11

Chapt
1 EXPRESSING CONCENTRATION OF SOLUTIONS ( ( 4) RAOULT'S LAW r6) COlUGATIVf PROPERTIES
Mass llf a component j ·, For non-v~lalile solute in volatile solvent
, IAass i;err..entage ( 11fw J :: ,
111ass o1 so1ut1lln
x 100
, Relative lowflring of vapour pressure
p; P,
Pwu.11i1u1 = PvJ1·11.1n1 Xv.11 '"°' p
C

Volume llf a comr,onent , For volatile liquids: 0

, /r,lumr, f,r,rr,entage lv/v J = T f · x 100 CJ (J ,, (J Q , Elevation in boiling pf!mt: AT• = 1,, - T• = K.m
,otal volume o solution P...I = P1 +Pi= P1X1 ➔ PiX-, = P, + (Pi P1)Xi
I , Mole fraction of any component In vapour phase· RX M1-' Tb
7

Mass of solute Where, K,. -

, fAass hJ 1<.ilume pc,[Link] ('Iii-I) - -. x 100 Y1= P,iPv,.1
Volume of solution 1000x11, H

Mass of r,olute ,,
(5) TYPE OF SOLUTIONS , Depression In frao,1,ng point ti r," 1 °- r, c: K,m
1
, Parh pr;r m1l11on (pprn) = - - - . - ~ 10 , ldoal solutions: A - B lntoractlons ara or same .2
Ma% of ~.olullon R~ M,q,
Whom, K,
magnitude ar, A A and B B lntor:ictlons. [Link]" 0 and
Mole of a component 1000 • i\,., H
' Moir, fraction (/41 Tola! molr;r, of all cornponc,nl.5 i\H 0 .,1 - 0
,, Osmotic prossuro:n - CRT (;) Rf
og.: n-hoxano and n-heptano, bromoelhana and
Molr;r. of ,;olutr: chloroothano, , Osmotic pressure method is widely ueetl to cJ
, M<Jlanty (M)
Volume of ~olution (I) , Non-Ideal solutions: A - aInteractions Aro or dlfforont molar moss of proteins, polymorb
magnllucJe than A - A and B - B lnhiracllons 11v,.,., ,, Isotonic solution llnvo ,ame osmotlr, pressure
Mai.•, of r,olutr, 1 0
, M<,lf,hly (m) ::- - , Osmotic prossuro assoc1ntod with tho fluid In
Mar;'! of solvent (rgI andi\H.,.., 1 0. blood cell ls equivalent to 0 .9% (mes11/vol) of NaCl
r, ~r,lub1lil/ 1Jf a -:[Link] Ir, it', rna1irnurn 1Jrn1Junt that i;::,n
di:,';l,iv,,d in a :,per,ifIod amount rJf •,otv,mt at a spriclfiod
t)(lj , (+)vo dovlatlons: A B lntoracllons aro waaker than
A- A and B- B lntoractlons. (1) van't Hoff FACTOR AND ITS SIGNIFICAN
tt,rnr,r,mtum. Observad value or colllgit_!!:'e r!_operty
( Calculated veluo of colllgalive property

j,
(2; SOLUBILITY OF A SOLID IN A LIOUID cg: r-Jcetona ➔ athanol, Normal molar mess
, ',;rJmf11.,;;nl1y 1Jffw,;ted by ternprmitur<: ch;;ngr;, (- )vo dovlatlons: A B Interactions are stronoer than Abnormal molar mass
, 1'r1,· :,1Jrt: cjc,r;~ not hav,: any sigruf1cant effer;t A A and 13 OInteractions. , r or normal solute (1 = 1)
• i\H,,..,<0,AV.,.,"o,r.., <P, 1 , For association, I < 1
(
'3./ SOLUBILITY OF A GAS IN A LIQUID , f or dlssoGlalion, I > 1
ag: nllriG acid; water, chloroform ➔ ai;etone
, Hf,(1r)"1., 1,,..,. p - Y / ·, A1eotrope6 : i;onstant bolling mixtures whose ( 8 ) MODIFIED COi I IGArlVf: PROPERTIES
, ,:,.,,,,.,,,..,l:,l; ,11 ,
,nc;rf.;;;5'; 111 temperature.
composition does not cl Ianga on disUl/alion .
.1 \n'.,f'f:r;t~'1S wit' 1r,,•.rf.:&W in pressure. , P~...J.L = ln.z.
, T',1;: "'" '.S:lnf t of t','Jb::i divers ::ire diluted V11th He to 1:1voId / , Minimum bo/llng azeotrope: 95% C1H~OH and 5% p~ nl
\,t,1,')S. / Hpbyvolume , t\ r,. = IK~m
r,., , ,,,eot U-,•. v,,u1)1t ty ,JI r/J, Ir S'Jft drn,ks and soda water, , Marlmum boilfng aze1Jtrope: 68% HNO, and 32% H O I t\T, C ll<fn
1
j by mass '' /!=iCHT
 G) TYPE OF CELLS @ NERNST EQUATION @ ELECTROCHEMICAL SERIES

o Electrochemical cell : Device used to convert chemical o A negative E means that the redox couple is stronger
0

o For the reaction : M"' + ne·- - M

energy of a redox reaction into electrical energy. It is also reducing agent than the H'/H2 couple.
o A positive E means that the redox couple is a weaker
0

known as galvanic cell.

reducing agent than the H"/H 2 couple.
Electrolytic cell : Device which uses electricity to bring Oxidised fonm Reduced fonm E0 N
E = E•- 0.0591log-1- 2.87
about a non-spontaneous red ox reaction. F2(g)+2e· ➔ 2F
n [M"']
Co'· +e- ➔ Co 2' 1.81
o For the reaction : aA + bB~cC + dD Cli(g)+2e· ➔ 2cI- 1.36
@ DANIELL CELL 1.23
02(9)+ 4H" + 4e· ➔ 2H 2O
2 2
Cell reaction : Zn(s)+ Cu ' (aq.)-Zn '(aq.)+ Cu(s) E = E• - RT In [C]c[D]d C:.,
Br, +2e- ➔ 2Br- 1.09
cell cell nF [A]•(Bt en
cl'. Ag' +e· ➔ Ag(s) 0.80
When external opposite potential is applied to the cell in en
standard state o For a reaction at equilibrium, E"' = 0. C Fe3 ' +e· -> Fe2' 0.77
iii
'ij 0 2(9) + 2H' + 2e- ➔ H2O2 0.68
(a) E,., = 1.1 V, no flow of electrons.
o
E•
coll
2.303 RT I K
= __
0.0591 K
n_F _ og c = - n- 1og c
x0 12 + 2e· ➔ 21- 0.54
(b) E,.,> 1.1 V, electrons flow from Cu rod to Zn rod. 0 Cu2 ' +2e· ➔ Cu(s) 0.34
.t:.
@ GIBBS ENERGY i,, 2H'+2e· ➔ H2(9) 0.00
(c) E.,, < 1.1 V, electrons flow from Zn rod to Cu rod. C Pb2• + 2e· ➔ Pb(s) -0.13
o It is the reversible work done by the galvanic cell.
i Sn2'+2e· ➔ Sn(s) -0.14
@ CELL POTENTIAL o t.,G=-nFEoe1, "'en Cr3'+3e· ➔ Cr(s) -0.74

..
O C
o t.,G = -nF E;., iii ➔ Zn(s) -0.76
o Electrode potential : It is the potential difference developed zn2<+2e-
o t.,G0 = -RT In K = -2.303 RT log K ➔ Hig) + 2OH"(aq) -0.83
between the electrode and the electrolyte. When the ~ 2Hp+2e-
concentration of all the species involved is unity it is known ';:===================~
(j) CONDUCTANCE OF ELECTROLYTIC SOLUTIONS £" Na•+e· ➔ Na(s) -2.71
as standard electrode potential. Ca2' +2e· ➔ Ca(s) -2.87
o Cell potential : The difference between the electrode K'+e· ➔ K(s) -2.93
o Resistance: R = E!_ unit = ohm
potentials (reduction potentials) ofthe cathode and anode. A' Li'+ e· ➔ Li(s) -3.05
· o EMF of cell : The cell potential when no current is drawn RA
1 .
o Resistivity : p = unit = ohm-cm
through the cell. @ DILUTION EFFECT ON CONDUCTANCE
o Eco11 =E"9ht- E1,11 1 = "i'
o Conductance : G = R A unit= ohm 1 or S ., Conductivity always decreases with decrease in
o E::., = E~ -E~ concentration (means on dilution) both for weak and strong
11
o In a galvanic cell: Cell constant: G• = .!._, unit= cm·' electrolytes.
0
(a) Anode has negative potential w.r.t solution. A o For weak electrolytes, molar conductivity increases steeply

(b) Cathode has positive potential w.r.t solution. o Conductivity G{ ,

. . : " = -A unit = ohm 1cm -1 F dilution.
on to lect lyt s ol d 1· ·1 . I I
.., Standard hydrogen electrode : :, or s r ng e ro e , m ar con uc 1v1 y increases s ow y
with dilution.
H (aq.) + e - i H (g),
2
E0 = 0 Volt (Assumed)
~(~1b~ar~l_ _ _ _ _ _ _ _ _ _ __,
o Molar conductivity: Am= KX ~OOO, unit = S cm mol
~----------__c....----------" '---------"'----'"'----------_,../
2 1
:, For strong electrolyte: Am= A~ -AJc.
'-~

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 NCE
IZI Electroc hemistr y

.'.!)
---
KOHLRAUSCH LAW OF INDEPENDENT
---"\ @BATTE RIES
,, Secondary batteries: Which can be recharged
(1) Lead storage battery:
MIGRATION OF IONS o Primary Batteries: Which cannot be reused
) L mt ng molar conduct,v I) of an electrolyte can be (1) Dry cell: (Leclanche cell) Pb(s) +Pb02 (s) • 2H2 S04 (aq.) ~
represe~'.ed as :he sumo' the •nd1v,oual contributions of the Anode:Z n(s)---tZn:1, +2e- 2PbSO.(s).
an,on and cat,o," of the e'ectrolyte at infinite dilution.
Cathode: Mn02 + NH; + e- ---t MnO(OH) + NH3 (2) Nickel cadmium cell : It has longer life •
) II an e,ectrolyte on oissociation g:ven v cations and v_anions
storage cell :
then \~ ;. V • - V
Carbon rod Cd(s) + 2Ni(OHlJ(s) ➔ CdO(s) + 2Ni(OH)i(s) •.
(cathode)
o Fuel cells : Galvanic cell that converts the energy
• ;.;.: 01-f >SO~- >Br >Cr >Cf\COo- during combustion of fuel directly into electrical ener
• For a ·~.ea!< e'ectroiyte a = \_/.\ ~ e.g: H2 - 02 fuel cell
Ca2 C.\ 2
"' Anode : H2(g)+20H- (aq.)---t2 H,O(, )+2e-
• For aceticacid· K = - =
a 1-a .\:(A: -.\m)
Cathode: 0 2(g) +2H20(l )+4e --+40H- (aq.)
The cell was used in Apollo space programme
'§_ FARADAY'S LAW OF ELECTROLYSIS H,O + Cathode
, Firstlaw :w= ZO = Zit = -E- x lt
96500 l
Anode-
i
Zinc cup Mn02 +
w, E, Aqueous el
, Secondla w: - = -
(anode) carbon black NaOH
w2 E2 + NH4 CI paste
:, 1F = Charge on 1 mol electron= 96487 C = 96500 C Fig. A commercial dry cell consists of
a graphite (carbon) cathode in a zinc
container; the latter acts as the anode.
@ PRODUCTS OF ELECTROLYSIS
I:, Molten NaCl : Anode : Cl2, Cathode : Na (2) Mercury cell: Cell potential(= 1.35 V) remains constant
during its life
,, Aqueous NaCl: Anode : Cl2, Cathode : H2
Anode: Zn(Hg) + 20H- ---t ZnO(s) + H,0 + 2e-
:, Dilute H2S0, :Anode . 0 2, Cathode : H2
Cathode: HgO + H,0 + 2e- ---t Hg(F) + 20H- Fig. Fuel cell using H2 and 0 2 produces electricitj
J Concentrated H2SO,: Anode : s,o;- , Cathode : H2

@)CORR OSION

:, It slowly coats the surfaces of metallic objects with oxides or other salts of metal.
, Corrosion of iron is called rusting. It is an electrochemical phenomenon.

" Rust is Fe20 3 • xH 20 .

'J Prevention of rusting can be done by
2
(i) Covering the surface with paint or by chemicals (e.g., bisphenol) Oxidation : Fe(s) ➔ Fe •(aq) + 2e-
Reduclion : 0 2(g) + 4W(aq) + 4e- ➔ 2H20(1)
(ii) Cover the surface by other metals (Sn, Zn etc.)
Atmospheric oxidation : 2Fe •(aq) + 2H,0(1) + 1/202(g) ➔ FepJ • Ill'
2

(iii) Provide a sacrificial electrode ofother metal (Mg, Zn etc.) Fig. Corrosion of iron in atmosphere

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 13
Chapter

CD RATE OF REACTION ® INTEGRATED RATE EQUATION AND HALF LIFE @ TEMPERATURE DEPENDENCE OF THE RATE OF
REACTION
0 For a reaction, aA + bB---> xX + yY Zero order reaction:
0 For a chemical reaction with rise in temperature by 1 o•,
-1 d[A] -1 d[B] _ 1 d[X] _ 1 d[Y] ., Rate = -d[R] = k[R] 0
rate= a di - b dt x dt - y dt dt the rate of reaction is neart~.,doubled

Unit of rate of reaction : o [R] = [R] 0 - kt o Arrhenius equation : k = Ae "'

[R,l
(i) mol L-'s-' -, t - [Rlo ~ ..-,slope=-k f _.!!'lercept = lnA
-1
i- 2k
(ii)atms
[Rlo
~ slope=-~.,
-~[R) -([R 2 ] - [R 1l) ., t,oo¾ =-k-
Average rate 0 1--+
~t t, -t, First order reaction:
0 1/T--+
Instantaneous rate = - d[R] = d[P] , Rate = -d[R] = k[R]1
dt di dt
1
a ln[R]=ln[R] 0 -kt 0
@ORDER log( ( ) = 2.3~•3 R [ \ ~ : ]

k = 2.303 [R] 0
For a rate law equation : rate= k[A]' [B]'order of 109 o The energy required to form the reaction intermediate.
t [R]
reaction = x + y slope = _~
2 03 called activated complex, is known as activation energy (E.)
Order of reaction can be 0, 1, 2, 3 and even a fraction. 0 k = 2.303 log [R] 1
(t 2 - t 1 ) [Rl, o Threshold energy=Activation energy
Order of reaction is an experimental quantity.
+ energy possessed by
Order is applicable to elementary as well as complex
reaction. reacting species.
2
For complex reaction, order is given by slowest step. th
. :_E,
o For n order reaction, t 1 oc [R 0 ] 1- n o Forbiomolecularreact,on. Rate= PZ""eRT
@ MOLECULARITY where, Pis steric factor and ZAe is Collision frequency.
o It is the number of atoms, ions are molecules that must
collide simultaneously with one another to result into a
®
PSEUDO FIRST ORDER REACTIONS
® EFFECT OF CATALYST
o Hydrolysis of ethyl acetate in acidic medium
chemical reaction
o Inversion of cane sugar in acidic medium o Catalyst increases the rate of reaction by reducing the
" It cannot be zero or a non-integer
a It is applicable only for elementary reactions
0 ORDER OF SOME REACTIONS
activation energy of reaction.

Reaction Order ,., A small amount of the catalyst can catalyse a large amount
of reactants
© Reaction order Unit of rate constant Zero
o A catalyst does not alter Gibbs energy, ~G of a reaction
Zero molL- 1 s- 1 2 Hl(g) Gold '::'rface) H,(g) + 12(g) Zero
·, Catalyst does not change the equilibrium constant of a
First s
-1 Radioactive decay First
reaction
Second First
o A catalyst can catalyse the spontaneous reactions only.

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 1
Chap
i GROUP 15 ELEMEN1 S 13. All oxidation statos + 1 to +4 for nitrogon tond to 21 Preparation of ammonia
d1~proportmnato In acid solution. (i) NH2Ca-lH2 2HiO-+(N H,J:iC03 =2N~ •
Pn\C\O{lon,: N, P. Ai;, Sb, Bl. Uup ,.\ ,!, ,?
'---' ..__.. '---' 3HNO 2 ~ HNO3 + H7O t 2NO (ii) 2NH4CI • Ca(OH)2 ➔ 2NH:J - 2H O - Ca
2
non bis Mcl311010, 111,11.,ls Anomnlous behaviour of nitrogen is due to Its (iii) Haber's process: N (g) + 3H (g) = 2NH (
2 2 3
2 Pt-) t propc1t1c~ (I) smull size 22. NH 3 behave as a lewis base
• Cc, (ii) High oloctronegativity h
ntrn,111 N<P<As <Sb~H, Cu (aq)+4NH3(aq)- [Cu(NH ),Jh (aq)
(Iii) High ionization enthalpy 3
\Ion, 11lhalp1 N > P >As'> Sb> 81 (blue) (deep blue)
(iv) Non-availability of d-orbltals
• ElcctronegJ\IV1ty N > P > A~ > Sb= 81 AgCl(s)+ 2NH 3 (aq)--. [Ag(NH )z] Cl (aq)
I 15. All elements of this group form hydrides of type MH3 (white ppl)
3
(colourless)
N ~ n sagas \\h1ch all r,.m1a1mng elements are (I) Melting point: NH 3 > SbH 3 > AsH 3 > PH 3 23. Oxides of nitrogen:
i(j• (ii) Bolling Point: BiH 3 > SbH 3 > NH 3 > AsH 3 > PH3 N2O Neutral NH4NO3~ N2O + 2H O
4 r:-. ~en 1s :i d,mom1c molecule with very large bond (Iii) Bond angle: NH3 > PH 3 > AsH 3 > SbH 3 2

!py(941 4 kJ mol ) (iv) Bond enthalpy: NH 3 > PH 3 > AsH 3 > SbH 3 NO Neutral 2NaNO2 + 2FeSO + 3HiSO,
4
5 P\e bo:ltng points in general increase from top to (v) Basiclty: NH3 > PH3 > AsH3 > SbH 3 ;,: BiH Fe2(SO 4 }.i +2NaHSO4 +2Hi
3
16. All elements of this group form two types of oxides:
boltOm n the group tiut melhng points increases upto 250K
E2O3 and E2O5 N2O3 Acidic 2NO+N2O4 ~ 2 N2O3
ersen,c and then decreases upto bismuth.
N2O3, P20 3 , As2O3, Sb2O3 , Bi O3
6 Ody n trogen 1n this group is capable of forming I I'-----~~
2 NO2 Acidic 2Pb(NO3 Ji 673 K 4NO2 +2P
p-,-p~ mul~ple bonds within itself and with carbon, Acidic Amphoteric Basic
2NO Cool• N 0
orygen etc due lo small size Phosphorus and other 17. Except nitrogen, the rest of the elements form two type of 2~ 2 4

e ements do not form p;i-pn multiple bonds. halides : EX3 and EX5 . Nitrogen does not form pentahalide
Phosphorous and arsenic can form dn-dn bond. due to absence of d-orbltals. Among trihalides of nitrogen
24. Preparation of nitric acid on large scale 1s
7 &cept rutrogen. all elements show allotropy only NF3 is stable.
Ostwald's process.
8 Single N-N bOnd 1s weaker than single P-P bond 18. Preparation ofDinitrogen PVRh gauge catalyst
4NH3 (g) + 502( g ) - - - - - - + 4NO(g)-
9 ti.a, mum covalency of N and P are 4 and 6 (i) NH4Cl(aq) + NaNO 2 (aq)➔ N (g) + 2H O( P) + NaCl(aq) (lrom air) 500 K, 9 bar
2 2
res;:,ect;,ely
(ii) (NH4 )iCr2O7 ~ N2 + Cr O + 4H O 2NO(g) + 0 2(9) ;;=====2NO2 (g)
10 Commonoxida~onstate:-3. +3and+5 2 3 2
3N02(g) + H2O( tl---➔ 2HNO (aq) • NO(g)
3
11 Due to inert pair effect, stability of +5 oxidation state (iii) Ba(N3)2~Ba+ 3N2(verypure)
25. Concentrated nitric acid attacks most meta~
decea~ and stability of + 3 state increases on noble metals such as Pt and Au.
19. Nitrogen combines with CaC to form nitrolim (CaCN + C) at
2 2
movlng down the group. dil. HNO3
100°c, which is used asa fertilizer. Cu -~-=..:.➔ Cu(NO3lz + NO
12 T'le only we I charactensed Bt'° compound is BiF 20. Liquid dinitrogen is used as a refrigerant to preserve
5
biological materials and in cryosurgery.

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 El
Z:, 3(.~ "'"!, .l!S' 1' :,,,;;>/.CS :1 'l:CSC~r,r,s·
"'r~ - ~ -> C l.C~- ~--C
- -- Charact:er:st.c.
\lai,,e i'~rmufa .:ordsard ii - ,gr ;;,er..:rorer,a
~e,r~umter
lesercecfc~r:: ta s
,:7 e,..cs.;c::,r ,s.~.- ~.s • <' " l,,""C,,J;;fa r,.rcr.,1c r,r•·s Ore:,_ c)I-'
W'"ite YO<;.(.hr,r .s s es& Slatle ard "'[Link]
Jy~rr,sc~crcus
?'·,osphr IC,
,..;~P':\:i
-Nr,, ~ - 1_.
- , I ,reei~errscfgrvuc-·:: ·er- · yc:-r;es :frr:;e- =
•"'"f"/?r -w.. ,e ~ar i-~Ot-~St".,,IG 'lasP...s .,rW ....cr.:'laJ Qre=-"c

~:;.rr,; vs :f'./d ar~e :.i~ ::.oiscro.,s scJtJtie r CS,

o..-.i- ccrcsohcr= ,~3PG3 -,,cP-C'-"
=-~[Link].,c) One:, - r'
~rt! ~.:';,1 -S r ~r'< ✓ er· · ,~- i'"esr...ari:.e
One"=O AcCc.-:at...ra: -t, Te>·- '-5e>~~S>,...~:.
:>yrop~ospncrous TNo P-Or'
H.i"20s a S. Se -e a;d :Jo fCl"'r. ox;des cf ':JP'= EO:. anc E8 a a-:
Two 0 - u
TwoP=O acid,c .n ·a:_ra

r:yoophosphcnc H4P20a FourP-OH 9. ~ese e1ements forn halides of rpe EX. EX. ,n: =X::
-woP"O
=·g . f/01\e e,r,[Link]~s (i) Stab1lit1 orcer of halides ; F- > C > Br- > I
One P-P
,i, Red [Link]:,r,o•us • ~,cr.-po,soncuS and insoluble in Orthophosphonc Three P-OH (u) SF, ,s excepl!onally stable
H3PO4
CS; • ,s c.o•y~e,,c and 1ess reactive than whrte I OneP=O {iii) All elements except oxygen form cfict ,onoes and
;.,rie,sp.,.10"::;us Pyrophosphoric I H.iP20, I Four P-OH
TwoP=O
dibrom,des

One P-O-P (iv) Dimenc halides undergo disproportionation

I

ICyciotrimetaphosphoric (HPOJh l Three P-OH 2s~cI,--➔ SeCI, + 3Se

Three P = 0 10. Preparation of di oxygen
l Three P-O- P
.l
Fig Red phosphorus .i {i) 2KClO3 --- 2KCI + 302
32. (1) 4HpO3 --+ 3~PO, - PH3 MnO2
{;ii, Black phosphorus : tt has two forms u and f}-
(ii) 4AgNO3 + 2H2O + H3 PO2 ➔ 4 Ag + 4HNO3 + H3PO4 A
phospno,us. {ii) 2Ag2O - 4Ag + 0 2
r
28. Preparation of phosphine: ~ GROUP 16 ELEMENTS 11. Hydrazines with liquid oxygen is used as fuel ,n rockets
(i) Ca3P2 6Hp- 3Ca(OH)2 + 2PH3 I
1. Chalcogens; ~ ~ l'.'.J Lv 12. (i) Mixed oxide; Pb,04 , Fe,O,, Mn,04
{Ii/ P, . 3NaOH + 3Hp- PH3 + 3NaH2PO2 (ii) Simple oxides:
non-metals metalloid Metal

29. PH 0 becomes inflammable due to presence of P2H4 and (a) Acidic oxide ; SO2 , Cl2O7 • N2O5
2. (-[Link]):S>Se>Te>Po>O.
P4 vapours. Spontaneous combustion of phosphine is {b) Basic oxide: Cao, Na2 O
3. Oxygen (02) is a gas whereas sulphur {S8) exist as solid.
technically used in Holme's Signals. {c) Amphotericoxide :Al,03
4. Oxygen shows generally negative oxidation state-2.
30. Preparation of PCl 5: 5. The stability of +6 oxidation state decreases down the (d) Neutral oxide :CO, NO, N20
(i) P4 + 10Cl2 -'>4PCl5 group and stability of +4 oxidation state increases due to 13. Ozone Is allotropic form of oxygen and prepared by
(ii) P4 + 10SO2Cl2 -'> 4PCl5 + 10SO2 inert pair effect. passing silent electric discharge through dry oxygen.

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m n, 0 p-Block Elements

3 Chc'll1calpropert1es
(1) Ox1dIsinq power F7 > Cl2 >Br,> 12 q, GROUP 18 ELEMEms
Noble gas He N OJ
[Link] ~, /e Rn
(11) Reaction with H ,0
2. 6H~·Ne>Ar Kr>Xe>Rn>He
• 2F (g) + 2H,O(I) >4HF + O,
• Cl (g)+H,O(I)- ~HCl+HOCI 3.
compound of noble gas e
ement s !en-,
a • , , c terms ' R.11omb1c 4 All the halogens react with hydrogen to form volatile Bartlett on the
covalent hydrides of type HX. conceptofs,mllarlPoro; andi"e
1i-,;,lphur)
(i) Ac1d1c nature: HI> HBr > HCI > HF Xe+PtF6 -,xe·[PtF,.f
(ti) Boiling point: HF> HI> HBr > HCI I 4 Xenon-fluorine compound5
(iii) Melting point: HI> HF> HBr > HCI preparation:
5. Halogen formed many oxide with oxygen.
I
II (i) Xe
(excess)
+ F
2
673>< ltar
XeFi,s
(i) Fformedtwooxides OF2 and O2F 2
(ii) Stability order of oxides form by halogen: I> Cl> Br (ii) Xe + F2
873 K.1 ba,
XeF,(s)
6. Preparation of Cl 2 1 5

F19 ,..,~ <:t , ctures o a S nng in (i) MnO2 + 4HCI- MnCl2 + 2H 2O + Cl2 573 K. 60-70 bar
(iii)Xe + 3F2 ---..c..:.=..... XeF (s)
m, 10, sJ phur ano (b) S0 form (ii) 2KMnO4 + 16HCI- 2KCI + 2MnCI 2 + 8H 2O + 5Cl2 1 20
mt "" ;,MJT transform into monoclinic sulphur (iii) Deacon's process:
XeF• .. o,
36~ K A' eJe,ate.:1 temperature (- 1000 K). S, Is
t ,;x,.., e< and ,s paramagnetic hke O;
, , c,c•d~Jphurared1bas1cac1d.
' I
7
4HCI + 0

Reactions ofCl 2
2
CuCI2
(iv) XeF, + 0 2 F2 ~
5. Hydrolysis reactions

H Sv ,,_, phurous aod H SO Sulphuric acid. H ~s,o, : · (i) 2XeF, + 2H, O---+ 2Xe +4HF +o,
(i) 2NaOH + cI, - NaCl+ NaOCI + H,O
Pyrosulphuric acid (Cold and d1I.) (ii) 6XeF, + 12Hp ---+4Xe+2Xe0 T24HF
O .im H S O o,th,on,c ac,o (ii) 6NaOH + 3Cl2 - 5NaCI + NaCIO3 + 3H2 O
(iii)XeF6 +3H 20 - XeO3 +6HF
8 H SO, < r,a..,ufactureo by contact process (Hot and cone)
(explosive)
~~so vo 50 [Link] H S,O, (iii) 2Ca(OH), + 2CI,--> Ca (OCI), +Caci,+ 2H,O
(Bleaching powder) 6. Xenon fluoride reaction with F- donors and
Ga!Jlyst Oleum
8. Aqua regia (3HCI + HNO,) is used for dissolving noble
metals. (i) XeF2 + PF5 -[XeFf [PFJ'
3 GROUP 17 ELEMENTS
Au-AuCI4 -, Pt-Ptc1r (ii) XeF4 + SbF5 - [XeF:J'[SbFJ'
1 H ogeM F Cl Br [Link]
Fluorine forms only one oxoacid (HOF), other Halogen-
2 [Link] physical properties of halogens (lii)XeF6 +NaF-Na' [XeF,r
forms several oxoacids.
1 Bond energy Cl > Br > F, > I, HOXO HOXO2 HOXO3 7. He is used in filling balloons for me
HOX
E octron alrinity Cl > F > Br > I Hypohalous Halous Halie Perhalic observations
acid acid acid acid
E cclroncg.1t,v1ty F >Cl> Br ., I 8. Liquid He is used as cryogenic agent
10 lnterhalogen compound: XX', XX'3 , XX's, XX'7
Ph [Link] stale F , Cl1 , Br1, 11 9 Ne is used in discharge tubes and ft
ga) 11,q) tSoiodl
(i) All the solid or liquid at298 Kexcept CIF

J
advertisement display
Br. I, (ii) These are more reactive than Halogen except F 2
Red v~ (iii) CIF + H1 O - ► HF+ HOCI
---------~
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 -- 15
Chapter

CD d-BLOCK ELEMENTS 12. The 1" ionisation enthalpy in any d-series generally 25. Many Cu(I) compounds are unstable in aqueous solution
The d-block of the periodic table contains the elements of
increases but the magnitude of increase in 2nd and 3rd and undergo disproportionation.
the group 3-12. ionisation enthalpies for the successive elements, is 2cu·---.+cu2• +Cu
Transition metals : Metals which have incomplete much higher along a series.
d-subshell either in neutral atom or in their ions.
13. The trend of steady increase in 2nd and 3rd ionisation
26. The stability of cu2' (aq) rather than Cu ' (aq.) is due to the I
General electronic configurations much more negative oHydH° of Cu2• (aq.) than Cu • (aq),
1 10 12
(n -1)d - ns • , but this has several exceptions due to
energies for 1st transition series breaks for the formation
2
of Mn • and Fe'' respectively as both ions have ct5
which more than compensates for the second ionisation
enthalpy of Cu.
I
very little energy difference between (n - 1)d and ns
configuration. 27. Ferrales (Feo, j2" are formed in alkaline media but they
orbitals.
14. The three terms responsible for the value of ionisation
There are mainly four series of the transition metals : 3d readily decompose to Fe2O3 and 0 2•
enthalpy are attraction of each electron towards nucleus,
series (Sc to Zn), 4d series (Y to Cd), 5d series (La and Hf repulsion between the electrons and the exchange 28. The highest Mn fluoride is MnF4 whereas highest oxide is
to Hg), and 6d series (Ac and Rfto Cn) energy. Mn2O7
Zn, Cd and Hg are not regarded as transition metals. 15. Ionisation energy of Mn' is lower than er• as there is no 29. Mn 2 O7 is a covalent oxide in which each Mn is
With the exceptions of Zn, Cd, Hg and Mn, these have one
loss of exchange energy at d" configuration. tetrahedrally surrounded by O's including Mn-0-Mn
or more typical metallic structures at normal
16. Mn exhibits all the oxidation states from +2 to+7. bridge.
temperatures.
17. Sc(ll)virtuallyunknown. 30. Order of oxidising power: VO2< Cr o~- < MnO
With the exception of Zn, Cd, and Hg, these metals are 2 4
18. The only oxidation state of Zn is+2. 31. Ti & V, in practise, are passive to dilute non-oxidising acids
very hard and have low volatility.
19. In group-6, Mo(VI) and W(VI) are found to be more stable at room temperature.
These elements have high melting and boiling point. In any 3 2
thanCr(VI) 32. E (M '/M ') values shows that Mn3' and Co3• ions are
0

row the melting points of these metals rise to a maximum at

20. Among 3d series elements, E0 (M2'/M) is positive only for strongest oxidising agents in aqueous solutions among
l except for anomalous values of Mn and Tc.
3d series.
copper because high energy to transform Cu(s) to
These metals have high enthalpy of atomisation due to 2
2
Cu '(aq.) is not balanced by its hydration enthalpy. Only 33. The ions Ti ', v2' and Cu2•
are strong reducing agents
strong interatomlc interactions. Metals of 2'111 and 3rd
oxidising acids (nitric and hot concentrated sulphuric) among 3d series and will liberate H2 from dilute acids.
series have more enthalpies of atomisation than the
reacts with Cu. 34. Each unpaired electron has a magnetic moment
corresponding elements of 111 series due to much more
21 . Among 3d series, the value of E (M2'/M) for Mn, Ni and Zn
0 associated with its spin angular momentum and orbital
frequent metal-metal bonding.
are more negative than excepted from the trend. angular momentum.
Tungsten (W) has highest melting point among d-block
22. In halides of 3d series, the highest oxidation numbers are 35. For the compounds of first transition series metals,
elements.
achieved in TiX4 , VF5 and CrF6• magnetic moment is determined by 'spin only' formula :
The filling of 4f before 5d orbitals results in a regular µ= Jn(n + 2) BM
decrease In atomic radii called lanthanold contraction. 23. v' 5 halide is represented only by VF5, the other Halides
36. The colour of some aquated transition metal ions :
nd rd
The net result of it is that the 2 and 3 d-series exhibits undergo hydrolysis to give oxohalides VOX • 3 2
3
Sc ', Ti'', Zn ': Colourless, v'', Fe2' , Nt: Green , Fe3•:
similar radii (e.g. Zr and Hf). 24. Cu(II) halides are known except the iodide.
- - - - - - - - - -- - -- -- ~ , ____ ____ ________ _____, 2
Yellow, Mn ' :
- - - - - - -pink.
- - - - - - - - ------ --'
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MJ•I The d- and f-Block Elements Nee
The overall decrease in atomic and ionic ra,
37. These metals forrn a large number of complex ; i 48. lnacidicsolution,K2 Cr2 0,isusedasoxidisingagentas I l to Lu due to poor shielding to 4f is
comoou'1cis due to comparatively smaller sizes of the 1
::,eta! ions. their 1-iigh ionic charges and the availability of
I, 2- • - c 3• + ?H o (E• = 1 33 V)
Cr2O 7 + 14H + 6e ----+ 2 r 2 • lanthanoid contractions

--
Most common oxidation state is +3
c-crJ ta s for;:ne oond formation. 49. Preparation ofKMnO4
Pr, Nd, Tb and Dy also exhibit +4 oxidaUon
3-3. 1:-:ese meta·s a:1d t:1e;•co'.Tipounds are used as a catalyst .) M nO KOH
O K2MnO, - H. MnO,- + Mn02
(1 2
c:1e t::: t.>:e,r a;i, .i, to adopt rnJlt;ile oxidabon states and to 2 (Green) (Pink) only in oxides, MO 2
,~~ cc--:;[Link]~ 2 Eu and Yb also exhibit +2 oxidation states.
(ii) Lab method : 2Mn - + 5sp;- +BHP ➔ 2Mn0~
39. .', ·-e- s-a a:orns ~e ~ C or, are trappeo inside the
+ 10 so;- + 16 H. Their melting point range between 1000 to 1
~o:s::a 1a~ce c: ::--ese -.e ~ s. L..,.e cor--b1nation are ca':ed
Sm melts at 1623 K
~
a l co--p~ .... -~s ,, "' ~ci,-. are usua1 ;r non-
-:e . . s~
50. KMnO, decomposes at 513 K as : 3
Ln • ions may be coloured due to pres
s~:-- ,:;:-"C.- -e!r-. ::.
..... C!t:a ;.o s - a· ~= :: :ra-s: o:i ~eta!s form a::oy. 2KMnO, ~ K2 MnO, + MnO 2 + 0 2 f-electrons
e,;;. 3-ass .Cc.-::- 3~-u:e Cc.-S~ 51. KMnO, behaves as oxidising agent as Lanthanoids form Ln{OHh which are ba
t.~a:-;a-2se ::e=~-es .... r";stao e re at,,;e to
1 Basicmedium:Mno; +e --,Mno:- alkaline earth metal hydroxides.
-.a--;a-ese ' . i) a::d. :;-a-:;a-ese acic ic so1Jtion \ :"
Neutral/faintJy alkaline medium: Mischmetal is an alloy which consists Ian
:3:'. 1 -:::::-:- - ~ - ---"2'.t~2: - •,•-0: - 2-.:0 (-95%) and Iron (-5%)
0
- -· _:!....3-:: -----e:a.s ~-s \'0 ~'-.-.::es e>.ce:-:sca~d,ur-t Mno: + 4H +3e- ----+MnO2+2H,O
4 Actinoids
.!.3 ~ l,t--:.:C~ s a~t: 1~. C . ..::,! is a_,::i"C:e.--i-c and C:0 1s basic ir Acidic medium: 2
Outer electronic configuration: sf"" 6do.• 7s
--a~t.. "i: Mno: + sH· + 5e- __,Mn'"+ 4H 2 O
.... :>:-e,~~5;:;:::-:.1 '.:C::0- : All aclinoids are radioactive elements
52 KMnO, oxidises I into 1 and 103 respectively 1n acidic
2 There is gradual decrease in the size of alo
/I.e..:-:::. ri-SO,
FeCr:O. ~ .i"a;:O, - co_ - Na_ CrO, ~ Na:Cr:0- and fainUy alkaline medium. l ions across the series known as actinoid
C."l:.:-i-it~: 2 'l e:ro,~ ,Orange 53 Permangnate titrations in presence of HCI are which is greater than lanthanoid contraction
= Keil
K:Cr:O- ~ unsatisfactory since HCI Is ox1d1sed to Cl 2• Their general oxidation state is +3 but these
45 Na;Cr:O- IS "10re soluble than K:Cr;O, can show variety of oxidation states.
46 Chromate and d1chromate are m1erconvert1ble m @ f-BLOCK ELEMENTS ----
aqueous solution depending upon pH of the solution 1. The (-block consists of elements in which 4f and 5f @ APPLICATION OF d- AND f-BLOCK ELEM
0 orbitals are progressively field and known as inner-
2Cr0~- + 2H ---+ cr,o;· + H:O no is used in pigment industry
transition elements.
cr0; + 2OH----+ 2cr0~- + HP
The two series of inner transition elements: 4f (Ce to Lu) 2 Mn02 is used in dry battery cells
2 2 and 5f (Th to Lr) are known as lanthanoids and actinoids
47. o......_ '"~t::,... ,o:;cil ( - 3. ncI. and Al(CH 3 ),, Ziegler catalyst is used to
O ] - respectively.
Cr "'--" Cr manufacture polyethene
CrO~- .,.....t, cr,o;- .,..... I 126° 'o I
[0 3. Lanthanoids (Ln) :
[ o Io 0 0 4. PdCl 2 is used as catalyst in Wacker process-
0 Outer electronic configuration:
(d1chromate ion)
(tetrahedral) 4( _,. 5,J'- 1 6s2 5. AgBr is used in photographic industry.
(Chromate ion )
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 =
16
tffiGtillJ ~ •• ~ Chapter
G) WERNER'S THEORY © STRUCTURAL ISOMERISM
·:i In coordination compounds metals posses two type of valences: primary
and secondary o Ionisation isomerism : Isomers give different ion in solution eg. [Co(NH,).SOJBr and [Cot ·~H BrJSO,.
'l The primary valences are nonnally ionisable and are satisfied by o Solvate isomerism : Different number of solvent molecule bonded to metal eg. [Cr1H.O'.JC~ and
negative ions. [Cr(H,O),Cl]CI, · H,O
•J Secondary valences are non-ionisable and satisfied by neutral o Coordination Isomerism : The ligands are interchanged in both the cationic and anionic ions. eg. [Co{NHJJ
molecules or negative ions.
[Cr(CN),] and [Cr(NH,)J [Co(CN)J
o Linkage isomerism : It is due to presence of ambidentate ligand eg [Co(NH j,ONO]CI and
G) SOME IMPORTANT TERMS [Co(NH,),NO,]CI,.
sJ Double salts : Which are stable in solid state but broken down into
individual constituents when dissolved in water eg. Mohr's salt, [FeSO, . ® STEREOISOMERISM
(NH,),SO, · 6H,0] and potash alum [KAl(SO,), · 12H,O]
o Geometrical isomers : Common in heteroleptic o Optical isomers : These are mirror images that
i ::> Coordination compounds : Which retain their identity in solid state as
1 complexes with in CN = 4 (square planar) and CN = 6. cannot be supenmposed on one another.
well as in solution eg K, [Fe(CN)J
(i) Square planar complex : [MX,L,l (2 isomers),
o Ligands : Species which are directly linked with the central metal in (i) [Co(en)J,. have d and /isomer
[MABXLJ (3 isomers) show cis-trans isomerism.
complex. These are Lewis base. 3 3
(ii) Octahedral complex : [MX,(L - L),l, [Ma,bJ (fac-
(a) Unidentate ligand : er, H,O, NH, mer isomers).
,e0 + en; 7 +
(b) Didentate ligand NH,CH,CH,NH,, C2 0!- NH 3 NH 3 "'- ) / (.__ . .,r--..
(c) Hexadentate ligand : EDTA... 0 2N~ / NH3
I H3N'\_ / N02
I e~Co") (Co'--7n
!';_Co'\. Co
(d) Ambidentate ligand : No,-, scN- Ol~'·~:J NH3 02N/ I"-N02 (_en en_}
'.> Coordination number : The number of atoms of the ligands that are N0 2 NH 3
dextro Mirror taevo
directly bound to the central metal Fae Mer (ii) Cis-[PtCI,( en ),]2" show optical activity
eg. [Fe(C,O,)J>-, here CN = 6, [Ni(NH,),f, here, CN = 4 )
'l Homoleptic complex : Only one kind of ligands are present eg.
[Co(NH,)J'"
© IMPORTANT COMPLEXES
Complex Coordination number Hybridisation Shape Nature Unpaired electrons
::> Heteroleptic complex : More than one kind of ligands are present eg. [Co(NH,)J'' 6 d'sp' Octahedral Diamagnetic
[Co(NH,),CI,]" Zero
[CoFJ,._ 6 sp'd' Octahedral Paramagnetic Four
[NiCIJ'· 4 sp' Tetrahedral Paramagnetic Two
G) NAMING OF COORDINATION COMPOUNDS [Ni(CO)J 4 sp' Tetrahedral Diamagnetic Zero
i 'J [Cr(NH,),(H,O)JCI, : Triamminetriaquachromium(III) chloride [Ni(CN)J'· 4 dsp' Sequare planar Diamagnetic Zero
[Mn(CN)J' 6 d'sp' Octahedral
) K,[Zn(OH)J Potassium tetrahydroxidozincate(II) Paramagnetic Two
[MnCI,]' 6 sp'd' Octahedral
) [Ni(CO)J Tetracarbonyl nickel(O) Paramagnetic Four
[Fe(CN)J' 6 d'sp Octahedral Paramagnetic One
) [CoCl;(en)J" Dichloridobis(ethane-1 ,2-diamine)cobalt(III) ion. [FeFJ~ 6 sp'rf Octahedral Paramagnetic Five
,._1 [Pt(NH,),Ci(NO,)] Diamminechloridonitrito-N-Platinum(II) [Co(C,0,),l' 6 d'sp' Octahedral Diamagnetic Zero
j
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....._
- Coordination Compounds
7) CRYSTAL FIELD THEORY (CFT)
Accord~ng lo CFl under the influenec, of ligand field , degeneracy ol d-orb,tals 1s destroyed and they split into two or more energy levels The extent of sp111ihng depernh UPOn !hi!
TETRAHEDRAL COMPLEXES OCTAHEDRAL COMPLEXES . I!•,
d,., d,., d
d,-, I ,, d.,-_,_., ,., I
Ji 3
..,/ 5¼
.•,·' Barycentre
.,, .·. I ;,. - ~
.,..,, l:
I:, d,,. d,,, d,;·.
Metal d orb1lals ':,J ====i,
l;____-Je
d,: y·, d, 2 Spl111itlg cl d 01b1a1s
d,,, d,,, d., Average energy of the
d,2 y2' d,2 d orbitals ,n sphencal rnoctahedrai aySla
A"""'ge energy of 100 Sphfllng of d ort>,lels
crystal field field
dOlbllalsln!ll)hencal In tetrahedral crystal Free metal Ion
aysta!6old (,ek1
@ METAL CARBONYLS
0 COLOUR OF COMPLEXES , The metal-carbon bond in metal carbonyls possess
ands morder or increasing field s/renglh / , Colour of complex can be explained by d-dtransillon
rr character.
0
S2 < t < OH < C20J' "H,0 // , Metal a/om/ion of cf or d' configuration do not show d- , The M - C cr bond is formed by the donahon or lone
NH3 er< CN < CO electrons on the carbonyl carbon into a vacant ortltta
/ d/ransilion
x ,s hlg~ spin and r,gand ,5 weak field ligand metal.
/, The colour of /he complex is complemen/ry to that
x •slow sp,r and t,gand is strong field ligand 1 , The M - C rr bond is formed by the donation of a
which is absorbed. electrons from a filled d orbital of metal into the
Complex Colour antibonding rr• orbital of carbon monoxide.
[Ti(H_O),] Violet , Metal to ligand bonding is known as synergic effect.
rr•
ted bylllrat,onwllh [Link] TA (Cu(H.O)J'' Blue
~rr~ ~
(Co(NH,),)" Ye/low orange . • M ~ = 0. .
ri,on catalyst ts used for I
(CoCl(NH,JJ Violet
CuSO, SH.O Blue
~Ii-~ -
and Fe are removed by tho chelating ligands D- Synergic bonding
[Co(CN),)'" Pale yellow 0
and de5feniox1me 8.
eg eg. fl
(Ni(H.O)j'' Green f0 co ?~co /CVCO
oc,
OC-Mn---Mn-CO OC-Co-Co-CO
(Ni(H,OJ.(en)J'' Pait! blue oc/ 'c/'co
11h11 growth of IUnKY.S. oc-1 oc' I
co co II
(N l(H,O},(enJij" Blue/Purple 0
lJ0/'l on reaction [Link] I (Mn_.(CO), J (Co,(CO)J
(N,(en}J'" Viole/ Octacarbonyldicoball
) Decacarbonyldimanganese(O)
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 ~
r? . 17 Chapter
CLASSIFICATION ~ CHEMICAL REACTIONS
{II) ~~::11,c subshlul~CHJ ~ REACTION OF HALOALKAf(E
theb:::.$ol [Link]: <'f ha"iog<>-.n a~◊~1 !=,
C,H~.X CE, - CH· CH •· CH - CH2 {A) N1JcJeopM,c substiluf10n •e3d,or,
I ' I . I . Fe;:arl<
~
X
I I ~ 0x •~ ,+
X X X X Nu+ )c- X ~ )c- Nu• [
oi~.\ '-"3\a"t? -nha1oa1,ane X I I
• Fluoro compounds are not prepared by this method Mechanism Th,s reaci,on Mas ~~- [Link] lo
due to high reactivity of nuorine. process by two different mecharlSf"
,AA)I l'\a,o,>s o· "la>oa ·,a~es R - X) (1) Substitutlon nucleophllic bimolecular (Sl42/ :
{111) Sandmeyer's reaction
O•_-:;a-y , , Secoc,aary , 2· Tert,ary (3' ) • The reaction ber1;een CH30 a'ld Ori ,o r, t::, yl!li,
NH2 ~2X- ©X
'- • ,c "la,ioes NaN02+ HX Cu2X2 ) + N2i
0 methanol follows a second or:ler k,r>e!JCS , L e . l'le ~
Senzyi,c halides
273-278 K [X=CI, Br] depends upon the concentra:ion cf ~• r ~
~x lfx ©r ©r
(1v) From alkenes H H
OH + H ""'i'- ~ f H07"' Cl ~ ; \ ·• 5
c) eot:.pounos conta,m~g sp2 C - X bond • Addition of halogen halides :
HCI HH
[TS

f -'- HO!'£
,,,,,,c; t'.a lldes (11) Aryl halides· I
• Transition state (T.S.) is formed
..A:::-+H-l~A• ~I
• Reaction is generally carried out in acetor:e CY.
AxOx ox Major Minor
• Addition of halogen:
polar aprotic solvents
1~ METHOD OF PREPARATION Addition of Br 2in CCl 4 to an alkene results in (ii) Substitution nucleophilic unimolecular (SN11
discharge of reddish brown colour of Br 2 • It occurs in two steps
a) Fro'T, alcohol~
ZnCI~ ..A:::-~ Ho-+ (CH3)3C-Br ~ (CH:i)J C-OH • Br-
• R - OH• HCI ~ R - Cl • HzO CCl4 ~Br
H;,$04
Br Step-I
vlc-dlbromide + Br-
• R- OH+ llaBr ----'--'---7 R - Br+ NaHS0 4 • H.,O (CH3)3CBr E > ~
{c) Halogen Exchange Slow
• 3P. - OH+ PX,~ 3R- X + H:,PO·;(/ • Cl, Br)
• Flnkelstoln reaction : - Step-It
@ + OH ---:-'--7 (CH3)JCOH
• P - OH + PC!~ ~ R - Cl + POCI•, + HCI ~ Fast
R - X + Nal -> R - I + NaX [X, Cl, Br]
• P. - (JH Pr,d P//l • Swarts reaction :
R - 1. • Greater the stability of carbocation greater is the
Y1 B111, l7 CH 3 - Br+ AgF >CH 3 - F + AgBr! rate of reaction
• R - OH + $0(,ll ~ R (;I + SOi + HCI
• SN 1 and S~ order can be generalised as
l~I Frr,rn 1t1rJr,,<,11rlJ<Jr1\ @ PHYSICAL PROPERTIES
For S~ reaction
{,) f mo r.11J1u1l hulc,<Jorw11r,n Bolling point of alkyl halldo docreese In the order:
RI > RBr> RCI > RCI > RF Tertiary halide, secondary halide, primary halide, CH_y(
ClilJVhfJhl
-✓ --- ~ ' /'.( Bolling polnl ol lsomorlc heloalkanes docreose with
t,rtuml Cl For SN1 reaction
Cl
l: lncrooso In branching
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 ~
• For a given alkyl group react1vIty of halide follows . an d recemisation
(d) Inversion , retention • Replacement by hydroi•• n
same order m both the mechanisms , , ,r0<,i~
C2Hs C2Hs C2Hs
Cl
q I > R - Br > R - Cl » R - F H .... ,,L- y y /., ••H ~ /,, .. ,•H
Stereochemical aspects of nucleophillc
substitution reaction :
(inversion) ,~
H3C
B
~ x'i''
CH3
y~

A
CH3
(retention)
© (i) NaOH, 623K, 300 atm
(ii) H• ~
((,..
C,
/
Some important concepts Pres~nce_of an electron with draWing 1¥(>_
(a) Optical activity : A + B pos11ions increases the reactivity of ha ·
iOa-;,
50% 50%

0
The compounds which rotate plane polarised Cl OH

~ (I) N:OH, 443 K

(racemisation)
hoht are optically active
: If a ex>mpound rotates plane polansed light m (B) Elimination reactions
Br
~(ii)H ~
dockwise direction It is called dextrorotatory I
~~
Ale. N02 N0
2
~~~ Hofmann
and , 1 rotates in anti clock wise direction it is KOH/6
Major KOH/A Minor product
called laevorotatory (8) Electrophilic substitution reactions :
(b) Molecular asymmetry, Chirality and enantiomers: Saytzeff product
Haloarenes undergo electrophilic reactions
1

• 11 the spatial arrangment of four different groups benzene ring such as halogenation, nitratio,
(C) Reaction with metal
around the central carbon is tetrahedral then the
• Preparation sulphonation and friedel crafts reaction.
carbon Is called asymmetric carbon dry MgBr
/'--.../ Br + Mg -:-'---7./"-.../
ether
• The compounds which are non-superimposable on Reaction with metals
their mirror images are Chiral and are called Grignard reagent (i) Wurtz-Fittig reaction
(Organometallic compound)

~ •Na>RX ~ ©fR
enantiomers
• The stereo,somers having no mirror image RMgX + H20 ~ RH + Mg (OH)X
Hydrocarbon
relationship are called diastereomers.
Reaction of Haloarenes
• Amixture containing two enantiomers in equal (ii) Fittig reaction
(A) Nucleophilic substitution : Ary! halides are extremely

©
proportions will have zero optical rotation. Such X
mrxture 1s known as racemic mixture. less reactive towards nucleophilic substitution reactions
due to following reasons : 2 + 2 Na Ether©@
(c} Retention : In general, if during a reaction, no
bond to the stereocentre is broken, the reaction is (i) Resonance effect : Lone pair of chlorine is in Diphenyl
said to proceed w11h retention of configuration conjugation with benzene resulting in double bond Polyhalogen Compounds
character of C - Cl bond. As a result bond cleavage
CM
, J ~ !
<?H,
in haloarene is difficult. 2CHCI 3 + 0 2 ~ 2COCl2 + 2HCI
H - r - CHi-OH •HCI --"-? H j-CH2-Cl+H2') Phosgene
CH CH2 (ii) Difference in hybridization of carbon atom in C- X bond
I , I (iii) Instability of phenyl cation
CH1 CH3
(iv) Repulsion between haloarene and approaching
(-)-2-methylbutan-1-o, (+)-1-chloro-2-methylbutane
nucleophile

'---------------
Corporate Office: Aakash Tower, 8, Pusa Road New Delhi' 11000S Ph
' - . one: 011-47623456
 - 18
Chapter
r1,i PR[PARAflON or ALCOHOi
rom 11lk11M1Jti
) Hy odtl Ul\lllY!ifJd liydralltm
s
(n) , (2) PREPARATION OF PHENOLS
rom haloarenes _Na'
• Acidity of alcohols : Acidic strength order

0 0,Q
R R'\.
R- CH,OH >R)CHOH > RFICOH
CII.C,11 C,ll, 1 11,0, 11' '·CH ~11 CH,(MrJjor)
b) ey hy,frohcJrolion 0l<lcfr1tln11
CII (,It
OH
C,H,1 (II tlli.), • CH CH, CHr BIi, 6 + NaOH 623 K )
300atm
(b) I rom ben,ono sulphonlc acid
I
-s:::
~
HCI Acidity of phenols : Phenols are more acidic than alcohol be~use
conjugate base of phenol (phenoxide ,on) is resonance slabthsed

(CH c,I IJ~H,)

lt,Ot3tt,Oj()II
jj
J,1I,CAI (,II
--
tel I CH- Cl t,
(Cl I C,I1,CI t,),BI t

0 Oloum ) 0SO ,H
(I) N~O~
v(ll)H
(c) From dlazonlum oalte+
I ~
u Cf-~-~-6-6
(ii) Esterificatlon : H+

15
'j(,fl /,H,UI/JH, [J(OH) Ar/R- O- H + R'COOH ~ Ar/ROCOR' + H,O
• lht. :1l1,,1Jh<JI f<Jr1111,tJ lrmka 11b II II hfl[j bnon frm11ud
by 1t1,, a,Jdlllim of wal 1J1 !CJ ,1lk1m1J In 'J w;,iy <ippoollu A NaNO,) 6N~Iu H,O OH
Ester
COOH
to M:J1hJmlkov'·1 r1Jl 1J,
F1u111 ,,:ir!Jonyl 1,wn11r11Jnd~
(o) fjy t1J<Jur,tltJfl ol ~Jltfohyd1J11 ~Jrld ~rJl!lf11Jl1 •
1-{(;H() 1 II, .bl, H(,H,0I1
V 2~r,1278 K
(d) From cumcme

CH(CH ,),
HC
lt:c_;c-o OH 0
Warm l l )

6 OH

Salicylic acid
+ AococH
+ (CH,CO),O ~ v + CH .COCH
(Aspirin)

1'<,ow lfaHH, ;,- H

011
(ill
I{' A
V
O
~ 0~ V H,O
1 ~
b
+ [Link],
(b) Reactions Involving cleavage of C-O bond in alcohols
(I) Reaction with hydrogen halides : (Lucas test)
ROH + HX > R- X + H,O
r • 0 no Cumono • Lucas reagent (Cone. HCI and ZnCI,)
O>) fly rurJur;tlm1 of ,,;;rbr!lyllc. ,'J<,irJu 11nrJ 1Jul1m, _,urn hydroporoxide • Tertiary alcohol produce turbidity with Lucas reagent lmmediatelv
~ l i t, • Primary alcohols do not produce turbidity at room temperature.
HGOOH (lijH,CJ >HCH,OH (3) PHYSICAL PROPERTIES
(II) Reaction with phosphorus lrihalides :
I llgh bolling points or alcohols are mainly due to the 3R OH + PX, > 3R- X + H,PO, (X = Cl, Br)
HC/JOH 1-''0H > H(,QOR' ~ RCH OH proijonco of lntermoi(JCUlar hydrogen bonding In them.
H
) f'rorn Gngmird nwyunl
Pd '
+ R'OH [ Solubility of alcohols and phenols in water Is due to their
ability to form hydrogon bonds with waler
(Ill) Dehydration
4~oK )
: C,H,OH ~ CH, = CH, + H,O
Relative ease of dehydration : Tertiary > Secondary > Primary
HCHO + f'Mq/ , RCH,OMg/H,O>RCH,OH
1• alcohol r (1) CHEMICAL REACTIONS .
[A) Reaction of alcohols
(iv) Oxidation
• RCH,OH ~ RCHO
HO PCC
PCHO-1 Fl'Mg/ ,R - yH-OMg/ ~ (a) Reactions involving cleavage of O-H bond • CH CH=CH CH,OH ~ CH,-CH=CH ..CHO
R' R H OH (i) Acidity of alcohols and phenols
1 • Reaction with metals _ ,. • R-CH-R'~ R-C-·R'

R
R' 2• alcohol 2R -0 H + 2Na , 2RONa + H, 6H ~
• Phenol reacts with aqueous NaOH Cu C
RCOP ~ R'MgX , R - 6 OMgX H,O ·i • RCH,OH 573 K) RCHO R-CH R ' ~ R-C- R'
I
R'
R-q
~
OH
X
u•NaOH ➔
A
ll)+HO
CH,
• CH -6-0H ~CH,-C=CH,
I
OH
573 K
0
11

I 573 K I
3' alcoho~ CH, CH,

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 - Alcohols, Phenols and Ethers

(BJ Reaction of phenols @ PREPARATION OF COMMERCIALLY IMPORTANT ALCOHOLS I Mechanism

(a) Electrophilic aromatic substitution ZnO-Cr2 0 3 CH
(i) Nitration . Methanol : CO + 2H, - - - - ' - - - ' - CH,OH I <t> Slow +
200-300 aim CH,-C b'tiO-CH ·~ (CH,),C+c~
OH OH OH
573-673 K I H s~~e ~r1,,..
lnvertase CH, --~"'
•0 Dilute ➔ o~ NO, + Ethanol : C,2 H220 11 + H,O ➔ C6 H,2 O6 + C6 H,,O6 +
V H N 03 Glucose Fructose (CH,), C + I Fast ➔ (CH,),C - I
6
0y
Zymase (ii) Electrophilic substitution
C6 H,,O6 > 2C,H5 OH + 2CO,
OH OH NO, (a) Ha/ogenation
• Ethanol is made unfit for drinking by mixing in it some copper
2 sulphate and pyridine. It is known as denaturation of alcohol. 1()0CH,
O,N◊,N0
Cone. > / (Picric acid) . AH
HNO, 9 @ ETHERS 8 r, in ➔
(Poor yield) Preparation of ethers H SO
·6 OH NO, OH (a) Dehydration of alcohols : CH3 CH, OH ; K• ➔ C, HsOC,H,
Ethanoic acid y+
4 3 Br M11i::
S03H O,N◊N02 -+ S2
Cone. > Cone.> / (b) Williamson synthesis : R-X + R' - ONa ~ R- 0-R' + NaX Major
• Alkyl halide is primary (b) Friedel-Crafts reaction :
H,SO, HN03 ~ .
-6 Q • Alkoxide ion can be primary, secondary or tertiary. • Alkylation
S03H NO, CH3...------.-. . ~ CH3
(ii) Halogenation I .:. + "' r~ I OCH, ~ H
OH OH CH3-C-0Na + CH,-Br ➔ CH,-C-0-CH,
I I c!;iJ+ CH,CI anhg;,AIC~, Q
Br, in CS, > 0 + c~ c~
.(5 273K • If tertiary alkyl halide is used, then only alkene is formed.
y ()"' CH3 H,
Br (Minor) I - + Major
(Major) CH,-C-Br + CH3- 0Na ~ CH,-C=CH +
2
I I
CH, CH,
Chemical reactions :
A Br,,}yBr
(i) Cleavage of C- 0 bond in ether : R-0- R + HX ➔ RX + R-OH
•v ~~ > (White ppt)
• The order of reactivity of halogen halides HI > HBr > HCI
y • Cleavage of ether takes place with concentrated HI or HBr • Acytation Minor
(b) Kolbe's reaction : 2, 4, 6-Tribromophenol at high temperature. OCH, H,
OH ONa OH Example 1 : Excess
CH,-O- C2 H, HI > CH3-I + C,H,-1 anhyd>
A NaOH> (_i_) C?') ~COOH @+CH,COC/
A/Cl,
V
0
V S 1· ••~ft H
tep- · CH,-Q- CH2 CH3 + H- 1~ ➔
<u)H(Salicylic
V acid)
(c) Reimer-Tiemann reaction
CH3-0-CH CH, + T
+ 2 0~ CH,
-
q H S2 Major
OH ONa ON a OH Step-2: I H3c i- CH, CH3 - - 4 CH3-I + CH, CH, OH
-+ j -+ +
CHC/ CHO
CHC/ I~ ~ Nao7, --1£.:,.~CHO
aq Naoi-r' fll ~
V v- V Step-3:CH, CH,- .. ~- fa,::;:--)
I ~ CH CH -0H + -I
3 2
(d
6 ~
Reaction with Zinc dust and chromic acid
0 OH
Sa/icylaldehyde
Step-4: n + S,2
2 l9J 'CH,
(c) Nitration :
I + yH,~H,---"---> CH,CH,-1 + H,O Minor
OCH,
~~~r,O +ZnO CH, CH,
NO, o C H,
0 ~ o--:::,~
yff) , . ~ I S 1 A H,so.
Example 2 : CH,-C-0-CH, + Hl--4cH,OH + (CH,),C-1 HNO, ➔ + I
___.!f, •nzogu,none I V ~
CH.,
----=---=------------__,, '-------
6
Minor
~~~
No
Major
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 19
Chapter

ALDEHYDES AND KETONES

(D PREPARATION OF ALDEHYDES (ii) From nitriles
NMgBr R 0
II R;=o+ r-°H HCl gas ,
(i) From acyl chlorides (Rosenmund reduction) PhMgBr
/ O J+Hp
CH 3CH 2C = N ~ C H 3CH 2 - C - Ph
R LoH ' dil HCI
0 R
~I H, ~O H,O. II Ketone

u__} Pd-BaSO, V --'---CH 3CH 2 - C - Ph

(iii) From aromatic hydrocarbons o
0
(ii) From Nitriles and Esters
~ +R-CII_ anhyd.
0 Stephen reaction V Cl AICl3
HO'
RCN + SnCl 2 + HCl-+RCH = NH-2......... RCHO (d) Addition of ammonia and its derivative

(Reduction by DIBAL-H
@) CHEMICAL REACTIONS
Z = alkyl, aryl, - OH, - NH 2 , C6H5NH etc
(i) Nucleophilic addition reactions
~ (i) DIBAL-H ~ Carbonyl derivative Product name
Reagent
'--: CN (ii) H,O ~ CHO (a) Addition of hydrogen cyanide (HCN)

~ C2H5
O
(i) DIBAL-H .,,,,......__/'-.. ,,..H
(ii)H,O • - g
'&- __,,_f,, JS ..,-- f
_9, = 0 + CN ..,--
CN
.J:L,. , ))H
CN
Ammonia >=NH lmine

Cyanohydrin Schiffs base

(iii) From Hydrocarbons Amine >=NR

r
{b) Addition of NaHSO3
~ Etard reaction
CH 3 CHO + NaHSO3 x O3

ONa
H Hydroxylamine >=N - OH Oxime

6 ~ + cr02c12
s
'
__
1 /.
(Chromium
Complex)
H(OCrOHCI,), Ho'
6
--2.......+ 1 /.
Proton
' transrer
\/ \J30
_
OH
Na3 Hydrazine >=N-NH 2
Hydrazone

NO2
-, Gatterman-Koch reaction (Crystalline)
CHO o Bisulphite addition product is crystalline 2,4-DNP )=N - NH-@- NO 2 2, 4- Dinitrophenyl-
A CO, HCI A o It is water soluble and converted back to original carbonyl
hydrazone
V [Link] ~ compound by treating it with acid or alkali
0
Semicarbazide )=N-NH J!-NH 2 Semicarbazone
o It is useful for separation and purification of aldehydes.
@ PREPARATION OF KETONES (c) Addition of alcohols :
(ii) Reduction
Ct) From acy1 chlorides
OR' OR' (a) Reduction to alcohols . Aldehydes and ketones are
R'OH / R'OH /
2R- Mg- X + CdCl 2-R,Cd + 2 Mg(X)CI RCHO ~ - CH ~R-CH reduced to primary and secondary alcohols respectively]
HClgas "\OH H' "\
0 0 OH by NaBH 4 or LiAIH 4
II II Aldehyde Hemlacetal Acetal
2P' C - Cl + R,Cd ---+2R' - C - R + CdCl 2 (b) Reduction to hydrocarbons

- - - - - - -------::--:::----::--:---:--::-- -:-:::-----::---:--:-:---=----::--:-----:~--=--- - - - - - - - - -- - -- - - - - - - -
Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone: 011-47623456
 -- . H (Cl
)=o z~.:.is + 2O emmensen red t· )
> uc ,on '(il} Cross aIdol conden
I \" I stat ion (c) From rntn
)=o k'i,.=._NH fes and:--:--am-id-es--"
' N -N H 2 _ l<OHIOHOH -
_..... 0
1 )-+ N t @CHOO@ ' -
2
>= I
O + 0 - 0
1 R - CN H or O H R fl
HO
OH
(W o lf f- K is h - C- N 11° r,o
(Iii) Oxidation n e cr e d -o ) O II 2 H2--=-~ -i
J Aldehydes ar
j CH = CH - C
0 I- -- .
e 0XK11sed to
~ CONH
carboxylic ac Other reactio 2 COO H
w.:h co m m on id s on treatm
ent ns -@
ox id is in g ag (v) Cannizz
en ts lik e H aro reaction
N 03, K M nO
K2Cr20 1 etc ,, 0
2 HCHO Cone KOH
Mild o xi d is
in ~
CH 0 H + H II
@~@•NH,
g a g e n ts
(T es ts o f 3 - C - 0 -K• (d) From Grig
To lle n· s te a ld e h yd e s) nard reagents
st : Silver
a ld e h yd e mirror is fo
rmed on w CHO
w it h fr e sh arming CH;OH
ly p re p a re
d am m on
COO-Na• R - Mg - X + Dry 0
A gN 0 solutio
3 n (To ia ca l 0 = C= 0 -R II
i/en ·s reagent) Ethe - C r o1
-v
RCHO + 2 [A
g(NH H,o•
,@°"°,~•" @,@
3)if + 3OH-+ RC
OO- + 2Ag (vi) Electroph
2H20 + 4NH ili c substitutio -- -- + R -
3 n reaction (e) From acyl
halides
Fehting's Te 0 and anhydrides
st :
J On heating al X HNO,IH,SO,
RCOCI H,O
dehyde with ~OCHO R - CO0H +
brown precip Fehling·s re
agent, a redd lS J (C H CO);O
er
itate is obtained ish 27 3- 28 3K 6 5 H ,O 2C 0 C 0 0 H
6 5
R - CHO • 2C 2
l 2 , lN0
u • + 50H-+R 2
COO + Cu 0 (f) F ro m esters
2 v+ 3H20 I 1
JA ro m at c alde (red-brown COC H
hydes do no ppt) 2 5 COOH
t respond to
© CARBOXYLIC ACID
Haloform re
ac tio n : this test o Methods S
of Preparatio
OXidatJon of n
methyl ketone (a) From prim
0 s ary alcohols
II 0
@~@•C,H
,OH
X,,
R -C -C H
3~R
II RCH20H Walkaline KMnO, 0
- C - 0 .N •
a+ ··i H •
(11 30 RCOOH NaOH
..[Link].,........__ ~
CHXiX = Cl, CH3CH2C
, lodoform re Br, I) CH (CH ) CH
Et hy l bu ta no H2C0O -Na + C
action with i}N 3 2 a 2OH era, - H,so, at e
aO H is used Jones reagen
for detection t CH3'C
C H1C O or of (b) From al H2)8COOH 1H 0 '3
CH 3CH(OH
) groups ky lbenzenes
C \i, C H O grou w hi ch produces
p on oxidation. CH3CH CH
2 2 COOH
CH3 Bu ta no ,c ac
(iv) Reactio
n due to CL-h COOK ,d
ydrogen COOH
Aldol condensa @ PHYSICAL
0
PROPERTI
tion reaction
: D ue to e xt ES
e n si ve as
2CH, - CHO dJ NaOlf ,
@"~r'™ @~@ so ci at io n
b y in te rm ol
CH 3 - yH - H-bonding ca ec ul a
CH2 CHO rb ox yl ic ac id
s ha ve hi gh
OH al de hy de s, er bo ili ng point than
~
-H CH
ke to ne s an
,0 3- CH = CH - C d al co ho ls
HO
J @~~.-,., ~~
--- molecular m o f co m pa ra
-- ass. bl e
~OH
'- 0
In vapour ph
as e or in ap
rotic so lv en
Corporate O --__
, / '--
acids exist as
di m er
t m os t carb
oxy/ic I
ffice Aakas
h Tower, 8,
Pusa Road, l
N e w Delhi-1
- - - - - ~ - - - ~ -~ -
10005. P h o
n e : 0 1 1 -4 7
--)
623 456
 Aldeh des, Ketones and Carboxylic Acids -

-
~' CHEMICAL REAC~;-----...., ,
(b) Reaction 1 - , -
Reactions involving cleavage of 0 _ nvo vlng cleavage of C- 0H bond (c) Reaction, ln-,oMng - COOH group
(.) H bond
(Acidity) (I) Formation of anhydrides (i) ReduclJon

2RC00H + 2Na ➔ 2RCOO-Na • + H2

,? 0
\\ · 0 0
RC00H + NaOH ➔ RCOO-Na • + H20 CH3- C + C - CH ~ _jj \\-
\ I 3 or \ / (ii} Decarboxylation
OH HO P,0,/6 0
RC00H + NaHC03 ➔ RCOO-Na++Hp+ co 2t Ethano,c anhydride

., eart>oxylic acids evolve CO 2 gas on reaction with NaHco . (ii) Esterification

3 (d) Substitution reactions in the hydrocarbon part
This is used to detect the presence of carboxyl group in an R H'
COOH + R'0H ~ RC00R' + H20 (i) Halogenation (Hell- Volhard-Ze nsry reaction)
organic compound .
(iii) Reaction with PCls, and S0Cl2 X
Carboxylic acids dissociate in water to give resonance 0))(/RedP I
RCH 2 - - - - o R - CH - COOH
C00H - (ii-) ~ 0
stabilised carboxylate anions and hydronium ion RCO0H + PCls ➔ RC0CI + P0Cl 3 + HCI X = C B•

RC00H + S0Cl2➔ RC0CI + S0 2+ HCI (ii) Ring substitution

(iv) Reaction with ammonia o Aromatic carboxylic acids undergo electrophilic

J Effect of subslituents on the acidity of carboxylic acids :

~COOH
V + NH3~ I "
-+
OC00NH
4
....:
~
-H20
6C0NH
1/
~
I
2
substitution reaction
o They do not undergo Friedel-Crafts reaction because
the carboxyl group is deactivating and catalyst
Ammonium Benzamide
9
Electron withdrawing group (EWG) benzoate aluminum chloride gets bonded to carboxyl group
~ - ( stabilises carboxylate anion and increases -+
o Nitration
O acidic stength C00H @(COONH 4
(Phthalic acid) + N3 H ~ Q
. ~?_ Electron donating group (EOG) destablises
@( C00H CO0N'J:i 4
Ammonium A
C00H CO0H

@g:) 7 the carboxylate anion and decreases phthalate

~
Conc. HNO3
Cone. H2SO,
0 acidic strength
J Acidic strength order of some carboxylic acid
CF,COOH > CCl,COOH > CHCl,COOH > NO,CH,COOH>
0 +-'",01 o Bromination m-nirtobenzoic aad

NCCH,COOH > FCH,COOH > CICH,COOH > BrCH, COOH >

HCOOH > CICH,CH,COOH > C,H,COOH> C,H,CH,COOH >

(Phthalimide)
c¢ 0
~ C 0 N H2
NH~
heating C0NH 2
Phthalamide 6~
C00H C00H

Br
CH,COOH > CH,CH,COOH
m-bromobenzoic acid
Direct attachment of groups such as phenyl or vinyl to the carboxylic

acid increases the acidity of corresponding carboxylic acid,

Contrary to the decrease expected due to resonance effect.

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 rv
CHEMICAL REACT/Ofi~

RNH
CLASSIFICATION

R 'N - H
R,
R
'N - R"
R''
II f

I
(Ill) Reduction of Nitrites

R CN
LIAIH4
or H /NI or Nn(Hg)ICz H50H

(Iv) Redttioa of amides

R CH2-NH2
(I) Basic character of amines
'J Order of bascity of amines mgase01Js ~a-*
tertiary amine> secondary amine,, r,r1tr:;• ~
Pnmal)
1) (2 )
Seco~dary r,~~~ry I
11
R - C - NH2
(I) LIAIH,
(Ii) H,O
R _ CH _ NH2
2
0 Basic nature of amines maqueous me,, u~
1

Am nes re said lo be simple when all !he alkyl groups are b . I hthalimlde Synthesis (a) (C2Hs)2NH > (C2Hs)3N > C2HsNH2>t,~

A
.:~~,::::::~;! CHJ-NH-CH,CHJ
1@:'°" o}•R-X cr5-R o 0
0 ry
(b) (CH3)2NH > CH3NH2 > (CH3)3N >NH
A I amines are less basic than alkylam res ::,,.-2
. . ,.,..
arylamine the lone pair on nitrogen ,nvo.1,,.1 -
resonance.
,s
Propan 2-am ne O

6H,l,
N-methylethanamine
(ii) Alkylation
coo-
Cr
JNaOH(aq) R - NH2 + CH3 - Br~ RNH - CH3 + HBr
R-NH2
_ + (1°-amine)
~NH coo
(iii) Acylation
Propan-2-en-1-amine N,N-Dimethylbenzenamine ;) This method is useful in the preparation of aliphatic 0
primary amine ••
C2 H5NH 2
l ~ C2 Hs - NH - 0C - C-
+ CH3 - CII - CBase
3 PREPARATION OF AMINES (nY NH2
0
Aromatic primary amine ~ is not prepared by
(I) RCKfuction of n1tro compounds (iv) Carby/amine reaction (chemical test)
R - NH2 + CHC/3 +3KOH ~ R - NC+ 3KCi - JH;O
H~ this method because arylhalide donot undergo
a PhNOz Elharlal PhNHz nucleophilic substitution reaction.
(vi) Hoffmann bromamide degradation reaction
It is used as a test for primary amines
b PhNO 6n'HCI PhNH 0
1
~Fe• HCI
II (v) Reaction with nitrous acid (With primary alipha!JC a:
Ammonofysls of Alkyl Halides R - C - NH2 + Br2 + 4NaOH - R - NH + Na CO
2 2 3 R - NH+ HNO2 NaNo,➔ {R- Z2cn H,o,, ROH+ N2 · f;

~ RNHz
2 HCI
Wi •R '"
·0 x- RN•H X, + 2NaBr + 2H2O
:.> Primary amine formed contains one carbon less than that (vi) Reaction with ary/su/phonyl chloride
present in the amide.
R/,ix (Hinsberg's reagent)
RNH RX RiNH RY R3N ~ Quaternary
-. (? ) - (J•) ammonium salt I @ PHYSICAL PROPERTIES o Reaction with primary amine
AmrYlonolys ha disadvantage or y,elding a mixture of
5
primary &eCOndary tertJary amines and also quaternary
I,
Aniline and other arylamines are usually colourless but
get colour on storage due to atmospheric oxidation
PhS02 CI+ C2 Hst.JH2 - PhS0 NHC H
2 2 5
(Soluble ,n a11<a1,,
8 [Link] 1 / , Lower aliphatic amines are soluble in water because they o Reaction with secondary amine
p marya ersobla nedasmaiorproductbylakinglarge / , form hydrogen bonds with water molecules. PhS02 CI+ (C2 H5 ) 2 NH- PhS02 N(C2HsJ2
er ofUH _j Order of boiling points of isomeric amines: Primary > (insoluble ,n a"-86)
Secondary> Tertiary
u Tertiary amines do not react with benzensulphony/ /
--J, chlorides. __
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Aakash Tower, B, Pusa Road, New De/hi-110005. Phone: 011-47623456
 Amines -
) [Link] substitution reaction ;
(a) eronilnatlon r
II\
(8\DIAZONIUM SALTS (b) Hc?[Link] by IOdidc Klf'
NH NH.
ArN2Cf +Y.1 ➔ Ari + -'. cl + r12

I
Primary alip lrn tlc amine s form highly un stabl e
'Br,
(S;HP
Br~ ' -
Q J Br
(While prec,plluto)
(2, 4, 6-lnbromoanlllno)
alkylctlazonlum salts

' Primary aromatic amines form arenodiazonium salts

(C) [Link] U/ fiu':lflde \00
. -\
ArMzC! + HBF• ➔ ArN;,BF'. - AI-F •BF+ N2
Br Which are stable for a short time in solution al low
0 0 temperature (273-278 K) due to resonance I (d) Replacement by H 1dr09en

NHA A IDf:\/ ID e ID e ID 41 \ ArNp + Hpo2 + HzO ➔ ArH + Nz • ~ o + HC

6C ~
fl.

0
N==N N=N N= N N!~ N= N 1

d-Ur-6) --:O- tJ
ArNp + CH)CHzOH ➔ ArH ... 1~2 .. C~CnO .. nC1
(CHCO),O
Pynd1ne 3~~-0H--.
-H- ~:--~
(e) Replacement by hydro1yl group
(l)
Br 2831<
ArN• 2CI. + H P ~ ArOH + tJ '-'Cl
,1
Br ''2 ..

N CIe
(Major) (i) Method of preparation of C H ID
6 5 2
(f) Replacement by - N0 2 group
(b) Nitration

\ Np N2BF N02
(ii) Physical properties 1
~ NatlO? 6
6"";:;so, ~+(~l~o,@No, solid and readily soluble in water.
~.......
Q
✓
+HBF. - - Q -
✓ Cu,~~
10
lJ t

N02 (47%) (2%) '.) It is stable in cold but reacts with water when warmed . B Reactions involving retenation of diazo group
(51%) Benzenediazonium Fluoroborate is water insoluble (Coupling reaction)
and stable at room temperature.
Controlled nitration reaction
CI-
(iii) Chemical reactions N
NH2 NHCOCH 3 NH COCH 3 NH Ill

~
2
A. Reactions involving displacement of nitrogen
~o y ~ ~o
~o N. OH

0 (CH3CO)P)
pynd1ne ~
HN03·H, SO,
288K y 0-H
(a) Replacement by halide or cyanide ion

Sandmeyer reaction @H2) ~ @-N•N-@-oH

N02 N0 2 phenol (Orange dye)
(Major) Cu 2CIJ HCI
ArCI + N2 p-hydroxyazobenzene
(c) Sulphonation Cu 2BrJ HBr CI-
Ar1\ x- ArBr + N2 N

6 ~so, 6 ~ ~~
♦

NH2 NH 3Hso; Ill

CuCN/KCN N• NH 2
ArCN + N2

Anilinium
453-473 K

so;
Gatterman reaction
Cu/HCI
: ArCI + N2 + CuX
@HS) ~@-N•N-@-NH,
hydrogen
sulphate
S0 3H
Sulphanilic Zwitter ArN2X- ~ Cu/HBr ArBr + N2 + CuX
aniline (Yellow dye)
p-aminoazobenzene
acid ion

u · .. Aakash Tower· 8· Pusa Road ' New Delhi-110005. Phone: 011-47623456

Corporate O111ce
 l /
I.) carbonyl group presemt is an aldehyde is confirmed by
1 CARBOHYDRATES

crasslflcatlon of Carbohydrates:
A. Monosacchartdes: A carbohydrate that cannot be
II the given reaction
CHO
{6HOH)4
COOH
~ (6 ~ 0H)4 (Gluconic acid) H 4 OH H~
t,ydrolysed fu:ther to g,ve simpler unit of polyhydroxy I HP ' s •• H I,
ad yde or ketone Examples· Glucose, fructose CH20H CH,PH
Acetylation of glucose gives glucose pentaacetate which
H QH l7
aT8b,noseetc .)
CH2 OH CH2 OH C•
6
a Oligouccharldes: These carbohydrates yield two to ten / / confirms presence offive OH groups tJ-0-t·,i;
CHO CHO O
a-0-( + )-glucose
monosacc:haride units on hydrolysis. They are further
I Acetic I II
ied as d sacdlandes, tnsacchandes etc. / / (CHOH)4 --- (CHO - C - CH3 )4 a and f3 forms of glucose are called anorr"T
C Polysaccharldes: They yield a large number of
I anhydride o
CH20H I II membered cyclic structure of glucose is called 11(
monosacchande units on hydrolysis. CHP-C-CH3
structure
Starch CeUulose etc
·) Gluc_ose an_d gfuconic acid is oxidised to saccharic acid
Monosaccharides. by mine acid. This indicates presence of primary OH CH2 0H H CHPH r
! a monosacchande contains an aldehyde group. 1I is group -
JlOWfl as an aldose and If contains a keto group, 11 is CHO COOH
~.atose I O. COOH H
(6Ho Oxidation

(a) Glucose· It 1s an aldohexose

I
CH20H
H)4--::.::..::.:..:....
I
(CHOH) < Xldalion
4 '
(fHOH)4
HO
H
H HO
H
COOH
Structure of glucose CH2 0H
Saccharic acid
Gluconic H OH H
1\85 beer assigned lhe structure
I J Fischer suggested followin
acid a-D-(+) -Glucopyranose
OH

CHOH • on tho basis of following evidences. II glucose g configuration

(b) Fructose
0
H~C~HO Fructose is a ketoh

I/ II
F exose
fomiua1sfoundtobeC H
. .o.
hea ng With HI 1! forms n-hexane,
HO
H
-H
-OH
0
,
o/lowing structur
es have been assigned to this mot
H -OH CH2 0H
w.l~;!,rl!:1 cal'bOr are bnked in slra1ghl chain / /
of carbonyl group Is confirm&d by the following I Cyclic Struc
C ,,OH Ho*',6:Ho 0 ~ c~H20H HOH2c"
H O·H : 0 OH
5
, The given observat10 tur of Glucose H • OH H HO ~ •

CHO
OH
I of glucose ns coul not explain ch
(1) II dot,s not react w1lh NaH 0
a1n structure
H

•CH,OH
' OH H •
, OH H H
•
HO CH
, '
UH OH 9HaN
OH• .:.::.:z;_ • fCHOlij
' . Pentaacetate of gluco
(11) or Sch1Jfs reagent
(111)Glucose exist in two d1~e d< es not react With NH 0
D-(-
)-fructose
u
_0
OH H
OH
·(-)-Fructofuranose /J·D-(->-F H

T:~: ;'
H H CHOH rvctofuranose
forms ere; t crystalline for , H
ms, uandlJ Both glucose Glucose and Fructose
Coq,orata Oft1co Aakash Feh/1ng's s0Ju11on Th ructose reduce Toi/en's reage t
rower
•
a' p usa Road l>J ey are a/so called red n and
ucmgsugars
• ew De/hi-110005
Phone
011 -4 7623456 -
~
teRT~::;..
5
---------------- ----------~~~~I M!llg1
Biomolccukw - . .

rw ,_,053cchandes
...,..
2 DISACCHARIDES
ore 101ncd together by an oxide
,
I 3 POLYSACCHARIDES
5 VTJAM
•e
1,. g 1orriod b)' loss of woter molecule forming a (i) Starch{ Amylase (15-20% of starch)
lido Such a hnkoge between two monosacchando Amytopochn (80 85% of starch)
(11) Water soluble vita
ttlr0ll!lh oxygen otom 1s called glycos1dic ltnkage
' Amylosu is water soluble component It ts long are water soluble vitammt
(I) Sucrose
unbranched chain with 200 1000 11•D·(+) glucose units
Name of Vitamin
' Amylopeclin Is water insoluble component. It is branched
1. VrtaminA
chain polymer of u·D glucose units.
2 '/rtam1n B (Tt-1amme)
(ii) Cellulose
3 Vitamin B2 (RiboflaVln)
I J It is a straight chain polysaccharide
Glycosidic Per~.;aous ~
H OH linkage 0 It is composed of P-D-glucose units 4. Vrtamin B, 2

0 .0-glucose
OH H
0-D-fructose (iii)Glycogen I15 Vrtamin C (Ascorbic acid) Sa;rvy
6. Vitamin D Rickets ~

l
0 It is called animal starch. osteomaiaaa ~ ~
1115 dextrorotatory 0 Its structure is similar to amylopectin and is rather more
lttS non reducing sugar Increased bloOd do: :'llJ t'le
7. Vitamin K
highly branched.
(ii) Maltose --------
6
CHpH @ PROTEINS
o All proteins are polymers of a-amino acid
0 The amino acids which can be synthesised in the body, are known as non-essential amino acidS
0 o The amino acids which cannot be synthesised in the body and must be obtained through diet are known as essef!'.
amino acids.
H OH H OH o In aqueous solution, the carboxyl group can lose a proton and amino group can accept a proton givmg nse to a dpolancn
o-D-glucose a-0-glucose
known as zwitter ion
, II Is dextrorotatory 0 0
> 1t1sreducIng sugar II II
R-CH-C-OH =" R-CH-c-o·
i It gives positive test with Tollen's reagent and Fehling's I I (Zwitter ion)
NH2 ~H 3
solubon
(iii) Lactose
Structure of Proteins
o Proteins can be classified into two types on the basis of their molecular shape

(a) Fibrous proteins:

0 ':> The polypeptide chains run parallel and held together by hydrogen and disulphides bonds gr.. ing fibre lii-.e structure

o They are insoluble in water e.g. keratin, myosin

H OH H OH (b) Globular proteins:

~-D-galactose ~-D-glucose In this case polypeptide chains coil around to give a spherical shape
0
, ltisdextrorotatory and is a reducing sugar 0 ------------~----~--~-----_ _,,
They are soluble in water e.g. insulin, globulin
' It reduces Tollen's reagent and Fehling's solution

~· . A kash liower 8 Pusa Road New Delhi-110005. Phone: 011-47623456

Corporate O,,,ce . a , ' '
 -----~
I~'.
@ NUCLEIC ACIDS
Complete hydrolysis of DNA(o, RNA) yields a pentose sug8', phosphoric acid and nitrogen containing hetemcyc/ic compound (called bases)
In DNA molecule, the sugar mo,ety is 0-O-2-deoxyribose whereas in RNA molecules, it is ~-0-ribose

HOH:Cw~
o H ~H HOH:Dc:
0
H ~H
H H
3 2
H H
3 2

OH OH
OH H
/3-D-ribose
:> Bases m DNA:Adernne (A). guanine (G), Cytosine (C) and thymine (T) /3-D-2-deoxyribose
:> Bases m RNA. Adenine (A), guanine (G), cytosine (C) and uracil (U)

s· 0
_ II s·
HO -H;_cpo
H ~~Se
O-r-O-H
2
wc~
o H ~~se
H H
3' 2' H H
3' 2'
HO OH
nuc/eoside HO OH
nucleotide

----------
Corporate Office · Aakash Tower, 8 , Pusa Road, New De/hi-

110005. Phone: 011-47623456