

.. . ~t
on of brine
obtained by crystallisati
" • ~. - I I

3. Crud e so diu m ch lor ide NEET 2019

ocation, lower will be lution do es no t co ntain MgSO 4.
f Higher the stability of carb . JEE 2023
so
ion of 1:1 mixture of ortho
and
hydride affinity. 4. Method of separat n. N£ET 2017
test for is ste am distillatio
NH • HCI give positive pa ra-n itroph en ols
. on fusing with Na, CH3 2 . "JEE 2023 t a Le wis acid.
NEET 2015
2 en. hile is ~o
both nitrogen and halog 5. Nu ~leop
NaCN + NaCl
CH NH2 • HCI N~ion >
3 Fus
test for nitrogen.
- NaCN gives positive
t for halogen.
- NaCl gives positive tes