UNIT2;1

( SO<I= STATE )

STUDY MATERIAL QUESTIONS BASED ON HIGH ORDER THINKING SKILL

1 MARK QUESTIONS Q. 1. Name a liquefied metal which expand !n !lidificati!n. An . Gallium (Ga) is a silvery white metal, liquid at room temp. It expands by 3.1% on solidifi a!tion. Q. ". #!w man$ num%e& !f m!lecule pe& unit cell which c&$ talli'e in the f!&m !f end face cent&ed (m!n!clinic) lattice with a m!lecule at each lattice. An . ". Q. *. +hat i the c!!&dinati!n num%e& !f ca&%!n, in diam!nd An . # and its unit ell has $ atoms. %&he spa e latti e of diamond is '(() Q. .. Name the !lid which ha wea/e t inte&m!lecula& f!&ce An . I e Q. 0. A&&an1e the f!ll!win1 t$pe !f inte&acti!n in c!&&ect !&de& !f thei& inc&ea in1 t&en1th 2 3!4alent, h$d&!1en %!ndin1, 5ande& +aal , dip!le dip!le An . *ander +aals , dipole dipole , hydro-en bondin- , ovalent. Q. 6. 7i4e &ea !n f!& the appea&ance !f c!l!u& in al/ali metal halide . An . .ue to '! entres. Q. 8. +hich t$pe !f defect !ccu& in A1 9& An . / hott0y defe t and 're0el defe t. Q. :. 7i4e !ne example !f d!pin1 which p&!duce p;t$pe !f emi;c!nduct!& .
1

An . Ge doped with 1l. Q. >. Out !f (a) 7&aphite and (%) 3a&%!&undum which !ne i ha&de& An . (arborundum. Q. 1?. #!w can a mate&ial %e made am!&ph!u An . 2y meltin- the material and by oolin- it rapidly. " MARKS QUESTIONS Q. 1. 7i4e Rea !n 2 The ene&1$ &equi&ed t! 4ap!&i'e !ne m!l !f c!ppe& i ene&1$ &equi&ed t! 4ap!&i'e 1 m!l !f diam!nd. An . (opper is a metalli solid havin- metalli bonds while diamond is a ovalent solid havin- ovalent bonds. 3etalli bonds are wea0er than ovalent bonds and thus less amount of ener-y is required to brea0 metalli bonds than ovalent bonds. Q. ". The unit cu%e len1th f!& <i3l (Na3l) i 0.1. @A. A umin1 ani!n;ani!n c!ntact. 3alculate the i!nic &adiu f!& 3hl!&ide i!n. An .
Cl A

malle& than that !f

Li

Interioni distan e of 4i(l 5 6.1# 7 " 5 ".68 1 1( 5 5 AB 2 + BC 2 2.572 + 2.572

5 3.93 therefore, radius of (l: 5 ; < 3.93 5 1.$1 1 Q. *. 7i4e &ea !n 2 (a)
(%) An . (a)

=iam!nd and &h!m%ic Sulphu& a&e c!4alent !lid , %ut the latte& ha l!we& meltin1 p!int .
Am!n1 Na3l and 3 3l, 3 3l i quite ta%le. .ue to wea0 *ander +aal=s 'or e in /ulphur mole ule. "

(b)

(s(l oordination number is $. It is surrounded by $ anion ti-htly. 1

Q. .. #!w man$ unit cell a&e p&e ent in a cu%e haped ideal c&$ tal !f Na3l !f ma 1m An . 3ass of 1 unit ell 5 volume < density 5 a> < d 5 5 ?o. of unit ells in 1 -m a3 M Z N0a3 58.5 4 6.023 1023 5 173 5 9.@"3 < 1@"3 7 6$.6 < # 5 ".68 < 1@"1

Q. 0. In the mine&al pinalA ha4in1 the f!&mula M1Al"O.. The !xide i!n a&e a&&an1ed in 33B, M1"C i!n !ccup$ the tet&ahed&al 4!id . +hile Al *C i!n !ccup$ the !ctahed&al 4!id . (i) (ii) An . +hat pe&centa1e !f tet&ahed&al 4!id i !ccupied %$ M1"C i!n +hat pe&centa1e !f !ctahed&al 4!id i !ccupied %$ Al*C i!n -

1 ordin- to the formula, 3-1l"A#. If there are # oxide ions, there will be 1 3- "B ions and " 1l3B. 2ut if the # A": ions are and $ tetrahedral voids. (i) Cer enta-e of tetrahedral voids o upied by 3-"B 5 (1 7 $) < 1@@ 5 1".6% (ii) Cer enta-e of o tahedral voids o upied by 1l3B 5 (" 7 #) < 1@@ 5 6@% p in arran-ement, there will be # o tahedral

Q. 6. 7i4e &ea !n 2 (a) %) (c) An . (a) +ind!w 1la +ind!w 1la !f !ld %uildin1 l!!/ mil/$. !f !ld %uildin1 i thic/ at %!tt!m.

3a3l" will int&!duce Sch!tt/$ defect if added t! A13l c&$ tal. .ue to annealin- over a number of years -lass a quires some rystalline 3

hara ter.

(b)

Glass is not a true solid. 2ut a super! ooled liquid of hi-h vis osity. It has the property to flow.

( )

" 1-B will be repla ed by 1 (a"B ions to maintain ele tri al neutrality. &hus a hole is reated and latti e site for every (a"B ion introdu ed.

Q. 8. Anal$ i

h!w that nic/el !xide ha the f!&mula NiO .>:O1.??. +hat f&acti!n !f

nic/el exi t a Ni"C and Ni*C i!n An . ?iA.D$A1.@@ 4et ?i"B be x and ?i3B be @.D$ : x &otal har-e on ompd. is equal to Eero. %" (?i"B) B 3 (?i3B) : " (A":)) 5 @ " x B 3 (@.D$ : x) : " 5 @ x 5 @.D# &herefore ?i"B % 5 0.94 < 1@@ 5 D9% 0.98

?i3B 5 #% Q. :. +hat t$pe !f defect can a&i e when a !lid i heated - +hich ph$ ical p&!pe&t$ i affected %$ thi and in what wa$ An . +hen a solid is heated va an y defe t arises. &his is be ause on heatin- some atoms or ions lea ve the latti e site ompletely some latti e sites are va ant. 1s a result of this defe t the density of the substan e de reases, be ause some atoms leave the stru ture ompletely. Q. >. (a) (%) +hat happen when a De&&!ma1netic !& De&&ima1netic !lid i heated The i!n !f M1O and NaD all ha4e the ame num%e& !f elect&!n and inte&m!lecula& di tance a&e a%!ut the ame ("*0 E "10 pm). +h$ a&e the meltin1 p!int a&e ! diffe&ent ("6." @3 E >>" @3 An . (a) spins. (b) &he ions in 3-A arry two unit har-es. In ?a(l only one unit har-e. Fen e ele trostati for es of attra tion in 3-A are stron-er. Q. 1?. (a) If the &adiu !f the 9& i!n i ?.1:" nm, h!w la&1e a cati!n can fit in each !f the tet&ahed&al h!le. It han-es into parama-neti at hi-ht temperature due to randomiEation of

(%)

A1I c&$ talli'e in a cu%ic cl! ed pac/ed FnS t&uctu&e. +hat f&acti!n !f tet&ahed&al ite i !ccupied %$ A1 i!n -

(c) An . (a)

At what temp. &an1e, m! t !f the metal %ec!me 'or a tetrahedron the limitin- ratio is @.""6 : @.#1#

upe& c!nduct!& -

'or lar-est ation hi-hest value @.#1# would be onsidered. rB 7 r: 5 @.#1# rB 5 @.#1# < @.1$" 5 @.@86 nm. (b) ( ) In '(( there are $ tetrahedral voids. Aut of this ; is o upied by 1- ation. " 0 : 6 0.

Q1. Gxamine the illustration of a portion of the defe tive rystal -iven below and answer the followin- questionsH

(i) +hat are these type of va an y defe t alledI

(ii) Fow is the density of a rystal affe ted by these defe tsI

(iii) ?ame one ioni

ompound whi h an show this type of defe t in the rystalline state.

(iv) Fow is the stoi hiometry of the ompound affe tedI (" ma&/ )

Q". 1nalysis shows that a metal oxide has the empiri

per enta-e of 3 and 3 ions in this rystal. (" ma&/ )
"B 3B

al formula 3 A . (al ulate the

@.D9 1.@@

Q*. In an ioni ompound the anion (? ) forms ubi o upy one third of the tetrahedral voids.
!

lose pa 0in-, while the ation (3 )

B

.edu e the empiri al formula of the ompound and the oordination number of (3 ) ions. (" ma&/ )
B

Q.. &he radius of opper atom is 11$ pm. If opper rystalliEes in a fa e! entered ubi latti e, what is the siEe of the unit ellI (" ma&/ )

Q0. +hy are amorphous solids to be onsidered as super ooled liquidsI (" ma&/ )

J1. +hat is meant by the term (o!ordination noI 1nsH! ?o of atoms (sphere) by whi h the entral atom is surrounded. J". +hat is the o!ordination no of atomsH! (a) In a ubi lose pa 0et stru ture !1" (b) In a body entred ubi stru tureH!$ J3. 1 ubi solid is made of two elements C and J. 1toms of J are at the orner of the ube and C at the body entre. +hat is the formula of the ompoundI +hat are the o! ordination ?o. of C and J. 1nsH!CJ J6. 1nalysis shows that ni 0el oxide has the formula ?i@.D$ as I1.@@. +hat fra tion of ?i exit as ?i"B and ?i3B ionsI 1nsH! 4et the no of ?i"B ion 5 K ?i3B ion 5 @.D$ : K 1s per the question " K B 3(@.D$! K) 5 " " K B 3 K @.D$ !3 K 5" " K : 3 K 5 " ! 3 K @.D$5"!".D# K 5 @.D# K 5D# /o fra tion of ?i "B 5 D#% 1nd ?i3B 5 @9% J#. +hat is differen e between 'ren0el and s hott0y defe tI (any two) 1nsH! 'ren0el defe t / hott0y defe t (a) In this defe t shiftin- of i on (a) In this defe t there is missin- of equal from its position to interstitial site. no of ation and anion. (b) .ensity remain same. (b).ensity de reases. J6. /ilver (rystallises in f latti e. If ed-e len-th of the ell is #.@88 K 1@!$ mand density is 1@.6 - m!3. (al ulate the atomi mass of silver. 1nsH! density 51@.6 -m7 m3, L5#
d = zxM # xM = 3 "3 N @ xa 9.@"" x1@ x (#.@88 x1@ $ )3

+e Mnow

9.@"" x1@ "3 x1@.6 x ( #.@88)3 x1@"# # = 1@8.1# gm M =

Fen e atomi mass of silver51@8.1# -m. J9. (lassify ea h of the followin- as bein- either a p!type or an n!type /emi ondu tor. (a) Ge dopped with In!!!!p!type. (b) 2 dopped with /i!!!!n!type. J8. Lin oxide is white but it turns yellow on heatin-. GxplainI 1nsH! +hen Lin oxide is heated it loses oxy-en. LnA!!!!!!!! Ln"B B 17" A" B "e! Ln"B adopt the interstitial void and ele tron in the nei-hbourin- voids. .ue to presen e of ele tron in void, the olour is yellow. 8

J$. If ?a(l is doped with 1@!3 mole % /r(l".+hat is the on entration of ation va an iesI 1nsH! /in e 1@@ mole of ?a(l are doped with 1@!3 mol of /r(l" 1 mole of ?a(l are doped with 51@!371@@ mol51@!6 mol 1s /r"B ion introdu ed one ation va an y (on . Af ation *a an y51@!6 K 9.@""K1@"3 mol!1 59.@""K1@1$ mol!1 JD. +hat type of defe t arise when a solid is heatedI +hi h physi al property is affe ted by it and what way I 1nsH! *a an y defe t is reated, it is be ause on heatin- some atoms leaved the latti e site ompletely also the density de reases. J1@. +hat is the affe t of pressure on ?a(l type rystals I 1nsH! &he oordination ?o. of ?a(l in reases from 9 to $ . J11. 1l rystalliEes in a ((C stru ture. Its metalli radius is 1"6 pm. (i) +hat is the len-th of side of the unit ellI (ii) Fow many unit ells are there in 1 m3 of 1lI 1nsH! (i) In ((C a5 " " r 5" K #.1# K 1"6 pm 5 36# pm

(ii) *olume of 1 unit ell 5 (3.6#K1@!1@)3 5 #.## K 1@!"3 m3 1 = "."6 X 1@ "" unit ell in 1 m3 5 #.## x1@ "3 J1". +hat happens when ferrima-neti 'e3A# is heated to $6@ M and whyI 1nsH! 'e3A# on heatin- to $6@ M be omes parama-neti . &his is due to -reater ali-nment of domains in one dire tion on heatin-.

DOR 9E<O+ A5ERA7E ?1 Ma&/ Que ti!n

1. +hat is the number of atoms per unit ell in a i) ii) iii) ". /imple ube7primitive ube. 2ody entered ube. 'a e entered ube.

?ame the element with whi h sili on an be doped to -ive a (i) p!type semi ondu tor (ii) n!type semi ondu tor

3.

1 ube solid is made of two elements C and J. 1toms of J are at the orner of the ube and C at the body entre. +hat is the formula of the ompoundI +hat are the o! ordination number of C and J. $

#. 6. 9. 8. $. D. 1@.

+hat ma0es the rystal of M(l appear some time violetI +hat is the effe t of / hott0y and 'ren0el defe ts on the density of rystalline solidI ?ame a substan e whi h on addition to 1-(l auses ation va an y in it. +hat happens when ferroma-neti 'e3A# is heated at $6@ M and whyI +hat is urie temperatureI +hat is ferroma-netism different from parama-netismI +hat stru tural han-es will o ur if ?a(l rystal is subNe ted to hi-h pressureI

DOR A5ERA7E
1. 1n element (at. 3ass59@) havin- f stru ture has a density of 9."3 - m !3. +hat is the ed-e len-th of the unit ellI (1v-. onst. ? 5 9.@" x 1@"3 mol!1) ". &he density of (s2r, whi h has a 2(( stru ture, is #.# - m !3. &he ed-e len-th of the unit ell is #@@ pm. (al ulate the interioni distan e in rystal of (s2r (?15 9.@"3 x 1@"3, 1t. 3ass of (s5 133, 2r5 $@) 3. &he omposition of a sample wustite is 'e@.D3 A1.@@, what per enta-e of the iron is present in the form of 'e(III)I #. ?a(l rystalliEes in '(( stru ture. Its density is ".196 -m m !3. If the distan e between ?aB and its nearest (l! is "$1 pm. 'ind out the 1vo-. ?o. (?a5"3 - mol !1, (l 5 36.6 - mol!1) 6. &he ompound (u(l has Ln/ stru ture and the ed-e len-th of its unit ell is 6@@ pm. (al ulate the density. (1t. 3ass, (u593, (l536.6, ?159.@" x 1@"3)

DOR 9E<O+ A5ERA7E ?" !& ?* Ma&/ Que ti!n

1. (al ulate the effi ien y of pa 0in- in a ase of metal rystals for simple ube or body entered ube or fa e entered ube (with the assumption that atoms are tou hinea h other) ". Fow an you determine the atomi mass of an un0nown metal if you 0now its density and the dimension of its unit ellI Gxplain. 3. If the radius of the o tahedral void is r and radius of the atoms in lose pa 0in- is R. derive relationship between r and R. #. Gxplain the followin- with suitable examplesH (a) 'erroma-netism (b) Carama-netism D ( ) 'errima-netism

(d) 1nti ferroma-netism (-) / hott0y defe t (N) .opin-

(e) 1"!19 -roups

(f) 13!16 -roups

(h) 'ren0el defe t

(i) '! entre (l) p!type semi ondu tor

(0) n!type semi ondu tor

(m) (ondu tor7 Insulator7 /emi ondu tors.

NUMERI3A< BRO9<EMS
1. ". If ?a(l is doped with 1@!3 mol%. +hat is the on entration of ation va an iesI 1luminum rystalliEes in a ubi of aluminumI 3. /ilver forms ccp latti e and x!ray studies of its rystal show that ed-e len-th of its unit ell is #@$.9pm. (al ulate the density of silver (1tomi mass 5 1@8.D u) #. ?iobium rystalliEes in body entre ubi stru ture. If density is $.66 -m7 . lose pa 0ed stru ture. Its metalli radius is 1"6pm.

(a) what is the ed-e len-th of unit ellI (b) Fow many unit ells are there in 1.@@ m3

(al ulate atomi radius of niobium usin- its atomi mass D3. 6. /ilver rystalliEes in fa e latti e. If ed-e len-th of the ell in #.@8 x 1@!$ m and density is 1@.6 -m7 . (al ulate the atomi mass of silver. 9. Gold (atomi radius 5 @.1## nm) rystalliEes in a fcc unit ell. +hat is the len-th of a side of the ellI

8.

1n element (1tomi mass 5 9@) havin- fcc stru ture has a ell ed-e of #@@ pm. +hat is its densityI ?1 5 9.@"3 x 1@"3.

DOR A9O5E A5ERA7E

1. ". 3. #. 6. 1nalysis shows that ni0el oxide has the formula ?i.D$A1.@@. +hat fra tion of ni 0el exists as ?iB" and ?iB3 ionsI 1n element (atomi mass 5 9@) havin- fa e entred ubi unit ell has a density of 9."3 -m7 . what is ed-e len-th of unit ellI 3etalli -old rystalliEes in a fcc stru ture and has a density of 1D.3 -m7 . (al ulate the radius of -old atom. %atomi mass of 1u51D8, ?15 9.@"3 x 1@"3) Onit ell of an element (1tomi mass 5 1@$ and density 1@.6 -m7 ) has an ed-e len-th #@D pm. .edu e the type of rystal latti e. 1n element has a body entred ubi stru ture with a ell ed-e of "$$ pm. &he density of the element in 8." -m7 . Fow many atoms are present in "@$ -m of the elementsI

1@

UNIT2;" SO<UTION

STUDY MATERIAL
1. ". a) b) ) d) e) f) -) h) i) 3. a) /olution H Fomo-eneous mixture of two or more pure substan es. &ypes of solutions H /olid in solid solution. G-H 2ronEe, 2rass. 4iquid in solid solution. G-H Lin !amal-am. Gas in solid solution. G-H /olution of hydro-en in palladium. /olid in liquid solution. G-H 1queous /odium (hloride sol. 4iquid in liquid solution. G-H Gthanol dissolved in water. Gas in liquid solution. G-H (arbondioxide dissolved in water, ammonia dissolved in water. /olid in -as solution. G-H Iodine vapour in nitro-en . 4iquid in -as solution. G-H +ater vapoursin air, (hloroform vapour in nitro-en. Gas in -as solution. G-H +ater -as, Crodu er -as. (on entrations of solution H 3ole fra tion ( K)H

Ksolvent 5 nsolvent 7nsolvent B nsolute Ksolute 5 nsolute 7nsolvent B nsolute b) ?ormality (?) H

? 5 +27G2 x 1@@@7* ) 3olarity (3) H 3 5 +2732 x 1@@@7* d) 3olality (m) H m 5 +2732 x 1@@@7+1 +2 5 3ass of solute in -ram. +1 5 3ass of solvent in -ram. 32 5 3olar mass of solute. * 5 *olume of the solution. G2 5 Gquivalent wei-ht of the solution. #. Fenery=s 4aw H 3ass of -as dissolved per unit volume of the solvent is dire tly proportional to the pressure of the -as in equilibrium with the solution. 4imitations H ?ot appli able when pressure is very hi-h. 11

?ot appli able when the temperature is too low. ?ot appli able when the -as is hi-hly soluble. ?ot appli able when the -as rea t hemi ally with solvent and disso iate and asso iate in the solvent. 6. (olli-ative Croperties H Croperties of solution whi h depends upon the number of solute parti les dissolved in it. G-H P.4.*.C, Asmoti pressure, Glevation of boilinpoint. 9. 8. $. *apour Cressure H Cressure exerted by vapours in equilibrium with its liquids at a -iven temperature. 4owerin- of vapour Cressure H Q C 5 C1@ : C (C1@ 5 v.p of pure solvent, p 5 v.p of sol.) Pelative lowerin- of vapour pressure H Patio of lowerin- of vapour pressure of pure solvent.

P.4.*.C 5 (C1@ : C)7 C1@ D. Pault=s 4aw H a) Cartial pressures of omponents in the solutions are dire tly proportional to their mole fra tions. b) P.4.*.C. of solution ontainin- non volatile solute is equal to mole fra tion of the solute. 1@. 4imitations of Paults 4awR a) 1ppli able only to dilute solution. b) 1ppli able only to homo-eneous solution. ) 1ppli able to the solution in whi h solute doesnot under-o asso iation or disso iation. 11. 2oilin- Coint H &emperature at whi h vapour pressure of the liquid is equal to atmos%heri pressure. 1". Glevation of boilin- Coint H Q &b 5 &@ : & 5 0b x m. Fere &@ and & are 2oilin- points of pure solvent and solution. m 5 molality , 0b 5 Gbullios opi onstant. 1. 'reeEin- points H &emperature at whi h liquids and its solid phase have same vapour pressure. ". .epression of freeEin- point H Q &f 5 & ! &@ 5 0f x m. Fere &@ and & are freeEin- points of pure solvent and solution m 5 molality , 0f 5 (ryos opi onstant. 3. Asmoti pressure H Gxternal pressure applied to the solution to Nust prevent osmosis. #. 6. 9. 8. Asmosis H /pontaneous flow of solvent mole ule from lower on entrated solution to hi-her on entrated solution throu-h semi permeable membrane. Peverse Asmosis H +hen the applied pressure is -reater than osmosis pressure, the reverse osmosis ta0e pla e. (used in desalination plants to meet potable water) Isotoni solution H &he solutions havin- same osmoti pressure. 1Eeotropi mixture H 2inary mixture of liquids havin- same omposition in liquid and vapour phase and boils at the onstant temperature. 1"

a) b) $.

3aximum 2oilin- 1Eeotropes H 1Eeotropes boils at the temperature hi-her than the boilin- point of its omponents. G-H 3ixture of F?A3 (9$ %) and water (3"%) 3inimum 2oilin- 1Eeotropes H 1Eeotropes boils at the temperature lower than the boilin- point of its omponents. G-H 3ixture of Gthanol (D6%) and water . Ideal /olutionsH /olutions obeyin- Pault=s 4aw and solvent : solute mole ular for es are same as that of solvent : solvent and solute : solute mole ular for es.

G-H /olution of ?! Fexane and ?! Feptane, /olution of 2enEene and &oluene et . D. Cositive .eviation from Pault=s 4aw H /olutions havin- solvent : solute mole ular for es are wea0er than that of solvent : solvent of solute : solute mole ular for es .

Q Fmix 5 B ve, Q*mix 5 Bve and C S C1 B C2 . G-H solution of ethanol and a etone, solution of arbondisulphide and a etone. 1@. ?e-ative .eviation from Pault=s 4aw H /olutions havin- solvent : solute mole ular for es are stron-er than that of solvent : solvent or solute : solute mole ular for es. Q Fmix 5 ! ve, Q*mix 5 ! ve and C , C1 B C2 11. 1bnormal mole ular mass H 3ole ular mass al ulated by measurement of olli-ative properties differ from normal value due to asso iation or disso iation of solutes in solution.

3odified equation for olli-ative properties are a) b) ) d) 1". Q C7 C1@ 5 i K2 Q &b 5 i 0b x m. Q &f 5 i 0f x m. T 5 i ( P &. *anthoff fa tor H i 5 3 normal 7 3 observed ratio of observed value of olli-ative properties and normal value of olli-ative properties is alled vanthoff fa tor. 13. .e-ree of disso iation (U) 5 (i !1) 7 (n!1).

n 5 no. of parti les formed from disso iation of 1 mole ule. 1#. i 5 van=t hoff fa tor. .e-ree of asso iation (U) 5 (i !1) 7 (17n!1).

n 5 no. of simple mole ule to form an asso iated mole ule. 16. a) i S1 (solute under-oes disso iation). b) i ,1 (solute under-oes asso iation). ) i 51 (solute under-oes neither disso iation nor asso iation). 13

Important JuestionsH 1. .efine the 3ole 'ra tion of a substan es in a solution. +hat is sum of mole fra tion of all omponents in a three omponent systemI ". 3. #. 6. 9. Fow is the molality of a solution different from its molarityI (al ulate the density of F"/A# solution if molality and molarity are D#.6 and 11.6 respe tively. Fow many ml of @.1 (3) F(l required to rea t ompletely with a 1 -m mixture of sodium arbonate and sodium bi arbonate ontainin- equimolar amount of both. /tate Fenery=s 4aw for a solubility of a -as in a liquid. Give its appli ations (three) and limitationsI Gxplain the si-nifi an e of Fenery=s 4aw onstant MF . 1t the same temperature hydro-en is more soluble in water than Felium. +hi h of them will have a hi-her value of MF and +hyI +hat on entration of nitro-en should be present in a -lass of water at room temperatureI 1ssume a temperature of "6@ el ius. 1 total pressure of 1 atm and mole fra tion of nitro-en in air is @,8$ (MF for nitro-en is $.#" x 1@!8 37mm F-). Fenery=s 4aw onstant for (A" in water is 1.98 x 1@$ Ca at "D$ M. al ulate the quantity of (A" in 6@@ ml of soda water when pa 0ed under ".6 atm (A" pressure at "D$ M. 3ention some limitations of Pault=s 4aw. Orea form ideal solution of water. .etermine the vapour pressure an aqueous solution ontainin- 1@ % by mass of urea at #@@ (. (*.C of water at #@@ ( 5 66.3 mm F-.). .erive the equation to express the relative lowerin- of vapour pressure for a solution is equal to its mole fra tion of the solute in it when the solvent alone is volatile. &wo liquids K and V boil at 11@@ ( and 13@@ (, whi h one of them has hi-her vapour pressure at 6@@ (. 2enEene and &oluene forms ideal solution over entire ran-e of omposition. &he vapour pressure of pure 2enEene and &oluene at 3@@ M are 6@.81 mm F- and 3".@9 mm F- respe tively. (al ulate the mole fra tion of 2enEene in vapour phase if $@ -m of 2enEene is mixed with 1@@ -m &oluene. 1n aquous solution of " % non : volatile solute exerts a pressure of 1.@@# bar at normal boilin- point of solvent. +hat will be the molar mass of solute. (*.C of pure water 5 1.@13 bar).

8.

$.

D. 1@.

11.

1". 13.

1#.

1#

16. 19. 18.

1 person sufferin- from hi-h blood pressure is advised to ta0e minimum quantity of salt. +rite the name of two inor-ani substan e ( ompounds) whi h an be used as semipermiable membrane. 1@@ m- protein is dissolved in enou-h water to ma0e 1@ ml of solution if this solution has an osmoti pressure of 33.3 mm F- at "6@ ( . what is the molar mass of protein. ( P 5 @.@$"1 4 atm mol!1 M!1 and 89@ mmF- 5 1 atm). /tate ondition resultin- in reverse osmosis. Give one of its appli ation. .efine the followin- with a suitable example H a) 3aximum and minimum boilin- aEeotropes. b) .esalination ) Ideal solution d) 1bnormal mole ular mass

1$. 1D.

"@.

a) .efine *anthoff fa tor. b) +hat is the *anthoff fa tor for a ompound whi h under-oes tetramerisation in an or-ani solvent. ) +hat would be the value of *anthoff fa tor for 1) dilute solution of M"/A# in water ") ?a"/A#.1@F"A in water 3) Gthanoi a id in 2enEene d) +hen is the value of *anthoff fa tor 1) more than one ") less than one 3) equal to one

FintsH 3. m 5 1@@@ 3 7 (1@@@d : 332) , 35molarity, 32 5 molar mass of solute, d5 density of sol. d 5 1."# -m7 m3 #. 168.$ ml 8. Cartial pressure of nitro-en in atmosphere (C?") 5 Ctotal x K?" C?" 5 6D".$ mm F/olubility of ?" 5 MF x C?" 5 #.DD x 1@!# (3) $. MF 5 1.98 x 1@$ Ca , C(A" 5 ".6 atm 5 ".6 x 1.@13"6 x 1@!6 Ca C(A" 5 MF x K(A" , K(A" 5 1.618 x 1@!3 n(A"7(n(A" B nF"A) 5 1.618 x 1@!3 n(A" 5 #".1# x 1@!3 mole. 16

1@. 'rom Paults 4aw H (C1@ :C)7C1@ 5 K2 5 n27n1 C 5 63.#9 mm F-. 1". K has hi-her vapour pressure than V. 13. nbenEene 5 $@78$ 5 1.@"9 moles ntoluene 5 1@@7D" 5 1.@$8 moles KbenEene 5 @.#$9 , Ktoluene 5 @.61# 'rom Pault=s 4aw H C2en 5 C2en@ x K2en 5 "#.96 mm FC&ol 5 C&ol@ x K&ol 5 19.#$ mm F3ole fra tion of 2enEene in vapour phase 5 C2en7C2en B C&ol 5 @.9@. @ @ 1#. (C1 :C)7C1 5 K2 5 n27n1 32 5 #1.3# -m mol!1 19. (al ium phosphate , (opper 'erro yanide 18. 5(xPx& 5 +2 x P x &732* 32 5 13D$@.#6 -m 3ol!1 1$. Gxternal pressure -reater than osmoti pressure .esalination plant . "@. a) Patio of observed value of olli-ative properties to the normal value of olli-ative properties is alled *anthoff fa tor. b) i 5 W ) 1) 3, ") 3, 3) ; d) 1) solute under-oes disso iation in the solution ") solute under-oes asso iation in the solution 3) solute under-oes neither disso iation nor asso iation

1 MARK QUESTIONS Q. 1.The 4ap!u& p&e u&e !f delique cent u% tance i le !& m!&e than that !f wate& 4ap!u& in ai& 1ns. 4ess than that of water vapours in air. Q. ". If i the de1&ee !f di !ciati!n !f Na"SO. then w&ite the 5ant #!ff fact!& u ed f!& calculatin1 the m!lecula& ma . 1ns. 5 i : 1 7 m : 1, 5S (m : 1) 5 i : 1, 5S 1 B (m : 1) 5 i, 5S i 5 1 B (3 : 1), 5S i 5 1 B " . Q. *. If 6.?"* G 1?"? m!lecule !f u&ea a&e p&e ent in 1? ml !f it !ln. then what i the c!nc. !f u&ea !ln.1ns. ?@ 5 9.@"3 < 1@"3 5 1 mol 9.@"3 < 1@"@ mole ules 5 @.@@1 mol in 1@ ml N 1000 .001 1000 5 H ?.?1 M. v 10 1000 Q. ..+h$ camph!& i u ed in m!lecula& ma dete&minati!n 1ns. 2e ause it has very hi-h ryos opi onstant. It has lar-e depression in m. p. when an or-ani solute is dissolved in it. Q. 0.?.??. M !ln !f Na"SO. i i !t!nic with ?.?1 M !ln !f 1luc! e at the temp. +hat i the appa&ent de1&ee !f di !ciati!n !f Na"SO. 35 19

1ns. 86% Q. 6.+hat happen when man1! i placed in dilute aque!u !ln. !f #3l1ns. +hen man-o is pla ed in dilute aqueous soln. of F(l it swells. Q. 8. Out !f (a) "?? ml !f " M Na3l S!ln. and (%) "?? ml !f 1 M 1luc! e S!ln. which !ne ha hi1he& ! m!tic p&e u&e1ns.H (a) "@@ ml of " 3 ?a(l /oln. ?a(l is an ele trolyte whi h dissolve to -ive ions. Glu ose and urea are non ele trolytes. &hus -lu ose has minimum on . and hen e minimum osmoti pressure. Q. :.Out !f (a) ?.?1 M KNO*, (%) ?.?1 M Na"SO. which aque!u !ln. will exhi%it hi1h 9. B.1ns. (a) @.@1 3 ?a"/A# Q. >.Out !f (a) 1 M 3a3l" (%) 1 M Al3l* which aque!u !ln. will h!w max. 4ap!u& p&e u&e at *?? K 1ns. (a) 1 3 (a(l3, if we assume 1@@% disso iation, i for (a(l" 5 3 and 1l(l3 5 # and relative lowerin- of *. C. is dire tly proportional to i. Q. 1?. Out !f (a) #NO* C #"O and (%) 36#6 C 36#03#* which will f!&m max. %!ilin1 a'e!t&!pe 1ns. (a) F?A3 B F"A. " MARKS QUESTIONS Q. 1.Tw! !ln !f a u% tance (n!n;elect&!l$te) a&e mixed in the f!ll!win1 manne& I .:? ml !f 1.0 M (Di& t S!ln) C 0"? ml !f 1." M (Sec!nd S!ln). +hat i the m!la&it$ !f the final mixtu&e M1V1 + M2 V2 1.5 480 + 1.2 520 1ns. &otal molarity 5 5 5 1.*.. M V1 + V2 480 + 520 Q. ".T! 1et the ha&d %!iled e11 , wh$ c!mm!n alt i added t! wate& %ef!&e %!ilin1 the e11 1ns. .ue to addition of ommon salt the 2. C. of the salt ontainin- water elevated, hen e the e-- at hi-h temperature be omes hard. Q. *.Equim!la& S!ln. !f Na3l and 9a3l" a&e p&epa&ed in #"O. =. D. pt. !f Na3l i f!und t! %e I " @3. +hat f&ee'in1 p!int d! $!u expect f&!m 9a3l" !ln 1ns. i for ?a(l 5 " i for 2a(l" 5 3 32 &herefore &' (2a(l") 5 2 = 3 , &' for 2a(l" 5 3 X( , 'reeEin- Coint of 2a(l" /olution is TD H I * @3.

Q. ..+h$ wate& cann!t %e epa&ated c!mpletel$ f&!m eth$l alc!h!l %$ f&acti!nal di tillati!n1ns. Gthyl al ohol and water (D6.#% ethyl al ohol and #.9% water) form onstant boilinmixture (aEeotrope) boilin- at 361.1 M. Fen e, further water annot be separated ompletely from ethyl al ohol by fra tional distillation. Q. 0.+h$ a pe& !n uffe&in1 f&!m hi1h %l!!d p&e u&e i ad4i ed t! ta/e minimum quantit$ !f c!mm!n alt 1ns. Asmoti pressure is dire tly proportional to the on . of solutes. Aur body fluid ontains a number of solutes. An ta0in- lar-e amount of salts, ions enter the body fluid there by 18

raisin- the on . of the solutes. 1s a result osmoti pressure in reases whi h may rapture the blood ells. Q. 6.3hl!&! acetic acid i a m!n!p&!tic acid and ha Ka H 1.*6 G 1?I*. 3alculate %. p. !f ?.?1 M aque!u !luti!n- (K% H ?.01 / /1Jm!l) 1ns. Mb 5 @.61 0 0-7mol 5 Ma 7 ( 5 1.39 < 1@:3 7 @.@1 5 @.39$8 i51B 5 1 B @.39$8 5 1.39$8 &b 5 i < Mb m 5 1.39 < 1@:" < .61 5 @.@@9D X(

Q. 8.+hich c!lli1ati4e p&!pe&t$ i p&efe&&ed f!& the m!la& ma dete&minati!n !f mac&! m!lecule - +h$ 1ns. Asmoti pressure is preferred over all other olli-ative properties be ause H (a) even in dil. soln the !. p.values are appre iably hi-h and an be measured a urately. (b) !. p. an be measured at room temp. on the other hand elevation in 2. C. is measured at hi-h temp. where the solute may de ompose. &he depression in freeEin- point is measured at low temp. Q. :. #!w much eth$l alc!h!l mu t %e added t! 1 lit&e !f wate& ! that the !luti!n will f&ee'e at 1. @D (Kf f!& wate& H 1.:6 @3Jm!l) 1ns. (1# : 3") 7 D 5 ( 7 6 ( 5 6 < (: 1$) 7 D 5 : 1@ X( K 1000 Wb &' 5 F +b 5 mass of solute Wa Mb 3b 5 molar mass of solute +a 5 mass of solvent 1.86 1000 Wb 1000 46 +b 5 "#8.31 Q. >. 80." 1 !f phen!l i di !l4ed in !l4ent !f KD H 1., if the dep&e i!n in f&ee'in1 p!int i 8 /. +hat i the K !f phen!l 1@ 5 1ns. 3b 5 M' 5 1# 1000 K F W2 W1 TF &a0in- the solvent as 1 03b 5 1000 14 75.2 1000 7k 5 16@.# - per mol phenol (molar mass) Y D# -7mol Cal !la"#$ %&la' %a(( i5 )b(#'v#$ %&la' %a(( 5 D# 7 16@.# 5 @.9"6 " (9F6AF ZYYZ ((9F6AF)" 1 @ 1: 7" &otal 5 1 : B 7 " 51:7" i 51:B7" 5 1 : 7 " 5 @.9"6 7 " 5 @.386 5 @.86 % of asso iation 5 86%

1$

Q. 1?. #!w man$ ml !f ?.1 M #3l a&e &equi&ed t! &eact c!mpletel$ with 1 1m mixtu&e !f Na"3O* E Na#3O* c!ntainin1 equim!la& am!unt !f %!th 1ns. 4et the amount of ?a"(A3 be x 4et the amount of ?aF(A3 be 1 : x /in e no. of moles of both are equal * 1 * = N+Na2C)3 , M+Na-C)3 , * 1 * = 106 84 $# x 5 1@9 : 1@9 x x 5 @.668$ x?a"(A3 5 @.668$ 7 1@9 5 @.@@6"9 x?aF(A3 5 @.@@6"9 ?a"(A3 B " F(l YYYZ " ?a(l B (A" B F" ?aF(A3 B F(l YYYZ ?a(l B (A" B F"A 31*1 5 " 3"*" B 33*3 @.1 < *1 5 " < @.@@6"9 B @.@@6"9 *1 * 5 0.01578 0.1 5 @.168$ 4 5 168.$ ml.

Q.11 7i4en %el!w i the /etch !f a plant f!& ca&&$in1 !ut a p&!ce . (i) Name the p&!ce !ccu&&in1 in the a%!4e plant (ii) T! which c!ntaine& d!e the net fl!w !f !l4ent ta/e place (iii) Name !ne SBM which can %e u ed in thi plant (i4) 7i4e !ne p&actical u e !f the plant 1ns. (i) &he pro ess is alled Re4e& e O m! i . %Re4e& e O m! i 2 If the pressure applied on solution side ex eeds the osmoti pressure then the ! m! i an be reversed (i.e. pure solvent an be for ed out of the solution to pass throu-h the pores of membrane in opposite dire tion). &his is alled Re4e& e ! m! i ). (ii) &he solvent moves from sea water ontainer to fresh water ontainer. (iii) (ellophane (It is one of the semi!permeable membranes that an be used) (iv) &his pro ess is used for de alinati!n of sea water. Q.1" On inc&ea in1 the tempe&atu&e the !lu%ilit$ !f m! t !f the 1a e in wate& dec&ea e . An imp!&tant c!n equence !f thi effect i the thermal pollution of water, uch a !ccu& a&!und p!we& plant c!!led %$ a &i4e& !& t&eam. #!w i the u&4i4al !f fi h affected %$ the&mal p!lluti!n !f wate&1ns.H +hen the water temperature of the river or stream is in reases the solubility of oxy-en in water de reases. .ue to this de rease in dissolved oxy-en the survival of fish be omes difficult.[ Q.1* #!w much NaO# i &equi&ed t! p&eap&e 0? ml !f aque!u !luti!n with 8?m1 !f NaC i!n pe& ml. !f the !luti!nAn . 2 ?aB ions in 1 ml 5 8@ m?aB ions in 6@ ml 5 8@ < 6@ 5 3.6-

1D

Q.. 5!latile h$d&!ca&%!n a&e n!t u ed in the %&a/e !f aut!m!%ile a lu%&icant , %ut n!n;4!latile h$d&!ca&%!n a&e u ed a lu%&icant . An .2 &he vapour pressure of volatile hydro arbons is very hi-h and they -et evaporated leavin- behind the system. .ue to this they are not used as lubri ants in automobiles. ?on! volatile hydro arbons havin- low vapour pressure are used as lubri ants. Q.0 +hen f&uit and 4e1eta%le that ha4e d&ied a&e placed in wate&, the$ l!wl$ well and &etu&n t! the !&i1inal f!&m. Explain wh$ - +!uld a tempe&atu&e inc&ea e accele&ate the p&!ce - Explain. An .2 &he ell walls of the fruits and ve-etables have semi!permeable membrane. +hen they have dried, on entration inside is hi-her. An pla in- in water, water enters into the ells, i.e., osmosis ta0es pla e. Fen e, they swell and return to the ori-inal form. &he pro ess will be a elerated with in rease of temperature be ause osmosis be omes faster with in rease of temperature. J1. .efine osmoti pressure. 1nsH! &he extra pressure that must be applied to the solution side to prevent the flow of solvent mole ules into solution throu-h a semi permeable membrane is alled osmoti pressure. J". /tate Paoult=s 4aw for a binary solution ontainin- volatile omponents. solution ontainin- volatile liquid is dire tly propositional to its mole fra tion. J3. .efine *ant Foff fa tor. 1nsH!It is the ratio of experimental value of a olli-ative property to the theoreti al value. J#. +hat do you understand by olli-ative propertiesI but not on the nature of solute are alled olli-ative properties. J6. /tate any two hara teristi s of ideal solution. 1nsH! (hara teristi s of an Ideal solution . (i) mix H = @ (ii) p A =P A @ A , pB = pB @ B

1nsH! 1t a parti ular temperature the partial vapour pressure of ea h omponent of a

1nsH! Croperties of solutions whi h depend on the number of solute and solvent parti les

J9. 3ention a lar-e s ale use of the phenomenon alled reverse osmosis 1nsH! In desalination of sea water. J8. +hen is the value of *an=t Foff fa tor less than 1I 1nsH! *alue of *ant Foff fa tor is less than 1 in ase of asso iation of solute in solution. J$. +hen is the value of *an=t Foff fa tor more than 1I 1nsH! *alue of vant Foff fa tor is more than 1 in ase of disso iation of solute in solution. JD. +hy does molality of a solution remain un han-ed with han-e in temperature while its molarity han-esI "@

1nsH! 3olality of a solution depends on the mass of solvent and man does not vary with han-e in temp. where as molarity depends on volume of solution and volume han-e with han-e in temp. J1@. +hat are aEotropesI 1nsH! 1 liquide mixture whi h distills over without han-es in omposition is alled oEeotropes or oEeotropi mixture. J11. +hat are maximum boilin- aEeotropesI Give one exampleI 1nsH! 1 mixture whi h boils at temp. bri-hter than the boilin- point of its omponents the mixture is 0nown as maximum boilin- aEeotropes. G-! a mixture of F(l and F"A ontainin- "@."% of F(l by wei-ht. J1". +hat are minimum boilin- aEeotropesI Give one exampleI 1nsH! 1 mixture whi h boils at temp. lower than boilin- point of its omponents the mixture is 0nown as minimum boilin- aEeotropes. G.- water and 2enEene. J13. +hat is expe ted value of \i= for M#%'e((?)9) in dilute solutionI 1nsH! Gxpe ted value of n in M#('e((?)9) is 6. J1#. +hat are isotoni solutionsI 1nsH! &hose solutions are said to be isotoni whi h have the same osmoti pressure. J16. .efine molal elevation onstant or ebullios opi onstant. 1nsH! It is equal to the elevation in boilin- point of1 molar soln. i.e one mole of a solute dissolved in 1 0- of the solvent. J19. +hat are non!ideal solutionsI Gxplain as to why non!ideal solutions deviate from Paoult=s 4aw. 1nsH! ?on ideal solution are those whi h do not obey Paoult=s law. +hen the mole ular intera tion between solute mole ules solvent. /olvent mole ules is not same as the mole ular intera tion between solute ] solvent mole ules then deviotion o urs. J18. +hat are olli-ative propertiesI 3ention them. 1nsH!these are the olli-ative properties. (a) Asmoti pressure (b) Pelative lowerin- of vapour pressure (b) Glevation in 2.C (d) .epression in '.C NUMERI3A<S J1. (al ulate the mole fra tion of ethylene -ly ol (("F9A") in solution ontainin- "@ % of ethylene -ly ol by mass. 1nsH! 3ole fra tion of ethylene -ly ol 5
!o.of .mole.of .t ele!e.glycol No.of .moles.of .water + No.of .moles.ofC" H 9O"

"1

i.e
glycol = !glycol 7 !water + !glycol =
= "@ X 9" X 1$ D = = @.@989 9" X 63"@ 133 "@ 7 9" "@ 7 9" + $@ 7 1$

/o H

"O

= 1 glycol = 1 @.@989 = @.D3"3

J". 1n aqueous solution of -lu ose made by dissolvin- 1@ - of -lu ose ((9F1"A9) in D@ of water at 3@3 M. if vapor pressure of pure water at 3@3 M be 3".$ mmF-. +hat would be the vapor pressure of solution 1nsH! Fen e w25 1@ -, 3251$@, +15D@ -, 3151$ C@153".$ mmF-. C/5I

1@ P A P" P A P" p = B = = 1$@ = 1 @" = 1 7 D@ @ @ D@ 7 1$ P A P A P A P" 1 $D $D = 1 P" = P @ A = 3".$ = 3".#3mmHg @ D@ D@ D@ P A

@ @

J3. 1 solution 3.$ - of sulphur in 1@@ - of (/" (2oilin- point5#9.3 @ () boils at #9.99 @ . what is the formula of sulphur mole ules in the solution .(1tomi mass of sulphur is 3" - mol!1 and Mb5 ".# M 0- mol!1) 1nsH! +e have H! M B = Fere
%# = ( "83 + #9.99) ( "83 + #9.3) = @.39 & MB = 3.$ 1@@@ ".# 89@ = = "63.3 @.39 1@@ 3

$B 1@@@ & B %# $A

?o of atoms of sulphur /53ole ualar wt.71tomi +t. 5 "63.3373" $ Fen e the formula of sulphur 5 /$

J#. (al ulate the osmoti pressure of a solution obtained by mixin- 1@@ m3 of @."6 3 /olution of urea and 1@@ m3 of @.13 soln of ane su-ar at "D3 M (P5@.@$" 4 atm ""

mol !1M!1) 1nsH! +e 0now ' = !R%

@."6 + @.1 ) @.@$"1 "D3 " Ar @.36 @.@$"1 "D3 = = "1.@""atm " @." @." = (

J6. " - of benEoi a id ((9F6(AAF) dissolved in "6 - of benEene shows a depression in freeEin- point equal to 1.9" M. 3olal depression onstant for benEene is #.D M 0- mol!
1

. what is the per enta-e asso iation of a id if it forms dimmer in soln.I

1nsH! Given that

% f =1.9" & +25"- , Mf5#.D MM-mol!1, +15"6 -,

+e have
MB = $B 1@@@ & f % f $A = " 1@@@ #.D = "#1.D$ gmol 1 1.9" "6

1lso "(9F6(AAF ((9F6(AAF)" Initially 1 ( 1!x) @ x7" mole

(1 x ) + x x =1 " "

&otal no. of parti les at equilibrium. 5

i = 1 x "

?ow i5(?ormal mole ular mass71bnormal mole ular mass) 51""7"#1.D$ &hus 1""7"#1.D$51! x7" Ar x7" 51! (1""7"#1.D$) 5@.#D6$ /o x 5 @.DD19 &he de-ree of asso iation of benEoi a id in benEene is DD.19 % LLLLLLLLLLLLLLL

DOR 9E<O+ A5ERA7E ?1 Ma&/ que ti!n "3

1. ". 3. #. 6. 9. 8. $. D. 1@. 11. 1". 13. 1#. 16. 19. 18.

/tate Fenry=s law. .efine osmoti pressure. Fow pressure effe t the solubility of a solid in a liquid. /tate Paoult=s 4aw for a binary solution ontainin- volatile omponents. .efine Fenry=s law about solubility of a -as in a liquid. .efine *ant Foff fa tor. +hat do you understand by olli-ative propertiesI .efine an ideal solution. /tate any two hara teristi s of ideal solution. .istin-uish between molarity and molality. +hat is a non! ideal solutionI 3ention a lar-e s ale use of the phenomenon alled reverse osmosis. +hat is antifreeEeI Give one example. +hen is the value of *an=t Foff fa tor less than 1I ?ame the two fa tors on whi h the vapour pressure of the liquids depend. .efine mole fra tion of a substan e in a solution +hen is the value of *an=t Foff fa tor more than 1I

DOR A5ERA7E 1. ". 3. #. 6. 9. 8. $. D. 1@. 11. 1". +hy is the elevation in b.p. of water different in the followin- solutionsI (i) @.1 3 ?a(l solution (ii) @.1 3 /u-ar solution. +hat are aEotropesI +hat happens when blood ells are pla ed in pure waterI +hy is the oo0in- temperature in pressure oo0er hi-her than in open panI +hy does molality of a solution remain un han-ed with han-e in temperature while its molarity han-esI +hy is ether not mis ible in waterI +hat are maximum boilin- aEeotropesI Give one exampleI +hat are minimum boilin- aEeotropesI Give one exampleI +hy do do tors advi e -ar-les by saline water in ase of sore throatI +hy is boilin- point elevated when a non volatile solute is addedI 1 person sufferin- from hi-h blood pressure should ta0e less ommon salt, whyI +hy do -ases always tend to be less soluble in liquids as the temperature is raisedI

DOR A9O5E A5ERA7E 1. Fow mole fra tion of a solute and molality are relatedI "#

".

&wo liquids 1 and 2 boil at 1#6( and 1D@( respe tively. +hi h of them has a hi-her *.C. at $@(I

3. #. 6. 9. 8. $. D. 1@.

+hat is expe ted value of \i= for M#%'e((?)9) in dilute solutionI Fow molarity and molality of solute are related. +hat possible value of \i= will it have if solute mole ules under-o asso iation in solution. .efine molal elevation onstant or ebullios opi .efine molal depression onstant or ryos opi onstantI onstantI

+hy is osmoti pressure onsidered as a olli-ative propertyI An mixin- equal volumes of water and ethanol what type of deviation would you expe t from Paoult=s 4awI +hat are isotoni solutionsI

DOR 9E<O+ A5ERA7E ?" Ma&/ que ti!n 1. ". 3. #. 6. Onder what ondition *an=t Foff fa tor is (i) equal to one, (ii) -reater than 1, (iii) less than 1. &wo liquid 1 and 2 on mixin- produ e a warm solution. +hi h type of deviation from Paoult=s 4aw does it showI +hat are non!ideal solutionsI Gxplain as to why non!ideal solutions deviate from Paoult=s 4aw. +hat are olli-ative propertiesI 3ention them. .ifferentiate between molarity and molality of a solution. +hen and why is molality preferred over molarity in handlin- solutions in hemistryI DOR A5ERA7E 1 ". ?ame the fa tors whi h affe t the vapour pressure. 1mon-st the followin- ompounds, identify whi h are insoluble, partially soluble and hi-hly soluble in water. (a) Chenol (e)(hloroform 3. #. (b)&oluene ( ) 'ormi 1 id (d)Gthylene Gly ol (f) Centanol

+hat do you mean by relative lowerin- of vapor pressure I Fow is relative lowerinof vapor pressure related with mole fra tion of non volatile solute in a solutionI +ith the help of a suitable dia-ram show that the vapour pressure of a solution is lower than the pure solvent, auses a lowerin- of freeEin- point for the solution ompared to that of the pure solvent. "6

6.

(arbon tetra hloride and water are immis ible where as ethanol and water are mis ible in all proportions. (orrelate this behaviour with mole ular stru tures of these ompounds.

DOR A9O5E A5ERA7E 1. ". 3. #. 6. +hat do you mean by abnormal mole ular massI +hat are its auseI +ith the help of suitable dia-rams, illustrate the two types of non ideal solutions. /tate Paoult=s law for solutions of non volatile solutes in volatile solvents. .erive a mathemati al expression for this law. +hat is osmoti pressure and how is it related with the mole ular mass of non!volatile soluteI +hat is meant by abnormal mole ular mass of soluteI .is uss the fa tors whi h brinabnormality in the experimentally determined mole ular masses of solutes usinolli-ative properties. 9. 8. $. /tate Paoult=s 4aw. .is uss the fa tor responsible for the deviation from this law. /tate Fenry=s 4aw and mentions some important appli ation. Gxplain the si-nifi an e of Fenry=s (onstant (MF). 1t the same temperature, hydro-en is more soluble in water than helium. +hi h of them will have a hi-her value of MF and whyI D. 1@. Gxplain the differen e between osmoti pressure and vapour pressure of a solution. Give one example ea h of mis ible liquid pairs showin- positive and ne-ative deviation from Paoult=s 4aw. Give one reason ea h for su h deviations.

DOR A5ERA7EJ9E<O+ A5ERA7E ?" Ma&/ que ti!n (Nume&ical) 1. &he vapour pressure of pure liquid 1 and 2 are #6@ and 8@@ mm F- respe tively at 36@ M. 'ind out the omposition of the liquid mixture if total vapour pressure is 9@@ mm F-. ". 3. #. 6. (al ulate the mass per enta-e of aspirine((DF$A#) in a etonitrile((F3(?) when 9.6 of (DF$A# is dissolved in #6@ - of (F3(?. F"/, toxi -as with rotten a li0e smell, is used for qualitative analysis. If the solubility of F"/ in water at /&C is @.1D m. (al ulate Fenry=s law onstant. 1$ - of -lu ose is dissolve in 1 0- of water in a sau epan. 1t what temperature will water boil at 1.@3 barI Mb for water is @.6" M 0- mol!1. 1n aqueous solution of "% non!volatile solute exerts a pressure of 1.@@# bar at the normal point of the solvent. +hat is the molar mass of the soluteI "9

9.

&he boilin- point of benEene is 363."3 M. +hen 1.@$ -m of non!volatile solute was dissolved in D@ -m of benEene. &he boilin- point is rea hed to 36#.11 M. (al ulate the molar mass of solute. Mb for benEene is ".63 M 0- mol!1.

8. $.

#6 - of ethylene -ly ol is mixed with 9@@ - of water. (al ulate (a) the freeEin- point depression and (b) the freeEin- point of the solution. "@@ m3 of an aqueous solution of a protein ontains 1."9 - of protein. &he osmoti pressure of su h a solution at 3@@ M is found to be ".68 x 1@ !3 bar. (al ulate the molar mass of the protein.

D.

1 6% solution (by mass) of ane su-ar in water has freeEin- point of "81 M. (al ulate the freeEin- point of 6% -lu ose in water if the freeEin- point of pure water is "83.16 M.

DOR A9O5E A5ERA7E ?* Ma&/ Que ti!n (Nume&ical) 1. If ?" -as is bubbled throu-h water at "D3M, how many millimoles of nitro-en -as would dissolved in 1 ltr. of water. 1ssume that ?" exerts a partial pressure of @.D$8 bars. Given that Fenry=s law onstant for ?" at "D3 M is 89.#$ 0bar. ". @.9 m4 of a eti a id havin- density 1.@9 - m4 !1, is dissolve in 1 litre of water. &he depression in freeEin- point observed for this stren-th of a id was @.@"@6 ((. (al ulate the *an=t Foff fa tor and the disso iation onstant of a id. 3. 1@@ - of liquid 1 (molar mass 1#@ -7mol) was dissolved in 1@@@ - of liquid 2 (molar mass 1$@ - mol !1). &he vapour pressure of pure liquid 2 was found to be 6@@ torr. (al ulate the vapour pressure of pure liquid 1 and its vapour pressure in the solution if the total vapour pressure of the solution is #86 &orr. #. " - of benEoi a id dissolved in "6 - of benEene shows a depression in freeEin- point equal to 1.9" M. 3olal depression onstant for benEene is #.D M 0- mol !1. +hat is the per enta-e asso iation of a id if it forms dimmer in solutionI 6. 9. .etermine the osmoti pressure of solution prepared by dissolvin- "6 m- of M "/A# in " litre of water at "6((. 1ssumin- that it is ompletely disso iated. &wo elements 1 and 2 from ompounds havin- formula 12 "and 12#. +hen dissolved in "@ - of benEene, 1 - of 12 " lowers the freeEin- point by ".3 M where as 1.@ - of 12# lowers it by 1.3 M. &he molar depression onstant for benEene is 6.1 M 0- mol!1. (al ulate atomi mass of 1 and 2. 8. 1n antifreeEe solution is prepared from """.9 - of ethylene -ly ol and "@@ - of water. (al ulate the molality of solution. If the density of the solution is 1.@8" -7mol, then what shall be the molarity of the solutionI

"8

^^^^^^^^^^^^^^^^^^^^^^^^^

UNIT 2;* E<E3TRO 3#EMISTRM

STUDY MATERIAL
"$

J1. .efine molar ondu tivity. Fow does it varies with dilution I 1nsH! 3olar ondu tivityH! It is the produ t of spe ifi mass of the ele trolyte.
& 1@@@ C

ondu tivity and volume of solution ontainin- 1 - mole ular

mol =

Onit5 /m" mol!1 ^ *ariation H!

/tron- Gle trolyteH!3olar ondu tivity in reases slowly with de rease in on entration. +ea0 Gle trolyteH! 3olar (ondu tivity in reases sharply for wea0 ele trolyte on dilution .J". /tates Moahlraus h law. 1nsH! 4imitin- molar ondu tivity of an ele trolyte is the sum of molar ondu tivity of ation and anion at on entration approa hes Eero. mol = +
@ @ @

@ + 53olar (ondu tivity of ation @ 53olar (ondu tivity of anion

J3.

+at do you mean by fuel ellI +rite athode and anode rea tion in fuel ell. a fuel li0e (F", (A et .) dire tly into ele tri al ener-y GxH!F"!A" fuel ell.

1nsH! 'uel (ellH! &hese are ele tri al ells whi h an onvert the ener-y of ombustion of

Pea tion H! 1node rea tionH! F"(-)B"AF!(aq) !!! "F"AB"e_.K " (athode rea tionH! A"(-) B"F"AB#e !!!! #AF! "D

Averall rea tion H!"F"(-) B A"(-) !!!!!! "F"A(l) J3. +hat do you mean by (orrosionI Fow it is a ele tro hemi al phenomenaI 1nsH! in orrosion a metal is oxidiEed by a lose of ele trons to oxy-en and metal oxide is formed. It is an ele tro hemi al phenomenon. 3hemi t&$ !f c!&&! i!n !f i&!n2; &he sport where iron under -oes oxidation is onsidered as anode. 1t anodeH "'e !!!! "'e"B B #e! 1t another sport on the metal these ele trons redu e oxy-en in presen e of FB. 1t anode HA"(-) B #FB B #e! !!!! "F"A(4) &he overall rea tion is "'e B A" B #FB !!!!! "'e"B B "F"A &he ferrous ions formed are further oxidiEed to ferri ions by atmospheri oxy-en and produ ts omes out as rust in the form of 'e"A3KF"A(hydrated 'erri oxide) J#. 1 solution of (u/A# is ele tolysed for 1@ minutes with a urrent of 1.6 amperes. +hat is the mass of opper deposited at athodeI 1nsH! t5 1@K9@59@@ /e . I51.6 amperes. J5n' ((u"B B"e !!! (u) 5"KD96@@( J5It51.6K9@@ 5D@@ (

" K D96@@ ( har-e deposited 93 - of opper

D@@ (

har-e deposited

93 D@@ -m of opper " D96@@

5@."D3$ -m. J6. &he resistan e of a ondu tivity ell ontainin- @.@@1 3 M l solution at "D$ M is 16@@

. +hat is the ell onstant If ondu tivity of @.@@1 3 M l solution "D$ M is @.1#$ K
1@!3 / m!1. 1nsH! P516@@ M5@.1#$ K 1@!3 / m!1 3@

l =(ell (onstant 5 I a l =PM a

516@@ K @. 1#$ K 1@!3 5@.""" (m!1 J9. (ondu tivity of @.@@"#1 3 a eti a id is 8.$D9 K 1@!6 / m!1. (al ulate its molar ondu tivity and if @ for a eti a id 3D@.6 / m" mol!1. what is its disso iation onstantI 1nsH! M58.$D9 K 1@!6 / m!1
@ = 3D@.6"cm "
C =
=

& 1@@@ C

8.$D9 1@ 6 1@@@ 8$D9 = = 3".D3 @.@@"#1 "#1

C 3".D3 = = @.@$3$ @ 3D@.6 & = "C = (@.@$3$) " @.@@"#1 = 1.$6 1@6

J8. Pepresent the ell in whi h the followin- rea tion ta0es pla e. 3-(/) B "1- B(@.@@@1 3) !!!!! 3-"B(@.13@3) B "1-(s) (al ulate its G.3.' when G@53.18* 1nsH! (ell rea tion 3- !!!!! 3-"B B "e !! ! ! ! ! Axidation at anode "1-B B "e !!! " 1- !!! ! ! ! ! ! !Pedu tion at athode Pepresentation of ell 3-`3-"B (@.13@ 3) `` 1-B(@.@@@1 3) `1(1
@.6D1 C lo- " ! C1

("

G.3.' of the ell G5

) +

@.@6D1 Ag + lo53.18 B " Mg " +

[ [

"

31

@.@6D1 (@.@@@1) " lo53.18 B " ( @.13@ )

53.18 !@."1 G5".D9 * J$.

@ mol for ?a(l, F(l and ?a 1(((F3(AA?a) are 1"9.#, #"6.D and D1.@ / m" mol!1 @ mol for F1(((F3(AAF, 1 eti 1 id).

respe tively. (al ulate 1nsH!

@ HAC = @ CH a COO + @ Na + + @ H + + @ Cl @ Na + @ Cl = D1.@ + #"6.D 1"9.# = 619.D 1"9.#

53D@.6 / m" mol !1 JD. /tates 'araday=s laws of ele trolysis. 1nsH 1 t lawH! &he amount of substan e deposited durin- ele trolysis is dire tly proportional to quantity of ele tri ity passed. m J, m5L J 5Lit +here L5ele tro hemi al equivalent.

"nd lawH! If same han-e is passed throu-h different ele trolytes, the mass of substan e deposited at ea h ele trodes will be propositional to their equivalent wei-hts. +17G15+"7G" +here + is mass of substan e and G is its equivalent wei-ht. J1@. (al ulate bG@ for Ln!(u ell at standard onditions. Given 1nsH!
) @ cell = ) @ Cat
ode

) @ +! " + 7 " ! = @.89' , ) @Cu " + 7 Cu = + @.3#' , * = D96@@C

) @ a!ode

= +@.3# ( @.89) = @.3# + @.89 = 1.1@' . @ = !) @ * = " 1.1@' D96@@c = "1".",-mol 1

J11. .epi t the -alvani

ell in whi h the rea tion 3"

Ln(s)B"1-B(aq) !!! Ln"B(aq) B "1-(s) ta0es pla e. (a) +hi h of the ele trode is ne-ative ha-e. (b) &he arries of the urrent in the ell. ( ) Individual rea tion at ea h ele trode. 1nsH (ell Pea tion
A% a!ode +! +! " + + "e oxidatio! A% cat ode " Ag + + "e " Ag Pe ductio! +! + " Ag +! " + + " Ag

(ell representation
+! +!
" +( a/ )

Ag + Ag )a!ode

) = )+ ) = )cat

ode

( ) 1- ele trode is ne-ative har-ed. (d) 1-B and Ln"B ions arries the urrent in the ell. (urrent flow from 1ele trode to Ln ele trode. (e) 1t anode
+! +! " + + "e Oxidatio!

1t athode.
" Ag + + "e " Ag Pe ductio!

1 MARK QUESTIONS Q. 1. +hich !luti!n will all!w 1&eate& c!nductance !f elect&icit$, 1 M Na3l at ">* K !& 1 M Na3l at *"* K and wh$ An . 1 3 ?a(l at 3"3 M as the ioni mobilities in rease with in rease in temperature.

Q. ". +hat d!e the ne1ati4e 4alue !f E@cell indicate An . G will be positive, the ell will not wor0.

Q. *. +h$ i the equili%&ium c!n tant K, &elated t! !nl$ E@cell and n!t Ecell An . &his is be ause G ell is Eero at equilibrium.

Q. .. +hat i the i1n !f 7 f!& an elect&!l$tic cell An . Cositive. 33

Q. 0. Ru tin1 !f i&!n i quic/e& in aline wate& than in !&dina&$ wate&. +h$ i it ! An . In saline water, ?a(l helps water to disso iate into FB and AF:. Greater the number of FB, qui 0er will be rustin- of Iron. Q. 6. +hat w!uld happen if the p&!tecti4e tin c!atin1 !4e& an i&!n %uc/et i %&!/en in !me place An . Iron will orrode faster as the oxidation potential of 'e is hi-her than that of tin.

Q. 8. 3an a nic/el patula %e u ed t! ti& a !luti!n !f 3!ppe& Sulphate - Nu tif$ $!u& an we&. (E@NiOCJNi H I ?."0 5 An . E@3uOCJ3u H ?.*. 5)

Pedu tion potential of ?i is less than (u. ?i will repla e the (u from (u/A #. &hus ?i spatula annot be used to stir a solution of (u/A#.

Q. :. +hich !ut !f ?.1 M #3l and ?.1 M Na3l, d! $!u expect ha4e 1&eate& Pm and wh$ An . @.1 3 F(l will have -reater Zm be ause FB (aq) bein- smaller in siEe than ?aB (aq) and have -reater mobility. Q. >. Th&ee i&!n heet ha4e %een c!ated epa&atel$ with th&ee metal A, 9, 3 wh! e tanda&d elect&!de p!tential a&e 1i4en %el!w 2 A E@4alue I ?..6 5 9 I ?.66 5 3 I ?."? 5 I&!n I ?... 5

Identif$ in which &u tin1 will ta/e place fa te& when c!atin1 i dama1ed. An . Pustin- of iron will ta0e pla e when oated with metal ( as it is pla ed above iron more than other metal. Q. 1?. +hich will ha4e 1&eate& m!la& c!nducti4it$ - S!luti!n c!ntainin1 1 m!l K3l in "?? cc !& 1 m!l !f K3l in 0?? cc. An . 1 mol of M(l in 6@@ .

" MARKS QUESTIONS Q. 1. (a) #!w will the 4alue !f Ecell chan1e in an elect&!chemical cell in4!l4in1 the f!ll!win1 &eacti!n !f the c!ncent&ati!n !f A1C (aq) i inc&ea ed 3#

(%)

+hat will %e e. m. f. when the cell &eache equili%&ium 2 M1 ( ) C " A1C (aq) QQP M1"C (aq) C A1 ( )

An .

(a)

2+ 0.059 M. G ell 5 GX ell : lo+ 2 2 A.

1s the on entration of %1-B) ion in reases, G ell in reases. (b) Q. ". (a) e.m.f. 5 @ In a cell &eacti!n, the equili%&ium c!n tant K i le cell p! iti4e !& ne1ati4e (%) An . +hat will %e the 4alue !f K !f E@cell H ? 0.0591 lo- M / than !ne. I E@ f!& the

'or a ell GX 5

M , @ Z lo- M , @ i.e. lo- M is : ve. &hen GX ell will be ne-ative. (b) If GX ell 5 D then @ 5 lo- M 5 @ Z M 5 1 0.0591 lo- M /

Q. *. Kn!win1 that 2 3u"C (aq) C " eI QQQP 3u ( ) E@ H C ?.*. 5

" A1C (aq) C " eI QQQP " A1 ( ) E@ H C ?.:? 5 Rea !n !ut whethe&, 1 M A1NO* !luti!n can %e t!&ed in 3!ppe& 5e el !& 1 M 3uSO. !luti!n in Sil4e& 5e el. An . 1 solution of an ele trolyte an be stored in a parti ular vessel only in ase there is no hemi al rea tion ta0in- pla e with the material of the vessel. (u is a stron- redu in- a-ent and an lose ele trons to 1-B as GX of (u is less than that of (u. /o 1-?A3 annot be 0ept in (opper *essel. (u/A# solution an be stored in 1- *essel as no hemi al rea tion will ta0e pla e as 1- is pla ed above (u in the a tivity series and 1- is less rea tive than (opper. 36

Q. .. +hat i the num%e& !f elect&!n in !ne 3!l!um% !f elect&icit$ An . (har-e on one mole of ele trons 5 1 ' 5 D96@@ ( D96@@ ( of (har-e is present on ele trons 5 9.@"" < 1@"3 6.022 1023 1 ( of (har-e is present on ele trons 5 <1( 96500 C 5 9."# < 1@1$ Q. 0. +hich !f the f!ll!win1 pai& will ha4e 1&eate& c!nducti!n and wh$ (a) (%) An . (a) 3!ppe& wi&e at "0 @3 and 3!ppe& wi&e at 0? @3. ?.1 M acetic acid !luti!n !& 1 M acetic acid !luti!n (opper wire at "6 X( be ause with in rease in temperature metalli ondu tion de reases due to vibration of 0ernels. (b) @.1 3 a eti a id solution be ause with dilution de-ree of dissos iation

in reases and hen e no. of ions.

* MARKS QUESTIONS Q. 1. The f!ll!win1 cu&4e i !%tained when m!la& c!nducti4it$ (m) i pl!tted a1ain t the qua&e &!!t !f c!ncent&ati!n f!& " elect&!l$te A and 9. (a) (%) +hat can $!u a$ a%!ut the natu&e !f the tw! elect&!$lte A and 9 #!w d! $!u acc!unt f!& the inc&ea e in m!la& c!nducti4it$ m f!& the elect&!l$te A and 9 !n diluti!n -

400 % 200 A B 0.20000000.4 1 C

An . (a) (b) 1 is a stron- ele trolyte and 2 is a wea0 ele trolyte. 3olar ondu tivity of a stron- ele trolyte (1) in reases with dilution as ioni mobility in reases. In a wea0 ele trolyte molar ondu tivity in reases steeply with dilution as de-ree of disso iation in reases and hen e no. of ions in reases.

39

Q. ". I&!n and nic/el a&e u ed t! ma/e elect&!chemical cell %$ u in1 a alt %&id1e t! R!in a half cell c!ntainin1 1 M De"C (aq) in which a t&ip !f i&!n ha %een imme& ed t! a ec!nd half cell which c!ntain 1 M Ni "C (aq) in which a t&ip !f Ni ha %een imme& ed - A 4!ltmete& i c!nnected %etween the tw! metal t&ip 2 E@DeOCJDe H I ?... 5 (a) (%) (c) E@NiOCJNi H I ?."0 5

+&ite the name !f the cath!de and an!de. +&ite the half &eacti!n in4!l4ed +hat w!uld %e the effect !n the 5!ltmete& &eadin1 if De "C c!ncent&ati!n we&e inc&ea ed -

An .

(a) 1node H 'e (athode H ?i (b) Pea tion at anode H 'e YYYZ 'e"B B " e: Pea tion at athode H ?i"B B " e: YYYZ ?i ( ) *oltmeter readin- de reases.

Q. *. 3!n ide& the elect&!chemical cell 2 Fn ( ) J Fn"C (aq) JJ 3u"C (aq) J 3u. It ha an elect&ical p!tential !f 1.1 5 when c!ncent&ati!n !f Fn"C and 3u"C i!n i unit$. State the di&ecti!n !f fl!w !f elect&!ne and al ! pecif$ if Finc and 3!ppe& a&e dep! ited !& di !l4ed at thei& &e pecti4e elect&!de . +hen 2 (a) (%) (c) An . (a) an exte&nal !pp! ite p!tential !f ?.: 5 i applied. an exte&nal !pp! ite p!tential !f 1.1 5 i applied. an exte&nal !pp! ite p!tential !f 1.. 5 i applied. Gle trons flow from Ln rod to (u rod. Lin dissolved and (opper -ets deposited. (b) ?o flow of ele trons and urrent. ?o han-e observed at Lin and (opper ele trodes (system is at equilibrium). ( ) Gle trons flow from (u rod to Ln rod. Lin is deposited and (opper -ets dissolved. Q. .. 7i4en that 2 3O*C C eI QQQP 3O"C E@ H 1.:" 5 E@ H I 1."* 5 38

" #"O QQQP O" C . #C C. eI

Explain wh$ 3O*C i n!t ta%le in aque!u An . &he GX ell an be al ulated as H # %(A3B B e: YYYZ (A"B) GX 5 1.$" * " F"A YYYZ A" B # FB B# e:

!luti!n -

GX 5 : 1."3 *

YYYYYYYYYYYYYYYYYYYYYY (ell rea tion H # (A3B B " F"A YYYZ (A"B A" B # FB GX ell 5 1.$" * : (: 1."3 *) 5 3.@6 * /in e GX ell is positive, the ell rea tion is spontaneous. (A 3B iron will ta0e part in the rea tion and hen e unstable in aqueous solution. Q. 0. D!& the &eacti!n 2 A1C C #1 QQQP A1 C #1""C E@ H ?.:? 5 E@ H ?.8> 5

B&edict the di&ecti!n in which the &eacti!n will p&!ceed if 2 SA1CT H 1?I1 m!lJh S#1"CT H 1?I* m!lJh An . (ell rea tion is H " 1-B B " F- YYYZ " F- B F-""B G ell
2+ 0.0591 -.2 5 GX ell : lo+ 2 2 A.

103 0.0591 2 5 (@.$@ * : @.8D *) : lo101 2

5 @.@1 * : 5 @.@3D6 *

0.0591 (: 1) 5 @.@1 B @.@"D6 2

/in e G ell is positive, the rea tion will be spontaneous in the forward dire tion.

DOR A9O5E A5ERA7E ?1 Ma&/ Que ti!n

1. Gxpress mathemati al relationship amon- resistan e(P), /pe ifi and ell onstant. ". +rite relation between spe ifi ele trolyti . 3. /tate the Mohlraus h law. #. ?ame a metal that an be used for the athodi prote tion of iron a-ainst rustin-. 3$ ondu tan e and mole ular ondu tivity of an ondu tivity (M)

6. Fow are se ondary ells different from primary ellsI 9. +rite the rea tion o urs in fuel ell. 8. +hat do you mean by standard ele trode potentialI $. +hat is -alvaniEation of ironI D. .efine stron- ele trolytes. 1@. .efine molar ondu tivity.

?" Ma&/ Que ti!n

1. ". 3. +hat is orrosionI Fow is rustin- of iron prote ted by athodi prote tion. Fow is athodi prote tion different from -alvaniEation in prote tion of iron from rustin-I +hat do you understand by equilibrium onstantI (al ulate the equilibrium onstant of the rea tion (u (s ) B "1- B (aq) c (u "B (aq) B "1- (s) Gd 5 @.#9 v . #. 6. 9. Pepresent Ln :(u ell and write ?ernst equation for the al ulation of emf of the ell. &he ondu tivity of @."3 solution of ?a(l at "D$ M is @.@"#$ / m !1. (al ulate its molar ondu tivity. &he standard ele trode potential for .aniell ell is 1.1v. (al ulate the standard Gibb=s ener-y for the rea tion Ln (s) B (u "B (aq) c Ln "B (aq) B u (s) 8. $. /tate and explain the 'araday=s laws of ele trolysis. +hat is the value of 'araday=s onstantI /tate reasons for the followin- : Pustin- of iron is said to be an ele tro hemi al phenomena. Pustin- of iron is qui 0er in saline water than in ordinary water. 1rran-e the followin- metals in the order in whi h they displa e ea h from the solution of their salts. 1l, 3-, 'e, (u, Ln

?* Ma&/ Que ti!n

1. +rite the ?ernst equation and al ulate the emf of the followin- ell at "D$ M. (u(s) 7 (u "B ( @.13@ 3 ) 77 1-B ( 1 x 1@!# 3 ) 7 1- (s). Given that G @ (uB" 7 (u 5 @.3# * and G@ 1-B 7 1- 5 @.$@ *, ele trodeI Gxplain. ' 5 D66@@ ( 3ol!1 ". +hat is standard hydro-en ele trodeI Fow it measures the ele trode potential of an

3D

3. +hat are se ondary ellsI Gxplain lead stora-e battery with ele trode rea tions. #. 1 -alvani ell is onstru ted in whi h the ell rea tion is Ln(s) B " 1-B (aq) c Ln"B (aq) B " 1- (s), ?ow writeH (a) ( ) +hi h of the metal ele trode is ne-atively har-edI Individual half ele trode rea tion for athode (al ulate the emf of the ell 3-(s) 7 3- "B ( @.1 3 ) 77 1-B ( @.@1 3 ) 7 1- at "6@ ( Given that G@ 1-B 7 1- 5 @.$ *, G@ 3-"B 7 3- 5 ! ".38 * (b) &he dire tion of the urrent (either anode to athode or athode to anode) 6. +hat are ele trode potential and emf of a ellI

?0 Ma&/ Que ti!n

1. +hat is G3' of a ellI (al ulate the emf of the ell 3-(s) 7 3-"B ( @.1 3 ) 77 1-B ( 1 x 1@!# 3) 7 1- (s) at "6@ (, Given that G@ 1-B 7 1- 5 @.$ * , G@ 3-"B 7 3- 5 !".38v ". +hat will be the effe t on G3' of the ell if on entration of 1- B is in reased to 1 x 1@!
3

3I differen e between these two phenomena and list two other appli ation of ele trolysis.

3. Gxplain the produ t of ele trolysis of molten ?a(l and aqueous ?a(l. Gxplain the #. 1 ell is formed as ?i (s) 7 ?i"B ( @.@1 3 ) 77 (u"B ( @.1 3 ) 7 (u(s) &he G@ values for ?i"B 7 ?i and (u"B 7 (u ele trodes are !@."6 * and @.3# * respe tively. (al ulate the ell potential, equilibrium onstant and wor0 done by the ell. 6. Gle trolysis of aqueous sodium hloride -ives F" -as at athode instead of sodium metal and (l" -as anode while ele trolysis of molten ?a(l -ives sodium metal at athode. Fow is this differen e in results explainedI Give ele trode rea tions for anode and athode.

DOR 9E<O+ A5ERA7E ?1 Ma&/ Que ti!n

1. ". 3. +hat is over volta-e in an ele trolyti rea tionI +hat is ?i 0el! (admium ellI Fow is unit of molar ondu tivity arrived atI #@

#. 6. 9. 8. $. D. 1@. 11.

Fow many faradays of ele tri ity are required to liberate " moles of hydro-en -as in ele trolysis of a solution I +hy does u not displa e 'e from 'e/A# /olutionI +hy does an al0aline solution enhan e the rustin- of ironI +hat is on entration ellI Give an example. In fun tion of a -alvani ell, one of its ele trodes does oxidation rea tion. +hat is the name of the ele trode and what is its polarityI +hat is the ele trolyte used in a fuel ellI /u--est one method to operate -alvani ell if the salt brid-e is absent. &he standard redu tion potential for the Ln "B aq7Ln (s) half ell is !@.89 *. +rite the ele trode rea tions of the ell when it is oupled with standard hydro-en ele trode (/FG). 1lso -ive the standard ell potential.

?" Ma&/ Que ti!n

1. +hy is it not allowed to determine the molar ondu tivity at infinite dilution of a wea0 ele trolyte by extrapolatin- is allowed in the -raph of stron- ele trolytes. Gxplain. ". If G@ for opper ele trode is B@.3#*R how will you al ulate its emf when the solution in onta t with it is @.1 3 in opper ionsI Fow does emf of opper ele trode han-e when on entration of (u"B ions in solution is de reasedI 3. (al ulate the potential of a Ein ! Ein ion ele trode in whi h the Ein ion a tivity is @.@@13 %G@ Ln"B 7Ln 5 !@.89 *, P5 $.31# eM!1mo1!1, '5D96@@ (mo1!1) #. &he molar ondu tan e of sodiuma etate, hydro-en hloride and sodium hloride at infinite dilutions are D1, #"9 and 1"9 /imen m" mol!1. (al ulate the molar ondu tan e of a eti a id at infinite dilution. 6. 9. Gstimate the minimum potential differen e needed to redu e 1l"A3 at 6@@X . &he QG for the de omposition rea tion "73 1l"A3 c #73 1l B A" is QG 5 D9@ Me. &he G@ *alues for two metal ele trodes are -iven below (i) (r3B7(r"B5 !@.#* (ii) 'e3B7'e"B 5 @.$* (omment on the result of treatin- a solution of (r (II) with a solution ontainin'e (III) ions 8. (al ulate the standard free ener-y han-e for the rea tion o urrin- in the ell LnfLn"B (I3) 77 (u"B (I3) 7 (u Given G@En"B7En 5 !@.89* and G@ u"B7(u5 @.3#*. 1D. Gxplain the ele trolysis of aqueous ?a(l and molten ?a(l with their (hemi al rea tions. Give reasons for this differen e and dedu e riteria for produ t formation. #1

"@.

Gxplain the ele trode rea tion of a fuel ell. .is uss the advanta-e of fuel ell in spa e pro-ramme.

?* Ma&/ Que ti!n

1. Credi t the produ ts of ele trolysis in ea h of the followin-H (i) 1n aqueous solution of 1-?A3 +ith 1- ele trodes. (ii) 1 .ilute solution of F"/A# +ith platinum ele trodes. (iii) 1n aqueous solution of (u(l" with platinum ele trodes. ". &he resistan e of a ondu tivity ell ontainin- @.@@1 3 M(l /olution at "D$ M is 16@@ ohms. +hat is the ell onstant if ondu tivity of @.@@1 3 M(l /olution at "D$ M is @.1#9K1@!3 / m!1. 3. (ondu tivity of @.@@"#1 3 a eti a id is 8.$D9K1@!6 / m!1, al ulate its molar ondu tivity and if g@m for a eti a id is 3D@.6 / m " mol!1. +hat is its disso iation onstantI #.. 6. hPustin- is an ele tro hemi al phenomena.i Gxplain this phenomena with the help of rustin- of iron with rea tions involved. /ilver is ele trodeposited on a metalli vessel of surfa e area $@@ m " by passinurrent of @." ampere for 3 hours. (al ulate the thi 0ness of /ilver deposited. (.ensity of 1- 51@.#8 - m!3, 1tomi mass of 1-51@$ amu)

?0 Ma&/ Que ti!n

9. (al ulate the potential of followin- ell rea tion at "D$ M /n#B(1.6@ 3)B Ln c /n"B(@.63)B Ln"B("3) &he standard potential G@R of the ell is @.$D*, whether the potential of the ell in rease or de ease (P5$.31# eM!1mol!1, '5D96@@ ( mol!1) if the on entration of /n"B is in reased in the ell. 8. &he ondu tivity of ?a(l at "D$ M has been determined at different on en!tration and the results are -iven belowH (on n 7 3 @.@@1 @.@1@ @.@"@ "3.16 @.@6@ 66.63 @.1@@ 1@9.8# 1@" x M7/ m!1 1."38 11.6$ value of gXm. $. (a) /tate the reasons for the followin- H! a. Iron does not rust even if Lin pipe. b. Gle trolysis of M2r (aq) -ives 2r" at anode, but that of M' (aq) does not -ive '". (b) +rite the ele trode rea tion of F"!A" (ell. #" oatin- is bro0en in a -alvaniEed iron

(al ulate gm for all on entrations and draw a plot between gm and (17". 'ind the

( )

(al ulate the G3' of the followin- ell at "D$ M /n7/n"B(@.13) 77 1-B(@.13) 7 1Given G@ /n"B7/n 5 !@.1#*, G@ 1-B71- 5 @.$*

D.

(a) (b) ( )

/tate Mholraus h=s law for ele tri al ondu tan e of an ele trolyte at infinite dilution. Give the omposition and rea tion of athode and anode in a mer ury ellI Give one use. /ilver is ele trodeposited on a metalli vessel by passin- a urrent of @." ampere for 3 hours. (al ulate the wei-ht of silver deposited. (1tomi mass of 1-51@$ amu)

DOR A5ERA7E ?1 Ma&/ Que ti!n

1. ". 3. #. 6. 9. 8. $. D. 1@. .efine the molar ondu tivity of an ele trolyti solution. Gxpress the relation between de-ree of disso iation of an ele trolyte and its molar ondu tivities. +hat does the standard ele trode potential of a metal bein- ne-ative G@ Ln"B7Ln 5 ! @.89 v showsI +hat happens when the prote tive oatin- of -alvaniEed iron is bro0enI Fow is ele troplatin- different from -alvaniEationI Fow does a fuel ell operateI Fow mu h har-e is required for the followin- redu tion of 1 mol of (u"B ions to u (s)I +hi h type of metal an be used for the athodi prote tion of ironI Give one differen e between primary and se ondary ells. +hat are uses of salt brid-e in a -alvani ellI

?" Ma&/ Que ti!n

1. ". 3. #. 6. 9. +hat is mer ury ellI Give an ele trode rea tionI 3a0e differen e between molar ondu tivity and equivalent ondu tivity. /u--est a ell to determine molar ondu tivity experimentally. Fow will you explain the sharp in rease in molar ondu tivity of a wee0 ele trolyte on dilutionI Fow is molar ondu tivity related to the de-ree of disso iationI &he ondu tivity of @."@ 3 solution of potassium hloride "D$ M is ".#$ x 1@ !" ohm!1 m!1 al ulate the molar ondu tivity I 1 solution of ?i (?A3)" is ele trolyEed between platinum ele trodes usin- a urrent of 6 1 for "@ minutesI +hat mass of ?i 0el is deposited at the athodeI #3

8.

&he Lin ! silver oxide ell has the followin- rea tions. Ln c Ln "B B " e! G@5 @.89 v 1-"A B F"A B "e! c"1-B B "AF! (al ulate the standard free ener-y in Noules G@5@.3#*

$.

Give reason for the followin- phenomenaH (i) Iron does not rust if oatin- is bro0en in a -alvaniEed iron pipe. (ii) Pustin- is said to be an ele tro hemi al phenomena

D. 1@. 11.

3olar ondu tan e of a 1.6 3 solution of an ele trolyte is found to be 13$ simen m ". +hat would be spe ifi ondu tan e of this solutionI +hat is rustin-I Gxplain how -alvaniEation -ives better prote tion than ele troplatinfor an iron obNe t from rustin-I .es ribe the hara teristi s of variation in molar ondu tivities (gm) stron- and wea0 ele trolytes on dilution.

?* Ma&/ Que ti!n

1. Given G@ (u"B 7 (u 5 @.3# volt and G@ 1-B 71- 5 @.$@ volt for a ell a) (al ulate ell potential for the ell ontainin- @.1 3 1-B and # 3 (u"B at "6X(. b) Fow many hours does it ta0e to redu e 3 moles of 'e"B with " amp urrent. ". (al ulate the standard ell potential, standard free ener-y har-e jrG@ and equilibrium onstant for the Galvani 3. #. ell "(r(s) B 3 (d"B "(r3B B (d

Given that G@(r3B 7(r 5 !@.8# v, G@ (d"B 7(d5 !@.#@ v .efine ondu tivity and molar ondu tivity for the solution of an ele trolyte. .is uss their variation with on entration. &he resistan e of a ondu tan e ell ontainin- 8.6 x 1@ !3 3 solution of M(l at "6@ (. was 1@@6 ohms. (al ulate the spe ifi onstant is 1."6 (m!1. 6. +hat happens durin- the orrosion of a metalI Gxplain the ele tro! hemi al basis of orrosion of iron with hemi al equation involvedI ondu tan e and molar ondu tan e of the solution if ell

?0 Ma&/ Que ti!n

1 +hat is G3' of a ellI Fow is it different from ell potential (G ell)I (al ulate the G3' of the ell rea tion /n#B (1.63) B Ln c /n"B (@.6 3) B Ln"B ("3 ) &he standard ell potential of the ell is @.$D v. ". Gxplain the primary and se ondary batteries. Fow are se ondary ells different from primary ellsI Give the omposition and rea tion of athode and anode in a mer ury ellI ##

3.. #

+hat do you mean by molar ondu tivity and equivalent ondu tivityI Gxplain the experimental .etermination of molar ondu tivity with help of ondu tivity ell. In the ele trolysis of aqueous solution of sodium hloride, there are two possible anode rea tions. "(l! (aq) c (l" B "e! G@ 5 1.39 v " F"A (l) c A" (-) B #FB (aq) B #e! G@5 1."3 v +hi h of the above rea tion a tually ta0es pla e and whyI 1lso -ive other utilities of ele trolysisI ^^^^^^^^^^^^^^^^^^^^

UNIT I ?. 3#EMI3A< KINETI3S

STUDY MATERIAL
3hemical Kinetic 2 /tudy of hemi al rea tions w.r.t. rea tion rate, effe t of various variables, rearran-ement of atoms and formation of intermediates. Rate !f Reacti!n 2 It is on erned with de rease in on entration of rea tant per unit time. Pate 5 ! d% )7 dt It an also be defined as in rease in on entration of produ ts per unit time. Pate5 d%p)7 dt A4e&a1e Rate2 It is rate of rea tion measured over a lon- time interval. 1vera-e Pate 5 QK7 Qt #6

In tantane!u Rate

t @

0t

X dX = % d%

i.e. rate of rea tion when the avera-e rate is ta0en over a very small interval of time. Rate law !& Rate equati!n 2 Pate law is relation between Pate of rea tion and on entration of rea tants.
Rateofreactio! = & [ A] [ B ]
x y

3ind always, it is not theoreti al but it is written when order of rea tions w.r.t. 1 ] order of rea tion w.r.t. 2 are 0nown experimentally. Rate 3!n tant 2 unity. It is defined as rate of rea tion when molar on entration of rea tant is

M!lecula&it$ 2 &otal number of mole ules of the rea tants in an elementary rea tion (/in-le step rea tion) is alled mole ularity of rea tion. Unim!lecula& &eacti!n 2 +hen mole ularity is one. ?F#?A" ?" B " F"A 9iM!lecula& Reacti!n 2 +hen mole ularity is two. "FI F"B I" T&im!lecula& !& Te&m!lecula& &eacti!n 2 +hen three spe ies ollide "?A B A" "?A" ?ote that 3ole ularity -reater than three is not observedI It is due to the probability that more than three mole ules an ollide and rea t simultaneously is very small. Fen e, the mole ularity -reater than three is not observed. O&de& !f Reacti!n 2 &he sum of the powers of the on entration of rea tants in the rate law is termed as order of the rea tion. It an be in fra tion. It an be Lero. Arder of a rea tion is an experimental quantity. It is appli able to elementary as well as omplex rea tions where as mole ularity is appli able only for elementary rea tions. 'or omplex rea tion, Arder is -iven by the slowest step and -enerally, mole ularity of the slowest step is same as the order of the overall rea tion. Fe&! !&de& Reacti!n 2 Pate 5 M%1)o &he rate of a rea tion does not han-e with the on entration of rea tants. Di& t O&de& Reacti!n 2 &he rea tion in whi h the rate of rea tion is dire tly proportionate to the on entration of rea tin- substan e. 2a"#030$*00030k4A5 0000000000000$" Pate onstant of first order rea tion is
& = ".3@3 a lot ax

#9

or & =

[A ] ".3@3 lo- @ [ A] t

+here a is initial on entration, (a!x) is the on entration of rea tants after time \t=. &he unit of M is s!1 or 3in!1. #alf <ife !f a &eacti!n 2 &he time ta0en for a rea tion when half of the startin- material has redu ed is alled half life of a rea tion.

t1 =
"

@.9D3 +here M5 rate onstant &

Sec!nd O&de& Reacti!n 2

Rate = dX 1 1 = & [ A] [ B ] d%

&he rea tion in whi h sum of powers of on entration terms in rate law or rate equation is equal to ". Thi&d O&de& Reacti!n 2 rate law is equal to 3 i.e.
Rate =

&he rea tion in whi h sum of powers of on entration terms in , +here xBy 53

dX x y = & [ A] [ B ] d%

B eud! Di& t O&de& Reacti!n 2 &he rea tion whi h is bimole ular but order is one is alled Cseudo first order rea tion.
H CH 3 COOC " H 6 + H " O CH 3 COOH + C " H 6 OH
+

4ar-e Gx ess

Dact!& affectin1 &ate !f &eacti!n 2 Pate of rea tion is affe ted by

?ature of Pea tants

H " + Br" " HBr
1

Chysi al /tate

/urfa e 1rea

(on entration &emp.

Reacti!n !f f&acti!n !&de& 2

Rate = & [ H " ] [ Br" ]

"

#alf life !f Reacti!n !f nth O&de& 2 1 In -eneral, t 1" [ A@ ] !1 where n is order of rea tion. 'or t 1 " a for Lero order t; is independent for first order. 1 t 1 for se ond order. " a #8

t1
"

1 for 3rd order. " a

Acti4ati!n Ene&1$ (Ea) 2 It is extra ener-y whi h must be possessed by rea tant mole ules so that ollision between rea tant mole ules is effe tive and leads to formation of produ t mole ules. A&&heniu equati!n !f &eacti!n &ate 2 +here M 5 rate onstant 15 frequen y fa tor, Ga5 Gner-y of a tivation, P 5 -as onstant, &5 temperature in Melvin lnM 5 ln1 : Ga7 P& lo- M 5 lo- 1! Ga 7 ".3@3 P& Rate dete&minin1 tep H &he slowest step in the rea tion me hanism is alled rate determinin- step. Tempe&atu&e c!efficient 2 It is the ratio of rate ostant at temperature 3@$ M to the rate onstant at temperature "D$ M,
&emperature (oeffi ient 5 Pate (onstant=M= at 3@$ M 7 Pate (onstant=M= at "D$ M
)a

& = A.e

R%

#$

CHEMICAL KINETICS
9el!w A4e&a1e Student 2 J1. 1ns.H J". 1ns. J3. 1ns.H J#. 1ns.H 12 Mar, .efine rate of hemi al rea tionI It is defined as han-e in on entration of rea tants or produ ts per Onit time. +hat is the unit of rate of hemi al rea tion. 34!1/!1. .efineavera-e rate of hemi al rea tionI +hen han-e in on entration is measured over bi--er interval of time. It is alled avera-e rate. It is denoted by QK7 Q& where Q& is bi--er time interval. .efine instantaneous rate of hemi al rea tion I +hen han-e in on entration is measured over very small interval of time. It is alled instantaneous rate. It is denoted by dx7dt where QK is small han-e in on entration and dt is small interval of time. +rite the expression of rate onstant for first order rea tion

J6. 1ns.H

&=

[R ] ".3@3 lo- @ t [ R]

+here %P@) is the ori-inal on entration of rea tants %P) is the on entration of rea tant after time t. J9. 1ns. J8. 1ns.H J$. 1ns.H +rite the half life time expression for first order.

t1 =
"

@.9D3 &

Is half life time independent to initial on entration in first order rea tion. Ves +rite the 1rrhennius equation of rea tion rate.
)a

& = A.e

R%

where 1 is frequen y fa tor, Ga is a tivation Gner-y.

JD. 1ns.H J1@. 1ns.H

+hat is elementary rea tion. +hen rea tion is ompelled in sin-le step. +hat do you mean by mole ularity of rea tion. It is the number of mole ules ta0in- part in ea h a t of leadin- hemi al rea tion. Gxample H (1) de omposition of ?F#?A". NH # NO " N " + " H " O i.e. Onimole ular (") " H3 H " + 3 " i.e. 2imole ular rea tion

J11. +hat do you mean by order of rea tion. 1ns. H /um of powers of the om entarion of the rea tants in the rate law expression is alled the order of that hemi al rea tion. /uppose, Pate 5 M%1)x%2)y Fen e, Arder of rea tion 5 xBy J.1". 1ns. (al ulate the overall order ofn a rea tion whi h has the rate expression. Pate 5 M%1);%2)37" Fen e, Arder of rea tion 5 ; B 37" 5 " ( i.e. /e ond Arder)

#D

J13. 1ns.H J1#. 1ns. J16. 1ns. J19. 1ns.

+rite the Onit of M in Lero Arder rea tion. 3@4!1/!1 +hat is the Onit of M in first order rea tion. M5/!1 +hat is the unit of M in /e ond Arder rea tionI M53ol!1.4./!1 +rite the determination of se ond order rea tionI 3ole ularity is two ] order of rea tion is one. H CH 3 COOH + C " H 6 OH Gx H CH 3COOC " H 6 + H " O
+

J18. 1ns. J1$. 1ns.H

Identify the rea tion order if the unit of rate onstant is /e !1. 'irst order rea tion. +hat is the order of rea tion of ?u lear rea tion. 'irst Arder rea tion

D!& A4e&a1e Student 212 Mar, J1. 1ns.H /tate any one ondition under whi h a bimole ular rea tion may be 0ineti ally of first orderI
CH 3 COOC " H 6 + HOH CH 3 COOH + C " H 6 OH Rate = & %CH 3 COOC " H 6 )1 % H " O)@ i.e. F"A is in ex ess.

J". 1ns.H J3. 1ns. J#. 1ns. J6.

.efine a tivation ener-y. It is defined as extra ener-y to be supplied to the rea tants so that they an han-e into produ ts. 1 rea tion is 6@% omplete in " Frs and 86% omplete in # Frs.+hat is the order of the rea tionI 'irst Arder. &he plot of lo- M versus K is linear with a slope 5 !Ga7 ".3@3 P. +hat is KI K is 17&.

&he rate onstant of a rea tion is 1." x 1@!" 4.3ol!1/!1. +hat is the order of the rea tion I 1ns.H Arder 5" D!& A%!4e A4e&a1e Student 2 12 Mar, J1. 1ns.H J". +hat is temperature oeffi ient I R3@$

R"D$
'ill up the blan0s H )a % .% = 1 " .............. R %" %1

1ns.H

0!

R" R1

6@

J3. 1ns. J#. 1ns.H J6.

1 atalyst provides a path of _______. 1 tivation ener-y. 4ower In a photo hemi al rea tion, the ener-y of a tivation is provided by _____ Padiation +hi h of the followin- -raphs orrespond to first order rea tion I

(a) Pate (
1ns.H (a)

(b) Pate 17

( ) Pate (

(.) Pate ("

J9. Choto hemi al rea tion between hydro-en ] (hlorine on the /urfa e of water is a rea tion of (a) Lero Arder, (b) 'irst Arder, ( ) /e ond Arder, (d) &hird Arder 1ns. H Lero Arder J8. 'or a hemi al rea tion K1 y3. &he rate law is r5M%1)3. If the on entration of 1 is doubled the rea tion rate will be (a) .oubled, (b) Juadrupled, ( ) In reased by $ times, (d) On han-ed 1ns.H ( )

3#EMI3A< KINETI3S
9el!w A4e&a1e Student 214 Mar,s J1. .ifferentiate between order of rea tion and mole ularity of rea tion. 1ns. Arder of rea tion 3ole ularity 1. It is defined as sum of powers to whi h 1. It is the number of mole ules ta0in- part in on entration terms are raised in rate law hemi al rea tion. ". It is determined experimentally ". It is determined theoreti ally 3. It an be Eero or even in fra tion 3. It is always in whole number ex ept Lero. #. Arder of omplex rea tion an be determined, #. 3ole ularity of omplex rea tion an not be determined. J". 1ns. J3. 1ns.H 'or a rea tion 1BF"A 2, rate k &1. +hat is its i) 3ole ularity, ii) Arder of rea tions I I) Its mole ularity is " ii) Its order is 1. .efine pseudo unimole ular rea tion. Give two examples. &he rea tion whi h is mole ular but its order is one is alled pseudo unimole ular rea tion. G-.H
H 1.)CH 3 COOC " H 6 + H " O CH 3 COOH + C " H 6 OH i!vertage ".)C1" H "" O11 + H " O C 9 H 1" O9 + C 9 H 1" O9
+

Glu ose

'ru tose

J#.

?ame four fa tors affe tin- rate of redu tion.

61

1ns.H

1) ?ature of rea tants ") &emperature 3) (on entration #) (atalyst J6. +hen ould order an mole ularity of a rea tion i) be /ame ii) be different 1ns.H i) Arder and mole ularity will be same in sin-le step rea tion. ii) &hey will be different if rea tion is of two or more steps. D!& A4e&a1e Student 2 14 Mar,s J1. Clot a -raph between lo- one *s time and -ive expression value of M. 1ns. /lope5 !M7".3@3

4o((on .) time
J". 1ns.H J.3. 1ns.H &he rate onstant for a first order rea tion is @.@@6 min !1. (al ulate its half life.

t1 =
"

@.9D3 @.9D3 = = 13$9 Mi! & @.@6

+hat is meant by effe tive ollisionI &he ollision whi h leads to formation of produ t. 3ole ules is alled effe tive ollision. J#. +hen do mole ules under-o effe tive ollisionI 1ns.H 3ole ules under-o effe tive ollision if they ross ener-y barrier and orientation barrier, that is they possess a tivation ener-y and ollide in proper orientation. J6. Fow does on entration effe t the rate of rea tionI 1ns,H +hen we in rease on entration of rea tants, total no. of ollision will in rease, therefore, probability of effe tive ollision will in rease, hen e the rate of rea tion will in rease. D!& A%!4e A4e&a1e Student 2 14 Mar,s J1. 1n in rease of 1@ M in temp. rarely doubles the 0ineti ener-y of parti les but doubles the rate of rea tion, whyI 1ns.H +hen temp. is in reased 1@ M , 0ineti ener-y of mole ules in reases, no. of mole ules possessin- a tivation ener-y be ome double, therefore no. of effe tive ollision doubles hen e rate of rea tion. J". &he rate of onstants of a rea tion at 6@@ M ] 8@@ M are @.@" /e 1 respe tively. (al ulate the values of Ga ] 1. & )a %" %1 lo- " = &1 ".3@3R %1 .% "
!1

and @.@8 /e

lo-

@.@8 )a = @.@" ".3@3 $.31# 5& 1 mol 1

8@@ 6@@ 8@@ 6@@

@.6## = )a 6.81#
1ns.

1@ # 1D.16 1D.16 )a = @.6## = 1$"3@.$ 5 6.81# 1@ 1#

)a R% 1$"3@.$

"i!ce, & = Ae

@.@" = A.e $.31#6@@ @.@" A= = 1.91 @.@1"

6"

DOR 9E<O+ A5ERA7E STU=ENTS 216 Mar,s

".3@3 [ R ]o lo[ R] t 1ns.H +e 0now that rate of rea tion is proportional to the first power of on entration of the rea tant P. 'or Gx. R P d [ R] Rate = = & [ R] dt d [ R] or , = & .dt [ R]
J1. .rive the relation & = Inte-ratin- this equation, we -et 4n%P)5!MtB I !!!!!!!!!!!!!!!!!!!(1) 1-ainR I is the onstant of inte-ration and its value an be determined easily, +hen t5@, P5%P@), where %P@) is the initial on entration of the rea tant. 4n%P@)5!M x @ BI /o, 4n%P@)5I /ubstitutin- the value of I in Gquation (1) 4n%P)5 !Mt B 4n %P@) Pearran-in- this equation,

0!

[ R] @ 1 or , & = 0! t R [R ] ".3@3 or , & = 0og @ t R

J". .erive the expression t; 5 @.9D37 M for first order rea tion.

[ R] [ R] @

= &t

1ns,H

[R ] ".3@3 0og @ t R [R ] ".3@3 &= lo- O RO t1 " " ".3@3 &= lo- " t1
&=
" "

t 1 =

@.9D3 &

DOR A5ERA7E STU=ENTS 216 Mar,s J1. 1ns. .erive the relationship between a tivation ener-y ] rate onstant. 1rrhenius equation ener-y, P5 $.31# eM!1mol!1, & is temp. in Melvin.
)

& = A.e

R%

where \1= is frequen y fa tor, Ga is a tivation

63

)a R% ). ln & = ln A R%1 ln & = ln A ln , = ln A ln )a R%"

&" )a 1 1 = &1 R %1 %" &" )a %" %1 = &1 ".3@3R %1 .%"

lo-

D!& A%!4e A4e&a1e Student 2 16 Mar,s Q1. &he followin- results have been obtained durin- the 0ineti studies of the rea tion. "1 B 2 ( B . Gxperimental 1 " 3 # An .H
dx = & % A) x % B ) y (1) dt 8." 1@ " = & %@.3) x %@.#) y ( ") 8ividi!g (1) 7( "), weget , 1 1 = " y = " " # "7 y =" 9.@ 1@ 3 = & %@.1) x %@.1) y (3) ".#@ 1@ " = & %@.#) x %@.1) y ( #)

%1) 3 @.1 @.3 @.3 @.#

%2) 3 @.1 @." @.# @.1

Initial rate of formation of .73 min !1 9.@ x 1@!3 8." x 1@!" ".$$ x 1@!1 ".# x 1@!"

.etermined the rate law and the rate onstant for the rea tion.

.ividin- (3) by ("), we -et, 1 1 = x = 1 # #x dx = & % A) x % B ) y = & % A)1 % B ) " dt 9.@ 1@ 3 = & %@.1)1 %@.1) "
& = 9.@ M " " 1

Q". (al ulate the half life of a first order rea tion from their rate onstants -iven below H (a) "@@ /!1 (b) " 3in!1 ( ) # year!1 An .2 (a)

t1 =
"

@.9D3 @.9D3 = = 3.#96 1@ 3 "ec. 1 & "@@ " @.9D3 = 3.#96 min = @.36 min .. " Mi! 1 @.9D3 = @.183 years #
6#

(b)

t1 =
"

( )

t1 =
"

Q*.

Give the me hanism of the rea tion t H " ( g ) + Cl " ( g ) "u!lig " HCl ( g ) (hain initiation step H
Cl + Cl HN "Cl

An .H

(hain propa-ation step H " + Cl H + HCl H + Cl " HCl + Cl (hain termination step Q.. /tate the role of a tivated omplex in a rea tion and state the relation with ener-y of a tivation. An .H +hen the ollidin- rea tant mole ules possess the 0ineti ener-y equal to ener-y of a tivation then the onfi-uration of atoms of the spe ies at this state is different from the rea tants as well as the produ ts.&his state is alled a tivated or transition state and spe ifi onfi-uration of this state is alled a tivated omplex. &he rea tant mole ules do not han-e dire tly into produ ts, first they absorb ener-y equivalent to the ener-y of a tivation and form an a tivated omplex. &he a tivated omplex formed has a very short life spam and splits into the produ ts. &he a tivated omplex is at the top of the ener-y barrier -raph and possess the hi-hest ener-y. In this a tivated omplex, all the bonds are in the transition state. 4ow ener-y a tivation barrier means the a tivated omplex is readily formed and it is fast rea tion. Fi-h ener-y of a tivation barrier means the a tivated omplex is diffi ult to form and it is a slow rea tion.

1___.2 1 tivated omplex Gaf Gner-y

H o " = ) R ) P

GP eFo/ Pea tion ondition

UNIT I ?0 SURDA3E 3#EMISTRM

66

STUDY MATERIAL
1. Ad !&pti!nH! or liquid . It is the pro ess of attra tin- mole ular spe ies on the surfa e of solid

". Ad !&%ateH! &he mole ular spe ies whi h on entrates or a umulates on the surfa e 0nown as 1dsorbate. *. Ad !&%entH! as adsorbent . &he solid or liquid substan e on whi h adsorption ta0es pla e 0nown

.. =e !&pti!nH! &he pro ess of removal of adsorbed substan e from a surfa e of solid or liquid 0nown as desorption. 0. A% !&pti!nH! &he uniform distribution of mole ular throu-hout the bul0 of the solid 0nown as absorption. 6. S!&pti!nH! &he pro ess in whi h both adsorption and absorption ta0es pla e simultaneously 0nown as sorption. 8. Enthalp$ !f Ad !&pti!nH! &he amount of ener-y released by the attra tion of one mole of adsorbate on the adsorbent. :. T$pe !f ad !&pti!n H! &here are two types of adsorption H (a) P ysisorptio! or P ysical adsorptio!H! +hen the -as mole ules are attra ted or a umulated on the solid by *ander waal=s for es. (b) C emisorptio! or C emical adsorptio!H! +hen the -as mole ules are a umulated on the solid by hemi al bonds. >. D&eundlich ad !&pti!n i !the&mH! Fe -ave a relation between the quantity of -as adsorbed by unit mass of solid adsorbent and pressure at a parti ular temperature x7m50 C17n (nS1) +here x be the mass of adsorbate ,m be the mass of adsorbent 0 ] n be the onstants C be the pressure .&his relation an be han-ed at different CressureH! 1t low pressure x7m50 C 1 1t hi-h pressure x7m50 C @ 1t intermediate pressure x7m50 C 17n 1?. Ad !&pti!n f&!m !luti!n pha eH! It has similar relation with 'reundli h adsorption isotherm .Anly in pla e of pressure , on entration of solution is ta0en. &herefore x7m50 ( 17n 11. 3atal$ tH! 1 substan e whi h in rease or de rease the rate of hemi al rea tion and quantitatively un han-ed after the rea tion 0nown as atalyst. &here are two types of atalystH! (i) Cositive (atalyst and (ii) ?e-ative (atalyst. 1". 1*. 1.. pro B&!mte& H! 1 substan e enhan es the a tivity of atalyst. B!i !n H! 1 substan e de reases the a tivity of atalyst. #!m!1ene!u catal$ i H! +hen rea tants and atalysts are in same phase ,the ess is 0nown as Fomo-eneous atalysis. (g) " "O" ( g ) + O" ( g ) NO " "O3 ( g ) G-. 69

10. #ete&!1ene!u catal$ i 2; +hen rea tants and atalysts are in different phases, this pro ess is 0nown as Fetero-eneous (atalysis. G-.H ?"(-) B 3 F"(-) 'e(/) 16. " ?F3(-)

Mechani m !f hete&!1ene!u catal$ i H! &he steps are as follows H (i) .iffusion of rea tants on the surfa e of atalyst. (ii) 1dsorption of rea tants on the surfa e of atalyst. (iii) (hemi al rea tion between rea tants on the solid surfa e to form intermediate produ t. (ii) .esorption of produ t from solid surfa e. (iii) .iffusion of produ ts away from solid surfa e. 18. Shape; electi4e catal$ i 2 1 atalyti rea tion that depends upon the pore stru ture of atalyst as well as the siEe of rea tant ] produ t mole ules is alled /hape!sele tive atalysis. 1:. En'$me 3atal$ i 2 GnEymes are biolo-i al atalyst whi h atalyse spe ifi bio hemi al rea tions. &hey are omplex nitro-enous or-ani ompounds whi h are produ ed by livin- plants and animals havin- hi-h mole ular mass. &hey are hi-hly effi ient be ause they in rease the rate of rea tion by 1@$ to 1@"@ times. 9rease NH " CONH " + H " O " NH 3 + CO" G-. Orease is an enEyme used for the de omposition of Orea only. 1>. 3!ll!id !& 3!ll!idal S!luti!n 2 phase mixed in dispersion medium. 1 hetero-eneous solution in whi h dispersed

"?. <$!philic 3!ll!id 2 &hose olloids whi h are solvents lovin- or attra tin- they are reversible /ols. "1. <$!ph!%ic 3!ll!id 2; irreversible /ols. &hose olloids whi h are solvent hatin-. It is

"". Multim!lecula& 3!ll!id 2 1 olloid in whi h lar-e no. of atoms or smaller mole ules a--re-ate to-ether to form spe ies havin- siEe in olloidal ran-e for e-. 1 sulphur sol onsists of parti les ontainin- about a thousand of /$ mole ule. "*. Mac&!m!lecula& c!ll!id 2 1 olloid in whi h the siEe of dispersed parti les are in a olloidal ran-e. /u h dispersed phase in dispersion medium is alled 3a romole ular olloids. 'or G-. Croteins, /tar h and (ellulose form ma romole ular olloids. ".. A !ciated 3!ll!id 2 &hose olloids whi h behave as stron- ele trolyte at low on entration but at hi-h on entration behave li0e olloids due to formation of a--re-ated parti le of olloidal dimensions. 'or e-. 3i elles are asso iated olloids. "0. K&aft Tempe&atu&e 2 &he formation of 3i elles ta0es pla e only above a parti ular temp. is alled Mraft temp. "6. Bepti'ati!n 2 &he pro ess of onvertin- pre ipitate into olloidal sol by mixinsmall amount of ele trolyte into dispersion medium 0nown as peptiEation and the ele trolyte 0nown as peptiEin- a-ent. "8. =ial$ i 2 It is the pro ess of purifi ation of olloids by diffusion throu-h a semi permeable membrane. 68

":. Ult&a filt&ati!n2 It is the pro ess of separatin- the olloidal parti les from the solvent and the solute present in olloida solution by ultra filter paper. ">. T$ndal effect 2 &he pro ess of s atterin- of li-ht in olloidal solution by olloidal solute 0nown as &yndal effe t. &he bri-ht one of li-ht is alled &yndal one. *?. 9&!wnian M!4ement 2 &he ontinuous Ei- Ea- motion of dispersed phase in dispersion medium is alled 2rownian 3ovement. It is due to the unbalan ed bombardment of the parti les by the mole ules of the dispersion medium. *1. #elmh!lt' Elect&ical d!u%le la$e& 2 &he ombination of the two layers of opposite har-es around the olloidal solute is alled FelmholtE Gle tri al double layer. +hen the olloidal parti les a quire Bve or :ve har-e by sele tive adsorption of one of the ions, It attra ts ounter ions from the medium formin- a se ond layer li0e. 1- I 7 I ! MB 1-I 7 1-B I : *". Feta p!tential !& Elect&! /inetic p!tential 2 &he potential differen e between the fixed layer and the diffused layer of olloidal solution havin- opposite har-es. **. Elect&!ph!&e i 2 &he pro ess of mi-ration of har-ed olloidal solute towards the oppositely har-ed ele trode in olloidal solution is 0nown as Gle trophoresis. *.. 3!a1ulati!n 2 &he pro ess of onvertin- olloidal solution into pre ipitate by mixinsmall amount of oppositely har-ed ele trolyte 0nown as (oa-ulation. *0. 3!a1ulati4e 5alue 2 &he minimum no. of a milli moles of ele trolyte requires to oa-ulate one litre olloidal solutions. *6. #a&d$;Schult' Rule 2 It has two rules H a) Appositely har-ed ions are effe tive for oa-ulation. b) &he oa-ulative power of ele trolyte in reases with in rease in har-ed on the ion used for oa-ulation. 'or G-. H 1l3BS (aBB S ?aB for ne-atively har-ed olloids. /imilarly % 'e((?)9)#! S CA#3! S/A#"! S (l ! for positively har-ed olloids. *8. Emul i!n 2 1 olloids ontain dispersed phase and dispersion medium both in liquid state is 0nown as Gmulsion. &here are two types of emulsion. (i) Ail in water ] (ii) water in oil. *:. 3!tt&ell Sm!/e p&ecipitat!& 2 /mo0e is a olloidal solution of solid parti les li0e (, 1s ompounds and dust in air. It omes out throu-h the himneys of industrial plants. It onsists of two metal dis s har-ed to hi-h potential. &he har-ed dust and ( , 1s parti les -et dis har-ed towards oppositely har-ed metal dis in form of pre ipitate while -ases ome out throu-h himney.

1 MARK QUESTIONS 6$

Q. 1. +hat /ind !f ad !&pti!n i &ep&e ented %$ the f!ll!win1 1&aph 2

* M

T
An . (hemisorption.

Q. ". In the tit&ati!n !f !xalic acid %$ acidified KMnO ., the !xidati!n !f !xalic acid i l!w in the %e1innin1 %ut %ec!me fa t a the &eacti!n p&!1&e e . +h$ An . 1uto atalysis by 3nB".

Q. *. Out !f BO.*I,, SO."I,, 3lI,, which wil act a the %e t c!a1ulatin1 a1ent f!& f!& De (O#)* An . CA#3:.

Q. .. A&&an1e the f!ll!win1 in c!&&ect !&de& !f thei& c!a1ulatin1 p!we& 2 NaC, Al*C, 9a"C An . ?aB , 2a"B , 1l3B

Q. 0. +hich t$pe !f cha&1ed pa&ticle a&e ad !&%ed !n the u&face !f A "S* du&in1 it p&epa&ati!n A "O* C * #"S QQP A "S* C * #O# An . /":.

Q. 6. +hich t$pe !f metal act a effecti4e catal$ t An . &ransition metals.

Q. 8. The c!ll!idal !luti!n !f 1!ld p&epa&ed %$ diffe&ent meth!d ha4e diffe&ent c!l!u& . +h$ An . .ue to differen e in the siEe of olloidal parti les.

Q. :. At hi1h p&e u&e, the enti&e metal u&face 1et c!4e&ed %$ a m!n! m!lecula& la$e& !f the 1a . +hat i the !&de& !f the p&!ce An . Lero order. 6D -

Q. >. +hat i the te&m u ed f!& minimum c!ncent&ati!n !f an elect&!l$te which i a%le t! cau e c!a1ulati!n !f a !l An . 'lo ulation value.

Q. 1?. A liquid i f!und t! catte& a %eam !f li1ht %ut lea4e n! &e idue when pa ed th&!u1h the filte& pape&. +hat can the liquid %e de c&i%ed a An . (olloid.

Q. 11. If an elect&ic field i applied t! a c!ll!idal !l, the di pe& ed pha e pa&ticle a&e f!und t! m!4e t!wa&d the elect&!de !f !pp! ite cha&1e. If h!we4e&, the di pe& ed pha e i made tati!na&$, the di pe& i!n medium i f!und t! m!4e in the !pp! ite di&ecti!n. +hat i the te&m u ed f!& uch m!4ement !f di pe& i!n medium An . Gle tro osmosis.

Q. 1". Out !f 1luc! e, u&ea and d!dec$l t&imeth$l amm!nium chl!&ide, which !ne f!&m micelle in aque!u An . !luti!n a%!4e ce&tain c!ncent&ati!n -

.ode yl trimethyl ammonium hloride.

Q. 1*. A pl!t !f l!1 4e& u l!1 p f!& the ad !&pti!n !f a 1a !n a !lid 1i4e a t&ai1ht line. +hat i the l!pe equal t! An . 1 /

Q. 1.. The f!&mati!n !f micelle !ccu& !nl$ %e$!nd a ce&tain tempe&atu&e. +hat i the tempe&atu&e called An . Mraft temperature !f ad !&pti!n -

Q. 10. +hat a&e the i1n !f #, S and 7 f!& the p&!ce An . F 5 :ve / 5 :ve G 5 :ve

Q. 16. Out !f 3O and N#* which i ad !&%ed !n acti4ated cha&c!al t! a la&1e extent and wh$ An . 1mmoniaR be ause more easily liquefiable -as under-oes adsorption to a -reater extent. Q. 18. On pa in1 #"S th&!u1h dilute #NO* the c!l!u&le An . .ue to formation of olloidal sol of /ulphur. A1NO* !luti!n in KI !luti!n. +hat !luti!n %ec!me tu&%id. +h$ -

Q. 1:. A !l i p&epa&ed %$ additi!n t! exce

cha&1e i li/el$ t! de4el!p !n the c!ll!idal pa&ticle 9@

An .

Cositive.

Q. 1>. If we add equim!la& am!unt !f fe&&ic h$d&!xide !l and a& enic ulphide !l, what will happen An . 2oth the sols will -et oa-ulated. ha/en with a little am!unt !f dilute !luti!n !f De3l* An . It auses peptiEation leadin- to the formation of a positively har-ed sol of 'e (AF)3.

Q. "?. +hat happen when f&e hl$ p&ecipitated De (O#) * i

Q. "1. +hat happen t! a 1!ld !l if 1elatin i added t! it An . It auses stabilisation of -old sol.

Q. "". Out !f Na3l, M1SO., Al" (SO.)*, K.SDe(3N)6T, which !ne will %&in1 a%!ut the c!a1ulati!n !f a 1!ld !l quic/e t and in the lea t !f c!ncent&ati!n An . 1l" (/A#)3.

Q. "*. +hat i the unit f!& exp&e in1 fl!cculati!n 4alue An . millimole per litre. f!& A "S* c!ll!id An . 1l3B.

Q. ".. Out !f BO.*I, SO."I, Al*C and NaC, which will ha4e the hi1he t c!a1ulatin1 p!we&

" MARKS QUESTIONS Q. 1. 9leedin1 i An . t!pped %$ the applicati!n !f alum t! a w!und. +h$ -

2lood is a olloid alum bein- an ele trolyte, ma0es the blood to oa-ulate and form lot.

Q. ". +hat i the pu&p! e !f addin1 1elatin t! ice c&eam An . I e ream is a olloid. Gelatin imparts stability to it be ause -elatin is a prote tive olloid. Q. *. =ial$ i i a meth!d !f pu&ificati!n !f !l . 9ut p&!l!n1ed dial$ i !f the !l ma/e it un ta%le. +h$ An . &ra es of ele trolytes in the sol, impart har-e to dispersed phase parti les ma0in- it stable. Crolon-ed dialysis removes all ele trolytes thus ma0in- the sol unstable. Q. .. +hat i the functi!n !f 1um a&a%ic in the p&epa&ati!n !f Indian in/ An . Gum arabi is a prote tive olloid and thus provides stability to Indian in0.

Q. 0. +hat i c!ll!di!n - +hat i it u e -

91

An .

(ellulose dispersed in ethanol, is alled ollodion. It is used for ma0in- membranes for ultrafiltration.

Q. 6. +h$ the un l!!/ &ed at the time !f ettin1 - Explain !n the %a i !f c!ll!idal p&!pe&tie . An . 1t the time of settin-, the sun is at the horiEon. &he li-ht emitted by the sun has to travel a lon-er distan e throu-h the atmosphere. 1s a result, blue part of the li-ht is s attered away by the dust parti les in the atmosphere. Fen e the red part is visible. Q. 8. Additi!n !f #" t! acet$lene 1i4e ethane in p&e ence !f palladium %ut if 9aSO . and quin!line !& ulphu& a&e al ! added, the p&!duct i ethane. +h$ An . 2a/A# B quinoline 7 s poison the atalyst. Fen e, the effi ien y of the atalyst de reases and the rea tion stops at the first sta-e of redu tion. Q. :. SnO" f!&m a p! iti4el$ cha&1ed c!ll!idal !l in acidic medium and a ne1ati4el$ cha&1ed !l in the %a ic medium. +h$ An . /nA" is amphoteri in nature. It rea ts with a id e-. F(l to form /n(l # in the solution. &he ommon /n#B ions are adsorbed on the surfa e of /nA " parti les -ivin- them a positive har-e. /nA" rea ts with a base e-. ?aAF to form /odium /tannate in the solution. &he stannate ions are adsorbed on the surfa e of /nA " parti les -ivin- them a ne-ative har-e. Q. >. +h$ ph$ ical ad !&pti!n unim!lecula& An . (hemisorption ta0es pla e as a result of rea tion between adsorbent and adsorbate. +hen the surfa e of the adsorbent is overed with one layer, no further rea tion an ta0e pla e. Chysi al adsorption is simply by *ander +aal=s for es. /o any number of layers may be formed one over the other on the surfa e of the adsorbent. Q. 1?. +hat i meant %$ induced catal$ i - 7i4e an example. An . It is a phenomenon in whi h a hemi al rea tion in reases the rate of another rea tion whi h otherwise may not o ur in similar onditions. E1. /odium arsenite (?a31sA3) is not oxidised in air but if air is blown into a solution ontainin- ?a31sA3 and ?a"/A3, then both 1sA33: and /A3": ions are oxidised. Q. 11. +hat t$pe !f c!ll!idal !l a&e f!&med in the f!ll!win1 (i) (ii) (iii) Sulphu& 4ap!u& a&e pa ed th&!u1h c!ld wate&. +hite !f an e11 i mixed with wate&. 3!ncent&ati!n !f !ap !luti!n i inc&ea ed. 9" i multim!lecula& whe&ea chemi !&pti!n i

An .

(i) (ii) (iii)

3ultimole ular olloid 3a romole ular olloid 1sso iated olloid.

Q. 1". +hat i c!mm!n t! aqua !l and ae&! !l - In what &e pect d! the$ diffe& An . 2oth are olloids. In aquasol, water a ts as dispersion medium. In aerosol, air a ts as dispersion medium. Q. 1*. Explain a t! wh$ SnO" f!&m a p! iti4el$ cha&1ed !l in !luti!n with p# U 8 and ne1ati4el$ cha&1ed !l in !luti!n with p# V 8. An . Pefer 1ns. $. For average
Q.1 An .H Q". An . Q.*. An .H Q.. An H +hy does physisorption de rease with in rease of temperature I 2e ause the attra tion between -as mole ules and solid surfa e is very wea0 whi h easily over ome by in rease of temperature. +hy are powdered substan es more effe tive absorbents than their rystalline formsI .ue to in rease of surfa e area of powered substan es. +hat do you mean by a tivation of adsorbantI Fow is it a hievedI 1 tivation of adsorbent means in rease the extent of adsorption. It is a hieved by the in rease of surfa e area. .is uss the effe t of pressure and temperature on the adsorption of -ases on solids. Gffe t of pressure H 2y the in rease of temp., extent of adsorption de reases uniformly for physisorption but for hemisorption initially in reases then de reases. +hat is observed (i) +hen a beam of li-ht is pressed throu-h a olloidal sol (ii) 1n ele trolyte, ?a(l is added to hydrated ferri oxide sol. (iii) Gle tri urrent is passed throu-h olloidal sol. (i) &yndal Gffe t (iv) (oa-ulation (v) Gle trophoresis +hat do you mean by a tivity and sele tivity of atalysisI 1 tivity of atalyst means to in rease the extent of hemisorption. /ele tivity of (atalyst means to dire t a rea tion to form sele tive produ t. +hat is L/3!6I +hat is its formulaI L/3!6 is a Eeoli$te seine of mole ular porosity6. Its formula is Fx%(1lA")x(/iA")D9!x ) . 19F"A +hy adsorption is always exothermi I In 1dsorption, han-e of entropy Q/ is :ve i.e. non favourable ondition for exothermi han-e where as han-e of enthalpy QF is :ve i.e. favourable ondition for exothermi han-e. Averall QG be omes :ve in adsorptionR therefore adsorption is always exothermi . Gxplain the followin- terms H (i) Gle trophoresis, (ii) (oa-ulation, (iii) .ialysis (i*) &yndal Gffe t

Q0.

An .H

Q6. An . Q8. An .H Q:. An .H

Q>.

93

An .2

(i) Gle trophoresis H! &he immi-ration of olloidal solute towards oppositely har-ed ele trode under an ele tri potential is alled Gle trophoresis. (ii) (oa-ulation H! &he pro ess of settlin- down of olloidal part les is 0nown as oa-ulation. (iii) .ialysis H! It is a pro ess of removin- dissolved impurities from olloidal solution by means of diffusion throu-h a suitable membrane. (iv) &yndal effe t H! &he s atterin- of li-ht in olloidal solution by olloidal solute is 0nown as &yndal effe t. (omment on the statement that h olloid is not a substan e but state of a substan ei . 1 substan e shows different physi al properties in different medium. It may exist as olloid or rystalloids under ertain onditions. G-. ?a(l in water behaves li0e rystalloid while in benEene behaves li0e olloid. /imilarly dilute soap solution behaves li0e rystalloid whereas on entrated soap solution li0e olloids. It is the siEe of parti les whi h matters i.e. the state in whi h the substan es exists. If the siEe of the parti les lies in the ran-e 1 to 1@@@ no., it is in olloidal state. +hy are substan es li0e Clatinum and Calladium offer used for arryin- out ele trolysis in aqueous solution I Clatinum and palladium is inert ele trodes. &hey are not rea t with the ions of ele trolyte and produ ts of ele trolysis. Fen e they are used as ele trodes durin- ele trolysis. Fen e they are used as ele trodes durin- ele trolysis. Fen e they are used as ele trodes durin- ele trolysis in aqueous solution. +hy it is ne essary to remove (A when ammonia is obtained by Faber=s pro essI 2e ause (A a ts as poison for the atalyst in the manufa ture of ?F 3 by Faber=s pro ess. +hi h will be adsorbed more readily on the surfa e of har oal and why ?F 3 or (A"I &he riti al temperature ?F3 is more (A", therefore ?F3 is liquefied more easily than (A". Fen e ?F3 has hi-her intermole ular for es of attra tion and hen e it adsorbed more readily. +hat is similarity and dissimilarity in aqua solution and solid aerosolsI 1qua /ols and solid aerosols both have solid as dispersed phase and have different dispersion medium. 1qua solution ontain water and aerosol ontain air as dispersion medium. Fow an a olloidal solution and true solution of the same olour be distin-uished from ea h otherI 2y &yndal effe t( olloidal solution will s atter li-ht and path be omes li-hted where as no su h phenomena is observed in true solution.) +hy is ferri hloride preferred over potassium hloride in ase of a ut leadin- to bleedin-I 2lood is ne-atively har-e olloidal parti les. It is oa-ulated by Bve ions. 1s 'e BB ions has -reater number of har-es than M B ions. &herefore on the basis of Fardy!/ hulEe rule, (oa-ulation with 'eBBB is faster and hen e it is preferred. A!E"A#E ST$%ENTS &'(

Q1?. An .

Q11. An .H

Q1". An .H Q1*. An H Q1.. An . Q10. An .2 Q16. An .2

BELO

Mar) *ue+tion+

1. ". 3. #. 6.

.efine 1dsorption with one example. +hat is physisorption and hemisorption I +hat is 'reundli h adsorption isotheorem I +rite the relation between quantity of -as adsorbed by unit mass of /olid adsorbent and pressure at a parti ular temperature. .raw a -raph between rate of adsorption and pressure at different temperature li0e &1S&"S&3. 9#

9. 8. $. D. 1@. 11. 1". 13. 1#. 16. 19.

.efine atalysis with one example. +rite the use of L/3!6. +hat is 2io hemi al atalysisI +hat is (olloidsI .efine .ispersed phase and .ispersion medium. .efine 3i elle. +hat is CeptiEationI +hat is &yndal effe tI .efine (oa-ulation and Cre ipitation of /ol. +hat is GelI .efine CeptiEin- a-ent.

A!E"A#E ST$%ENTS &'( MA"K *$ESTIONS 1 ". 3. #. 6. 9. +hy the pressure of -as is de reased when a -as li0e A", F", (A, (l", ?F3 or /A" is ta0en in losed vessels ontainin- powdered har oal I +hy does physisorption de reases with in rease of temperatureI +hy are powdered substan es are more effe tive adsorbents than their rystalline formsI +rite the pro ess by whi h ve-etable oil onverted into ve-etable Ghee. +hat is shape!sele tive atalysisI +rite two examples of hetero-eneous atalysis. 12 Mar, .efine Gnthalpy of 1dsorption. +hat is the role of desorption in the pro ess of atalysisI .efine &yndal (one. +hat is Gle tro0ineti Cotential or Leta CotentialI .efine (oa-ulatin- *alue.

ABO!E A!E"A#E ST$%ENTS &

1. ". 3. #. 6.

SURDA3E 3#EMISTRM

Below Average Stu,ent+ &'- Mar)+ *ue+tion+

1. ". 3. #. 6. 9. Gxplain .esorption and /orption. +rite two differen es between physisorption and hemisorption. +hat is homo-eneous and Fetero-eneous atalysisI Give one example ea h. .efine Cromoters and Coisons. +rite two appli ations of atalyst in Industry. Gxplain leansin- a tion of soap. 96

8. $. D.

+hat are the methods for the preparation of olloids. +hat is purifi ation of olloidal solutionI ?ame the pro ess of purifi ation of olloids. +rite brief notes on (a) 2rownian 3ovement and (b) Gle trophoresis.

1@. 11.

/tate Fardy!/ hulEe Pule. +hat is its appli ationI +rite the example of olloids whi h is bein- used in our daily life.

A!E"A#E ST$%ENTS :

'- Mar)+ *ue+tion 1. ". 3. #. 6. 9. 8. +rite the me hanism of 1dsorption. +hy are substan es li0e Clatinum and Calladium often used for arryin- out ele trolysis of aqueous solutionI +hat is fun tion of promoters and CoisonsI +rite the name of pro ess and atalyst used for the preparation of ?F3 Fow an be 4yophobi olloids preparedI Give two examples for preparation of olloids by hemi al methods. +hat is demulsifi ationI ?ame two demulsifiers .

ABO!E A!E"A#E ST$%ENTS :

'- Mar)+ *ue+tion+ 1. +rite the me hanism of Fomo-eneous atalysis rea tion
( g) " "O" ( g ) + O" ( g ) NO ""O3 ( g )

". 3. #. 6.

.efine Mraft temperature (&M) and riti al 3i elle on entration ((3(). +hat is the role of ele trolyte in oa-ulation or pre ipitationI +rite the ause of formation of delta in brief. .efine Intrinsi and Gxtrinsi olloids with example.

9E<O+ A5ERA7E STU=ENTS :

'. Mar)+ *ue+tion+ 1 ". 3. #. 6. .efine 1dsorption, 1dsorbent and 1dsorbate. +rite three hara teristi s of physisorption and hemisorption. +rite at least three fa tors on whi h rate of adsorption depends. +rite three appli ations of 1dsorption. +hat are the hara teristi s of GnEyme atalysisI 99

9. 8. $. D. 1@.

+rite three differen es between 4yophili and 4yophobi .efine .ialysis, Gle tro dialysis and Oltra filtration.

olloids.

.efine 3ultimole ular, 1sso iated and 3a ro mole ular olloids. +hat is Gmulsion. +rite the types of Gmulsions. Fow an be testedI +rite at least three appli ations of olloids.

A!E"A#E ST$%ENTS :

'. Mar)+ *ue+tion+ 1. .raw a -raph between lox and lo- C. m

+rite the value of inter ept and slope. ". 3. #. 6. 9. 8. $. +rite a brief notes on a tivity and sele tivity of solid atalyst with example. +hat is LeoliteI +rite its stru ture and use. +hat are GnEymes. +rite the me hanism of GnEyme atalysis. +rite at least three differen es between true solution , olloidal solution and suspension. +rite the auses for the reation of har-e on olloidal parti les. Gxplain the terms with suitable examples (a) 1l osol, (b) 1erosol, ( ) Fydrosol ?ame the atalyst for Faber=s Cro ess, Astwald=s Cro ess and (onta t Cro ess.

A9O5E A5ERA7E STU=ENTS H

'. Mar)+ *ue+tion+ 1. ". 3. +rite the steps involve for me hanism of Fetero-eneous atalysisI +rite a brief note on me hanism on 3i elle formation. +hat do you mean by (ottrell smo0e pre ipitator.

98

UNIT I ?6 & 7ENERA< BRIN3IB<ES AN= BRO3ESS OD ISO<ATION OD E<EMENTS

STUDY MATERIAL
Important /oint+ & M!de !f !ccu&&ence !f element 2 Glements are found in nature either in the free state is also alled the native state, or in the ombined state i.e. found in the form of ompounds. &his is mainly due to the reason that different elements have different hemi al rea tivities. Nati4e State 2 Glements or metals whi h are not atta 0ed by moisture, oxy-en and arbon dioxide of the air o ur in the native state. GxamplesH (arbon, /ulphur, Gold, Clatinum, ?oble Gases et . 3!m%ined State 2 &he elements whi h are readily 7 easily atta 0ed by moisture, Axy-en and (arbon dioxide of air, o ur in the ombined state in form of their ompounds are alled minerals. In the ombined state, non!metals are found in the redu ed form i.e. X ( where x5 ',(l,2r, I) while metals are found in the oxidiEed form i.e. is oxides e-. 'e "A3, 1l"A3, /nA", 3nA" et . Mine&al 2 &he naturally o urrin- hemi al substan es in the form of whi h the metal o urs in the earth alon- with impurities are alled minerals. O&e 2 &he minerals from whi h the metal is onveniently and e onomi ally extra ted is alled an Ares. &hus all ores are minerals but all minerals are not Ares. 7an1ue !& Mat&ix 2 &he Garthy and sili ious impurities with ores are 0nown as matrix or Gan-ue. Crin ipal ores of some Important 3etals H
Metal O&e 3!mp! iti!n

1luminium Iron

2auxite Maolinite ( a form of (lay) Fematite 3a-netite Iron Cyrite (opper Cyrite 3ala hite (uprite Lin 2lend

1lAx(AF)3!"x % where @ , x,1) 'e"A3 'e3A# 'e/" (u'e/" (u(A3.(u(AF)" (u"A Ln/

(opper Lin

Sinte&in1 2 It is a pro ess of rushin- ores to reasonable siEe before on entration of ores. It is followed by heatin- of solid parti les below its m.p. to han-e it into sin-le mass. 3!ncent&ati!n 2 &he pro ess of removal of unwanted materials li0e sand, lay , ro 0 et from ore is 0nown as on entration or benefi ation or enri hment or dressin-. <eachin1 !& chemical epa&ati!n 2 It is a pro ess in whi h ore is treated with suitable rea-ent whi h dissolves ores but not the impurities. 9ea$e&W B&!ce !& pu&ificati!n !f %auxite %$ leachin1 2 2auxite ore is treated with austi soda (?aAF) , 1l"A3 dissolves in on entrated solution leavin- behind impurities.

9$

Al " O3( " ) + " NaOH ( a/ ) + 3H " O( l ) " Na% Al (OH ) # )( a/ )

&he aluminate in solution is neutraliEed by passin- (A" -as and hydrated 1l"A3 is pre ipitated. 1t this sta-e the solution is seeded with freshly prepared samples of hydrated 1l "A3, whi h indu es the pre ipitation.

" Na% Al (OH ) # )( a/ ) + CO" Al " O3 .xH " O + " NaHCO3 ( a/ )

&he pre ipitate of 1l(AF)3 is filtered, dried and finally heated to about 1#8@ M to obtain pure 1l"A3.
& Al " O3 .xH " O 1#8@ Al " O3 ( s ) + xH " O( g )

3!ncent&ati!n !f 7!ld E Sil4e& !&e %$ leachin1 2 In the metallur-y of 1- ] 1u the respe tive metal is lea hed with a dilute solution ?a(? or M(? in the presen e of air for oxy-en from whi h a metal is obtained later by repla ement.

#M ( s ) + $CN ( a/ ) + "H "O + O"( g ) #%M ( CN ) " )

( a/ ) +

#OH ( a/ )

+here 35 1- or 1u

#%M ( CN ) " )

( a/ ) +

+!( s ) %+!(CN ) # )" ( a/ ) + "M ( s )

EXTRA3TION OD 3RU=E META< DROM 3ON3ENTRATE= ORES 2;

Conver+ion of ore into o0i,e i1e1 ,e2ele3tronation of ore+ & It is a hieved by al ination and roastin-. 3alcinati!n 2 It is the pro ess of onvertin- an ore into its oxide by heatin- it stron-ly below its m.p. either in absen e or limited supply of air. &his method is ommonly used to onvert metal arbonates and hydroxides to their respe tive oxides..urin- the pro ess of al ination, the followin- hemi al han-es o urs. 1) 3oisture is driven out. ") *olatile impurities of /, 1s ] C are removed as their volatile oxides. 3) +ater is removed from hydrated oxides and hydroxides ores.
Al " O3 ." H " O Heat Al " O3 + " H " O
2auxite 4imonite 1lumina 'erri oxide
*e" O3 .3H " O *e" O3 + 3H " O

#) (arbonate ores are onverted into their respe tive oxides by loss of arbon dioxides.
CaCO3 CaO + CO"

4imestone 3ala hite

CuCO3 .Cu ( OH ) " "CuO + H " O + CO"

(al ium Axide

#) It ma0es the ore porous and hen e easily wor0able in subsequent sta-es. (al ination is usually arried out in a reverberatory furna e. R!a tin1 2 It is the pro ess of onvertin- an ore into its metalli oxide by heatin- stron-ly at temp. is suffi ient to melt in ex ess of air. &his pro ess is ommonly used for sulphide ores. &he followinhan-es o urs durin- roastin-. 1.3oisture is removed ".Ar-ani matter is destroyed 3.?on!3etalli impurities li0e that of sulphur, Chosphorous and 1rseni are oxidiEed and are removed as volatile -ases.

9D

" $ + $O" $"O" P# + 6O" P# O1@ # As + 3O" " Al " O3

#.

Ares are -enerally onverted into metalli oxides.

" +!" + 3O" " +!O + " "O" " P#" + 3O" " P#O + " "O" "Cu " " + 3O" "Cu " O + " "O3

6 .It ma0es the ore porous ] hen e easily wor0able in subsequen e sta-e.

1 MARK QUESTIONS Q. 1. +h$ ca&%!n &educti!n p&!ce aluminium !xide t! aluminium An . 2e ause aluminium metal itself a very powerful a-ent and an easily i n!t applied f!& &educin1

redu e (A formed durin- the rea tion ba 0 to arbon. Q. ". Explain wh$ the&mit p&!ce %&!/en pa&t !f a machine An . In thermit pro ess, oxides of metals are redu ed by aluminium in i quite u eful f!& &epai&in1 the

whi h lar-e amount of beat is evolved, metal is in the motten state ] is allowed to fall between the bro0en parts of a ma hine. heat 'e"A3 (s) B " 1l (s) YYYZ 1l"A3 B " 'e (l) B heat molen Q. *. D&ee ene&1ie !f f!&mati!n (f7) !f M1O ( ) and 3O (1) at 1"8* K and ""8* K a&e 1i4en %el!w 2 fG 3-A (s) 5 : D#1 Me7mol at 1"83 M 5 : 3## Me7mol at ""83 M fG (A (-) 5 : #3D Me7mol at 1"83 M H I 6": KNJm!l at ""8* K On the %a i !f the a%!4e data, p&edict the tempe&atu&e at which ca&%!n can %e u ed a &educin1 a1ent f!& M1O ( ).

An . &he redox rea tion is H 8@

3-A (s) B ( (s) YYYZ 3- (s) B (A (-) GX 5 fGX(Crodu ts) : fGXrea tant 1t 1"83 M 1t ""83 M GX 5 : #3D : (: D#1) 5 6@" Me mol:1 GX 5 : 9"$ : (: 31#) 5 : 31# Me mol:1

&he rea tion is feasible at ""83 M. Q. .. +h$ i Finc and n!t 3!ppe& u ed f!& the &ec!4e&$ !f Sil4e& f&!m the c!mplex SA1 (3N)"T An . Lin is stron-er redu in- a-ent and more ele tropositive than (opper. (GX 5 B @.3#*) Q. 0. 7&aphite i u ed a an!de and n!t diam!nd. A i1n &ea !n. An . In -raphite there are free ele trons whi h helps in

ele tri al ondu tivity. Q. 6. An . #!w i 1&anula& 'inc E 'inc du t !%tained Granular Ein is obtained by pourin- molten Ein in old water ] Ein dust by

meltin- Ein ] then atomisin- it with blast of air. Q. 8. f&!th An . ?a(? forms a layer of Ein omplex, ?a " %Ln ((?)#) on the surfa e of Ln/ #!w d!e Na3N act a a dep&e ant in p&e4entin1 FnS f&!m f!&min1 the

and thereby prevents it from the formation of froth. Q. :. In the p&!ce !f ext&acti!n !f 1!ld, R!a ted 1!ld !&e 2 O" R!a ted 1!ld !&e C 3NI C #"O QQQP SXT C O#I SXT C Fn QQQP SMT C Au Identif$ the c!mplexe SXT E SMT. An . Q. >. %K) 5 %1u ((?)"):, %V) 5 %Ln ((?)#)":

+h$ i the &educti!n !f a metal !xide ea ie& if the metal f!&med i in

liquid tate at the temp. !f &educti!n An . &he redu tion of metal oxide is as H

3"A (s) B x31 (s or l) YYYZ x 3 (s or l) B 31xA (s) &he entropy of liquid metal is more than entropy of the metal in solid state. G for the redu tion be ome more on ne-ative side. G 5 F : &/ 81

Q. 1?. An . Q. 11. An . Q. 1". An . ener-y. Q. 1*. An .

+hat i the &!le !f c!llect!& in f&!th fl!atati!n p&!ce

(olle tor enhan es non!wettability of the mineral parti les. At which tempe&atu&e di&ect &educti!n !f De"O* %$ ca&%!n i p! i%le 1bove 11"3 M, arbon an redu e 'e"A3. +h$ a 4e&$ hi1h c! mic a%undance !f i&!n i the&e 1 very hi-h osmi abundan e of iron is due to its hi-h nu lear bindin-

+h$ &ef&act!&$ metal a&e u ed in c!n t&ucti!n !f fu&nace Pefra tory metals are used in onstru tion of furna es be ause they an

withstand hi-h temperature. Q. 1.. An . +hat i p$&!metallu&1$ Gxtra tion of metals usin- heat is alled pyrometallur-y. It involves

on entration of ores, roastin- al ination, smeltin-, redu tion and refinin- of metals. /ulphide, arbonate, oxide ores et . are subNe ted to pyrometallur-y. Q. 10. An . #!w the m! t elect&!p! iti4e metal a&e i !lated f&!m thei& !&e &he most ele tropositive metals are isolated from their ores by ele trolysis of

fused ioni salts.

SOME IMORTANT QUESTIONS

Q.1. In -eneral whi h metals do you expe t to o ur in the nature in native stateI Give examples. An . H 3etals su h as (u, 1-, 1u, Ct et . whi h lie below hudro-en in ele tro hemi al series are not readily atta hed by Axy-en, moisture and (arbon dioxide of the atmosphere and hen e o ur in the native state in nature. Q.". (opper and /ilver lie below in the ele tro hemi al series and yet they are found in the ombined state as sulphide in nature.(omment. An . H .ue to hi-h polariEin- power of (u and 1- ions, their sulphides are even more stable than the metals. Q.*. +hi h metals are -enerally extra ted by ele trolyte pro essI +hi h positions these metals -enerally o upy in the periodi tableI An . H Gle trolyti pro ess is used for the extra tion of a tive metals li0e ?a, (a, 3-, M, 1l et . where all other methods fail. Gx ept 1l and few other metals, these metals belon-s to /!blo 0 elements of periodi table. Q... 1lthou-h thermodynami ally feasible, in pra ti e, 3a-nesium metal is not used for the redu tion of 1lumina in the metallur-y of aluminium.+hyI An . H 2elow the temperature(19"3 M) orrespoindin- to the point of interse tion of 1l "A3 and 3-A urves in Gllin-ham dia-ram, 3a-nesium an redu e 1lumina be ause the Q fGo value of 1l"A3 at temperatures below 19"3 M, is less ne-ative than that of 3-A. &herefore below 19"3 M 3- an redu e 1l"A3 to 1l. 2ut 3a-nesium is mu h ostier metal than 1luminium and hen e the pro ess will be une onomi al.

8"

Q.0.

+hy is the redu tion od a metal oxide easier if the metal formed is in the liquid state at the temperature of redu tionI An . H Gntropy is hi-her when a metal is in the liquid state than when it is in the solid state. &herefore, the value of entropy han-e (Qs) of the redu tion pro ess is more on the Bve side when the metal formed is in the liquid state and the metal oxide bein- redu ed is in the solid state. /in e the value of & Q/ in rease and that of QF remains onstant, therefore the value of QGo ( . @ = H @ %" @ l) be omes more on the :ve side and the redu tion be omes easier. Q.6. 1t a site, low -rade opper ores are available and Ein and iron seraps are also available. +hi h of the two seraps will be more suitable for redu in- the lea hed opper ore and why I 1ns. 2 &he G@ value for the redox ouple Ln"B7 Ln(!@.89*) is more ne-ative than that of 'e "B7 'e(! @.##) redox ouple. &herefore, Lin is more rea tive than iron and hen e redu tion will be faster in ase if Lin seraps are used, 2ut Lin is a ostier metal than iron so usin- iron s raps would be more e onomi al. Q.8. (1). ?ame the method used for refinin- of (i) ?i 0el (ii) Lir onium (2). &he Gxtar tion of 1u by lea hin- with ?a(? envolves both Axidation and Pedu tion. eustify -ivin- equations.

An . R (A) S i ) M!nd B&!ce H It is used to refine ?i 0el metal. +hen impure ?i 0el is heated in a urrent of (A at 33@!36@ M, it forms volatile ni 0el tetra arbonyl omplex leavin- behind the impurities. &his omplex a-ain on heatin- at hi-her (#6@!#8@M) it under-oes thermal de omposition -ivin- pure ?i 0el.
36@ & Ni + #CO 33@ Ni ( CO ) #

Impure ?i 0el

?i 0el tetra arbonyl

#8@ & Ni ( CO ) # #6@ Ni + #CO

Cure ?i 0el S ii T 5an A&/el meth!d H &his method is very useful for preparin- ultra pure metals by removin- all the Axy-en and ?itro-en present in the form of impurity in ertain metals su h as Lir onium and titanium whi h are used in spa e te hnolo-y. In this method, rude Lir onium is heated in a eva uated vessels with iodine at $8@ M, the ovalent volatile LrI# thus formed is separated. It is then de omposed by heatin- over a tun-sten filament at "@86 M to -ive pure Lir onium.
& +r( s ) + " 3 "( g ) $8@ +r3 #( g ) "@86 +r( s ) + " 3 "( g )

Impure

&un-sten

Cure filament

(9) .urin- the lea hin- pro ess, 1u is first oxidiEed to 1uB by Axy-en (A") of the air whi h then ombines with (?! ((yanide) ion to form the soluble omplex, /odium di yanoaurate(I). # Au ( s ) + $ NaCN ( a/ ) + " H " O + O"( g ) # Na[ Au ( CN ) " ] ( a/ ) + # NaOH ( a/ ) Impure /oluble (omplex Gold is then extra ted from this omplex, by displa ement method usin- a more ele tropositive Lin metal, In this rea tion, Ln a ts as a redu in- a-ent. It redu es 1u B 1u while it itself -ets oxidiEed to Ln"B whi h ombines with (?! ions to form soluble omplex, sodium tetra y anoEin ate(II) " Na[ Au ( CN ) " ] ( a/ ) + +!( s ) " Au ( s ) + Na " [ +! ( CN ) # ] ( a/ ) &hus extra tion of 1u by lea hin- with ?a(? involved both oxidation and redu tion. Q.:. 'ree ener-ies of formation (QfG) of 3-A(s) and (A(-) at 1"83 M and ""83 M are -iven below H

83

QfG(3-A)(s) 5 !D#1 Me7mol at 1"83 M QfG(3-A)(s) 5 !31# Me7mol at ""83 M QfG((A(-)) 5 !#3D Me7mol at 1"83 M QfG((A(-)) 5 !9"$ Me7mol at ""83 M An the basis of above data, predi t the temperature at whi h arbon an be used as a redu in- a-ent for 3-A(s). 1ns. H (a) 1t 1"83 M 1 i) Mg ( s ) + O" MgO ( s ) R f . = D#1&- 7 mol " 1 O" CO ( s ) R f . = #3D &- 7 mol " &he equation for redu tion of 3-A to 3- by ( an be obtained by substra tin- equation (i) from equation (ii). &hus MgO( s ) + C ( s ) Mg ( s ) + CO( g ) ii) C ( s ) +

r . = +9@" &5 7 mol

/in e QrG of the above redu tion rea tion is BveR therefore, redu tion of 3-A by ( is not feasible at 1"83 M. (b) 1t ""83 M 1 iii) Mg ( s ) + O" MgO ( s ) R f . = 31# &5 7 mol " 1 iv) C ( s ) + O" CO ( s ) R f . = 9"$ &5 7 mol " An substar tin- Gq.(III) from Gq.(I*), we have MgO( s ) + C ( s ) Mg ( s ) + CO( g ) R r . = 31# &5 7 mol /in e QrG for the above redu tion rea tion is :veR therefore redu tion of 3-A by arbon at ""83 is feasible. Q.>. 3etal sulphides o ur mainly in ro 0s and metal halides in la0es and seas. Gxplain. An .H 3etal halides bein- soluble in water, -et dissolved in rain water and are arried to la0es and seas durin- weatherin- of ro 0s. An the otherhand, metal sulphides bein- insoluble are left behind in the ro 0s as residue. Q1?. +hat are fluxesI Fow are they useful I An . H 'lux is a substan e that ombines with -an-ue whi h may still be present in the roasted on the al ined ore to form an easily fusible material alled the sla-. Q.11. +hat is a sla-I An H 1 sla- is an easily fusible material whi h is formed when -an-ue still present in the roasted or the al ined ore ombines with the flux. 'or exampleH in the metallur-y of Iron, (aA(flux) ombines with sili a(/iA") -an-ue to form easily fusible al ium sili ate ((a/iA3) sla-.
CaCo3 CaO + CO"

CaO + "iO" Ca"iO3( "lag )

Q.1". +hat is the Crin iple of Lone refinin- I An . H +hen the molten solution of an impure metal is allowed to ool, the pure metal rystalliEes out while the impurities remains in the solution. Q.1*. +hat is a depressantI Give one example.

8#

An .

(ompounds whi h prevent the formation of froth in froth flotation pro ess are

alled

depressants. 'or example, ?a(? an be used as a depressant for Ln/ in the separation of Ln/ from Cb/ ore. It forms a layer of Lin from formin- the froth. Q.1.. +hat is the role of a stabiliEer in froth floatation pro essI An .2 (hemi al ompounds li0e resols and aniline whi h tend to stabiliEe the froth are alled stabiliEers. Q.10. +hat types of Ares are roastedI An . H /ulphides ores are roasted to onvert them into their oxides sin e Axides are more easily redu ed to metal than sulphides. omplex, ?a"%Ln((?)#) on the surfa e of Ln/ and thus prevents it

Sh!&t Que ti!n 2'( Mar) *ery /hort answer questions H DOR 9E<O+ A5ERA7E STU=ENTS2 12 Mar,
1. ". 3. #. 6. 9. 8. $. Fow does minerals different from an Are I +hat do you mean by benefi ation pro ess or on entration or enri hment or dressin- I +hat is a sla-I Give one example of basi flux. +hy do a few elements o urs in the native state while others do not I +rite onstituents of bronEe with their use. +hy is Lin not extra ted from Lin Axide throu-h redu tion usin- (AI +hat is the role of ryolite in the metallur-y of 1luminiumI +hi h type of metals are refined by distillation methodI

DOR A5ERA7E STU=ENTS 212 Mar,

1. ". 3. #. 6. ?ame the hief form of o urren e of the followin- in the earth=s rust H a) 1luminium, b) Iron, ) (opper, d) Lin 1n Are sample of -alena (Cb/) is ontaminated with Lin blende(Ln/). ?ame ore hemi al whi h an be used to on entrated -alena sele tively by froth floatation pro ess. Fow is ast iron different from pi- ironI +hat is opper matteI +hy pine oil is used in the froth floatation methodI

D!& 9&i1ht Student 2

1. ". 3. #. 6. 9. ombined state as sulphides in nature. (omment.

12 Mar,

(opper and /ilver lies below in the ele tro hemi al series and yet they are found in the ?ame the ommon element present in the anode mud in ele trolyti refinin- of opper. +hy are they so presentI +hat is meant by the term hromato-raphyI +hat is the role of depressant in froth floatation pro essI +hat riterion is followed for sele tion of the stationary phase in hromato-raphyI +hat is the role of olle tor ] froth stabiliEer in froth floatation pro essI

86

D!& 9el!w A4e&a1e Student 2 '- Mar)+ *ue+tion+

1. ". 3. #. 6. 9. +hy opper metal is put in /ili a lined onverter I Givin- examples, differentiate between roastin- and al inations. .es ribe the method of refinin- of ?i 0el. Gxplain the 4ea hin- of /ilver or Gold. +rite two important ores of Iron, 1luminium, oppere ] Lin with their hemi al formula. +hat is aluminothermyI Gxplain with an example.

DOR A5ERA7E STU=ENTS2

'- Mar)+ *ue+tion+ 1. ". 3. #. 6. 9. 8. /tate the role of sili a in the metallur-y of opper. +hy is the extra tion of opper from pyrite diffi ult than that from its oxide ore throu-h redu tionI +rite hemi al rea tions ta0in- pla e in the extra tion of Lin from Lin blend. /ilver Ares and native -old have to be lea hed with metal yanides. /u--est a reason for this. +hat do you mean by vapour phase refinin-I .es ribe with suitable example. &he extra tion of 1u by lea hin- with ?a(? envolves both oxidation and redu tion. eustify -ivin- equationsI (opper an be extra ted by hydrometallur-y but not Lin explain.

DOR 9RI7#T STU=ENTS2

'- Mar)+ *ue+tion+
1. ". 3. #. Aut of ( and (A, whi h is a better redu in- a-ent for LnAI +hat is the role of -raphite in the ele trometallur-y of 1luminiumI +hat do you mean by lea hin-I Gxplain with an example. &he (hoi e of a redu in- a-ent in a parti ular ase depends on thermodynami fa tor, how far do you a-ree with this statementsI /upport your opinion with two examples. .is uss some of the fa tors whi h need onsideration before de idin- on the method of extra tion of metal from its ore.

6.

DOR 9E<O+ A5ERA7E STU=ENTS2

'. Mar)+ *ue+tion+

". 3. 3. #. +hat is the hief ore of ironI +rite hemi al rea tions ta0in- pla e in the extra tion of Iron from its Ares. Give the important uses of a) 1luminium, b) (opper, ) Iron .ifferentiate between (i) Gan-ue and 'lux (ii) 3inerals ] Ares +hat do you mean by followin- terms H 89

6. 9.

(i) Gle tro metallur-y (ii) Fydrometallur-y (iii) /meltin+hat is the si-nifi an e of leadin- in the extra tion of aluminiumI Gxplain the term H (i) .istellation (ii) 4iquation (iii) Colin- in term of refinin- of metals.

DOR A5ERA7E STU=ENTS2 '. Mar)+ *ue+tion 1. ". ?ame the pro esses from whi h hlorine is obtained as a bye!produ t. +hat will happen if an aqueous solution of ?a(l is subNe ted to ele trolysed. Gxplain how the followin- metals are obtained from their oxides by the redu tion pro ess. a) 3etal K whi h is low in the rea tivity series. b) 3etal V whi h is in the middle of the rea tivity series. ) 3etal L whi h is hi-h up in the rea tivity series a) .es ribe a method for refinin- of ?i 0el. b) &he extra tion of 1- by lea hin- with ?a(? involves both oxidation ] redu tion.

3.

D!& 9&i1ht Student 2 16 Mar,s 1. 1 ount for the followin- H i) &he redu tion of metal oxide is easier if the metal formed is in liquid state at the temperature of redu tion. ii) the redu tion of (r"A3 with 1l is thermodynami ally feasible yet it does not o ur at room temperature. iii) Is (arbon is satisfa tory redu in- a-ent for all metal Axides I ". ?ame the main ore of lead metal, write its formula. Fow is this metal obtained from its oxides I 3. .is uss briefly the hromato-raphi method used for purifi ation of elements. #. &he value of QfG@ for formation of (r"A3 is !6#@ Me7mol and that of 1l"A3 is !$"8 Me7mol. Is the redu tion of (r"A3 possible with aluminiumI 6. Fow an you separate alumina from /ili a in 2auxite ore asso iated with /ili aI Give equations if any.

88

UNIT

?8

T#E p;9<O3K E<EMENTS

Nit&!1en famil$ (7&!up 10 Element ) Mem%e& 2 ?itro-en, Chosphorous, 1rseni , 1ntimony, 2ismuth General ele troni onfi-urationH! ns"np3, valan e ele trons is five, the valen y may be 3 and 6 both. ?itro-en is only trivalent but phosphorous forms pentavalent be ause of va ant d! orbital. &he oxidation states are mainly B3 ] B6. .own the -roup B6 oxidation states espe ially is unstable due to inert pair effe t (i) the stability of hi-her oxidation state de reases down the -roup. (ii) 1s stated in (i) is due to relu tan e of ns " ele trons in bond ma0in- pro ess.) 7ene&al cha&acte&i tic 2 (i) 3atenati!n2 In reases down the -roup. Chosphorous has -reater power of atenation than nitro-en be ause in former the siEe is lar-er and availability of va ant d!orbitals, while in later the siEe is smaller and stability is a hieved throu-h C m : Cm bondin-. /in-le ? : ? bond is wea0er than p : p bond. (ii) Elect&! ne1ati4it$ t&end2 h?i be ause of hi-her ele tro ne-ativity is able to ma0e effe tive F! bond. &herefore ?F3 has hi-her 2.pt than phosphine. 1lso this property auses ammonia to be water soluble when ammonia ma0es F!bond with water. (iii) Sta%ilit$ !f #$d&ide J 9a ic cha&acte&i tic 2 1s siEe in reases down the -roup the bond len-th in reases and hen e stability of hydride de reases. &herefore a idi hara ter in reases 8$

down the -roup. In terms of basi stren-th ?F3 is more basi than CF3 be ause in hCi we have lar-er siEe ] va ant d! orbital. &herefore in spite of lone pair ele trons in both ases CF3 is less basi . i4) Reacti4it$ !f Element 2 3ole ular ?itro-en has a triple bond and with very hi-h bond ener-y it is relatively inert. +hite hpi is more rea tive than red hpi be ause in former we have only C# stru ture with lesser no of bonds while in later we have lar-er no. of bonds with repeatin- C# units. (4) An!mal!u cha&acte& !f YNZ2 (a) 2e ause of smaller siEe h?i is able to ma0e C m : Cm multiple bonds. &his also auses ?" to remain as dis rete mole ules and asso iated by wea0 *ander +aal=s for es. &his is why ? " is possible but C" is not. &his also auses ?" to remain in -aseous form. (b) h?i has no va ant d!orbital hen e only valen y of three is found while other in the -roup li0e hCi is trivalent and pentavalent both. (4i) #alide 2 hCi forms C(l3 ] C(l6 both. C(l6 is unstable be ause of two lon-er axial bonds. C(l3 fumes in moisture. (4ii) Ox! acid 2 (a) N2; &wo important oxo a ids viE ?itri a id and ?itrous a id. 2oth are mono proti . &he presen e of nitrate ion an be dete ted by addin- freshly prepare 'e/A # solution followed by addin- 1!" drop on . F"/A# by the side of test tube below tap water. &his ma0es a brown rin-. (%) B2; &hree important oxo a ids viE F 3CA#, F3CA3, and F3CA" . &hey are triproti , diproti and monoproti be ause of their stru tures. (4iii) Imp!&tant c!mp!und 2 1mmonia is prepared by Faber=s pro ess. Pequirement for -ood yield of ammonia are hi-h pressure, low tempt as per 4e! hatelier=s prin iple with iron oxide as atalyst and 0 "A, 1l"A3 as promoters. 1mmonia has sp3 hybridiEation. 4one pair ele trons on h?i ma0es its shape pyramidal. 1mmonia is a -ood omplexin- a-ent be ause of lone pair ele tron on nitro-en atom. (d) Bh! ph!&!u penta 3hl!&ide2 hCi is sp3d! hybridiEed and stru ture is tri-onal bipyramidal. OXM7EN DAMI<M(7&!up 16 Element ) MEM9ERS2; Axy-en is the 1st element of the -roup and other members are sulphur, /elenium, &ellurium and Colonium. General Gle troni onfi-uration, *alen y ] oxidation stateH &he -eneral ele troni onfi-uration is ns"np#. &he valen e ele trons are six and valen y varies from " to 9. &he oxidation state varies from !" to B9. &he maximum oxidation state of oxy-en is B". 7ene&al 3ha&acte&i tic 2 (i) An!mal!u cha&acte& !f !x$1en2 a) 2e ause of smaller siEe it ma0es effe tive Cm : Cm bond. &herefore remains as dis rete mole ule. 2ut sulphur be ause of expansion of valen y on a ount of va ant d! orbital exists as solid.

8D

%) 3atenati!n2 Axy-en has lesser ability of (atenation than sulphur be ause in later we have va ant d!orbital. &herefore valen y of sulphur -oes from two to six. &he sin-le bond ener-y in sulphur is lar-er than that of oxy-en. c) Ba&ama1netic %eha4i!u&H 2e ause of two unpaired ele trons in antibondin- mole ular orbitals of oxy-en it is parama-neti . Fowever sulphur is also parama-neti in vapour!state. d) 5alenc$2; Anly oxy-en is divalent, others are tetravalent and hexavalent also. e) Elect&!ne1ati4it$2 Anly oxy-en is able in ma0in- effe tive F! bondin-. Fen e F "A is a liquid and F"/ is -as. ii) Sta%ilit$ !f h$d&ideJ Acidic cha&acte& !f h$d&ide2; 1s siEe in reases down the -roup, the bond len-th between hydro-en and -roup member in reases. &his auses de reasin- bond ener-y down the -roup and a idi hara ter of hydrides in reases. iii) Ox! acid 2 /ulphuri a id is the most important oxo! a id of sulphur, whi h is prepared by onta t pro essesH i4) All!t&!p$2 a) AEone is the allotrope of oxy-en. Fi-h on n. Af oEone is dan-erously explosive. AEone is thermodynami ally unstable and onverts into dioxy-en. &he free ener-y for this is hi-hly ne-ative. 2e ause of this nas ent oxy-en so produ ed, AEone a ts as powerful oxidiEin- a-ent. AEone has two resonatin- stru tures. b) /ulphur has two allotropes viE Phombi (/tate at room temp) and 3ono lini (Crepared by heatin- rhombi sulphur).

#al!1en Damil$ (7&!up 18 Element )

Mem%e& 2; ', (l, 2r , I and 1t . 7ene&al p&!pe&tie 2 (1) Elect&!nic c!nfi1u&ati!n ; 1ll these members have ele trons (ns"np6) in their valen e shell. (") At!mic and i!nic &adii ; &hey have the smallest radii in their respe tive periods. Fowever siEe in reases downward the -roup due to in rease in no. of shells. (3) I!ni'ati!n enthalp$ ; &hey have very hi-h ioniEation enthalpy. It de reases down the -roup due to in rease in siEe. (#) Elect&!n 1ain enthalp$ ; &hey have maximum ne-ative ele tron -ain enthalpy in their periods as they have one ele tron short to attain stable ele troni onfi-uration. &hese values be ome less ne-ative downwards the -roup. (6) Elect&!ne1ati4it$ ; &hey are hi-hly ele trone-ative in nature. It de reases down the -roup. (9) 3!l!u& ; 1ll halo-ens are oloured . '" : yellow, (l" : -reenish yellow , 2r" : red , I" : violet. (8) ($) Oxidati!n tate I 1ll the members show !1 oxidation!state but (l , 2r and I shows B1 , B3 , B6 and B8 in addition to !1 state. Oxidi in1 p&!pe&tie I &he ready a eptan e of ele tron by halo-en ma0e them stron- oxidiEin- a-ent. 'luorine is 0nown to be the stron-est oxidiEin- a-ent amon- halo-ens. $@

(D) (1@)

(11) (1")

Reacti4it$ t!wa&d h$d&!1en 2; +ith hydro-en they form hydride of the type F! K. &he a idi nature of these varies in the order F' , F(l , F2r ,FI . Reacti4it$ t!wa&d !x$1en I +ith oxy-en they form different oxides. 'luorine forms two oxides A'" and A"'" but hlorine , bromine and iodine form oxides usin- oxidation state of B1 to B8. &he hi-her oxides are more stable than lower oxides. Reacti4it$ t!wa&d !the& hal!1en I +ith other halo-en they form interhalo-en ompounds of the types KK= , KK 3= , KK6= , KK8= (where K is lar-er in siEe than K=) Pea tivity towards metal : &hey form metal halides . &heir ioni nature de reases as follows 3' S 3(l S 32r S3I 1nomalous behaviour of fluorine 'luorine is anomalous in many properties due to followin- reasonsR (1) /mall siEe and hi-h har-e density. (") 1bsen e of va ant d! orbital in the outermost shell. (3) &he hi-hest ele trone-ativity.

INERT 7ASES (7&!up 1: Element )

MEM9ERS2; #e , Ne, A&, K&,Xe E Rn 7ene&al B&!pe&tie 2; 1. 1ll elements have o tet onfi-uration ex ept Fe, whi h has duet. &his ma0es them stable in omparison to other elements. ". IoniEation enthalpy de reases down the -roup. Mr ] Ke have low ioniEation ener-y ] hen e they ma0e ompounds with hi-hly ele trone-ative elements li0e fluorine ] oxy-en. 3. Important ompounds of xenon with its shape, hybridiEation ] stru ture H!

p*d $1

p*d"

Sp*d*

p*d"
OXO; A3I=S OD B#OSB#ORUS

p*

OXO; A3I=S OD SU<B#UR

#. &he ompounds whi h led to dis overy of inert -as ompounds are A "BCt'9 : ] Ke Ct'9 : 6. &he xenon fluorides hydrolyse ompletely ] partially leadin- to the formation of different ompounds li0eH! Ke'9 B F"A c KeA3 BF' ( omplete hydrolysis) Ke'9 B F"A c KeA'# BF' (partial hydrolysis)
B

9ina&$ 3!mp!und
&his se tion lists some binary ompounds with halo-ens (0nown as halides), oxy-en (0nown as oxides), hydro-en (0nown as hydrides), and some other ompounds of sulphur. 'or ea h ompound, a formal oxidation number for sulphur is -iven, but the usefulness of this number is limited for p!blo 0 elements in parti ular. 2ased upon that oxidation number, an ele troni onfi-uration is also -iven but note that for more exoti ompounds you should view this as a -uide only. &he term hydride is used in a -eneri sense to indi ate ompounds of the type 3xFy and not ne essarily to indi ate that any ompounds listed behave hemi ally as hydrides. $"

In ompounds of sulphur (where 0nown), the most ommon oxidation numbers of sulphur areH 6, ., ", and ;".

#$d&ide
&he term hydride is used to indi ate ompounds of the type 3xFy and not ne essarily to indi ate that any ompounds listed behave as hydrides hemi ally. IMBORTANT QUESTIONS +IT# MO=E< ANS+ER (1 ma&/ que ti!n ) 1. +hy is phosphine wea0er base than 1mmoniaI 1nsH C is bi--er than ?, therefore lone pair of ele trons are less available on C than ?. ". +hy is 1mmonia a -ood omplexin- a-entI 1nsH 2e ause of lone pair of ele trons on ?. 3. +hy ?itro-en is a -as whereas Chosphorous is a solidI 1nsH ?itro-en mole ules have less *ander +aal=s for es of attra tion whereas mole ular phosphorous has more *ander +aal=s for es of attra tion. #. +hy is ?itro-en relatively inertI 1nsH 2e ause of a triple bond with hi-h bond ener-y. 6. 1mmonia is water soluble. +hyI 1nsH It forms hydro-en bond with water. (" ma&/ que ti!n ) 1. +rite shape of followin- mole ulesH a) 1mmonia b) Chosphorous Centa hloride 1nsH a) Cyramidal b) &ri-onal bipyramidal ". Artho phosphori a id is triproti but phosphori a id is diproti . +hyI 1nsH 2e ause of their stru tures ortho phosphori a id and phosphori a id have three and two ionisable hydro-en. 3. Give reasonsH a) Chosphorous penta hloride is unstable. b) Chosphorous tri hloride fumes in moisture. 1nsH a) 2e ause of two lon-er axial bonds. b) 2e ause it rea ts with water and forms hydro hlori a id. (* ma&/ que ti!n ) #. ?itro-en shows anomalous behaviour in the -roup. +hyI 1nsH i) /mall siEe ii) Fi-h ele tro ne-ativity iii) 1bsen e of va ant d!orbital. 6. Fow is ammonia preparedI +rite hemi al rea tion involved in the Faber=s pro ess. $3

1nsH i) 1mmonia is prepared by the ombination of hydro-en and nitro-en in the ratio of 3H1. ii) &he used atalyst is iron oxide. &he promotors are potassium and aluminium oxides. iii) &he required onditions are hi-h pressure and moderate temperature. ?" B 3F" c "?F3 @9. (omplete the followin- rea tions H! i) Ke'9 B F"A c !!! B !!!! ( partial hydrolysis) ii) Ke'9 B F"A c !!! B !!!! ( (omplete hydrolysis ) iii) (l" B F"Ac !!! B !!!! 1nsH i) KeA'# B F' ii) KeA3 B F' iii) FA(l B F(l @8. 1rran-e the followin- in de reasin- order H! i) ?a', ?aI, ?a(l,?a2r( Ioni nature) ii) CF3, ?F3, ,1sF3,/bF3 ( 2asi /tren-th) iii) F',F2r,F(l,FI ( 1 id /tren-th) 1ns i) ?a'S ?a(l S ?a2rS ?aI ii) ?F3S CF3S 1sF3S /bF3 iii) FIS F2rS F(lS FI @$. 'ind hybridiEation and shape i) Ke'" ii) KeA3 iii) Ke'# 1nsH i) sp3d, 4inear ii) sp3, Cyramidal iii) sp3d", /quare planar @D. Give reasons i) F"A is a liquid but F"/ a -as. ii) 1mmonia has hi-her boilin- point than phosphine ii) Mrypton ] xenon ma0e ompounds. 1nsH i) Fydro-en bond is found in F"A but not in F"/. ii) Fydro-en bond is found in ?F3 but not in CF3. iii) 2e ause they have low ioniEation ener-y. 1@. +rite down the hemi al rea tions that ta0e pla e in the manufa ture of sulphuri a id by onta t=s pro ess. 1nsH i) / B A" c /A" *"A6 ii) /A" B A" /A3 iii) /A3 B F"/A# c F"/"A8 iv) F"/"A8 B F"A c "F"/A#

SOME IMBORTANT QUESTIONS +IT# ANS+ERS

J.1. +hy does A3 a t as powerful Axidisin- a-ent I 1nsH .ue to ease with +hi h it liberates atoms of nas ent oxy-en (A3 A" B@) "Cbs (/) B #A3 (-) Cb/A#(/) B #A" (-) J.". +hi h forms of /ulphur show parama-neti behaviour I 1ns H In *apour /tate sulphurCartly exists as /" mole ule whi h has two unpaired ele trons in the ^ Arbitals hen e exhibit parama-neti J.3. Falo-ens have maximum ne-ative ele tron -ain enthalpy in the respe tive periods in the C. & +hy I 1ns .ue to smallest siEe and hi-h effe tive nu lear har-e , readily a ept one ele tron $#

to a quire noble -as

ele troni

onfi-uration

J#. +hy is fluorine stron-er Axidisin- a-ent I 1nsH .ue to (a) 4ow enthalpy of disso iation (b) hi-h enthalpy of Fydration of '! J.6. Fow is the presen e of /A" dete ted I 1ns H 1. It has pun-ent hara teristi smell . ". It de olourises M3n A# solution 3. It turns a idified M" (r" A8 -reen J.9. 1re all the five bonds in C(l6 mole ule equivalent I 1ns : C(l6 has a tri-onal bipyramidal stru ture and the three equatorial p! l bonds are equivalent . while trhe two axial bonds are different and lon-er than equatorial bonds. J.8. +hy F3 CA3 is dibasi and F3CA# is tribasi I 1ns In F3CA3 only two repla able hydro-en but inF3CA# , three hydro-ens are repla able . J.$. +hy is helium used in divin- apparatus I 1nsH 2e ause heliun is very low solubility in blood J.D. Give reason for blea hin- a tion of (l" 1ns .ue to oxidation (l"BF"A "F(lB A (oloured substan e BA olourless substan e J1@ +rite the formula of tear -as . 1ns H ((l3 ?A" J11. +hi h aerosol deplete oEone layer I 1ns (.'.(

DOR 9E<O+ A5ERA7E

S?1 Ma&/ Que ti!n2T A. 7i4e &ea !n
@1. ?" is relatively inert in terms of rea tivity. @". ?F3 is a -ood omplexin- a-ent. @3. A3 a ts as a powerful oxidiEin- a-ent. @#. ?F3 forms hydro-en bond but CF3 does not. @6. 2ond an-le of ?F#B is hi-her than ?F3. @9. F"/ is less a idi than F"&e. @8. F"A is a liquid but F"/ is a -as. @$. ?F3 a ts as a lewis base. @D. Falo-ens a t as stron- oxidiEin- a-ent. 1@. .ioxy-en is a -as but sulphur is a solid at room temperature. 11. ?itro-en does not form ?(l6 whereas phosphorous does. $6

1". ?" is a -as but phosphorous is a solid. 13. ?" is possible but C" is not,+hyI 1#. ?F3 is more basi than CF33 16. '" and (l" are -ases but I" is a solid 19. ?F3 is soluble in water but CF3 is not. 18. CF3 has lower boilin- point than ?F3. 1$. C(l6 is unstable. 1D. (atenation in nitro-en is wea0er than phosphorous. "@. /tability of hydride of -roup 16 de reases down the -roup. "1. &he B6 oxidation state of 2i is less stable than B3. "". &he basi hara ter of hydride of -roup 16 de reases down the -roup. "3. ?F3 is pyramidal. "#. Ane of the noble -ases only xenon is 0nown to form real hemi al ompounds.

DOR A5ERA7E
@1. 'luorine is the stron-est oxidiEin- a-ent amon- halo-ens. @". F3CA3 is a diproti a id. @3. 2ond an-le in CF3 is less than ?F3 @#. ?oble -ases form ompound with fluorine and oxy-en only. @6. +hite C is more rea tive than red C. @9. C(l6 is more ovalent than C(l3. @8. /A" is air pollutant. @$. 2asi hara ter amon- the hydrides of -roup 16 elements de reases with in reasinatomi nos. @D. F3CA# is triproti but F3CA" is monoproti 1@. 2iF3 is a redu in- a-ent. 11. Gle tron affinity of fluorine is less than that of hlorine. 1". /ulphur vapours show parama-neti behaviour. 13. Falo-ens are oloured.

DOR A9O5E A5ERA7E

@1. F3CA3 and F3CA" show redu in- hara ter. ". (atenation in oxy-en is lesser than sulphur. 3. Group 19 members are alled hal o-ens. #. CMa value of FA(l is hi-her than that of FA(lA. 6. ?itro-en shows 3aximum ovalen y of four. $9

9. ?F3 has hi-her dipole moment than ?'3. 8. &rimethylamine is pyramidal but trisilylamine is planar. $. Fi-h on entration of oEone an be dan-erously explosive. D. Identify the neutral mole ule whi h is isoele troni with (lA!. Is that mole ule a lewis baseI 1@. CMa(I) for F"/A# is lar-er than CMa(II).

DOR 9E<O+ A5ERA7E

9.
1. ". 3. #. 6. 9.

3!mplete the f!ll!win1 &eacti!n 2;

Ke'" B F"A Ke'" BC'6 Ke'# BF"A Ke'9 BF"A Ke'# B/b'6 I"BF"AB(l"

DOR A5ERA7E
1. ". 3. #. 6. 9. 8. (a'"BF"/A# ?aAF B(l" '" B F"A C(l3 B F"A C(l6 B F"A ( B F"/A# 3a(O3l)3lC#3l

DOR A9O5E A5ERA7E

@1. C# B MAF BF"A @". Ke'# B A"'" @3. (a3C" B F"A @#. CA(l3 B F"A @6. CF3 BF?A3 @9. (uA B?F3 @8. 2rA3! B'" BAF!

3.

=educe t&uctu&al f!&mula !f the f!ll!win1A

D!& %el!w a4e&a1e2; D!& a4e&a1eH! D!& a%!4e a4e&a1e2; ?F3, C(l6, Ke'", Ke'#, Ke'9, /'9, I'8 F3CA#, F3CA", F3CA3, /'#, KeA3 (l"A8, C#A1@, ?"A6, KeA'#, KeA'", F"/"A$. $8

DOR 9E<O+ A5ERA7E

=.
1. ". 3. #. 6. 9. 8. $. D. 1@

+hat happen whenA

(on . F"/A# is added to (a'". /A3 is passed into water. (hlorine is passed throu-h a hot and on . /olution of al0ali, li0e 2a(AF)". Ke'# under-oes hydrolysis. Ke'9 under-oes hydrolysis. C(l6 is heated. ?a(l is heated with F"/A# in presen e of 3nA". (l" is passed throu-h a solution of ?aI in water. /A" -as is passed throu-h a solution of 'e(III) salt. +hite C is heated with ?aAF solution in an inert atmosphere of (A".

DOR 9E<O+ A5ERA7E E A5ERA7E E. A&&an1e the f!ll!win1 a menti!ned2

1. ". 3. #. 6. 9. 8. $. D. 3!', 3!(l, 3!2r, 3!I. '", (l", 2r", I". F"A, F"/, F"/e, F"&e. ?F3, CF3, 1sF3, /bF3. FI, F2r, F(l, F'. (.e reasin- order of ioni nature) (In reasin- order of bond ener-y) (.e reasin- order of boilin- points) (In reasin- order of basi nature) (In reasin- order of thermal stability)

FI, F2r, F(l, F'. (In reasin- order of redu in- power) FA(l, FA(lA, FA(lA", FA(lA3. (In reasin- order of a id stren-th) F"A, F"/, F"/e, F"&e. F(lA#, F2rA#, FIA#. (In reasin- order of a id stren-th) (.e reasin- order of a id stren-th)

D. S!me m!&e additi!nal que ti!n A (* E 0 ma&/ each)

1. ". 3. #. 6. 9. Gxplain the pro ess and ne essary onditions involved in the preparation of ?F3, F"/A# or F?A3. +hat are interhalo-en ompoundsI Fow are they lassifiedI .es ribe the hemistry of rin- test. +hy do noble -ases have omparatively lar-er atomi siEeI Give the reasons whi h prompted 2artlett to prepare first noble -as ompound. Gxplain the hemistry of -roup 16 elements with respe t to atenation, stability of hydrides, and relative stability of oxidation states. .es ribe the hief uses of fluorine, hlorine and their ompounds. Fow is blea hin- powder preparedI 3ention two of its uses . $$

8. +rite the three steps involved in the manufa ture of sulphuri a id by the onta t pro ess $. +hat are the ondition to maximiEe the yield of F"/A# in ontaq t pro ess I D. Fow an F"/A# rea ts with u metals I 1@. Fow ammonia is manufa tured by Faber=s pro ess on lar-e s ale I 11. 3ention the (onditions to maximiEe the yield of ammonia . 1". Fow does amminia a ts as a 4ewis base ,show it with the help of a hemi al . 13. Illustrate how opper metal an -ive diff. produ ts on rea tion with F?A3 . 1#. Fow F?A3 is prepared by ostwalds pro ess I +rite rea tion only at diff . sta-es 16. 2alan e the followin- equation H! (i) I" B F?A3 FIA3B?A"BF"A (ii) (B F?A3 (A" B?A" BF"A (iii) / B F?A3( on .) F"/A# B?A"B F"A (iv) C#B F?A3 ( on .) F3CA#B ?A"BF"A (*) F?A3 F?A3B ?AB F"A

$D

UNIT

?:

T#E d; 9<O3K AN= f;9<O3K E<EMENTS STUDY MATERIAL

T&an iti!n element H!&he elements lyin- in the middle of periodi table belon-in- to -r.3 to 1" are 0nown as transition elements. Elect&!nic c!nfi1u&ati!n H! (n!1)d 1!1@ ns 1!" .

<anthan!id 2!&he 1# elements immediately followin- lanthanum, i.e .(erium(6$) to 4utetium(81) are alled lanthanoids. Actin!id H!&he 1# elements immediately followin- 1 tinium($D),with atomi no.D@ to 1@3 are alled a tinoids. Inne& t&an iti!n element 2 Glments in whi h last ele tron inter in f!sub!shell of antipenultimate ener-y level. S!l4ati!n ene&1$ !& ene&1$ !f h$d&ati!nH!&he amount of ener-y han-e when 1 mole of solid substan e is han-ed into vapour state. 3#ARA3TERISTI3S OD TRANSITION E<EMENTS2; Croperties of transition metals i. metalli in nature ii. show variables oxidation states. iii. omplex ompounds. iv. oloured ompounds. v. -ood atalyst vi. parama-neti ompounds. vii. Interstitial ompounds Peason due to Fi-h enthalpy of atomiEation Cresen e of va ant d! orbitals /mall siEe, Fi-h har-e density d!d &ransition /uitable surfa e area in d!orbital Onpaired ele tron in d!orbital /imilar atomi siEe ] *a ant spa e in latti e

<anthan!id 3!nt&acti!nH!&here is steadly de rease in the atomi and ioni radii as the atomi no, in reases. It is be ause ,for every additional proton in the nu leus ,the orrespondin- ele tron -oes into the #f shell whi h is too diffused to s reen the nu leus as effe tively as more lo aliEed for the outermost ele tron in reases steadily with the atomi no. of lanthaoids. &his ontra tion in siEe is alled lanthanoid ontra tion. TRANSITION E<EMENTS DORM 2; 2asi Axide H! / "A3,&iA, &i"A3, *A,*"A3, 3nA ,'eA, (uA, (oA, ?iA, (u"A 1 idi AxideH!*"A6,3n"A8,(rA3, AsA# 1mphoteri AxideH!(uA,&iA",LnA,(rA3, (r"A3, 3n"A3,3nA",3n3A#'e3A# /pinelH! Ln'e"A#, ?on stoi hiometri ompoundsH'e@.D1A or 'e@.D6A Ioni FalidesR1ll flouoro i.e. (u'",1-' D@ .ue to lowest oxidation states .ue to hi-hest oxidation states .ue to intermediate oxidation states &ri ] divalent o upies o ta ] tetra! hedral hole .ue to defe ts in latti e rystal .ue to lower oxidation states

(ovalent FalidesH!(uI",(u(l",(u2r",1-(l,1-2r

.ue to hi-her oxidation states

Applicati!n !f d; E f; %l!c/ element 2; 1. Iron and steel used in onstru tion,as atalyst in Faber=s pro ess ". (rA" is used in ma-neti tapes 3. ?i is in hydro-enation #. + (&un-uston) in ma0in- ele tri al filament 6. 1-2r in photo-raphy 9. (u , 1-, 1u are oina-e metals 8. Ct is atalyst in manufa ture of F?A3 $. *"A6 is atalyst in onta t pro ess D. &itanium is in nu lear rea tions. 1@. Cd(l" is in +a 0er=s pro ess. =iffe&ence %etween <anthan!id and Actin!id 2; 4anthanoids (ommon oxidation state is B3, besides this B" ,B# Fave smaller tenden y of omplex formin.on=t form oxo! ions ?on!Padioa tive Gx ept Cromethium (ompounds are less basi Imp!&tant c!mp!und !f t&an iti!n metal H! 1.B!ta ium dich&!mate K"3&"O8 O&e2; 3h&!mate De3&"O# B&epa&ati!n2; #'e(r"A#B $?a"(A3 B 8A" $?a"(rA#B "'e"A3 B $(A" "?a"(rA#B F"/A# ?a"(r"A8 B "M(l St&uctu&e2; ?a"(r"A8 B ?a"/A# B F"A M"(r"A8 B "?a(l 1 tinoids (ommon oxidation state is B3, besides this B#,B6,B9, ]B8 also.B" quite rare /tron- tenden y of omplex formin.o form oxo!ions i.e. OA"B, CuA",OAB 1ll are Padio!a tive (ompounds are more basi

D1

B&!pe&tie 2; 1. (a) Oxidi in1 p&!pe&t$2 I!dide t! i!dine2

(r"A8 "! B 1#FB B 9e! "(r 3B B 8F"A 9I! 3I" B 9e! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! (r"A8 "! B 1#FB B 9I! "(r3B B 3I" B 8F"A (b)'errous to ferri H (r"A8 "! B 1#FB B 9e! "(r 3B B 8F"A 9'e"B 9'e3B B 9e! (r"A8 "! B 9'e"B B 1# FC "(r3B B 9'e3B B 8F"A ".3h&!m$l 3hl!&ide te tH! M"(r"A8 B #?a(l B 9F"/A# "MF/A# B #?aF/A# B "(rA"(l" B 3F"A OsesH It is used as an oxidiEin- a-ent 'or tannin- of leather 1s disinfe tant In volumetri analysis In hromyl hloride test. ". B!ta ium pe&mana1anate KMnO. O&e2; Cyrolusite ! 3nA"

B&epa&ati!n2; "3nA"B #MAF B A" "M"3nA# B "F"A #FC B 33nA#"; "3nA#; B 3nA" B"F"A
St&uctu&e2

2elow

B&!pe&tie 2; 1. In acidic !luti!n H! Iodine is liberated from potassium iodide 1@ I ; B "3nA#; B 19 FC "3n "C B $F"A B 6 I " 'e "C ion(-reen) is onverted to 'e *C (yellow) D"

OsesH 6'e "C B3nA# ; B $ FC 3n "C B #F"A B 6 'e*C ". In neut&al !& faintl$ al/aline !luti!nH! Axidation of iodide to iodine "3nA#!B F"A B I; $3nA" B 9/A# "; B "AF; U e 2; 1s disinfe tant 1s oxidiEin- a-ent 'or qualitative dete tion of halides, sulphites, tartarate In dry ell

QUESTION 9ANK 9el!w A4e&a1e 2 ?1 Ma&/ 1. +hat a&e d 9l!c/ Element 1nsH &hose elements in whi h d!orbital are pro-ressively filled up are 0nown as d!orbital. +hat i 1ene&al elect&!nic c!nfi1u&ati!n !f d I 9l!c/ element 1nsH (n!i) d1!1@ ns1!" +h$ a&e Fn , 3d , #1 a&e n!t &e1a&ded a t&an iti!n metal 1nsH It is be ause neither they nor their ions have in ompletely filled d! orbitals . +hat i the hi1he t !xidati!n tate h!wn %$ 3&. (".) , Mn("0) 1nsH (r. /hows (B9) and 3n /hows (B8) Axidation state . +h$ d! t&an iti!n metal ha4e hi1h enthalp$ !f at!mi'ati!n 1ns H it is due to stron- metalli bonds and additional ovalent bonds

". *. .. 0.

?" Ma&/
+hat a&e lanthanide - +&ite elect&!nic c!nfi1u&ati!n !f lanthanide . 1ns &he 1# elements after lanthanum (68) are alled lanthanides . &here outer ele troni onfi-uration is (n!") f1!1# (n!1)d @!1 ns" ". 'or /ome of first row of transition elements the G o value are * !1.1$ v (r !@.D1v 3n !1.1$ v 'e !@.## v (o !@."$ v ?i !@."6 v (u B@.3#* 1.

Give suitable explanation for the irre-ular trend in their values . 1ns : it is due to irre-ular variation of sum of sublimation and ioniEation ener-y in these elements . 3. +h$ i !&an1e !luti!n !f K"3&"O8 tu&n $ell!w !n addin1 Na O# 1ns H It han-es to (r A#!" ions whi h are yellow in olour . (r"A8!"B"AF!1 "(rA#!" yellow B F"A #. (o (II) is stable in aqueous solution but in the presen e of stron- li-ands and in air -et oxidiEed (oB3, +hy I

1nsH! /tron- li-ands and air AxidiEed (oB" to (oB3 by providin- ener-y released due to for e of attra tion between them and metal ions . D3

6. +h$ 3eC* 3an %e ea il$ Oxidi ed t! 3eC. 1ns H It is be ause (eB# has stable ele troni onfi-uration . ?* Ma&/ 1. Give balan ed equation for the preparation of M"(r"A8 from hromate ores . +hat happens when a idified di hromate soln. rea t with (i) 'e/o# (ii) F"s -as I 1ns H #'e(r"A# B 19 ?aAF B 8A" $ ?a"(rA# B ?a"/A#B "'e"A3 "Na 3&O. C "#"SO. C (3!nc) ?a"(r"A8 B F"A B ?a"/A# ?a"(r"A8 B "M(l M" (r" A8 B " ?a(l (i) 9'e B" B (r" A8!" B 1# FB 9'eB3 B "(rB3 B8F"A -reen !" B3 (ii) 3F"/ B (r" A8 B $FB3/B "(r B 8F"A ". .es ribe the preparation of M3nA# . Fow does the a idified perman-anate /oln. rea ts with (i) Iron (ii) /ulphurdioxide (iii)Axali a id I+rite the ioni eqn for the rea tions 1ns H "3nA" B #MAF B A"M"3nA# B "F"A 3nA#!" 3nA#!1 Be! (a) % 'e B" 'e B3 B e!)x 6 6e!B$FB 3nA#!1 3nB" B #F"A 6 'e B" B $FB 3nA#! 6'eB3 B 3nB"B #F"A

(b) "M3nA# B "F"@ B6/A" M"/A# B "3n/A# B "F"/A# ; 3OO [; "(A" B "e x 6 3OO n6e! B $FB B 3nA#!1 3n B" B # F"A) ox " 19 FB B " 3nA# !1 B 6("A#!" 6(A")" B "3nB" B $F"@ 3. +hat i an lanthan!id c!nt&acti!n - +hat i it cau e - 7i4e it c!n equence . 1ns &he de rease in atomi and ioni siEe with in rease in atomi no. in lanthanoid series is alled lanthanoid ontra tion . &he ause of lanthanoid ontra tion is poor shieldineffe t of d and f ele tron , due to whi h effe tive nu lear har-e in reases . . onsequen es H! (i) &he ion i siEe of lanthanoid is similar to ea h other , they o ur , to-ether and their separation be omes diffi ult . (ii) &he ioniEation ener-y of 6 d : transition series are hi-her than # d : transition series . (iii)&here is lose resemblan e between elements of # d and 6 d transition series . due to similar ioni

1vera-e @1 3ar0
(i) (ii) +h$ d!e 5"O0 act a catal$ t 1ns H It is be ause * shows variable A./ . +h$ a&e t&an iti!n metal and the&e c!mp!und 1ene&all$ c!l!u&ed 1ns It is due to present of unpaired ele trons in transition metals and their ions , that is why they absorbed li-ht from visible re-ion and under-oes d!d transition and radiate omplementary olour . +h$ a&e 3&C , A1C E ScC* 3!l!u& le D#

(iii)

1ns It is be ause they do not have unpaired ele trons ,therefore an not under -oes d!d transition . (iv) +h$ d! F& and #f h!w imila& p&!pe&tie I 1ns It is due to similar ioni siEe whi h due to lanthanide ontra tion . (4) +h$ i 3uC1 diama1netic and 3u C" pa&ama1netic It is be ause (uB does not have unpaired ele trons where as (uB" has unpaired ele trons in d!sub ell .

?" Ma&/
(i) +h$ a&e t&an iti!n metal flu!&ide a&e i!nic in natu&e whe&e a chl!&ide and %&!mide a&e c!4alent in natu&e . 1ns ! It is be ause of fluorine is most ele trone-ative where as (l and 2r are less ele tro ne-ative . Greater the differen e in ele tro ne-ativity more will be ioni hara ter . (ii) +h$ MnC" i m!&e ta%le than MnC* %ut De C* i m!&e ta%le than DeC" 1ns 3nB" has half filled d! orbital ,therefore it is more stable than 3nB3 'eB3 has half filled d! orbital, therefore it is more stable than 'e B" .

(iii) 1ns li-ht

+h$ a&e lanthan!id c!l!&ed and pa&ama1netic < It is due to presen e of unpaired ele trons, they are parama-neti and they absorb

'rom visible re-ion and under-oes f!f transition and radiate omplementary olour .

?* Ma&/
(i) +hat i meant %$ di p&!p!&ti!nati!n - 7i4e tw! example !f a%!4e &eacti!n in aqn. /olution . 1ns .isproportionation means the same substan e -et oxidiEed and redu ed, examples (uB (uB" B (u 3(rA#!3 B $FB "(rA#!" B (rB3 B #F"@ (ii) Explain the f!ll!win1 , 1i4in1 &ea !n . (a) &ransition metal and many of their ompounds show parama-neti behavior (b) &he enthalpy of atomisation of the transition metal is hi-h . ( ) &he &ransition metal -enerally form oloured ompounds . 1ns(a) It is due to unpaired ele trons . (b) It is due to stron- metalli bond and additional (ovalent bonds due to presen e of unpaired ele tron in d! orbitals ( ) It is due to presen e of unpaired ele trons ,they under-o d!d transition .

1bove 1vera-e H @1 mar0

(i)+h$ i K"3&"O8 1ene&all$ p&efe&&ed !4e& Na"3&"O8 in a 4!lumet&ic anal$ i .7i4e &ea !n . 1ns H It is be ause ?a"(r"A8 is hy-ros opi in nature that is why it absorbs moisture from atmosphere , therefore its standard solution an not be prepared . (ii) +h$ d! t&an iti!n metal ha4e hi1he& I.E than I%l!c/ element I D6

1nsH It is due to smaller atomi siEe than s!blo 0 elements , effe tive nu lear har-e is more , terefore I.G is hi-h. (iii) +h$ a&e TiC" and !the& t&an iti!n metal and thei& i!n pa&ama1netic I 1nsH &hese ions have unpaired ele trons in d! subshell. (iv) 3!mplete the f!ll!win1 eqn. &i(l#BF"A !!!!!!!!!!!B!!!!!!!!!! 1ns H &iA"B#F(l (v) +hi h trivalent ation is lar-est in lanthanoid series I 1ns 4aB3 Ma&/ ?" (1) +&ite an equati!n in i!nic f!&m t! &ep&e ent !xidi'in1 acti!n !f 3&" O8; " i!n in acidic Medium and d&aw it t&uctu&e . =&aw t&uctu&e !f 3&O. ;" al ! . 1ns! ioni equation 9 e! B 1# FB B (r"@8!""(rB3 B8F"A

(") 3!(ii) i ta%le in aqu!u !ln. %ut in p&e ence !f t&!n1 li1and and in ai& 1et Oxidi ed t! 3O C* , +h$ 1ns /tron-er li-ands and air Axidised (o B" &o (o B3 by providin- ener-y released due to for e of attra tion 2etween them and metal ions . (*)+hat happen when acidified KMnO. i added t! fe&&!u ulphate !ln.1ns 3nA#!1 B 6 'e B" B $FB 3nB" B6'eB3 B#F"A &he olour of M3nA# be omes oloursless and 'eB" is oxidiEed to 'eB3

A%!4e A4e&a1e ?* Ma&/

(1) (ompare the hemistry of a tinoids with that of lanthanoids with referen e to (i) ele troni onfi-uration (ii) Axidation state (iii) (hemi al rea tivity . 1ns H Gle troni onfi-. : In lanthanoids #f orbitals are pro-ressively filled whereas in a tinoids 6f orbitals are pro-ressively filled up . (ii) Axidation state lanthanoids /how B3 oxidation state ] same elements of this series show B" ] B# oxidation state also . 1 tinoids show B3 , B#, B6,B8 A./. 1lthou-h B3 , B#are the most ommon . (iii) (hemi al rea tivity H! 1 tinoids are more rea tive then lanthanoids due to bi--er atomi siEe and lower I.G D9

LLLLLLLLLLLLLLLLLLLLLLLL

UNIT ;?> 3O;OR=INATION 3OMBOUN=

STUDY MATERIAL

1 MARK E " MARKS QUESTIONS Q. 1. A cati!nic c!mplex ha tw! i !me& A E 9. Each ha !ne 3! *C, fi4e N#*, !ne 9& and !ne SO.". A 1i4e a white p&ecipitate with 9a3l " !luti!n while 9 1i4e a $ell!w p&ecipitate with A1NO* !luti!n. (a) (a) An . (a) (b) +hat a&e the p! i%le t&uctu&e !f the c!mplexe A and 9 +ill the tw! c!mplexe ha4e ame c!l!u& %(A (?F3)6 2r) /A# and %(A (?F3)6 /A#) 2r ?A

Q. ". DeSO. !luti!n mixed with (N#.)"SO. !luti!n in 1 2 1 m!la& &ati! 1i4e the te t !f De"C i!n %ut 3uSO. !luti!n mixed with aque!u amm!nia in 1 2 . m!la& &ati! d!e n!t 1i4e the te t !f 3u"C i!n. Explain wh$ An . +hen 'e/A# and (?F#)"/A# solution are mixed in 1 H 1 molar ratio, a double salt is formed. It has the formula 'e/A# (?F#)"/A# . 9 F"A. In aqueous solution, the salt disso iates. +hen (u/A# and ?F3 are mixed in the molar ratio of 1 H # in solution, a omplex %(u (?F3)#) /A# is formed. Q. *. If t! an aque!u !luti!n !f 3uSO . in tw! tu%e , we add amm!nia !luti!n in !ne

tu%e and #3l (aq) t! the !the& tu%e, h!w the c!l!u& !f the !luti!n will chan1e Explain with the help !f &eacti!n. An . In first ase, olour will han-e from blue to deep blue. %(u (F"A)#)"B B # ?F3 YYYZ %(u (?F3)#)"B B # F"A deep blue +hile in se ond ase, its olour will han-e to yellow. %(u (F"A)#)"B B # (l: YYYZ %(u(l#)"B B # F"A yellow D8

Q. .. A, 9 and 3 a&e th&ee c!mplexe !f 3h&!mi!um with the empi&ical f!&mula #1"O63l*3&. All the th&ee c!mplexe ha4e 3l and #"O m!lecule a the li1and . 3!mplex A d!e n!t &eact with c!nc. #"SO.. 3!mplexe 9 and 3 l! e 6.80K and 1*.0K !f thei& !&i1inal wei1ht &e pecti4el$ !n heatin1 with c!nc. # "SO.. Identif$ A, 9 and 3. An . .ata su--ests that the omplexes are hydrate isomers. 1s omples 1 does not lose any mole ule of F "A on heatin- whi h shows that no water mole ule of F"A is outside the o!ordination sphere. 1 5 %(r (F"A)@) (l3 1s 2 loses 9.86% a tual loss in wt. 5 < "99.6 5 1$ au 2 5 %(r (F"A)6 (l) (l" . F"A 1s ( loses 13.6% of wt. on heatin- whi h is twi e the loss in the first ase, ( isomer exists as a dihydrate H %(r (F"A)# (l") (l . " F"A S3NI DI

Q. 0. De*C QQQP (A) QQQP (9) exce exce

+hat a&e (A) and (9) - 7i4e IUBA3 name !f (A). Dind the pin !nl$ ma1netic m!ment !f (9). An . 1 5 'e (/(?)3, 2 5 %'e'9)3: IOC1( name of 1 5 trithio yanato iron (III) G. (. of 'e (III) 5 d6, unpaired e:s 5 6 /pin only ma-neti moment 5 5+5 + 2, 2. 3. 5 6.D19 2. 3. Q. 6. A c!mplex i p&epa&ed %$ mixin1 3O3l* and N#* in the m!la& &ati! !f 1 2 ., ?.1 M !luti!n !f thi c!mplex wa f!und t! f&ee'e at I ?.*8" @3. +hat i the f!&mula !f the c!mplex - 7i4en that m!lal dep&e i!n c!n tant !f wate& Kf H 1.:6 @3Jm. An . &he oreti al &f 5 Mf . m D$

5 1.$9 < @.1 5 @.1$9X observed &f 5 @.38"X

1s observed &f is double of the theoreti al value this shows that ea h mole ule of the omplex disso iates to form two ions. formula is H %(A (?F3)# (l") (l Q. 8. #!w t"1 and e1 !&%ital a&e f!&med in an !ctahed&al c!mplex An . In an o tahedral omplex, positive metal ion is onsidered to be present at the entre and ne-ative li-ands at the orners. 1s lobes of dxp : yp and dEp lie alon- the axes, i. e. alon- the li-ands repulsions are more and so is the ener-y. &he lobes of the remainin- three d!orbitals lie between the axes i. e. between the li-ands, the repulsions between them are less and so is the ener-y. Q. :. =imeth$l 1l$!xime i added t! alc!h!lic !luti!n !f Ni3l ". +hen amm!nium h$d&!xide i (a) (%) An . (c) (a) l!wl$ added t! it, a &! $ &ed p&ecipitate !f a c!mplex appea& . 7i4e the t&. !f the c!mplex h!win1 h$d&!1en %!nd. 7i4e !xidati!n tate and h$%&idi ati!n !f cent&al metal i!n. Identif$ whethe& it i pa&ama1netic !& diama1netic.

(b) ( )

A. /. 5 B " bybridisation 5 dspp diama-neti as no unpaired ele tron.

Q. >. Explain the &ea !n %ehind a c!l!u& !f !me 1em t!ne with the help !f example. An . &he olours of many -em stones are due to the presen e of transition metal ions ] olour are produ ed due to d!d transition. 'or example the mineral orundum 1l "A3 is olourless when pure but when various 3 3B transition metal ions are present in tra e DD

amounts various -em stones are formed. Puby is 1l "A3 ontainin- about @.6 : 1% (r3B. Q. 1?. #!w man$ E=TA (leth$lendiamine tet&a acetic acid) m!lecule a&e &equi&ed t! ma/e an !ctahed&al c!mplex with a 3a"C i!n. An . G.&1 is a hexadentate li-and therefore only one G.&1 mole ule is required to form o tahedral omplex. Q. 11. +hat i catal$ t An . +il0inson=s atalyst is (CF3C)3 Ph(l. In this Ph has dspp hybridisation and square planar shape. Q. 1". +hich 4itamin i a c!mplex c!mp!und !f c!%alt An . *itamin 21" is a omplex ompound in whi h entral metal atom is obalt. the h$%&idi ati!n !f cent&al metal i!n and hape !f +il/in !nW

Q. 1*. +&ite the IUBA3 name !f S3O (N#*). 91"T" SFn3l.T. An . &etraamminedibromo obalt (III) tetra hloroEin ate (II)

Q. 1.. +hat i the 4alue !f x in the c!mplex #x3O (3O) . !n the %a i !f EAN &ule. (At. N!. 3!\ H "8) An . x 5 39 : ("8 B # < ") 5 39 : 36 51 Q. 10. +h$ i the il4e& platin1 !f c!ppe&, K SA1 (3N)"T i u ed in tead !f A1NO* An . &his is be ause if 1-?A3 is used (u will displa e 1-B from 1-?A3. &he deposit so obtained is bla 0, soft, non!adherin-. &o -et a -ood shinin- deposit, %1- ((?) "): are used as it is a stable omplex, the on . of 1- B is very small in the solution. 1s su h no displa ement of 1-B ions with (u is possible. Sh!&t an we& t$pe que ti!n J. 1 +&ite the f!&mula !f the f!ll!win1 c!mp!und. (a) &etraamineaqua hlorido (obalt (III) hloride . (b) Cotassium tetrahydrooxoEin ate (II) ( )Cotassium trioxalatoaluminate (II) (d) Centaamine arbonato obalt (III) hloride An ; (a) (o (?F3)# (F"A) ao (l" (b) M" %Ln (AF) #) ( ) M3 (1l (("A#)3) (d) %(o (?F3)3 ((A) 3) (l Q" +&ite the IUBA3 name !f the f!ll!win1 3!;O&dinati!n c!mp!und. (a)% Ct (?F3)" (l (?A") (l(?A")) (b) M3 %(r(("A#)3) ( )%(o(?F3)6(A3 ) (l (d) % (o (l" (en)") (l

1ns! a) .ammie hloridonitrito :?!Clatinum(II) b) Cottassium trioxalato hromate (III) 1@@

) Centaamine arbonato obalt (III) hloride d) .i hloroidobis (ethane !1, " :diamine) obalt (III) hloride J.* SNi3l.T" i pa&ama1netic while SNi (3O) .T i diama1netic th&!u1h %!th !ne tet&ahed&al +h$(i) In % ?i ((A) # ) ?i is in Lero Axidation state but %?i(l#)" it is in B" oxidation state (ii) In the presen e of (o li-and , the unpaired d ele troni s of ?i pair up but (l bein- a wea0 le-and is unable to pair up the unpaired ele tron Q. Explain S3! (N#*) 6T*C i an inne& !&iental c!mplex when SNi (N#*)6T"C i an !ute& !&iental 3!mplex. 1ns H In %(o (?F3) 3B (omplex d" /C3 hybridisation involved formin- inner d orbital +here as In ?i (?F3) 9 omplex involved in /C3d" Fybridiasation formin- outer d :orbitals J6 +hat i meant %$ unidentate , didentate and am%identate li1and . 1i4e tw! example !f each 1nsH +hen a le-end is bound to a metal ion throu-h a sin-le diner atom, is said to be unidentate for ex! (l!, F"A ] ?F3 +hen a le-ande an bound throu-h two donor atoms as in F"? (F" (F"?F", or (" A# (oxalate) is said to be didentate le-end. +hen several donor atoms are present in a sin-le li-and, the li-and is said to be polydentate li-and whi h an li-ate throu-h two different atoms is alled ambidenate li-and Gx!?A", /(? J9. 1nsH +hat a&e diffe&ence %etween d!u%le alt and a c!mplex alt. (1) both double salts as well as omplex are formed by the ombination of two or more stable ompounds in stio hometri ratio (") &hey differ in the fa t that double salts su h as arnallite :M(l. 3-(l". 9F"@ , 3ohr=s salt 'e/A# (?F#) " /A# . 9 F"@ ] Cotash alum M"/A# 1l"(/A#) 3 .1"F"A et disso iati into simple ions when dissolve in water . Fowever when omplex ions su h as %'e ((?) 9)# of M# 'e ((?) 9 do not disso iate into 'e"B and (?! ions =i cu the natu&e !f %!ndin1 in metal ca&%!n$l &he homolepti arbonyls are formed by most of the transition metal. &hese (arbonyls. /how /imple tetrahedral , tri-onal bypyramidal and o tahydral /tru ture . It is /hown on po-e no. "66 of unit D ?(GP& *ol :I Menti!n an$ f!u& cha&acte&i tic !f 3!; O&dinati!n 3!mp!und (1) Fard ness of water is estimated by simple titration with ?a" G.&1. (") Gxtra tion of metals li0e 1- and 1u ma0e use of omplex formation . (3) Curifi ation of metals by the formation of (o! Ardination ompounds (#) 2iolo-i al appli ation li0e pi-ment formation photosynthesis, (hloropyll. Faemo-lobin pi-ment of blood . <i t 4a&i!u t$pe !f i !me&i m p! i%le f!& 3!; !&dinati!n c!mp!und . 1i4en an example . 1)/tereoisomerism (a) Geometri al isomerism : (is ] trans of % Ct (?F3)" l") (b) Apti al isomerism : d ] l of %(o (en)3)3B (2) /tru tural isomerism 1@1

J. 8. 1nsH

J. $. 1ns :

JD. 1ns

(a) 4in0a-e isomerism % (o (?F3) 6 (?A"))(l" (b) (o :ordination isomerism :% (o(?F3)9) %(r((?)9) ( ) Ionisation %(o(?F3)6 /A#) 2r ] %(o(?F3) 6 2r ) /A# (d)/olvate isomerism : %(r (F"@) 9 ) (l3 . J1@ (De ( #"O)6) * C i t&!n1l$ pa&ama1netic whe&ea S De(3N )6 T* i wea/l$ pa&ama1netic . Explain . In %'e ((?) 9 )3 only one ele tron is unpaired ] is stron- li-and forms d" sp3 hbridisation shows wee0ly parama-neti where as in presen e of F"A in ('e(F"@)9)3B wea0 li-and and five ele tron are unpaired and forms /C3 d" hybridiEation shows stron-ly panama-neti . Q11 3alculate the !4elall c!mplex di !ciati!n equili%&ium c!n tant f!& cu (N#*). "C i!n , 1i4en that ]. f!& thi c!mplex i ".1x1? 1* An 2 &he over all disso iation onstant is the re ipro al of over all stability onstant i.e 1 q7# 5 #.8K 1@ !1#.

@1 3ar0s Juestion ('or 2elow 1vera-e )

1. .efine li-ands ". +hat do yoy mean by omplex ompounds 3. Gxplain (o!ordination number. #. (al ulate (o!ordination no. of %(o(?F3)# ((l) (?A") ) l omplex 6. +hat do you mean by oxidation no7state of o!ordination ompounds .I 9. +rite the example of lin0a-e ammonium 8. +rite two use 7 appli ation of (o!ordination ompounds . $. +rite example of helatin- lin-ads D. +hat do you mean by helate effe tI 1@. +rite the IOC1( name of %(u (?F3)6(l) (l" omplex Ma&/ Que ti!n (D!& 9el!w A4e&e1e ) 1. Fow will you distinwi h Fomolepti ] hetrolepti ". +hat are the limitation of *2& 3. +hat are the merits of ('& #. Gxplain t"- and e- in the field of ('& /plittin-. 6. +hat is meant by stability at a (o!ordination (ompound in solutionI /tate the fa tor on whi h stability Af the omplex depends. 9. +hat is spe tro hemi al seriousI Gxplain the differen e between stron- field li-and wea0 field li-and. 8. Give reason why 'e/A# /oln mixed with (?F#) "/A# soln in 1H1 molar ratio -iven 1@"

omplex

the test of 'e"B ion but

uso# soln mixed with aqueas ammonia in 1H# molar ratio

does not -iven the test of (u"B ion $. out of -iven two (o!ordination ompound whi h is (hiral ] why explain (a) is : %(r(l" (ox)")3! (b) %(r (l"(ox)")3! D. Give eviden e that %(u (?F3)6(l /A# and %(o (?F3)6 /A#)(l are ioniEation isomerism . A5ERA7E E A9O5E A5ERA7E STU=ENTS ?1 Ma&/ que ti!n 1. %?i(l#)"! parama-neti whi h % ?i((@#)) is diamaq-neti why . ". Credi t the no of unfaired ele tron in %Ct ((?)#)"! 3. Credi t the oxidation no of obalt in M % (o ((A)#) #. Gxplain ma-neti moment of the omplex 6. (al ulate (o! ordination no. of the omplex is :% (r (en )"(l") (l 9. .is uss role of (o!ordination ompound in the field of medi inal hemistry 8 .is uss nature of bondin- in (?i((A))# $. Fow many (o!ordination numbers are there in ethylenediamine I D. ?ame two fa tors that fever a metal ions formin- omplex . 1@. +hat is meant by the denti ity of a li-and .

?" Ma&/ (9&i1ht achie4e&)

1. Gxplain -ivin- one examples role of (o!ordination (ompound in biolo-i al system ] 1nalyti al system ". (1) Fow many ions are present 7 formed from the omplex %(u?F3)9) (l" (b) 1mon-st the followin- whi h one has the hi-hest ma-neti moment valueI 3. %'e ((?9) # : and %'e (F"@) 9) " are of different olour in dilute solution. whyI (b) .raw fi-ure to show the splittin- at d!orbital in an o tahedral rystal field. #. Gxplain 1queous opper /ulphate /olution -ives (a) 1 -reen ppt with aqueous potassium fluoride. (b) 1 bri-ht -reen solution with aqueous potassium hloride 6. 1 (o! ordination ompound has the formula (o(l3 #?F3. it does not liberate ammonia but pre ipitate hloride ion as 1(4. Give the IOC1( name of the omplex and write its stru tural formula. 9. Gxplain why helatin- omplex is more stable than un healated omplex 1@3

8. ?ame two omplexes whi h are used in medi ines.

LLLLLLLLLLL UNIT ;1? #A<O A<KANE AN= #A<O ARENE

DOR A5ERA7E
?1 ma&/ que ti!n Q.1. +rite down the IOC1( name of the followin- or-ani (a) (F3(F(l" (b) (F3(F"(F"(F((((F3)3)(F(I)(F"(F3 ( ) F6(" (l An 2 ; (a) 1,1! .i hloroethane (b) 3!Iodo : # : (1,1 : dimethyl ethyl ) heptane ( ) 1! (hloro : # : ethyl y lo hexane J.". +rite down the stru tures of the followin- or-ani ompounds (a) 1! 2romo : # : se . butyl : " : methyl benEene (b) " : (hloro : 3 : methyl pentane ( ) *inyl hloride (a) ("F6 (F 2r ompoundsH !

An 2;

(F3 (F3 (b) (F3(F"(F((F3)(F((l)(F3 ( ) (F"5 (F(l J.3.+rite down the stru tures of the followin- or-ani (a) 1llyl (hloride (b) &eflon ( ) ....&. (d) C.*.(. 1nsH ! (a) (F"5(F!(F"(l ( b) %!('"!('"!)n (l ( ) ((l3(F (l
1@#

ompoundsH !

(d) %!(F" : (F ! )n (l J.#.+hi h one of the followin- has the hi-hest dipole moment, and whyI (a) (F"(l" (b) (F(l3 ( ) ((l# 1nsH! (F"(l" has the hi-hest dipole moment sin e both the (l! atoms are present on one side (on the head) of : atom and therefore ause a maximum dipole moment. In (F(l3 and ((l#, two (l : atoms and four (l : atoms an el out their dipole moments. J.6. +hat happens when a) 3ethyl (hloride is treated with M(? b) (hloro2enEene is subNe ted to hydrolysis ) Cropene is treated with (l" in the presen e of O.*. li-ht AP is heated. d) (hlorobenEene is treated with a etyl hloride in presen e e) of anhyd. 1l(l3 f) (hloroform is slowly oxidiEed by air in presen e of li-ht. 1nsH! a) (F3 : (l B M(? (F3 : (? B M l 3ethyl yanide b) (l B FAF FB Chenol O.*. 4i-ht or ( ) (F3 : (F 5 (F" B (l" (F" : (F5 (F" B F(4 Feat (l 1llyl (hloride A (l (l (d) anhyd. (A(F3 (l B (F3!(!(l B 1l(l3 (A(F3 1ir (e) (F(l3 B
1 "

AF B F(4

A"

(A(l" B F(l

'AP 1*GP1GG " mar0s questions

1@6

J.1. +hi h are the possible mono hloro stru tural isomers expe ted to be formed on free radi al mono hlorination of ((F3)"(F(F"(F3. 1nsH! &here are four possible produ t as follows (F"((l) (F : (F" : (F3, (F3 ((F3)" ( : (F" : (F3, (F3 ((F3)" (F : (F : (F3 and (l ((F3)" (F : (F" : (F"(l J.". Gxplain the followin- rea tions H (a) /andmeyer=s rea tion (b) Glimination rea tion J.3. 1rran-e the ompounds in in reasin- order of their boilin- pts. (a) (F3(F"(F"(F"2r, (F3(F"(F2r(F3 , ((F3)3( 2r (b) (F32r, (F"2r", (F2r3

1nsH (a) ((F3)3(!2r, (F3(F"(F2r(F3, (F3(F"(F"(F"2r 2oilin- point in reases. 2oilin- point de reasin- on in reasin- the bran hin-

(b)

(F32r, (F"2r", (F2r3

2oilin- point in reases 2oilin- point in reases due in reasin- mole ular mass. J.#. +rite the me hanism of the followin- rea tionH 'rideal (raft 1 ylation ( in (hlorobenEene)
1@9

1nsH! Pea tion (l B (F3(A(l 1l(l3 (A(F3 Pea tion 3e hanismH A (F3!(AY(l B 1l(l3 !1l(l#! (l B F
B

(l 1nhy.

(l (A(F3 B

(l

(F3(B B (l (F3(A B1l(l

! #

F(l (F3(A ! 1l(l3

J.6. Gxplain whyH ! (a) F"/A# annot be used alon- with MI in the onversion of an al ohol to an al0yl halide. (b) 1l0yl halide thou-h polar are immis ible with water. 1nsH ! (a) (b) F"/A# onverts MI to orrespondin- FI and then oxidise it into iodine. +hen halo al0ane intera ts with water mole ule , less amount of ener-y is released whi h is not suffi ient to brea0 the ori-inal F! bond between water mole ule and to form new F!bond with halo al0ane and water.

'or 1vera-e 3 mar0s questions J.1. Identify 1,2,(,.,G and P in the followin- hemi al rea tion . Ar-ani Ceroxide 1q. MAF M3nA# a) (F3(F5(F" B F2r 1 2 ( ?a7.ry ether
1@8

1l0.

b)

(F3

(F3 3-

(F3 . F"A (F3 G 1nsH! (a) 1 2 ( (F3

(F3

PK

(F3(F"(F"2r (F3(F"(F"AF (F3(F"(AAF

(b) P ((F3)3(! . ((F3)3(3-K G ((F3)3(F J.". +rite down the IOC1( name of the followin- or-ani (a) 2r 2r b) A! 2r! (9F#(F((F3)(F"(F3 ) ((F3)3((F5(F(9F#I!p 1nsH! a) #,#!.ibromo pentene b) "!methyl! "!(o!bromophenyl) butane ) 3,3!.imethyl!1!(p!iodophenyl) butane J.3. Fow an the followin- inter onversions are arried out (a) Gthanol to but!1!yne (b) 2enEene to #!bromo nitro benEene ( ) &oluene to benEyl al ohol 1nsH!

ompoundsH

(on . F"/A# 1. 2r" a) (F3(F"AF (F"5(F" @ 19@!18@ ( ".1l .MAF ("F6(l (F3(F"(5 (F

(F5 (F

?a?F" (F5 ?A" b) (on .F?A3

1@$

(?a ?A" 2r"7 ((l#

2r (F3 ) O.*.4i-ht (F"(l

J.#.Identify the followin- pair of stru tures H a) (F3 FA F (9F6 b) 2r F F F (l FA (l

(F3 F F (9F6 2r

(F3 1nsH!

(F3 (F3

(F3

a) .ia stereomers b) /tru tural isomers J.6. +hat is the formula of tartari a idI .oes it show opti al isomerism or not. .raw the stru tures of its opti al isomers. 1nsH ! &artari a id exists in three opti al isomeri form. (AAF (AAF FA AF F AF (AAF (AAF (AAF AF FA F F F F AF (AAF

1@D

l!&.1 3eso!&.1. DOR A9O5E A5ERA7E MARKS QUESTION2;

d!&.1.

J1. +rite down the IOC1( name of the followin- or-ani

ompound.

(a)(F3 (F5( ((l) (F" (F ((F3)" (b)(F3(F 2r (F (l (F3 ( ) (F3 ( ((l) (("F6) (F" (F3 (d) (F3 ((C!(l!(9F#)" (F (2r)(F3 1nsH! (a) 3! hloro!6!methyle hex!"!ene (b) "!(holoro!"!ethyl butane. (() "!2romo!3! hloro butane. (d) 3!2romo!","!bis(p! hloro phenyl) butane ompounds.

J". +rite down the stru ture of the followin- or-ani (a) 1! hloro!3!ethyl y lohexane. (b) C!bromo hloro benEene. ( ) Gthylene di hloride. (d) Gthylidene di hloride. (e) 2enEoyl hloride.

1nsH! (a) (l ("F6

(b)

(F"!(l (F"!(l

(l ( )2r (l (d) (F3!(F (l (A(l (e) DOR A9O5E A5ERA7E ?" Ma&/
11@

J1. +rite the stru ture of the maNor or-ani produ t in ea h of the followinrea tion. (a) 2r
Na"H +

(F"2r (l (b) A"? 1nsH! (a) (F"/F A"? J". Give the Creparation and uses of hloropi rin hlorotone. J3. Gxplain the formation of two produ ts in the followin- rea tion. (F3(h"(l B F"A (F3(F5(F (F"AF B (F3 (h(AF)(F5(F" J#. (a) +rite all Cossible isomers of (8F8(l (b) +rite the /tru tural formula of opti al isomer. Af the omponent havin- mole ular formula (#FD2r. ?A" 2r (b) ?A" A("F6 B ("F6A?a
a!ol + Heat et

1nsH! (a) # isomers (b)

F (F3!(!("F6 2r

J6.+hat mass of propene is obtained from 3#.@ -m of 1!iosopropane on treatin- with ethanoli MAF if yield is 39% 1nsH!3.@" -m. J9. 1rran-e the followin- ompound a ordin- to rea tivity towards nu leophili substitution rea tion with rea-ent mentioned.
111

# : nitro hlorobenEene, ", # : dinitro hloro benEene, and ", #, 9 : trinitro hloro benEene with (h3A?a 'or 1bove 1vera-e ?* Ma&/ J1. 1n Ar-ani ompound \1= havin- mole ular formula (#F$ on treatment with dil F"/A# -ives \2= : \2= on treatment with ione F l and anhydrous Ln l" -ives \(= and on treatment with sodium ethoxide -ives ba 0 \1= . Identify the ompound \1= , \2= and \(= and write equation involved. 1nsH 1 (F3 r ( 5 (F" f (F3 2 (F3 r ((AF) r (F3 f (F3 (F3 r (((l) r (F3 f (F3

J". 1lthou-h hlorine is an ele tron : withdrawin- -roup, yet it is ortho, para! dire tin- in ele trophili aromati substitution rea tions why I 1nsH (hlorin be ause of its :I! effe t withdraws ele tron from the benEene rinand hen e tends to destabiliEe the intermediate arbo ation formed durin- the ele trophili substitution. J3.Credi t the order of rea tivity of the followin- ompound in /? 1 and /?" rea tion. (a) &he four isomeri bromobutone (b) (9F6(F"2r, (9F6(F((9F6)2r, (9F6(F((F3)2r, (9F6(((F3)(9F62r 1nsH! (F3(F"(F"(F"2r,((F3)"(F (F"2r,(F3 (F" (F(2r)(F3,((F3)3(!2r Pea tivity towards /?1 Pea tion

11"

(F3(F"(F"(F"2rS((F3)"(F (F"2rS(F3 (F" (F(2r)(F3S((F3)3(!2r Pea tivity towards /?" Pea tion (b) Pea tivity towards /?1 Pea tion (9F6(((F3)((9F6)2rS(9F6((F((9F6)2rS(9F6(F((F3)2rS(9F6(F"2r Pea tivity towards /?" Pea tion (9F6(((F3)((9F6)2r,(9F6((F((9F6)2r,(9F6(F((F3)2r,(9F6(F"2r J#. Gxplain the followin- . (a) 1llyl hloride is hydrolysed more readily than n!propyl hloride. (b) *inyl hloride is hyolrolysed more slowly than ethyl hloride 1nsH! (a) 1llyl hloride readily under-oes ioniEation tpo produ e sesonan e stabiliEed allye arbo ation. / ien e arbo ation are re tive spe ies, therefore allyle otion readin- ombines with AF ions to form allyl al ohol. In ontrast n!propyl hloride does not under-o ioniEation to produ e n! propyl hloride. a. *inyl hloride -et rea tin- stabiliEation (arbon! hlorine bond a quires some double bond hara ter. In ontrast in ethyl hloride, the arbon! hlorine bond is a pure sin-le bond. &his *inyl hloride under -oes hydrolysis more slowly than ethyl hloride.

113

UNIT 11
A<3O#O<S, B#ENO<S AN= ET#ERS )
1 MARK QUESTIONS Q. 1. +hat i the main p&!duct !%tained when 4ap!u& !f t;%ut$l alc!h!l a&e pa ed !4e& c!ppe& at *??@ An . Isobutylene ("!3ethyl propene)

Q. ". +hat i u uall$ added t! eth$l alc!h!l t! ma/e it unfit f!& d&in/in1 pu&p! e An . 3ethanol and Cyridine. malle& dip!le m!ment than methan!l. (OR) +h$ a&e dip!le m!ment !f phen!l An . malle& than dip!le m!ment !f alc!h!l -

Q. *. Bhen!l ha

.ue to ele tron!withdrawin- effe t of the benEene rin-, the ( Y A bond in phenol is less polar but in ase of methanol due to ele tron!donatin- effe t of Y (F 3 -roup, ( Y A bond is more polar.

Q. .. Name the p&!duct !%tained when ani !le i t&eated with #I. An . Chenol and methyl iodide. !lu%le in ethe& %ut n!t in %en'ene -

Q. 0. +h$ a&e 7&i1na&d &ea1ent An .

Gri-nard rea-ents from o!ordination omplexes with ether but not benEene sin e the former has lone pair of ele trons but the later does not.

Q. 6. Alc!h!l a&e ea il$ p&!t!nated than phen!l . Nu tif$. An . In phenols lone pair of ele trons on the oxy-en atom are delo alised over the benEene rin- due to resonan e and hen e are not easily available for protonation. In ontrast in al ohols, the lone pairs of ele trons on the oxy-en atom are lo aliEed due to absen e of resonan e and hen e are easily available for protonation. Q. 8. =i;te&t %ut$l ethe& cann!t %e made %$ +illiam !nW An . $nthe i . Explain wh$ -

&o prepare di tert!butyl ether by +illiamson=s synthesis, we need tert!butyl bromide and /odium tertiary butoxide. /in e tert!butyl bromide bein- 3X!al0yl halide prefers 11#

to under-o elimination rather than substitution, therefore the produ t obtained is isobutylene rather than ditertiary butyl ether. Q. :. +hile epa&atin1 a mixtu&e !f !&th! and pa&a;nit&! phen!l %$ team di tillati!n, name the i !me& which will %e team 4!latile. 7i4e &ea !n . An . In o!nitrophenol, there is intramole ular hydro-en bondin- as follows H

In p!nitrophenol, there is intramole ular hydro-en bondin- as follows H

.ue to intermole ular F bondin- in p!nitrophenol, its b. p. is mu h hi-her than that of o!nitrophenol. Fen e o!nitraphenol due to its lower b. p. is steam volatile while p! nitrophenol is not. Q. >. #!w an Q O# 1&!up attached t! ca&%!n in the %en'ene &in1 acti4ate %en'ene t!wa&d elect&!philic u% tituti!n -

An .

&he lone pair of ele trons present on oxy-en atom enter into resonan e with the benEene rin-. 1s a result, the ele tron density be omes hi-her at o! and p! position 116

and due to hi-her ele tron density, the rin- -ets a tivated towards ele trophili substitution. Q. 1?. Ethe& a&e clea4ed %$ acid n!t %$ %a ed. +h$ An . &he ( Y A Y ( bond in ethers li0e the ( Y AF bond in al ohols is quite stron-. In order to wea0en it, the oxy-en atom must be protonated. 1 subsequent nu leophile atta 0 by a stron- nu leophile su h as 2r: as I: ion on the less hindered arbon atom of the protonated H B (YAY( f F bond brin-s about the leava-e of ethers to form an al ohol and an al0yl halide. &he a ids only an provide the FB ion required for protonation of A atom of ether and therefore only a ids an brin- about the leava-e of ethers and not bases. Q. 11. Bhen!l d! n!t unde&1! u% tituti!n !f the Q O# 1&!up li/e alc!h!l . Explain. An . &he ( Y A bond in phenols has some double bond hara ter due to resonan e and hen e annot be easily leaved by a nu leophile. In ontrast, the ( Y A bond in al ohols is a pure sin-le bond and hen e an be easily leaved by a nu leo phile. Q. 1". Alc!h!l act a wea/ %a e . Explain. An . &he oxy-en atom of the hydroxyl -roup has two lone pairs of ele trons. &herefore al ohols a ept a proton from stron- mineral a id to form oxonium ions. Fen e a t as wea0 bases. Q. 1*. +&ite the mechani m !f h$d&ati!n !f ethene t! $ield ethan!l. An . F"A B FB YYYZ F3AB Step (i) H Y Crotonation of al0ene to form arbo ation by ele trophili atta 0 H

6 0C 03 0C 000000+ 0000- 06 0) 06 0- 0006 6 6 006 0C 06 0C 000000+ 0- 2)

Step (ii) H Y ?u leophili atta 0 of water on arbo ation H

6 0 C 0 6 0 C 0 00 0 00 0+ 00 0 00 0 0- 2) 0 00 6 6 6 00 6 0 C 0 6 0 C 06 0 ) 0 6 0 Step (iii) H Y .eprotonation to form an al ohol H

)+

6 0C 06 0C 06 0) 06 0- 000000+ 00000- 2) 00006 6 6 006 0C 06 0C 06 000000+ 00000- 3) 119


Q.1 +hy is it that se ondary al ohols an only under-o a sin-le oxidation step in ontrast to primary al oholsI (" ma&/ ) 1. An e the oxidation has rea hed the 0etone sta-e, (primary al ohols on oxidation yield aldehyde where as se ondary al ohols on oxidation yield a 0etone), it is impossible to put more oxy-en atoms on the relevant arbon atom without rupturin- the ba 0bone of the mole ule.

J1. +hy phenol is a idi I 1nsH In phenol disso iation ta0es pla e as follows. AF Ar BFB (Chenol) ( Chenoxideion )

&he onNu-ate base of phenol ie. Chenoxide ion is resonan e stabiliEed. &his is why the ne-ative har-e on oxy-en atom is delo aliEed throu-h out the rin-. /o, the oxy-en 118

present in phenoxide ion has less tenden y to form undisso iated phenol mole ule and equilibrium lies towards ri-ht dire tion. J". +hile separatin- a mixture of ortho and para nitrophenols by steam distillation, name the isomes whi h will be steam volatile. Give reason. 1nsH A! nitro phenol will be steam volatile be ause there is intramole ular. F!bondin- in its mole ule. A AF ? Intramole ular hydro-en bondinss A 2ut in ase of p! nitro phenol there is asso iation of mole ules of p! nitro phenol due to intermole ular hydro-en bondin-. A A A A ss 77 ? AF ? ft f f

f AF

f ?

f AF

ss A A J.1 Give the me hanism of formation of al0ene from alwhol in preserve of a id atalyst. F F f f F!(!(!A!F f f FF Gthyl al ohol F F f f F! ( : ( ! AF" f f F F (Crotonated al ohol) !F"A

FF f f F!(5(!F !FB F!(!(!B f f f f F F F F (Gthene) ((arbo ation) J". .is uss the me hanism of fornsation of ether from al ohol in presen e of aid F F f f F!(!(!A!F B FB F3((F" ! BAF" f f FF Gthyla ohol (Cronated al o ol) 11$

atalyst.

F F f f F!(!(!A!F B F3((F"!ABF" f f FF

FF FF f f f f F!(!(!AB!(!(!F f f f f f F FF FF !FB

FF FF f f f f F!(!(!A!(!(!F f f f f f F FF FF J3. .is uss +illiamson systhe is. 1nsH! In this method symmetri al and unsymmehi al ethers are formed. In this synthesis an al0yle is allowed to rea t with sodium al0oxide. P : K B P= : A : ?a P : A : P= B ?aK Gthers ontains substitutes al0yl-soups an be prepared by this method. &he rea tion involveds /?" atta 0 of an al0oxide ion on primary al0yl halide. (F3 f F3 : ( : A!?aB B (F3 : 2r f (F3 (F3 f F3( : A : (!(F3 B ?a2r f (F3

In ase of se ondary and tertiany holides elimination ompletes over substitution. It a 3 al0yl holide is used an al0ene is the only rea tion produ t and no ether is formaed. (F3 f F3(!(!2r B ?aBA(F3 f (F3

F3(!(5(F"B?a2rB(F3AF f (F3 ( "! methyl propene )

J#. Artho and paranitrophenols are more a idi than phanel. .raw the resonan e stru tures of the orrespondin- phonoxide ion. 1nsH! Gle tronwithdrawal by nitro -roup ma0es the plenoxide ion more resonan e stabiliEed and so the stren-th of phenel in reases.

SOME MORE IMBORTANT QUESTIONS +IT# ANS+ERS 9E<O+ A5ERA7E 1 mar0 questionsH!
11D

J.1. Give the IOC1( name of 3#*O I 3# I 3#*

3#*

An 2; "; Meth!x$p&!pane J.". Give the IOC1( name of 36#0;;O I 3#" I 3#" I 3# I 3#*
1 An 2; *; Meth$l %ut!x$ %en'ene 1 3#"O# J.3. Give the IOC1( name of " * .

3#*

#*3 ;; 3# I 3#" I 3#;; 3# ; 3#*

6 0 . * "

3#*
An 2 ; ",0 I =imeth$l hexane I 1,* ; di!l J.# .

O#

Give the IOC1( name of 3#* 3#* ;; 3 ;; O# ( #*

An 2 ; ";Meth$l p&!pan!l

J.6. Give the IOC1( name of

O#

An 2; 9en'ene I 1,.; di!l J.9. +rite the stru tures of 1; Eth!x$p&!pane

# An 2 ; # #

O#

3"#0O ; 3 ; 3 I 3 ; # # # #
1"@

J.8. +rite the stru ture of "; Eth!x$ I * I meth$l pentane

# An 2 ; # 3#* O3"#0 #

# ; 3 ; 3 I 3 ; 3 ;; 3 ; # # # # #
#

J.$. Illustrate Rieme& Tiemann rea tion with one example 1ns H! O# KO#, 3#3l* (Bhen!l) J.D. +hy phen!l is a idi I 1nsH! .ue to resonan e stabiliEation of its c!nRu1ate %a e phen!xide i!n. J.1@. (onvert ani !le to phen!lI O3#* C #I An 2; C 3#* I (Ani !le) " Ma&/ Que ti!n 2; J.1. Give the equations of rea tion for the preparation of phenol from cumene. J.". +hy phen!l is more a idi than etan!l. J.3. Gxplain the followin- with an exampleH ! (i) K!l%eW &eacti!n (ii) +illiam !nW ethe& $nthe i J.#. /how how will you synthesise pentan; 1; !l usin- a suitable al0yl halideI J.6. +rite hemi al rea tion for the preparation of phenol from cumeneI J.9. +rite the equation of hydration of ethane to yield ethanol. (Bhen!l) O# FB ("; h$d&!x$ %en'aldeh$de) O# 3#O

1"1

J.8. (onvert the followin- H! (i) Eth$l alc!h!l and Acetic acid (ii) B&!pan I " I !l t! p&!pene J.$. Gxplain esterifi ation with example. J.D. (onvert the followin- H ! (i) Aniline t! Bhen!l (ii) Bhen!l t! pic&ic acid J.1@. 1l ohols are omparatively more soluble in water than hydro arbons of omparable mole ular masses. Gxplain this fa t. * ma&/ que ti!n J.1. &he followin- is not an appropriate rea tion for the preparation of t;%ut$l ethe&. 3 #* 3 #* 3"#0 ONa C O3"#0 (i) (ii) J.". (i) Gxplain why is !&th! ; nit&! phen!l more a idi than meth!x$ phen!l I (ii) +hy !;nit&! phen!l is steam volatile while p;nit&! phen!l has hi-her boilin- point. (iii) Give reason for the hi-her boilin- point of ethan!l in omparison to Meth!x$ methane. J.3. (i) +hat happens when phen!l is treated with De3l*I (ii) .istin-uish between phen!l and %en'$l alc!h!l. (iii) Gxplain the ouplin- rea tion with one example. J.#. Acc!unt f!& the f!ll!win1 2 ; (i) Alc!h!l a t as wea/ %a e . (ii) Bhen!l has smaller dip!le m!ment than methan!l. (iii)Chenols do not -ive p&!t!nati!n rea tion easily. J.6. (i) .raw the stru tures of all isomeri al ohols of mole ular formula
1""

3#* ; 3 ; 3#*

3#* ;; 3 ;;

( #* ( #* +hat would be the maNor produ t of this rea tionI +rite a suitable rea tion for the preparation of t; %ut$l ethe&.

(6F1"A. (iii) (lassify the isomers of al ohols as B&ima&$, Sec!nda&$ and Te&tia&$ alc!h!l . J.9. +hile separatin- a mixture of !&th! and pa&a nit&! phen!l by steam distillation, name the isomers whi h will be steam volatile. Give reason. J.8. (onvert the followin-H ! (i) Acetaldeh$de to I !p&!p$lalc!h!l (ii) Acet!ne t! t ; %ut$l alc!h!l. J.$. 1rran-e the followin- set of ompounds in order of their in reasinboilin- points. (a) Bentan I 1 I !l, 9utan I 1; !l, 9utan I "; !l, ethan!l, B&!pan I 1; !l, (b) Bentan ;1;!l, n; %utane, pentanal, eth!x$ethane and methan!l. J.D. (i) +hat is the 4u as testI (ii) .istin-uish Crimary, /e ondary and tertiary al ohols with the help of 4u as test. J.1@. (i) +hy the presen e of :AF -roup attra ted to benEene rina tivates the rin- towards ele trophili substitutionI

A5ERA7E ?1 ma&/ que ti!n 2 ;

J.1. +rite down the IOC1( name of #* 3 3#* O3"#0 J.". +rite down the IOC1( name of O# 3#* 3#*

J. 3. +rite down the stru ture of the produ t of the followin- rea tionH !
1"3

F3(!(F5 (F" _______. J.#. .istin-uish between AF

F"A7 FB

(AAF

and J.6. .istin-uish between (A(F3 A (!(9F6

and J9. +rite the stru ture of the produ t of the followin- rea tionH ! A ?a2F# F3( : (F" ! (F! ( !F _______. (F3 J.8. Give the me hanism of dehydration of al ohols to al0enes. J.$. Gxplain +illiiam !nW synthesis with one example. J.D. 1l ohols are omparatively more soluble in water than hydro arbons of omparable mole ular masses.

" ma&/ que ti!n

J.1. Fow is 1!propoxypropane synthesiEed form p&!pan I 1; !l. +rite me hanism of this rea tion. J.". +rite the equation of the followin- rea tions H ! (i) D&iedel 3&aft &eacti!n (ii) Nit&ati!n !f ani !le J.3. Gxplain the followin- with an example H (i) K!l%e &eacti!n
1"#

(ii) Reime& TiemannW &eacti!n J. #. (onvert the followin-H ! (i) Bhen!l to %e'ene (ii) Bhen!l to %en'!quin!ne J.6. .istin-uish between the followin- pair of ompounds H (F"AF (i) and (ii) ( and A ( F (! F F J.9. +rite the rea tions of +illiam !nW $nthe i of "; eth!x$; *; meth$lpentane. /tartin- from ethan!l and *; meth$lpentan;";!l. J.8. Vou are -iven %en'ene , 3!nc.#"SO. and NaO#. +rite the equations for the preparation of Bhen!l usin- these rea-ents. J.$. ?ame the rea-ents used in the followin- rea tionsH (i) (ii) J.D. 9en'$l alc!h!l and 9en'!ic Acid 9utan; "; !ne to 9utan I "; !l A AF

Gxplain the a idity of phen!l in the li-ht of resonan e stru tures.

J.1@. .istin-uish p&ima&$, ec!nda&$ and te&tia&$ alc!h!l usin- 3!ppe& as atalyst.

* ma&/ que ti!n

J.1. (a) +hen *; meth$l %utan I " I !l is treated with #9&, then followinrea tion ta0es pla e 2r

1"6

F3( : (F : (F : (F3 (F3 F3( AF

F2r

F3( : (F : (F" : F3(

(b) Gxplain the nitration of anisole J.". +rite the equations of the followin- rea tionsH ! (i) 9&!minati!n of ani !le in ethan!ic acid medium. (ii) D&iedel;3&aftW acet$lati!n of ani !le. J.3. (i) (ii) Gxplain why is !&th! ; nit&! phen!l more a idi than !; meth!x$ phen!lI +rite the me hanism of the rea tion of FI with meth!x$ methane. onversions arried outI B&!pan I 1; !l 9en'$l alc!h!l B&!pan I "; !l

J.#. Fow are the followin(i) (ii) (iii) J.6. (i) or (iii)

Eth$l ma1ne ium chl!&ide 9en'$l chl!&ide B&!pane

Gxplain the preparation of ethers by a id dehydration of se ondary tertiary 1l ohols is not a suitable method. Gxplain why propanol has hi-her boilin- point than that of the hydro arbon , butaneI

A9O5E A5ERA7E ?1 ma&/ que ti!n J.1. +hat is meant by hydro arbonation!oxidation rea tionI Illustrate with an example. J.". Artho and para nitrophenols are more a idi than phenol. .raw the resonan e stru tures of the orrespondin- phenoxide ions. J.3. .istin-uish between anisole and phenolI J.#. Creparation of ethers by a id dehydration of se ondary or tertiary al ohol is
1"9

not a suitable method. +hyI J.6. (onvert /ali yli a id to 1spirin. J.9. Credi t the produ t of the followin- rea tion. AF ((l#7 AF !! FB Chenols J.8. Credi t the maNor produ t of a idi J. $. 3#* 3#* ;; 3 I O ;; 3#* C #I ^^^^^ ( #* &eacti!n
(t;%ut$l meth$l ethe& )

atalysed dehydration of butan!1!ol.

B&edict the p&!duct in the a%!4e

" ma&/ que ti!n 2 ;

Q.1. Give the maNor produ ts that are formed by heatin- ea h of the followin- ethers unit FI. (i) (F"!A

(ii)

3#*

#*3 ;; 3#" I 3#" I O;; 3# I 3#"Q3#* 3#*

J.". +hy anisole under-oes bromination with bromine in ethanoi a id

1"8

even in absen e of iron (III) bromide atalyst. J.3. .urin- dehydration of al ohols to ethers, the method is suitable for the preparation of ethers havin- primary al0yl -roups only, whyI J.#. Gxplain the fa t that in aryl al0yl ethers (i) &he al0oxy -roup a tivates the benEene rin- towards the ele trophili substitution. (iii) It dire ts the in omin- substituents to ortho and para positions in benEene rin-. J.6. /how how ould you synthesise the followin- al ohols from appropriate al0enesI (i) (F3 AF AF (ii)

J.9. +rite /tru tures of the produ ts of the followin- rea tionsH A (i) ?a2F# (F"!(!A(F3 A (ii)
?a2F# F3( : (F" ! (F!! ( FA _______. (F3

* ma&/ que ti!n 2 ;

Q.1. (a) /how how the followin- al ohols prepared by the rea tion of a
1"$

suitable are Gri-nard rea-ent on methanolI (i) F3( : (F! (F"AF

_______. (F3

(ii)

(F"AF

( ) Give the me hanism of onversion of al0ene into al ohol in presen e of a id atalyst. J.". (a) +hi h of the followin- is an appropriate set of rea tants for the preparation of 1! methoxy!# : nitrobenEene and whyI (i) 2r B F3(AA?a ?A" ?A" (ii) A?a B (F32r

) &he bond an-le in al ohols is sli-htly less than the tetrahedral an-le. J.3. (i) 1rran-e the followin- ompounds in the in reasin- order of their a idi stren-th H Cropan : 1 : ol R ",#,9 trinitrophenolR 3 : nitrophenolR 3,6 dinitro!phenolR ChenolR #!methyl phenol (ii) Credi t the produ t of the rea tion -iven belowH!
1"D

3#* 3#* ;; 3 ;; 9& C NaC_3#* ^^^^^^.. ( #*

J.#. +hat is the ause of lar-e differen e of 2.C.s between ethyl al ohol, Gthylene -ly ol and -ly erolI (ii) Af benEene and phenol, whi h is more easily nitrated and whyI J.6. Give the stru tures and IOC1( names of the produ ts expe ted from the followin- rea tionsH (a) (atalyti redu tion of butanal. (b) Fydration of propene in the presen e of dilute sulphuri a id.
( )

(i)

Pea tion of propanone with methylma-nesium bromide followed by hydrolysis.

13@

UNIT 1"T# A<=E#M=E, KETONS AN= 3AR9OXM<I3 A3I=S

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS BASIC CONCEPTS: 1. Aldehydes and ke !nes :These a"e #a"$!nyl #!%&!'nds and #!n a(n #a"$!nyl ) *C+O, -'n# (!nal ."!'&.They ha/e .ene"al -!"%'la RCHO and RCOR0 "es&e# (/ely. The #a"$!n a !% !- he #a"$!nyl ."!'& (s SP 1 Hy$"(d(sed. The *C+O $!nd (s &!la" d'e ! he d(--e"en ele# "!ne.a (/( (es !- he #!ns ( 'en a !%s. Aldehydes )RCHO,, ke !nes)R2C+O, and #a"$!3yl(# a#(ds )RCOOH, a"e %!s (%&!" an and 4(dely 'sed #!%&!'nds (n !".an(# #he%(s "y. They &lay an (%&!" an "!le (n $(!#he%(#al &"!#esses !- l(-e.These #!%&!'nds and he(" de"(/a (/es a"e 'sed (n %any -!!d &"!d'# s, &ha"%a#e' (#als, -!" a" (-(#(al -la/!'"(n., as s!l/en s and -!" &"e&a"(n. a n'%$e" !- %a e"(als. The s "'# '"e !- #a"$!nyl ."!'& (s .(/en $el!4

2. PREPARATION O5 ALDEHYDES: )a, By !3(da (!n !- al#!h!ls

)$, By Dehyd"!.ena (!n !- al#!h!ls

131

)#, By !6!n!lys(s !- alkenes

)d, By hyd"a (!n !- alkynes

)e, R!sen%'nds "ea# (!n

)-, T"ea %en !- a#(d #hl!"(de 4( h d(alkyl#ad%('% .(/es ke !nes

).,5"!% n( "(les and es e"s Th(s "e# (!n (s #alled S e&hens "ea# (!n. N( "(les a"e sele# (/ely "ed'#ed $y (s!$' ylal'%(n('% hyd"(de )DIBAL7H, ! (%(nes -!ll!4ed $y hyd"!lys(s ! .(/e aldehydes. 13"

Es e"s a"e als! "ed'#ed ! aldeydes 4( h DIBAL7H.

N( "(les "ea# 4( h 8"(.na"d "ea.en 4h(#h !n hyd"!lys(s .(/es ke !nes.

)h, A"!%a (# aldeydes a"e &"e&a"ed -"!% a"!%a (# hyd"!#a"$!ns $y he -!ll!4(n. %e h!ds: ) a, E a"d0s "ea# (!n: T!l'ene "ea# s 4( h #h"!%yl #hl!"(de )C"O 2Cl2, (n Cs2 !" CCl9 ! -!"% $en6aldehyde.

)$, 8a e"%an7 K!#h "ea# (!n: :hen a %(3 '"e !- CO and HCl .as (s &assed h"!'.h $en6ene (n &"esen#e !- anhyd"!'s AlCl 1 ; C'Cl, $en6aldehyde (s -!"%ed.

133

)#, 5"(edel7 C"a- 0s a#yla (!n:

Phys(#al P"!&e" (es !- Aldehydes and Ke !nes (a) Phys(#al S a e : <!s !- he aldehydes ) e3#e& -!"%aldehyde 4h(#h (s .as , a"e l(='(d a "!!% e%&e"a '"e. The l!4e" ke !nes a"e #!l!'"less l(='(ds and ha/e a &leasan s%ell. The h(.he" %e%$e"s a"e #!l!'"less s!l(ds. A"!%a (# ke !nes a"e 's'ally s!l(ds 4( h a &leasan s%ell. (b) B!(l(n. P!(n s : Aldehydes and ke !nes ha/e "ela (/ely h(.h $!(l(n. &!(n s as #!%&a"ed ! hyd"!#a"$!ns !- #!%&a"a$le %!le#'le" %asses. I (s d'e ! he "eas!n ha aldehydes and ke !nes #!n a(n &!la" #a"$!nyl ."!'& and he"e-!"e hey ha/e s "!n.e" (n e"a# (!ns d(&!le d(&!le (n e"a# (!ns $e 4een he !&&!s( e ends !- C+O d(&!les. These d(&!le d(&!le (n e"a# (!ns a"e h!4e/e" , 4eake" han (n e"%!le#'la" H7$!nd(n. (n al#!h!ls.C!nse='en ly $!(l(n. &!(n s !- aldehydes and ke !nes a"e "ela (/ely l!4e" han he al#!h!ls !#!%&a"a$le %!le#'la" %asses.

D(&!le7 D(&!le (n e"a# (!n $e 4een 4! #a"$!nyl ."!'&s (C) S!l'$(l( y : The l!4e" %e%$e"s !- aldehydes and ke !nes )'& ! -!'" #a"$!n a !%s, a"e s!l'$le (n 4a e" . I (s d'e ! he(" #a&a$(l( y !- -!"%(n. 13#

hyd"!.en $!nds 4( h 4a e" %!le#'les . The s!l'$(l( y !- hese #!%&!'nds (n 4a e" de#"eases 4( h he (n#"ease (n he s(6e !- alkyl ."!'&. I (s $e#a'se !- he (n#"ease (n he %a.n( 'de !- n!n &!la" &a" s (n he %!le#'le. H!4e/e" h(.he" h!%!l!.!'s a"e s!l'$le (n !".an(# s!l/en s.

CHE<ICAL PROPERTIES O5 ALDEHYDES AND KETONES: Aldehydes and ke !nes a"e h(.hly "ea# (/e #!%&!'nds. B! h Aldehydes and ke !nes 'nde".! n'#le!&h(l(# add( (!n "ea# (!ns. E3&lana (!n: The "ea# (/e na '"e !- aldehydes and ke !nes (s $e#a'se !- he &"esen#e !- a &!la" #a"$!nyl ."!'&. As he !3y.en a !% (s %!"e ele# "!ne.a (/e, he"e-!"e, ( &'lls he ele# "!n dens( y a"!'nd ( sel- a#='("(n. a &a" (al ne.a (/e #ha".e 4he"eas a &a" (al &!s( (/e (s de/el!&ed !n he #a"$!n a !%. The &!s( (/ely #ha".ed #a"$!n a !% !- #a"$!nyl (s hen "ead(ly a a#ked $y he n'#le!&h(l(# s&e#(es -!" (n( (a (!n !- he "a# (!n. Th(s leads ! he -!"%ay(!n !- an (n e"%ed(a e an(!n 4h(#h -'" he" 'nde".!es he a a#k !- H ; (!n !" ! he" &!s( (/ely #ha".ed s&e#(es ! -!"% he -(nal &"!d'# . The n'#l!e&h(l(# "e#a (!n %ay $e #a alysed $y a#(ds !" $ases. The "ea# (!n (n .ene"al , %ay $e "e&"esen ed as:

Aldehydes a"e .ene"ally %!"e "ea# (/e han ke !nes d'e ! he -!ll!4(n. "eas!ns: (, P"esen#e !- 4! alky ."!'&s #a'se %!"e s e"(# h(nd"an#e (n he a&&"!a#h !- n'#le!&h(le ! #a"$!nyl #a"$!n. In aldehydes !nly !ne alkyl ."!'& (s &"esen . ((, In ke !nes ;I e--e# !- 4! alkyl ."!'&s "ed'#e he &!s( (/e #ha".e !#a"$!nyl #a"$!n and "ed'#es ( s ele# "!&h(l(#( y.

SO<E I<PORTANT N>CELOPHILIC ADDITION REACTIONS: a, Add( (!n !- hyd"!.en #yan(de) HCN,

136

P"esen#e !- $ase #a alyses he "ea# (!n $, Add( (!n !- s!d('% hyd"!.ens'l&h( e) NaHSO1,

#,Add( (!n !- al#!h!ls:

d,Add( (!n !- a%%!n(a and ( s de"(/a (/es:

139

e, Red'# (!n "ea# (!ns: (, >s(n. L(AlH 9 !" NaBH9 ! al#!h!ls

(((,

Red'# (!n ! Hyd"!#a"$!ns: Cle%%ensen "ed'# (!n 138

:!l-7 K(shne" "ed'# (!n

-, O3(da (!n :Aldehydes a"e eas(ly !3(d(6ed ! #a"$!3yl(# a#(ds 4( h #!%%!n !3(d(6(n. a.en s l(ke K<nO9, K2C"2O ?, N( "(# a#(d and e/en 4( h %(ld !3(d(6(n. a.en s l(ke T!llen0s "ea.en and 5ehl(n. s!l' (!n als!. Ke !nes a"e .ene"ally !3(d(6ed 'nde" /(.!"!'s #!nd( (!ns 4( h s "!n. !3(d(6(n. a.en s. O3(da (!n !- ke !nes (n/!l/e C7C $!nd #lea/a.e and as a "es'l a %(3 '"e !- #a"$!3yl(# a#(ds a"e -!"%ed.

T!llen0s Tes : The es (s 'sed ! d(s (n.'(sh $e 4een aldehydes and ke !nes. Aldehydes -!"% s(l/e" %(""!" 4( h a%%!n(#al s(l/e" n( "a e) T!llen0s "ea.en ,. Ke !nes d! n! "ea# 4( h ( .

5ehl(n.0s es : 5ehl(n. "ea.en + -ehl(n. s!l' (!n @A0 )a= C'SO 9, s!l' (!n B) Alk. S!d('% &! ass('% a" a"a e,

; 5ehl(n.

Hal!-!"% "ea# (!n: Aldehydes and ke !nes Ha/(n. a leas !ne ACH 1 8"!'& l(nked ! he #a"$!nyl #a"$!n .(/e h(s "ea# (!n.

13$

I!d!-!"% es : ) 's(n. he "ea.en NaOH;I 2, (s 'sed ! (den (-y he &"esen#e !-

."!'& !" (n a #!%&!'nd. ., C!ndensa (!n "ea# (!ns: (, Ald!l #!ndensa (!n: Th(s "e#a (!n (s .(/en $y h!se aldehydes and ke !nes 4h(#h ha/e B7hyd"!.en a !%. B7hyd"!.en !- #a"$!nyl #!%&!'nds (s a#(d(# d'e ! s "!n. ele# "!n 4( hd"a4(n. na '"e !- #a"$!nyl ."!'& (n &"esen#e !- a $ase.

Ald!ls ha/e $! h 7OH ."!'& and #a"$!nyl ."!'&.

((, C"!ss ald!l #!ndensa (!n:

13D

(/,

Cann(6a"!0s "ea# (!n:

Th(s (s a d(s&"!&!" (!na (!n "ea# (!n (n 4h(#h aldehyde 'nde".!es sel"ed'# (!n and !3(da (!n. h, Ele# "!&h(l(# s'$s ( ' (!n "ea# (!n: :hen #a"$!nyl ."!'& (s a a#hed ! $en6ene "(n., ( dea# (/a es he "(n. and ( (s %e a7 d("e# (n..

>ses !- aldehydes and ke !nes: (, >sed as s!l/en s and -la/!'"(n. a.en s. ((, (((, 5!"%aldehyde (s 'sed as -!"%al(n) 9CD s!l' (!n, $(!l!.(#al s&e#(%ens. ! &"ese"/e

>sed as s a" (n. %a e"(al -!" he &"e&a"a (!n !- a n'%$e" !- !".an(# #!%&!'nds, Dyes, &!ly%e"s e #.

CARBOXYLIC ACIDS )(, PREPARATION: 1#@

a, 5"!% &"(%a"y al#!h!ls and aldehydes

$, 5"!% alkyl$en6ene :

The alkyl #ha(n (n alkyl s'$s ( ' ed $en6ene (s #!%&le ely !3(d(6ed ! A COOH (""es&e# (/e !- he len. h !- he #ha(n. P"(%a"y and se#!nda"y alkyl ."!'&s als! .e !3(d(6ed, !nly e" (a"y ."!'& "e%a(ns 'na--e# ed.

#, 5"!% n( "(les and a%(des :

d, 5"!% 8"(.na"d "ea.en :

e, 5"!% a#yl hal(des and anhyd"(des :

1#1

-, 5"!% es e"s :

)((, PHYSICAL PROPERTIES: a, L!4e" %e%$e"s !- #a"$!3yl(# a#(ds )'& ! E7C, a"e l(='(ds a "!!% e%&e"a '"e, and ha/e -!'l !d!'". $, H(.he" %e%$e"s a"e s!l(d and !d!'"less. #, Ca"$!3yl(# a#(ds "e%a(n ass!#(a ed )d(%e", -!"% (n /a&!'" s a e and (n a&"! (# s!l/en s)l(ke !".an(# s!l/en s,.

d, In &"! (# s!l/en s l(ke H2O #a"$!3yl(# a#(ds "e%a(n (n d(ss!#(a e -!"%.

e, The s!l'$(l( y !- #a"$!3yl(# a#(ds de#"eases 4( h (n#"eas(n. n'%$e" !C7a !%s as he n!n7&!la" hyd"!&h!$(# alkyl &a" .e s $(..e". -, Ca"$!3yl(# a#(ds a"e s!l'$le !".an(# s!l/en s l(ke $en6ene, e he", #hl!"!-!"%, e #. CHE<ICAL REACTIONS O5 CARBOXYLIC ACIDS: A#(d(# #ha"a# e" !- #a"$!3yl(# a#(ds:7 #a"$!3yl(# a#(ds a"e 4eake" han %(ne"al a#(ds $' s "!n.e" han al#!h!ls and s(%&le &hen!ls. Ca"$!3yl(# a#(ds a"e s "!n.e" a#(ds han &hen!ls $e#a'se #a"$!3yla e (!n (s %!"e "es!nan#e s a$(l(sed han &hen!3(de (!n. As (n #a"$!3yla e (!n "es!nan#e s "'# '"e A/e 1#"

#ha".e (s !n ele# "!ne.a (/e O7a !%s 4h(le ( (s !n lesse" ele# "!ne.a (/e C7 a !%s (n &hen!3(de (!n "es!nan#e s "'# '"e.

Al#!h!ls a"e e/en less a#(d(# as alk!3(de (!n sh!4s n! "es!nan#e. Ca"$!3yl(# a#(ds d(ss!#(a es (n 4a e" ! .(/e #a"$!3yla e (!n and hyd"!n('% (!n.

H(.he" he Pka /al'e less (s he a#(d(# s "en. h. E--e# !- S'$s ( 'en s !n he A#(d(# S "en. h !- Ca"$!3yl(# A#(ds :7 Ele# "!n 4( hd"a4(n. ."!'& )E:8, (n#"eases he a#(d(# s "en. h as ( (n#"eases he &!la"( y )7I e--e# , !- AO7H $!nd -a#(l( a (n. he "elease !- H; (!n.

Ele# "!n 4( hd"a4(n. ."!'& s a$(l(6es he #a"$!3yla e (!n $y d(s&e"s(n. A/e #ha".e. P"esen#e !- ele# "!n d!na (n. ."!'&)ED8, de#"eases he a#(d(# s "en. h as ( de#"eases he &!la"( y !- AO7H $!nd d'e ! ( s ;I e--e# . Als! ED8 des a$l(shes he #a"$!3yla e (!n $y -'" he" (n#"ease e7dens( y !4a"ds he #a"$!3yla e (!n. The e--e# !- s!%e E:8s (s as -!ll!4s: Cl!se" he &"esen#e !- E:8 ! he #a"$!3yl(# ."!'& %!"e (s he a#(d(# s "en. h.

1#3

:hen #a"$!3yl(# ."!'& (s a a#hed ! /(nyl !" &henyl ."!'& ( s a#(d(# s "en. h (s d'e ! "es!nan#e.

The &"esen#e !- E:8 (n#"eases he a#(d(# s "en. h (n $en6ene "(n. 4h(le &"esen#e !- ED8 de#"eases a#(d(# s "en. h.

Rea# (!ns )(, 5!"%a (!n !- anhyd"(des

)((,

Es e"(-(#a (!n

)(((,

5!"%a (!n !- a#yl #hl!"(des

Th(!nyl #hl!"(de )SOCl2, %e h!d (s &"e-e""ed $e#a'se $! h he $y7&"!d'# s a"e .ase!'s as a "es'l &'"e &"!d'# (s !$ a(ned. )(/, Rea# (!n 4( h A%%!n(a

1##

)F,

Red'# (!n

)/,

S!dal(%e de#a"$!3yla (!n

)/(,

K!l$e0s ele# "!lys(s

)/((,

Hell F!lha"d Gel(nsky )HFG, "ea# (!n: By h(s %e h!d B7 s'$s ( ' ed #a"$!3yl(# a#(ds #an $e &"e&a"ed.

Th(s "ea# (!n (s .(/en $y !nly h!se #a"$!3yl(# a#(ds 4h(#h ha/e B7 H. @X0 (n B7 &!s( (!n !- #a"$!3yl(# a#(d #an $e "e&la#ed $y any ."!'& (n ( s "ea# (!n 4( h a= KOH, al#.KCN, e #.

1#6

)/(((, A"!%a (# #a"$!3yl(# a#(ds 'nde".! ele# "!&h(l(# s'$s ( ' (!n "ea# (!n. The ACOOH ."!'& a a#hed ! $en6ene "(n. (s a dea# (/a (n. ."!'& and (s %7d("e# (n..

Re#a&: S'%%a"y Aldehydes, ke !nes and #a"$!3yl(# a#(ds ha/e #a"$!3yl ."!'& and a"e h(.hly &!la" #!%&!'nds. Ca"$!3yl(# a#(ds al h!'.h #!n a(n ."!'& $' d! n! .(/e he "ea# (!ns .(/en $y aldehydes and ke !nes. Aldehydes and ke !nes ha/e h(.he" $!(l(n. &!(n s han he #!""es&!nd(n. hyd"!#a"$!ns and e he"s d'e ! h(.he" &!la"( y )s "!n.e" d(&!le7d(&!le (n e"a# (!ns, Ca"$!3yl(# a#(ds ha/e als! h(.he" $!(l(n. &!(n s d'e ! e3 ens(/e H7 $!nd(n.. Ca"$!3yl(# a#(ds a"e s "!n.e" a#(ds han &hen!ls and al#!h!ls $' 4eake" han %(ne"al a#(ds. A"!%a (# a#(ds a"e (n .ene"al %!"e a#(d(# han al(&ha (# a#(ds d'e ! he &"esen#e !- ele# "!n 4( hd"a4(n. $en6ene "(n..

H(.he" he &Ka /al'e !- an a#(d 4eake" (s he a#(d, i.e., ( (s &!!" &"! !n d!n!". Ke !nes a"e %!"e &!la" and ha/e h(.he" $!(l(n. &!(n han aldehydes !#!%&a"a$le %!le#'la" %ass. Aldehydes a"e %!"e "ea# (/e !4a"ds n'#le!&h(l(# s'$s ( ' (!n "ea# (!ns han ke !nes. Aldehydes !3(d(se ! .(/e #a"$!3yl(# a#(ds. Aldehydes !n "ed'# (!n .(/e 1H al#!h!ls. Ke !nes !n "ed'# (!n .(/e 2H al#!h!ls. Ke !nes a"e !3(d(sed !nly 'nde" d"as (# #!nd( (!ns and $"eak(n. !- CI C $!nd akes &la#e a he #a"$!3yl ."!'&. 1#9

Ald!l #!ndensa (!n (s .(/en $y !nly h!se aldehydes and ke !nes 4h(#h ha/e Cann(6a"!0s "ea# (!n (s .(/en $y !nly h!se aldehydes 4h(#h d! n! ha/e Aldehydes and ke !nes #an $e #!n/e" ed ! #!""es&!nd(n. hyd"!#a"$!ns )ha/(n. sa%e n'%$e" !- C7a !%s, $y Cle%ens!n0s "ed'# (!n and :!l-7K(shne" "ed'# (!n. Ca"$!3yl(# a#(ds !n "ed'# (!n .(/e 1H al#!h!ls. S!dal(%e de#a"$!3yla (!n %e h!d #an $e 'sed ! "ed'#e a C7a !% (n #a"$!3yl(# a#(ds. Hell F!lha"d Gel(nsky "ea# (!n (s 'sed ! (n "!d'#e a s'$s ( ' e l(ke CN, IX, IOH, etc., a (n a #a"$!3yl(# a#(d. Ca"$!nyl ."!'& and #a"$!3yl(# ."!'& $! h a"e "(n. dea# (/a (n. and m7 d("e# (n. ."!'&s 4hen a a#hed ! $en6ene "(n.. Aldehydes #an $e !3(d(sed 4( h %(ld !3(d(s(n. a.en s l(ke T!llen0s "ea.en and 5ehl(n.0s s!l' (!n $' n! ke !nes. A"!%a (# aldehydes a"e !3(d(sed $y T!llen0s "ea.en $' n! 4( h 5ehl(n.0s s!l' (!n. J5!"%(# a#(d (s he !nly a#(d 4h(#h .(/es he es s .(/en $y aldehyde ."!'&s.

1 MARK QUESTIONS Q. 1. Name the &eacti!n and the &ea1ent u ed f!& the c!n4e& i!n !f acid chl!&ide t! the c!&&e p!ndin1 aldeh$de . An . ?ame H Posenmund=s rea tion Pea-ent H F" in the presen e of Cd (supported over 2a/A #) and partially poisoned by addition of /ulphur or quinoline. A ff Cd72a/A# A ff

P Y ( Y (l B F" YYYYYYYYZ P Y ( Y F B F(l B / or quinoline Q. ". Su11e t a &ea !n f!& the la&1e diffe&ence in the %!ilin1 p!int !f %utan!l and %utanal, alth!u1h the$ ha4e ame !lu%ilit$ in wate&. An . &he b. pt. of butanol is hi-her than that of butanal be ause butanol has stronintermole ular F!bondin- while butanal has wea0 dipole!dipole intera tion. Fowever both of them form F!bonds with water and hen e are soluble. Q. *. +hat t$pe !f aldeh$de unde&1! 3anni'a&! &eacti!n An . 1romati and aliphati aldehydes whi h do not ontain hydro-ens. 1#8

Q. .. Out !f acet!phen!ne and %en'!phen!ne, which 1i4e i!d!f!&m te t - +&ite the &eacti!n in4!l4ed. (The c!mp!und h!uld ha4e 3#*3O;1&!up t! h!w the i!d!f!&m te t.) An . 1 etophenone ((9F6(A(F3) ontains the -roupin- ((F3(A atta hed to arbon) and hen e -iven iodoform test while benEophenone does not ontain this -roup and hen e does not -ive iodoform test. (9F6(A(F3 B 3 I" B # ?aAF YYYZ (FI3 B (9F6(AA?a B 3 ?aI B 3 F"A 1 etophenane Iodoform I"7?aAF (9F6(A(9F6 YYYZ ?o rea tion Q. 0. 7i4e Dehlin1 !luti!n te t f!& identificati!n !f aldeh$de 1p (!nl$ equati!n ). Name the aldeh$de which d!e n!t 1i4e Dehlin1W An . !ln. te t. P Y (FA Y " (u"B B 6@ F: YYYZ P(AA: B (u"A Z 3 F"A 2enEaldehyde does not -ive 'ehlin- soln. test. (1romati aldehydes do not -ive this test.) Q. 6. +hat ma/e acetic acid a t&!n1e& acid than phen!l An . Greater resonan e stabiliEation of a etate ion over phenoxide ion. n!t 1i4e #5F (#ell 5!lhand Felin /$) &eacti!n %ut

Q. 8. +h$ #3OO# d!e 3#*3OO# d!e An .

(F3(AAF ontains hydro-ens and hen e -ive F*L rea tion but F(AAF does not ontain !hydro-en and hen e does not -ive F*L rea tion.

Q. :. =u&in1 p&epa&ati!n !f e te& f&!m a ca&%!x$lic acid and an alc!h!l in the p&e ence !f an acid catal$ t, wate& !& the e te& f!&med h!uld %e &em!4ed a !!n a it i f!&med. An . &he formation of esters from a arboxyli a id and an al ohol in the presen e of a id atalyst in a reversible rea tion. F"/A# P(AAF B P=AF (arboxyli a id al ohol P(AAP= B F"A Gster

&o shift the equilibrium in the forward dire tion, the water or ester formed should be removed as fast as it is formed. Q. >. A&&an1e the f!ll!win1 c!mp!und in inc&ea in1 !&de& !f thei& acid t&en1th.

1#$

9en'!ic acid, .;Nit&!%en'!ic acid, *, .;dinit&!%en'!ic acid, .;meth!x$ %en'!ic acid. An . /in e ele tron donatin- -ps. de rease the a id stren-th therefore #!methoxybenEoi a id is a wea0er a id be ause methoxy sp. is G. .. G. than benEoi a id. 'urther sin e ele tron withdrawin- -ps. in rease the a id stren-th, therefore both # nitrobenEoi a id and 3, #!dinitrobenEoi a ids are stron-er a id than benEoi a id. 'urther due to the presen e of additional ?A" -p at m!position wrt (AAF -t, 3, #!dinitrobenEoi a id is a latti e stron-er a id than #!nitrobenEoi a id. &hus the in reasin- order of a id stren-th will be H #!methoxybenEoi a id , benEoi a id , #!nitrobenEoi a id , 3, #, dinitrobenEoi a id. Q. 1?. #!w i te&t;%ut$l alc!h!l !%tained f&!m acet!ne An .

Q. 11. 7i4e IUBA3 name !f the f!ll!win1 c!mp!und 2

An .

"!methyl y lopent!3!ene!1!oi a id

Q. 1". #!w will $!u di tin1ui h %etween methan!l and ethan!l An . 2y Iodoform test H Gthanol havin- !methyl -p will -ive yellow ppt. of iodoform whereas methanol does not have !methyl -p will not -ive ppt. of iodoform. Q. 1*. =i tin1ui h %etween 2 (i) (ii) An . (i) Acetaldeh$de and acet!ne Methan!ic acid and Ethan!ic acid. 1 etaldehyde will -ive positive tests with &ollen=s rea-ent and 'ehlin- /olns. whereas a etone will not -ive these test. (ii) 3ethanoi a id -ives &ollen=s rea-ent test whereas ethanoi a id does not due to differen e in their boilin- points. Q. 1.. +h$ a&e aldeh$de m!&e &eacti4e than /et!ne 1#D

An .

It is be ause of " reasons H &he arboxyl ompounds (both aldehydes ] 0etones) under-o nu leophili addition rea tion. (i) B I effe t H &he al0yl -roup in 0etones due to their e : releasin- hara ter de rease the ele trophili ity 7 B ve har-e on !atom and thus redu e its rea tivity. (ii) /teri hindran e H .ue to steri hindran e in 0etones, they are less rea tive.

Q. 10. 7i4e the c!mp! iti!n !f Dehlin1 A and Dehlin1 9 An . 'ehlin- 1 5 aq. (u/A# 'ehlin- 2 5 al0aline sodium potassium tartarate (Po helle /alt) Q. 16. Name !ne &ea1ent which can di ti1ui h %etween ";pentan!ne and *;pentan!ne An . "!pentanone has a (F3(A!-roup, hen e -ives positive iodoform test. 3!pentanone does not have a (F3(A!-roup, hen e does not -ive positive iodoform test. Iodoform test YYYZ I"7?aAF A ff I" (F3(F"(F" Y ( Y (F3 B ?aAF YYYZ (FI3 (yellow ppt.) A ff (F3 Y (F" Y ( Y (F" Y (F3 YYYZ ?o rxn. Q. 18. +h$ pcc cann!t !xidi e methan!l t! methane and while KMnO. can An . &his is be ause p only. +hile M3nA# bein- stron- oxidisin- a-ent oxidises it to methanoi a id. Q. 1:. +!uld $!u expect %en'aldeh$de t! %e m!&e &eacti4e !& le nucle!phlic additi!n &eacti!n than p&!panal - Explain. An . (!atom of arbonyl -roup of benEaldehyde is less ele trophili than (!atom of arbonyl -roup in propanal. Colarity of arbonyl -roup is in benEaldehyde redu ed due to resonan e ma0in- it less rea tive in nu leophili addition rea tions. &eacti4e in is a mild oxidisin- a-ent and an oxide methanol to methanal

) 77 C

) +
16@

&here is no su h resonan e effe t in propanal and so the polarity of arboxyl -roup in it is more than in benEaldehyde. &his ma0es propanal more rea tive than benEaldehyde. Q. 1>. +hat a&e #emiacetal and acetal An . Femia etal and a etals are formed by addition of al ohols on arboxyl ompounds.

Q. "?. +h$ d!e methanal n!t 1i4e ald!l c!nden ati!n while ethan!l 1i4e An . &his is be ause only those ompounds whi h have hydro-en atoms an under-o aldol rea tion. Gthanol possesses !hydro-en and under-oes aldol ondensation. 3ethanal has no hydro-en atoms, hen e does not under-o aldol ondensation. Q. "1. +h$ d!e methanal unde&1!e 3anni'a&!W &xn An . 2e ause it does not possesses hydro-en atom. Anly those aldehydes an under-o (anniEaro rea tion whi h do not possess hydro-en atoms. Q. "". A&&an1e the f!ll!win1 in !&de& !f inc&ea in1 %!ilin1 p!int 2 3#*3#"3#"O#, 3#*3#"3#"3#*, 3#*3#" Q O3#"3#*, 3#*3#"3#"3#O An . (F3(F"(F"(F3 , ("F6A("F6 , (F3(F"(F"(FA , (F3 ((F")" AF (hydro-en) (ether) (aldehyde) (al ohol) YYYYYYYYYYYYYYYYYYZ in rease in bond polarity. !lu%ilit$ dec&ea e with inc&ea in1 m!lecula& ma in ca&%!x$lic

Q. "*. +h$ d!e acid An .

2e ause of in rease in al0yl hain len-th whi h is hydrophobi in nature.

Q. ".. Alth!u1h phen!xide i!n ha m!&e n!. !f &e !natin1 t&uctu&e than ca&%!x$late i!n, ca&%!x$lic acid i a t&!n1e& acid. +h$ An . (onNu-ate base of phenol YZ phenoxide ion has non equivalent resonan e stru tures in whi h :ve har-e is at less ele trone-ative (!atom and Bve har-e is at more ele trone-ative A!atom. Pesonan e is not so effe tive.

161

In arboxylate ion, : ve har-e is delo alised on two ele trone-ative A!atoms hen e resonan e is more effe tive.

) 2 06 0C ) 2 06 0C

) 0000002 06 0C )

Q. "0. The&e a&e tw! Q N#" 1&!up in emica&%a'ide. #!we4e&, !nl$ !ne i in4!l4ed in f!&mati!n !f emica&%a'!ne . +h$ An . 1lthou-h semi arbaEide has two Y ?F" -roups but one of them is involved in resonan e. A A: A: ff B f .. f B F"? Y ( Y ?F"?F" ZYZ F"? 5 ( Y ?F Y ?F" ZYZ F" ? Y ( 5 ?F Y ?F" 1s a result, e: density on one of the Y ?F" -roup is redu ed and hen e it does not a t as nu leophile. 4one pair of other Y ?F " -roup is not involved in resonan e and is available for nu leophili atta 0. " MARKS QUESTIONS Q. 1. A&&an1e the f!ll!win1 ca&%!x$l c!mp!und in inc&ea in1 !&de& !f thei& &eacti4it$ in nucle!philic additi!n &eacti!n . Explain with p&!pe& &ea !nin1 2 9en'aldeh$de. p;t!lualde$de, p;nit&!%en'aldeh$de, Acet!phen!ne. An . 1 etophenone is a 0etone while all others are aldehydes, therefore it is least rea tive. In p!tolualdehyde, there is methyl -roup ((F3) at para position w.r.t. to the arboxyl -p, whi h in reases ele tron density on the arbon of the arboxyl -p by hyper onNu-ation effe t thereby ma0in- it less rea tive than benEaldehyde.

- 06 0C 03 00000000000003 0C 16"

- 06 0C 06 00000000000006 0C 06 0-

) -

#" .

An the other hand, in p!nitrobenEaldehyde, the ?A " -p is a powerfuil ele tron! withdrawin- -p. It withdraws ele trons both by indu tive and resonan e effe t thereby de reasin- the ele tron density on the arbon atom of arboxyl -p. &his fa ilitates the atta 0 of the nu leophile and hen e ma0es it more rea tive than benEaldehyde.

&herefore, the overall order of in reasin- rea tivity H a etophenone , p!tolualdehyde , benEaldehyde , p!nitrobenEaldehyde. Q. ". A&&an1e the f!ll!win1 c!mp!und in inc&ea in1 !&de& !f thei& %!ilin1 p!int . Explain %$ 1i4in1 &ea !n . 3#*3#O, 3#*3#"O#, 3#*O3#*, 3#*3#"3#*. An . &he mole ular masses of all these ompounds are omparable H (F3(FA (##), (F3(F"AF (#9), (F3(A(F3 (#9), (F3(F"(F3 (##). (F3(F"AF exists as asso iated mole ule due to extensive intermole ular hydro-en bondin- and hen e its boilin- point is the hi-hest (361 M). /in e dipole!dipole intera tion are stron-er in (F3(FA than in (F3A(F3, hen e boilin- point of (F3(FA ("D3 M) is mu h hi-her than that of (F 3A(F3 ("#D M). 'urther, mole ules of (F3(F"(F3 have only wea0 *ander +aals for es while the mole ules of (F3A(F3 have little stron-er dipole!dipole intera tions and hen e the boilin- point of (F3A(F3 is hi-her ("#D M) than that of (F 3(F"(F3 ("31 M). &hus the over all in reasin- order of boilin- points is H (F3(F"(F3 , (F3A(F3 , (F3(FA , (F3(F"AF Q. *. +hich acid !f each pai& h!wn he&e w!uld $!u expect t! %e t&!n1e& 3#*3O"# !& D3#"3O"#

An .

in reases the ele tron arboxyate

the ele tron density in the 163

liEes the

arboxylate

the

density in the A Y F dispersinbond thereby ma0inhar-e. the relase of a proton diffi ult.

A Y F bond thereby ma0in- the release of a proton easier.

ion by intensifyinthe : ve har-e.

ion by the : ve

&hus due to lesser ele tron density in the A Y F bond and -reater stability of '(F"(AA: ion over (F3(AA: ion '(F"(AAF is a stron-er a id than (F3(AAF. Q. .. +hich acid i D*3 Q t&!n1e& and wh$ Q 3OO# !& #*3 P Q 3OO#

An .

'3 ( Y

Y(

(F3 P

Y(

('3 has a stron- : I effe t. It stabilises the arboxylate ion by dispersin- the : ve har-e.

(F3 has a wea0 B I effe t. It stabilises the arboxylate ion by intensifyin- the : ve har-e.

&herefore due to -reater stability of ' 3( Y (9F# Y (AA: (p) ion over (F3 Y (9F#(AA: (p) ion, '3( Y (9F# Y (AAF is a mu h stron-er a id than (F 3 Y (9F# Y (AAF. Q. 0. A&&an1e the f!ll!win1 c!mp!und in inc&ea in1 !&de& !f thei& &eacti4it$ t!wa&d #3N. Explain it with p&!pe& &ea !nin1. Acetaldeh$de, Acet!ne, =i;te&t;%ut$l /et!ne, Meth$l te&t;%ut$l /et!ne. An . 1ddition of F(? to the arboxyl ompounds is a nu leophili addition rea tion. &he rea tivity towards F(? addition de reases as the B I effe t of the al0yl -p7s in reases and7or the steri hindran e to the nu leophili atta 0 by (?: at the arboxyl arbon in reases. &hus the rea tivity de reases in the order.

YYYYYYY B I effe t in reasesYYYYYYYZ YYYYYYY /teri hindran e in reasesYYYYYYYZ YYYYYYY Pea tivity towards F(? addition de reases YYYYYYYZ 16#

In other words, rea tivity in reases in the reverse order, i. e., .itert!butyl Metone , tert!2utyl methyl Metone , 1 etone , 1 etaldehyde Q. 6. +&ite t&uctu&al f!&mulae and name !f f!u& p! i%le ald!l c!nden ati!n p&!duct f&!m p&!panal and %utanal. In each ca e, indicate which aldeh$de act a nucle!phile and which a elect&!phile. An . (i) Cropanal as nu leophile as well as ele rophile. AF (F3 6 # 3f "f 1 (F3(F"(FA B (F3(F"(FA YYZ (F3(F" Y (F Y (F Y (FA Cropanal Cropanal 3!hydroxy!"!methyl pentanal (ii) Cropanal as ele trophile and butanal as nu leophile. AF (F" Y (F3 6 # 3f "f 1 (F3(F"(FA B (F3(F"(F"(FA YYZ (F3(F"(F Y (F Y (FA Cropanal 2utanal "!ethyl!3!hydroxy pentanal (Gle trophile) (?u leophile) (iii) 2utanal as ele trophile and propanal as nu leophile. AF (F3 9 6 # 3f "f 1 (F3(F"(F"(FA B (F3(F"(FA B YYZ (F3(F"(F" Y (F Y (F Y (FA 2utanal Cropanal 3!hydroxy!"!methyl pentanal (Gle trophile) (?u leophile) (iv) 2utanal both as nu leophile as well as an ele rophile. AF (F"(F3 9 6 # 3f "f 1 (F3(F"(F"(FA B (F3(F"(F"(FA B YYZ (F3(F"(F" Y (F Y (F Y (FA 2utanal (Gle trophile) 2utanal (?u leophile) "!ethyl!3!hydroxy hexanal

Q. 8. An !&1anic c!mp!und with the m!lecula& f!&mula 3 >#1?O f!&m ", .;=NB de&i4ati4e, &educe T!llenW &ea1ent and unde&1!e 3anni'a&! &eacti!n. On 4i1!&!u An . (i) !xidati!n, it 1i4e 1, ";%en'enedica&%!x$lic acid. Identif$ the c!mp!und. /in e the -iven ompound with 3. '. (DF1@A forms a ", #!.?C derivative and redu es &ollen=s rea-ent, it must be an aldehyde. (ii) /in e it under-oes (anniEaro rea tion, therefore (FA -p. is dire tly atta hed to the benEene rin-. 166

(iii)

/in e on vi-orous oxidation, it -ives 1, "!benEene di arboxyli a id, therefore it must be an ortho substituted benEaldehyde. &he only o!substituted aromati aldehyde havin- 3. '. (DF1@A is "!ethyl benEaldehyde. 1ll the rea tions an now be explained on the basis of this stru ture.

C))

1- Z B
C 25

%1- (?F3)")B AF: ZYYYYYYY &ollen=s rea-ent

C-)

%A) YYYYZ

C)) -

C 2-

C) ) -

/ilver mirror "!ethyl benEoate

"!ethyl benEaldehyde 1, "!benEene di arboxyli a id (3. '. (DF1@A) ", #!dinitrophenyl hydroEene
N)
2

C - 0 3 0 N N - 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6 0 N ) 20 + 0 - 2) C 2-

", #!.?C derivative

Q. :. Explain wh$ !;h$d&!x$%en'aldeh$de i a liquid at &!!m tempe&atu&e while p;h$d&!x$%en'aldeh$de i a hi1h meltin1 !lid. An . .ue to interamole ular F!bondin- ortho!hydroxy benEaldehyde exists as dis rete mole ule whereas due to intermole ular F!bondin-, p!hydroxybenEaldehyde exists as asso iated mole ules. &o brea0 these intermole ular F!bonds, a lar-e amount of ener-y is needed. (onsequently, p!hydroxybenEaldehyde has a mu h hi-her m. pt. and b. pt. than that of o!hydroxy benEaldehyde. 1s a result, o!hydroxy benEaldehyde is a liquid at room temperature while p!hydroxy benEaldehyde is a hi-h meltin- solid. Q. >. Identif$ A, 9 and 3 and 1i4e thei& t&uctu&e 2

) C8
3

9&"
3

#C 169

C) C-

QQQP A C 9 QQQP 3 (318#1"O) NaOh

An .

&he -iven ompound (I) ontains (F3(A -p and hen e in the presen e of 2r"7?aAF under-oes haloform rea tion to -ive sodium salt of arboxyli a id (1) and bromoform (F2P3 (2). (1) on protonation -ives the orrespondin- a id (II). (II) bein- a !0etoa id readily under-oes de arboxylation to -ive "!methyl ylohexanane (().
) C3

C) C8

2r"7?aAF YYYYYYZ Faloform rea n

(F2r3 B (2) (1)

C-

C))

FB YYYZ

FB YYYYYYZ

(Y (A") YYYYYYYZ .ex arboxylation (1 !0eto a id) "!methyl y lo

hexanone

(() 3. '. 5 (8F1"A 1 +rite the stru (i) (ii) (iii) (iv) (v) (vi) (vii) ture of the followin- ompounds #!AKA pentanal ", # .imethyl pent 3!one. 3!3ethylbutanal #! hloropentane !"!one 3!brome!#!Chenyl pentanoi a id Cara!methyl 2enEaldehyde #!3ethyl pent!3!ene!"!one

1nsH! (i) FAFF A f ff f f ff F!(!(!(!(!(!F f f f F F F (ii) (F3 A (F3 168

f ff f F3(!( !!!!(!(!(F3 f f F F (iii) (F3!(F!(F"!(FA (h3 (iv) (F3!(F!(F"!(!(F3 (l A

(v) (F3 ! (F ! (F ! (F" ! (AAF (9F6 ! (vi) (F3 ! 2r !(FA

(vii) (F3!(!(F5(!(F3 ff f A (F3 " (i) +rite IOC1( ?ames of the followin-sH! (F3 (FA (ii) (F3 (iii) ((F3 )" (F(A(F(((F3 )" (iv) (F 3 : (F (A(F3) (FA (v) (F3!(F!(F"(F"!(FA f (F3 (vi) CF(ACF (vii) (F3!(F"!(F!(F"!(F!(FA f f 2r (F3 (viii) (9F6(F5(F!(FA (ix) ((F3)3!((F"(AAF 1nsH (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) (ix) 3! 3ethyl y lohexane arbaldehyde "! 3ethyl (y lo hexanone ",# .imethyl Cantan !3! Ane "! 3ethoxy Cropanal #!3ethyl pertanal .iphenylmethanone #!2romo!"!3ethyl Fexanal. 3!.hehyl Cropernal 3,3!dimethyl 2ytasnan e a id A

3.

1rran-e the followin- ompound in in reasin- order of their boilin- points. 16$

(a) (b) ( ) (d) (e)

(F3!(FA (F3!(F"!AF (F3!A!(F3 (F3!(F3 (F#

1?/H! (F# , (F3!(F3,(F3!A!(F3,(F3!(FA,(F3!(F"!AF #. (i) (ii) 1rran-e the followin- ompound in the in reasin- order of their properties as indi ated 1 etaldehyde, 1 etone, .i!tert!2utyl Metone(Pea tion towards F(?) 2enEoi a id, # :?itro benEoi a id, 3, # .initro benEoi a id, #!methoxy benEoi a id (a id stren-th) 1nsH! (1) .i!tert!2utyl , Metone , 1 etone, 1 etaldehyde (") #!methoxy 2enEoi 1 id, 2enEoi 1 id,# :?itro benEoi a id,3, # .initro benEoi a id 6 (i) (ii) (iii) (iv) Give simple hemi al test to distin-uish between the followin- pair of ompoundsH! Cropanal ] propanone 2enEaldehyde and 1 etophenone Gthanal ] Cropanal 1 etophenone ] 2enEophenone

1nsH! (i) Cropanal ] propanone (ii) 2enEaldehyde and 1 etophenone (i) Gthanal ] Cropanal (ii) 1 etophenone ] 2enEophenone 9. Fow will you distin-uishI (i) (ii) Chenol ] 2enEoi 1 id 2enEoi 1 id ] Gthyl benEoate.

&ollen=s rea-ent &est 2y Iodoform &est.

1nsH! 2y /odiumbi arbonate test, 2enEoi a id -ives efferves en e. (AAF B ?aF(A3 (AA?a f B (A" B F"A

Chenol and ethyl benEoate do not -ive this &est. 8. Fow will you distin-uish the followin- pairsH! (i) Centan! "!one and Centan! 3!one (ii) Cropanol ] Cropanal (iii) 3ethanal ] Gthanal A A ff ff 16D

1nsH! (F3!(F"!(F"!(!(F3, +ill Give Bve Iodoform test (iii)

(F3!(F"! (!(F"!(F" .o not -ive Bve Iodoform test

Cropanol will -ive sodium metal test.

Cropanol will -ive Bve 'ehlin-=s /olution &est $. 1rran-e them in the in reasin- order of rea tivity in esterifi ation rea tion i. ii. (F3AF, ((F3)3(AF, ((F3) "!(F!AF, (F3(F"AF ((F3) 3((AAF, (F3(AAF, ((F3) "!(F(AAF,F(AAF 1nsH! (i) ((F3)3(AF,((F3) "!(F!AF, (F3(F"AF, (F3AF D (ii) ((F3) 3((AAF, ((F3) "!(F(AAF, (F3(AAF, F(AAF 1rran-e the followin- a id derivatives towards in reasin- order of nu leopheli /ubstituion rea tion (a) P(A?F", P(AA(AP, P(A(I ] P(AAP (b) 1 id derivative unli0e aldehyde and 0etones show mu leophi substitution 1nsH! (a) P(A?F" , P(AAP 13I.G G/&GP ,P.(A.A.(AP 1(I. 1?FV.PI.G ,P(A(l 1(I. (F4API.G

(b) 1 id derivatives althou-h ontain S(5A -roup, yet do not under -o the usual properties of arbonyl -roups due to the presen e of resonan e. >. +hat happen 2; @1. +hen primary al ohol vapours are passed over (u metal at 683 0 (u,683M 1nsH! P(F"!AF P(FA (orrespondin- 1ldehyde is formed. @". +hen se ondary al ohols treated with hromi anhydride ((rA3) (rA3 1nsH!P!(F!P= P!(!P= f %A) AF A (orrespondin- Metone is formed. @3. Gthyne treated with F"A in the presen e of F"/A# ] F-/A#
F"A

1nsH (F 5 (F
F"/A#!F-/A#

(F3!(FA

(orrespondin- 1 etaldehyde is formed. @#. &oulene is treated with hromyl hloride ((rA"(l") followed by hydrolysis. 1nsH (F3 (FA f (i) (rA"(l" f 19@

(ii) F"A (orrespondin- 2enEaldeiyde is formed. @6. Cropanone is treated with F(? 1nsH! (F3!(!(F3BF(? ff A (? f (F3!(!(F3 f AF

(orrespondin- (yanohydrim of problem is formed. @9. Gthanal is treated with ?aF/A3. 1nsH! (F3(FAB?aF/A3

(F3!(F!/A3F f A?a

(F3!(F!/A3?a f AF (orrespondin- /odiumbisulphite of ethanol is formed. @8. Croponal is treated with 3ethyl ma-nesium bromide. 1nsH! (F3!(F"(FAB(F33-2r F f %(F3(F"!(!A3-2r) f (F3 F"A (F3!(F"(F!AF f (F3

(orrespondin- 2utane ":@% is formed. @$. 3! Centanone is treated with M3nA# at hi-h pressure 1nsH! A ff M3nA# (F3!(F"(FA!(!(F"(F3 (F3!(F"!(AAFB(F3!(AAF
Fi-h Cress

(orrespondin- 1 mixene of ethonoi a id and propanoi and propanoi and is formed @D. Gthanal is treated with dil ?aAF. 1nsH! dil?aAF "(F3(FA (F3!(F!(F"!(FA (F3!(F5(F!(FA f !F"A AF 1ldolH(ondensation ta0en!pla e -ivin- rise to a mixume of salt of 2emoi and 2enEylal ohal. 191

1@. 2enEaldehyde is treated with hot 1l0ali 1nsH! " (FA (AA?a (F"AF 2enEoi B .isproportionation re tion ta0es pla e -ivin- rise to a mixture of salt of a id and 2enEylal ohol. 1@. 1 eti a id is treated with C(l6. 1nsH! C(l6 (F3(AAF (F3(A(l 1 etyl hloride is formed. 11. 2enEoi a id is treated with ?F3 1nsH! (AAF (i) ?F3 (ii) (A?F"

2enEamide is formed. 11. 3OMB<ETE T#E DO<<O+IN7S (i) A ff (!(l

F" Cd! 2a/A#

(FA

1. 1lF(i!2u)" (ii)(F3!(? " F"A ?F" (iii) (F(l3 B al . MAF (A("F6 (iv) A ff 1l(l3 (/" (v) (F3!( 5 (!F (vi) F (on ?aAF 19" F(AA?a B (F3AF F-"B,F"/A# F"A (F3(A(F3 ?( (F3(FA

("F6!(!(l

" F

( 5@

(vii)

A ff B F"? !?F

?A" f ?A"

?A" f 5?!?F!!

!?A"

(viii)

(F"!(F"!(F3 (AF 1. M3nA# MAF ". F"A I 4i1lF#

(ix) (F3!(AAF ". F3A 1". T&an f!&mati!n2 i. Gthanol to butane 1,3 diolR 1nsH! %A) ("F6AF (F3(FA
B

(F3(F"AF

F dil ?aAF f (F3!(!(F"!(FA f AF %F) (F3!(F!(F"!(F"!AF f AF 2utane 1,3,!diol

ii. 1nsH!

3 nitro brome benEene to 3 ! nitro benEoi a id ?A" ?A" ?A" f f f 3-7dryether (A" 2r 3-2r
ff

?A" f (AAF 3! ?itro 2enEoi a id

(!A!3-2r A

(iii) 2utanal to butanoi a id 1nsH!

SOT

(F3!(F"!(F"!(FA 193

(F3!(F"!(F"!(AAF

KMnO.

(iv) 1 eti a id to Gthan amine 1nsH! ?F3 (i) 4i1lF# (F3(AAF (F3(A?F" (F3(F"?F" (ii) F"A (v) 2romo benEene to benEoi a id 1nsH! 2r 3.ry ether 3-2r (A" A
ff

3OO#

(!A3-2r F"A

(vi) 2enEene to m!nitro a etophenone 1nsH! ?A"

(on on F?A3!F"/A# (F3(A(l

?A" 1l(l3(1nhy) (A(F3

(vii) 2enEoi a id to benEaldehyde. 1nsH! (AAF

C(l6

A
ff

(!(l
F"

(FA

Cd!2a/A#

K>ESTION BANK 5OR BRI8HT ST>DENTS K.1 C!%&le e ea#h syn hes(s $y .(/(n. %(ss(n. s a" (n. %a e"(al, "ea.en !" &"!d'# s )(,

)((,

19#

)(((,

)(/,

)/,

)/(,

)/((,

)/(((,

)(3,

)3,

)3(,

196

Ans: T"y y!'"sel-

K.2 P"ed(# he &"!d'# s !- he -!ll!4(n. "ea# (!ns: )(,

)((,

)(((,

)(/,

ANS: )(,

)((,

199

)(((,

)(/,

K.1 :"( e he s "'# '"es !- &"!d'# s !- he -!ll!4(n. "ea# (!nsL )(,

)((,

)(((,

)(/,

198

ANS: )(,

)((,

)(((,

)(/,

19$

K.9 :"( e s "'# '"al -!"%'las and na%es !- -!'" &!ss($le ald!l #!ndensa (!n &"!d'# s -"!% &"!&anal and $' anal. In ea#h #ase, (nd(#a e 4h(#h aldehyde a# s as n'#le!&h(le and 4h(#h as ele# "!&h(le. ANS:)(, Tak(n. 4! %!le#'les !- &"!&anal, !ne 4h(#h a# s as a n'#le!&h(le and he ! he" as an ele# "!&h(le.

)((, Tak(n. 4! %!le#'les !- $' anal, !ne 4h(#h a# s as a n'#le!&h(le and he ! he" as an ele# "!&h(le.

)(((, Tak(n. !ne %!le#'le ea#h !- &"!&anal and $' anal (n 4h(#h &"!&anal a# s as a n'#le!&h(le and $' anal a# s as an ele# "!&h(le.

)(/, Tak(n. !ne %!le#'le ea#h !- &"!&anal and $' anal (n 4h(#h &"!&anal a# s as an ele# "!&h(le and $' anal a# s as a n'#le!&h(le.

19D

K'es (!n M: An !".an(# #!%&!'nd #!n a(ns NE.??D #a"$!n, 11.N1D hyd"!.en and "es !3y.en. The %!le#'la" %ass !- he #!%&!'nd (s ON. I d!es n! "ed'#e T!llens0 "ea.en $' -!"%s an add( (!n #!%&!'nd 4( h s!d('% hyd"!.ens'l&h( e and .(/e &!s( (/e (!d!-!"% es . On /(.!"!'s !3(da (!n ( .(/es e han!(# and &"!&an!(# a#(d. :"( e he &!ss($le s "'# '"e !- he #!%&!'nd. ANS: D !- #a"$!n + NE.?? D

D !- hyd"!.en + 11.N1 D D !- !3y.en + P1CC Q )NE.?? ; 11.N1,RD + 1O.N D Th's, he "a (! !- he n'%$e" !- #a"$!n, hyd"!.en, and !3y.en a !%s (n he !".an(# #!%&!'nd #an $e .(/en as:

The"e-!"e, he e%&("(#al -!"%'la !- he #!%&!'nd (s C MH1CO. N!4, e%&("(#al -!"%'la %ass !- he #!%&!'nd #an $e .(/en as: M S 12 ; 1C S1 ; 1 S 1N + ON <!le#'la" %ass !- he #!%&!'nd + ON The"e-!"e, he %!le#'la" -!"%'la !- he #!%&!'nd (s .(/en $y C MH1CO.

he

S(n#e he .(/en #!%&!'nd d!es n! "ed'#e T!llen0s "ea.en , ( (s n! an aldehyde. A.a(n, he #!%&!'nd -!"%s s!d('% hyd"!.en s'l&ha e add( (!n &"!d'# s and .(/es a &!s( (/e (!d!-!"% es . S(n#e he #!%&!'nd (s n! an aldehyde, ( %'s $e a %e hyl ke !ne. 18@

The .(/en #!%&!'nd als! .(/es a %(3 '"e !- e han!(# a#(d and &"!&an!(# a#(d. Hen#e, he .(/en #!%&!'nd (s &en anQ2Q!l.

The .(/en "ea# (!ns #an $e e3&la(ned $y he -!ll!4(n. e='a (!ns:

K.M A""an.e he -!ll!4(n. #!%&!'nds (n (n#"eas(n. !"de" !- he(" &"!&e" y as (nd(#a ed: )(, A#e aldehyde, A#e !ne, D(7tert7$' yl ke !ne, <e hyl tert7$' yl ke !ne )"ea# (/( y !4a"ds HCN, )((, CH1CH2CH)B",COOH, CH1CH2CH2COOH )a#(d s "en. h, CH1CH)B",CH2COOH, )CH1,2CHCOOH,

)(((, Ben6!(# a#(d, 97N( "!$en6!(# <e h!3y$en6!(# a#(d )a#(d s "en. h,

a#(d,

1,97D(n( "!$en6!(#

a#(d,

97

ANS:)(, :hen HCN "ea# s 4( h a #!%&!'nd, he a a#k(n. s&e#(es (s a n'#le!&h(le, CNQ. The"e-!"e, as he ne.a (/e #ha".e !n he #!%&!'nd (n#"eases, ( s "ea# (/( y 4( h HCN de#"eases. In he .(/en #!%&!'nds, he ;I e--e# (n#"eases as sh!4n $el!4. I #an $e !$se"/ed ha s e"(# h(nd"an#e als! (n#"eases (n he sa%e

181

Hen#e, he .(/en #!%&!'nds #an $e a""an.ed a##!"d(n. ! he(" (n#"eas(n. "ea# (/( (es !4a"d HCN as: D(7tert7$' yl ke !ne T <e hyl tert7$' yl ke !ne T A#e !ne T A#e aldehyde )((, A- e" l!s(n. a &"! !n, #a"$!3yl(# a#(ds .a(n a ne.a (/e #ha".e as sh!4n:

N!4, any ."!'& ha 4(ll hel& s a$(l(se he ne.a (/e #ha".e 4(ll (n#"ease he s a$(l( y !- he #a"$!3yl (!n and as a "es'l , 4(ll (n#"ease he s "en. h !- he a#(d. Th's, ."!'&s ha/(n. ;I e--e# 4(ll de#"ease he s "en. h !- he a#(ds and ."!'&s ha/(n. QI e--e# 4(ll (n#"ease he s "en. h !- he a#(ds. In he .(/en #!%&!'nds, QCH1 ."!'& has ;I e--e# and B" Q ."!'& has QI e--e# . Th's, a#(ds #!n a(n(n. B"Q a"e s "!n.e". N!4, he ;I e--e# !- (s!&"!&yl ."!'& (s %!"e han ha !- n7&"!&yl ."!'&. Hen#e, )CH1,2CHCOOH (s a 4eake" a#(d han CH1CH2CH2COOH. Als!, he QI e--e# ."!4s 4eake" as d(s an#e (n#"eases. CH1CH)B",CH2COOH (s a 4eake" a#(d han CH1CH2CH)B",COOH. Hen#e, he s "en. hs !- he .(/en a#(ds (n#"ease as: )CH1,2CHCOOH T CH1CH2CH)B",COOH CH1CH2CH2COOH T CH1CH)B",CH2COOH T Hen#e,

)(((, As 4e ha/e seen (n he &"e/(!'s #ase, ele# "!n7d!na (n. ."!'&s de#"ease he s "en. hs !- a#(ds, 4h(le ele# "!n74( hd"a4(n. ."!'&s (n#"ease he s "en. hs !- a#(ds. As %e h!3y ."!'& (s an ele# "!n7d!na (n. ."!'&, 97 %e h!3y$en6!(# a#(d (s a 4eake" a#(d han $en6!(# a#(d. N( "! ."!'& (s an ele# "!n74( hd"a4(n. ."!'& and 4(ll (n#"ease he s "en. hs !- a#(ds. As 1,97 d(n( "!$en6!(# a#(d #!n a(ns 4! n( "! ."!'&s, ( (s a sl(.h ly s "!n.e" a#(d han 97n( "!$en6!(# a#(d. Hen#e, he s "en. hs !- he .(/en a#(ds (n#"ease as: 97<e h!3y$en6!(# a#(d T 1,97D(n( "!$en6!(# a#(d T Ben6!(# 18" a#(d T 97N( "!$en6!(# a#(d

K.N P"ed(# he &"!d'# s -!"%ed 4hen #y#l!he3ane#a"$aldehyde "ea# s 4( h -!ll!4(n. "ea.en s. )(, Ph<.B" and hen H1O; )((,T!llens0 "ea.en )(((, Se%(#a"$a6(de and 4eak a#(d )(/,E3#ess e han!l and a#(d )/, G(n# a%al.a% and d(l' e hyd"!#hl!"(# a#(d ANS:)(,

)((,

)(((,

)(/, 183

)/,

K.? H!4 4(ll y!' &"e&a"e he -!ll!4(n. #!%&!'nds -"!% $en6eneU Y!' %ay 'se any (n!".an(# "ea.en and any !".an(# "ea.en ha/(n. n! %!"e han !ne #a"$!n a !% )(, <e hyl $en6!a e )((, m7N( "!$en6!(# a#(d )(((, p7N( "!$en6!(# a#(d )(/, Phenyla#e (# a#(d )/, p7N( "!$en6aldehyde.

ANS:)(,

)((, 18#

)(((,

)(/,

186

)/,

Q. 8 Na%e he "ea# (!n and he "ea.en 'sed -!" he #!n/e"s(!n !- a#(d #hl!"(des ! he #!""es&!nd(n. aldehydes. Ans. Name : Rosenmunds reaction Reagent : H2 in the presence of Pd (supported over BaSO 4) and partia ! poisoned "!addition of Su phur or #uino ine$

K.E H!4 (s e" 7$' yl al#!h!l !$ a(ned -"!% a#e !neU Ans.

K. 1C. :hy &## #ann! !3(d(se %e han!l ! %e hane and 4h(le K<nO 9 #an U Ans. %his is "ecause pcc is a mi d o&idising agent and can o&ide methano to methana on !$ 'hi e ()nO 4 "eing strong o&idising agent o&idises it to methanoic acid$ K. 11. :ha a"e He%(a#e al and a#e al U 189

Ans. Hemiaceta and aceta s are formed "! addition of a coho s on car"o&! compounds$

K. 12. :h(#h a#(d (s s "!n.e" and 4hy U 51C I CNH9I COOH !" H1C I CNH9I COOH Ans. *+, has a strong - . effect$ *H, has a /ea0 1 . effect$ .t sta"i ises the car"o&! ate ion .t sta"i ises the car"o&! ate ion "! dispersing the - ve charge$ "! intensif!ing the - ve charge$ %herefore due to greater sta"i it! of +,* 2 *3H4 2 *OO- (p) ion over *H, 2 *3H4*OO- (p) ion4 +,* 2 *3H4 2 *OOH is a much stronger acid than *H,2 *3H4 2 *OOH$ Q. 1*. An !&1anic c!mp!und with the m!lecula& f!&mula 3 >#1?O f!&m ", .;=NB de&i4ati4e, &educe T!llenW &ea1ent and unde&1!e 3anni'a&! &eacti!n. On 4i1!&!u !xidati!n, it 1i4e 1, ";%en'enedica&%!x$lic acid. Identif$ the c!mp!und. An . (i) /in e the -iven ompound with 3. '. ( DF1@A forms a ", #!.?C derivative and redu es &ollen=s rea-ent, it must be an aldehyde. (ii) /in e it under-oes (anniEaro rea tion, therefore (FA -p. is dire tly atta hed to the benEene rin-. (iii) /in e on vi-orous oxidation, it -ives 1, "!benEene di arboxyli a id, therefore it must be an ortho substituted benEaldehyde. &he only o!substituted aromati aldehyde havin- 3. '. (DF1@A is "!ethyl benEaldehyde. 1ll the rea tions an now be explained on the basis of this stru ture. %1- (?F3)")B AF! %A) ! 1- B ("F6Y(9F#Y(AA YYYYY!(FAY(9F#Y("F6 YYS (AAFY(9F# &ollen=s rea-ent "!ethyl benEaldehyde f /ilver mirror "!ethyl benEoate (AAF 1, "!benEene a id di arboxyli

DOR 9E<O+ A5ERA7E

?1 Ma&/ QUESTIONS 1. +rite the stru ture of the followin- ompounds (viii) (ix) (x) (iv) (v) (vi) (vii) #!AKA pentanal ",# .imethyl pent 3!one. 3!3ethylbutanal #! hloropentane !"!one 3!brome!#!Chenyl pentanoi a id Cara!methyl 2enEaldehyde #!3ethyl pent!3!ene!"!on 188

".

+rite IOC1( ?ames of the followin-sH! A

(i) (F3

(FA

(ii) (F3

(iii) ((F3 )" (F(A(F(((F3 )" (v) (F3!(F!(F"(F"!(FA f (F3 (vi) CF(ACF (vii) (F3!(F"!(F!(F"!(F!(FA f f 2r (F3 (viii) (9F6(F5(F!(FA (ix) ((F3)3!((F"(AAF

(iv) (F 3 : (F (A(F3) (FA

DOR A5ERA7E
?" Ma&/ QUESTIONS 3. 1rran-e the followin- ompound in in reasin- order of their boilin- points. (f) (F3!(FA (-) (F3!(F"!AF (h) (F3!A!(F3 (i) (F3!(F3 (N) (F# 1rran-e the followin- ompound in the in reasin- order of their properties as indi ated (iii) (iv) 1 etaldehyde, 1 etone, and .i!tert!2utyl Metone (Pea tion towards F(?) 2enEoi 1 id, #:?itro benEoi a id, 3, # .initro benEoi a id, and #!methoxy benEoi a id (a id stren-th)

#.

DOR A9O5E A5ERA7E

?" Ma&/ QUESTIONS 6. Give simple hemi al test to distin-uish between the followin- pair of ompoundsH! (v) Cropanal ] propanone (vi) 2enEaldehyde and 1 etophenone (vii) Gthanal ] Cropanal (viii) 1 etophenone ] 2enEophenone 9. Fow will you distin-uishI (iv) Chenol ] 2enEoi 1 id (v) 2enEoi 1 id ] Gthyl benEoate. 18$

8.

Fow will you distin-uish the followin- pairsH (i) Centan "!one and Centan 3!one (ii) Cropanol ] Cropanal (iii) 3ethanal ] Gthanal

DOR A5ERA7E
?" Ma&/ QUESTIONS $. 1rran-e them in the in reasin- order of rea tivity in esterifi ation rea tion. iii. iv. 1". (F3AF, ((F3)3(AF, ((F3) "!(F!AF, (F3(F"AF ((F3) 3((AAF, (F3(AAF, ((F3) "!(F(AAF,F(AAF

1rran-e the followin- a id derivatives towards in reasin- order of nu leopheli /ubstituion rea tion (a) P(A?F", P(AA(AP, P(A(I ] P(AAP (b) 1 id derivative unli0e aldehyde and 0etones show mu leophi substitution

DOR A9O5E A5ERA7E

?" Ma&/ QUESTIONS 1@. +rite me hanism for the followin-sH! (a) (b) ( ) 11. ?u leophili addition in aldehydes and Metones 1ldol ondensation Gsterifi ation of arboxyli a ids

+hat happensH! 1. +hen primary al ohol vapours are passed over (u metal at 683 0 ". +hen se ondary al ohols is treated with hromi anhydride ((rA3) 3. Gthyne is treated with F"A in the presen e of F"/A# ] F-/A# #. &oulene is treated with hromyl hloride ((rA"(l") followed by hydrolysis. 6. Cropanone is treated with F(? 9. Gthanal is treated with ?aF/A3. 8. Croponal is treated with 3ethyl ma-nesium bromide. $. 3! Centanone is treated with M3nA# at hi-h pressure D. Gthanal is treated with dil ?aAF. 1@. 2enEaldehyde is treated with hot 1l0ali. 11. 1 eti a id is treated with C(l6. 1". 2enEoi a id is treated with ?F3.

1". (i)

(A3C4G&G &FG 'A44A+I?G. A 18D

(!(l

F" I Cd! 2a/A#

1. 1lF(t!2u)" (ii) (F3!(? " F"A ?F" f (iii) A (iv) 1l(l3 (F(l3 B 1l MAF I I

("F6!(!(l
(/"

F-"B,F"/A# (v) (F3!( 5 (!F I

(vi) F (on ?aAF " ( 5@ F A ?A" f B F"? !?F ?F" I

(vii)

ff

(viii)

(F"!(F"!(F3 1. M3nA# MAF ". F"A I 4i1lF#

(ix)

(F3!(AAF ". F3AB 1$@

13. Poad 3ap problems A ff (i) P" ( ?F3 1

Identity 1 ] 2. F"f ?i 2

(u (ii) (F3!(F"!AF 683 M A ff (iii) (F3!( :F 1. (F33-2r 1 ". F"A A ff (iv) (F3!(!(F3 1. (F33-2r 1

di ?aAF 2

",#,.?C 2

(u 1 2. 863 M

". F"A

F-/A# (v) F( 5 (F F"/A# 1

(F33-K %o) 2 (

DOR A9O5E A5ERA7E

?" Ma&/ QUESTIONS 1#. &ransformation (i) Gthanol to butane 1, 3 diolR (ii) 3! nitro bromobenEene to 3! nitro benEoi a id (iii) 2utanal to butanoi a id (iv) 1 eti a id to Gthan amine (v) 2romo benEene to benEoi a id (vi) 2enEene to m!nitro a etophenone (vii) 2enEoi a id to benEaldehyde

16.

I.G?&I'I(1&IA? &VCG JOG/&IA?/

(a) 1n or-ani ompound \1= mole ular formula (3F9A is resistant to oxidation but forms a ompound \2= ((3F$A) on rea tion. \2= rea ts with F2r to form bromide \(= with an treated with al oholi MAF form an al0ene . (3F9 dedu e the stru ture 1,2,(,.. 1$1

(b) 1n or-ani ompound \1= with mole ular formula ( $F$A forms an oran-e red pre ipitate with "!# .?C rea-ent ] with yellow pre ipitate with on heatin- with iodine in the presen e of sodium hydroxide. It neither redu e &ollens or fehlin- rea-ent nor does it de oloriEe bromine water. An drasti oxidation with hromi a id, it -ives a arboxyli a id (2) havin- mole ular formula n ( 8F9A". Identify the ompound h1i and h2i and explain the rea tion involved. ( ) 1n or-ani ompound h1i ($F9 on treatment with dilute F"/A# ontaininF-/A# -ives ompound h2i whi h an also be obtained from a rea tion of benEene with a id hloride in presen e of 1l(l3I h2i on treated with I" in aq MAF -ives ( and yellow ompound \.= identify 1,2,(,and . . Give the hemi al rea tion involved

DOR 9E<O+ A5ERA7E

?1 Ma&/ QUESTIONS 19. ?13G PG1(&IA?/H (+rite ?otes on) (i) Posen mund redu tion (ii) (anniEaro rea tion (iii) (ross aldol ondensation (iv) 1ldol (ondensation (v) (lemensen=s redu tion (vi) +olff : Mishner rea tion 18. .G/(PI2G &FG 'A44A+I?G &GP3/H (i) 1 etylation (ii) .e arboxylation (iii) /ilver mirror test

DOR A9O5E A5ERA7E

?1 Ma&/ QUESTIONS 1$. GI*G &FG PG1/A? 'AP &FG 'A44A+I?G/H (i) &he boilin- points of aldehyde and 0etones are lower than the orrespondinal ohols and arboxyli a id . (ii) &he boilin- point of arboxyli a id is hi-her than the (orrespondin- esters (iii) 1ldehydes and 0etones under -oes a number of nu leophli addition rea tion (iv) 1ldehydes under -o nu leophli addition rea tion more readily than 0etones (v) 'ormaldehyde -ives (anniEaro rea tion where as a etaldehyde -ives aldol ondensation (vi) .i! tert. butyl 0etone does not -ive ?aF/A3 addu t but a etone -ives (vii) 'loroa eti a id is a stron-er a id than hloroa eti a id. (viii) &he CMa value of hloroa eti a id is lower than CMa value of a eti a id (ix) S( 5 A -roup behaves differently in aldehyde and a id . (x) &he meltin- point of an aliphati arboxyli a id ontainin- an even number of arbon atoms is hi-her than next lower and next hi-her homolo-ues ontaininAdd number of arbon atoms. (xi) Gle trophili substitution on benEoi a id ta0es pla e at meta position.

^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

1$"

UNIT ;1* OR7ANI3 3OMBOUN=S 3ONTAININ7 NITRO7EN AMINIES

1l0yl amines are more basi than ammonia and aryl amines are less basi than al0yl amines due to presen e of ele tron density on ?!atom. &his is as followsH .. .. .. ?F3 , P!?F" S 1r!?F" In al0yl amines ma-nitude of ele tron density on ?!atom is in reased 2y presen e of ele tron releasin- -roup ie al0yl -roups whereas the ma-nitude of ele tron density is de reaed on ? :atom in aryl amines .ue to ele tron withdrawin- -roup ie aryl -roup . &he less basi ity of aryl amine is due to resonati- stru tures.

1$3

B ?F"

1$#

9ASI3ITM AMON7 BRIMARM, SE3ON=ARM E TERTIARM AMINES2 2asi ity amon- al0yl amines is found as se ondary amines S pr.aminesS tert. 1mines . &he irre-ular trends amon- amines is explained on the basis of ele tron doner al0yl -roup atta hed to an atom. Cr. 1mines have less no. of al0yl -roup,hen e less basi in se ondary amines presen e of two al0yl -roups ma0e more basi than pr. 1mines but in tert. 1mines presen e of three al0yl -roups reats steri hindran e resultin- in repulsion between el trons ma0es low ele tron density on ?!atom. .. .. .. P!!!?!!!P S P!!!?F" S P"!!!?!!!!P &he above basi ity of amines an be explained on the basis of Mb ] pMb. hi-her the Mb values or lower the pMb value shows hi-her basi hara ters . /e . amines S tert. 1mines , pr. 1mines pMb 3.@@ 3."D 3."6 BREBARATION OD AMINES2; I. (a) PG.O(&IA? A' ?I&PA (A3CAO?./Y F"7Cd 1r?A" !!!!!!!!!!!!!!!!!!!!!!!! 1r?F" Gthanol
/n7 F(l

(b) II.

1r?A" !!!!!!!!!!!!!!!!!!!!1r?F" 1mmonolysis of al0yl halides!!!

1n al0yl or aryl halides rea t with ethanoli solution of ammonia under-o nu leophili substitution in whi h halo-en atom is repla ed by amino -r. PK PK P?F"!!!!!!!!!!! P"?F !!!!!!!!!!!! P3? CP 1mine. /G(. &GP&. .I/1.*1?&1GGY2y this method a mixture of amines are prepared and not separated easily. III. Reducti!n !f nit&ile ;; F"7?i P(?!!!!!!!!!!!!!!!!!! P(F" ?F" a. Reducti!n !f amide ;;;;; 41F P(A?F" !!!!!!!!!!!!!!!!!!!!! P(F"?F" +1&GP 5. Foffmann bromamide de-radation rea tionY Cr. amines are prepared by this rea tion in whi h amide ombines with bromine in aq. Ar ethanoli solution of sodium hydroxide. P(A?F" B 2r" B# ?aAF !!!!!! P?F" B2yprodu ts 1$6

Imp!&tant chemical p&!pe&tie ;;; (i) 9a ic p&!pe&tie ;; Cresen e of ele tron density on ? atom is the reason of basi property. Fi-her the ele tron density on ? atom , hi-her the basi hara ter . (ii) S!lu%ilit$ in wate&;;; 4ower al0yl amines are soluble in water due to F! bondin- . Fih-er a0yl amines are insoluble in water. v. Ac$lati!n &eacti!n ;;; 1mines ombines with a yl halides to form ?!al0yl ethanamine. ("F6?F" B (F3(A(l !!!!!! (" F6 ?F(A( F3 vi. 3a&%$lamine &eacti!n ;;;Crimary amine ombines with hloroform in ethanoli potassium hydroxide to form iso yanide with pun-ent smell. Feat P?F" B(F(l3 B 3 MAF !!!!!!!! P?( B 3 M(l B 3F"A 4ii. Reacti!n with nit&!u acid ;;;;;; ?a?A"BF(l P?F" B F?A" !!!!!!!!!!!!!PAF B ?" BF(l FAF =IAFOTIFATION REA3TION E =IAFONIUM SA<TS 2; &he onversion of primary aromati amines into diaEonium salt is 0nown as diaEotiEation rea tion.&he diaEotiEation rea tion is hara teriEe in the Noinin- two ?!atoms (diaEo)throu-h double bonds. CPGC1P1&IA?H! &he ommonly 0nown diaEonium saltie benEene diaEonium hloride is repared by rea tin- aniline with sodium nitrite and hydro hlori a id. "83Y"8$ M 1r?F" B ?a?A" BF(l !!!!!!!!!!!!!!!!!!!!!1r?" B(l! B?a(l B"F"A BROBERTIES OD =IAFONIUM SA<TS2;; It is a olourless rystalline solid. It is in soluble in water .It is easily de omposable in dry state. I3CAP&1?& PG1(&IA?/H!! (I) /andmeyer=s rea tion H! &he rea tion of diaEonium salt with halo a id in presen e of opper halide to have halobenEene is alled sandmeyer=s rea tion. 1r!?"(l B (u(l B F(l !!!!!!! 1r!(l B ?" Gatterman rea tion H!!! &he rea tion of diaEonium salt with halo a id in presen e of opper powder is alled Gatterman rea tion. 1r!?"(l B (u B F(l !!!!!!!!!! 1r!(l B ?" B (u(l Fydrolysis rea tion !!!!! .iaEonium salt on hydrolysis upon "$3 M -ives phenol. FAF, "$3M 1r!?"(l !!!!!!!!!!!!!!!!!!!!!!!!!! 1r!AF B ?" B F(l Pedu tion of diaEonium salt !!!!! .iaEonium salts on redu tion with mild redu in- a-ent li0e phosphorous a id or ethanol redu ed to arene .

(II)

(III)

(I*)

1r!?"(l B F3CA" B FAF !!!!!!!!! 1rF B ?" B F3CA3 B F(l (*) ?itration rea tion !!!!!! .iaEonium salt on treatment with 1$9

F2'# followed by sodium nitrite ] opper at hi-h temperature -ives nitroarene. B ! ?a?A" 1r!?"(l B F2'# !! 1r!?"2'# !!!!!!!!! 1r?A" B ?" B ?a2'# (*) (ouplin- rea tion !!!!&he rea tion between diaEonium salt with aryl ompounds throu-h :?5?! is alled ouplin- rea tion. Gx.Y2enEene diaEonium hloride rea ts with phenol in basi medium , phenol oupled with diaEonium salt to the para position of phenol to produ e p!hydroxy aEobenEene( oran-e dye). AF: 1r!?"(l B 1rAF !!!!!!!!!!!!!! 1r!?5?!1rAF B (l! B FAF

1 MARK QUESTIONS Q. 1. +h$ the p&e ence !f a %a e i e ential in the amm!n!l$ i !f al/$l halide An . .urin- ammonolysis of al0yl halides, the a id liberated durin- the rea tion ombines with the amine formed to form amine salt. &o liberate free amine from the amine salt, a base is needed. Q. ". Alth!u1h Q N#" 1p i an !&th! and pa&a di&ectin1 1p, nit&ati!n !f aniline 1i4e al!n1 with !&th! and pa&a, meta de&i4ati4e al !. An . ?itration is arried out with a mixture of (on . ?A3 B (on . F"/A# (nitratin- mix). In the presen e of these a ids, most of aniline -ets protonated to form anilinium ion. &herefore, in the presen e of a ids, the rea tion mixture onsists of aniline and anilinium ion. ?ow : ?F" -p in aniline is A, p!dire tin- and a tivatin- while :? BF3 -p in anilinium ion is m!dire tin- and dea tivatin- hen e a mixture of all three:ortho, para and meta derivatives is formed. Q. *. B/% !f aniline i m!&e than that !f meth$l amine. An . In aniline, the lone pair of ele trons on the ?!atom are delo aliEed over the benEene rin-. 1s a result ele tron density on the nitro-en de reases. In ontrast in (F "?F", B I effe t of (F3 in rease the ele tron density on the ?!atom. &herefore, aniline is a wea0er base than methylamine and hen e its C0 b value is hi-her than that of methylamine. Q. .. Aniline 1et c!l!u&ed !n tandin1 in ai& f!& a l!n1 time. +h$ An . .ue to stron- ele tron!donatin- effe t (B P effe t) of ?F" -p, the ele tron density on the benEene rin- in reases. 1s a result, aniline is easily oxidised on standin- in air for a lon- time to form oloured produ ts. 1$8

Q. 0. 3#*3ON#" i a wea/e& %a e than 3#*3#"N#". An . .ue to resonan e, the lone pair of ele trons on the nitro-en atom in (F 3(A?F" is delo alised over the 0eto -p. &here is no su h effe t in (F 3(F"?F". .ue to redu tion in ele tron density on ? of (F3(A?F", it is a wea0er base than (F3(F"?F". Q. 6. A&!matic p&ima&$ aminie canWt %e p&epa&ed %$ 7a%&iel phthalimide $nthe i . An . &he preparation of aromati primary amines (1niline) by Gabriel phthalimide rea tion requires the treatment of pot. phthalimide with ( 9F6(l or (9F62r, whi h is a nu leophili substitution Pxn. /in e aryl halides do not under-o nu leophili substitution under ordinary laboratory onditions, therefore (9F6(l or (9F62r does not rea t with pot. phthalimide to -ive ?!phenyl. Chthalimide and hen e aromati primary amines an=t be prepared by this method. Q. 8. Acc!mpli h the f!ll!win1 c!n4e& i!n 2 (i) Nit&!%en'ene t! %en'!ic acid An . (ii) 9en'$l 3hl!&ide t! ";phen$lethanamine N-2 (i) N ) 2 ?a?A" B F(l (i) 'e7F(l "83 : "8$ M YYYYYZ YYYYYZ ) ) (ii) ?aAF .iaEotiEation 1niline 2enEonitrile F3BA YYYYYZ Fydrolysis
C)) )

N + N C l )
(u(?7F(? YYYYYZ 2enEene .iaEanium (hloride

CN )

2enEoi a id (ii)
C - 2C l2 )

C - 2C N

2 1 C - 2C - 2N -

M(? (aq) YYYYYZ : M(l

4a1lF# YYYYYZ Pedue Chenyl ethanenitrite

2enEyl (hloride phenylethanamine

"!

Q. :. 7i4e the t&uctu&e !f A, 9 and 3 in the f!ll!win1 c!mp!und 2 Na3N O#I NaO# C 9&" (i) 3#*3#"I QQQQQQQP A QQQQQQP 9 QQQQQQP 3 Ba&tial #$d&!l$ i N#* NaO9& NaNO"J#3l (ii) 3#*3OO# QQQQQQQP A QQQQQQP 9 QQQQQQP 3 1$$

= An . A ?a(? AF: ff (i) (F3(F"I YYYYYYZ (F3(F"(? YYYYYYZ (F3 Y ( Y ?F" (Cartial Fydrolysis) Cropanenitrile (1) Gthanamide (2) ?aAF B 2r" YYYYYYYYYYYZ (F3 Y ?F" Fofmann bromamide rea n 3ethanamine (() ?F3 ?aA2r ?a?A"7F(l (ii) (F3(AAF YYYZ (F3(A?F" YYYYYYYZ (F3?F" YYYYYYZ (F3AF . (Fofmann bromamide [ Z Gthanoi a id 3ethanol (() Q. >. +h$ i it difficult t! p&epa&e pu&e amine %$ amm!n!l$ i !f al/$l halide An . 2y ammonolysis of al0yl halides, a mixture of primary, se ondary and tertiary amines is formed. /o it is diffi ult to separate it. Px Px Px Px ?F3 YYYZ P Y ?F" YYYZ P" Y ?F YYYZ P3 Y ? YYYZ P# ?B K: 1X amine /alt Q. 1?. 3an te&tia&$ amine unde&1! acet$lati!n &eacti!n - Explain. An . 'or an amine to under-o a etylation, it should have a repla eable hydro-en atom . &ertiary amines annot under-o a etylation rea tions be ause these do not have repla eable hydro-en atom. Q. 11. Sulphanilic acid ha acidic a well a %a ic 1&!upA %ut it i in !lu%le in mine&al acid . Explain. An . /ulphanili a id exists as Lwitter ion as H
N) 9)
3 + 3

Gthanoimide (1)

rea .)

3ethanamine (2)

"X amine

3X amine

Juaternary

!lu%le in al/ali %ut

In the presen e of dil. ?aAF the wea0ly a idi Y ?F 3B -roup transfers its FB to AF: to form soluble salt C Y ?F"(9F#/A3:?aB. An the other hand, Y /A3B -roup is a very wea0 base and does not a ept FB from dil F(l to form ?F3(9F#/A3F and therefore, it does not dissolve in dil F(l. Q. 1". +h$ a&e aliphatic amine m!&e %a ic than a&!matic amine 1$D

An .

In 1romati amines, due to resonan e, ?!atom a quries Bve har-e and lone pair of ?!atom is less available. + N-2 N-2 + N+ N In aliphati amines, due to e: releasin- nature of al0yl -roups lone pair of e : on ?! atom is more available. 3ore basi .

N-

Q. 1*. Explain wh$ 2 (i) (ii) (iii) Eth$lamine i !lu%le in wate& %ut aniline i n!t.

Aniline d!e n!t unde&1! D&iedel 3&aft &eacti!n. =ia'!nium alt !f a&!matic amine a&e m!&e ta%le than that !f aliphatic amine .

An .

(i)

Gthyl amine dissolves in water due to formation of F!bondin- with water F F f f FY?!!!!!!!!!!!!FYA!!!!!!! FY?!!!!!!!!FYA!!!!!

mole ules.

! f ("F6 f F f ("F6 f F

FY?YF f ("F6 Fowever in 1niline, due to lar-er hydrophobi al0yl part extent of F!bondinde reases onsiderably insoluble in water. (ii) 1niline bein- a 4ewis base rea ts with 4ewis a id 1l(l3 or 'e(l3 to form a salt. (9F6?F" 4ewis base B 1l(l3 YYYZ (9F6?F"B1l(l3:

4ewis a id

1D@

1s a result, ?!atom a quires B ve

har-e and hen e a ts

as a stron-

dea tivatin- -roup for ele trophili rea tion. (iii) .iaEonium salts of aromati amines are more stable due to dispersal of Bve har-e on benEene rin- due to resonan e.

+ N N

N +3 N 0 +

+ N3 N

N +3 N 0 +

+ N N

+
In aliphati amines, there is no su h dispersal of B ve har-e due to absen e of resonan e. Q. 1.. +h$ 1@ amine ha4e 1!t hi1he& %!ilin1 p!int than *@ amine An . .ue to presen e of two F!atoms, in 1X amines they under-o extensive hydro-en bondin- while due to absen e of F!atom in 3X amines do not under-o F!bondin-. !!!!!!!! F P F!!!!!!!! f f f PY?YF!!!!!!!! ?YF!!!!!!!!?YP f f F F!!!!!!!!

!!!!!!!!FY?YP f F

.ue to extensive hydro-en bondin- in 1X amines, they have hi-her boilin- point : 8 than 3X amines. Q. 10. #!w can $!u di tin1ui h %etween 1@ and "@ amine An . (i) (arbylamine test H P Y ?F" B (F(l3 B 3 MAF YYYZ P Y ?( B 3 M(l B F"A (pun-ent smellin-) "X amines do not -ive this test. (ii) 1ryl sulphonyl hloride test H

1D1

7 Q. 16. #!w can $!u di tin1ui h %etween a&!matic and aliphatic amine An . &he diaronium salts of 1romati amines under-o ouplin- rea tions with phneol or andine to form oloured ompounds used as dyes.

?o su h rea tions are -iven by aliphati amines. Q. 18. #!w can t&i u% tituti!n !f 9&!mine %e p&e4ented in aniline OR #!w can we p&epa&e m!n! %&!m! aniline An . 2e ause of hi-h rea tivity of aromati amines substitution tends to o ur at o! and p! positions. 3onosubstituted aniline an be prepared by prote tin- Y ?F " -roup by a etylation with a eti anhydride, then arryin- out substitution followed by hydrolysis of substituted amide.

" MARKS QUESTIONS Q. 1. 7i4e inc&ea in1 !&de& !f &eacti4it$ t!wa&ad elect&!philic u% tituti!n &eacti!n !f the f!ll!win1 c!mp!und 2
C-

C)
An .

N )

CC-

3 3

C - 30 6 0 N 0 6 0 C )

C - 20 6 0 N 0+ C - 3, 3 )

Fi-her the ele tron density in the benEene rin-, more rea tive is the aromati ompound towards ele trophili substitution rea tion. ?ow due to the presen e of a 1D"

lone pair of ele trons on the ?!atom whi h it an dire tly donate to the benEene rin-. ? ((F3)" (due to two al0yl -roups on ?) is a mu h stron-er ele tron donatin- -p than (F3 -p. (only one al0yl -roup on ?). &he remainin- two -ps ontain a positive har-e on the ?!atom and hen e a t as ele tron withdrawin- -ps. 2ut in ((F3)3 ?B Y -p, the Bvely har-ed ? is dire tly atta hed to the benEene rin-, therefore, its ele tron withdrawin- ability is mu h stron-er than Y (F"?B ((F3)". 'rom the above, it follows that the ele tron density in the benEene rin- in reases in the order H

&herefore, their rea tivity towards ele rophili substitution rea tions also in reases in the same order. Q. ". +hich !ne i m!&e acidic - Explain 2

An .

.ue to powerful : I effe t to the '!atom, it withdraws ele trons from ? BF" -p. 1s a result, ele tron density in the ? Y F bond of p!fluoroanilinium ion de reases and hen e release of a proton from p!fluoroanilinium ion is mu h more easier than from anilinium ion. &herefore, p!fluoroanilinium ion is more a idi than anilinium ion.

Q. *. Explain the !&de& !f %a icit$ !f the f!ll!win1 c!mp!und in (i) 7a e!u pha e and (ii) inaque!u !ln. 2

(3#*)*N, (3#*)"N#, 3#*N#", N#* An . .ue to B I effe t of al0yl -ps, the ele tron density on the ?!atom of 1X, "X and 3X amines is hi-her than that on the ?!atom in ?F 3. &herefore, all amines are more basi than ?F3. (i) In -aseous phase, solvation effe ts are absent and hen e the relative basi ity of amines depends only on B I effe t of the al0yl -ps. ?ow sin e B I effe t 1D3

in reases in -oin- from 1X to "X to 3X amine, so the basi ity of amines de reases in the order H 3X amine S "X amine S 1X amine ((F3)3? S ((F3)"?F S (F3?F" S ?F3 (ii) In aq. soln, the basi ity depends upon two fa tors H (a) (b) B I effe t of (F3 -p and /olvation effe t.

/tabiliEation of the onNu-ate a id (formed addition of a proton to amine) by F!bondin- explained above on the basis of B I effe t, the order will be H ((F3)3? S ((F3)"?F S (F3?F" An the basis of /tabilisation of onNu-ate a ids by F!bondin- alone as explained below H

&he order will be H (F3?F" S ((F3)"?F S ((F3)3? &he ombined effe t of these two opposin- fa tors is that ((F 3)" ?F is the stron-est base. In ase of (F3?F" and ((F3)3 ?F, the stability due to F!bondin- predeminates over stability due to B I effe t of (F 3 -p, thereby ma0in- (F3?F" stron-er than ((F3)3 ?F. /o the overall order in aq. soln will be H ((F3)" ?F S (F3?F" S ((F3)3? S ?F3 3!nceptual Que ti!n J 1. Give reasonsH!!! a. Crimary amines are more basi than ammonia. b . /e . amines are more basi than pr.amines.

1D#

1nsY a. In pr. 1mines, al0yl -roup in reases ele tron density on the ?!atom ma0init more basi than ammo b. In se . amine, there are two al0yl -roups in rease ele tron density on ?!atom more than ?!atom in pr. amines in whi h there is one al0yl -roup. J.". +hy are amines always less a idi than omparable al oholsI 1ns.!!! 1mines are less a idi than al ohols be ause of oxy-en hi-her ele trone-ative ] smaller siEe. &herefore A!F brea0es easily than ?!F bond. +hy is amide more a idi than an amine I 1ns.YIn amide there is (5A -roup atta hed ?F" , ele tron withdrawin- ] in reases a idi nature of amide whereas in amines there is al0yl -roup whi h is ele tron releasin- and ma0es it more basi ] hen e less a idi . Fow is aniline distin-uished from ?!methyl aniline I 1ns.YAn addin- (F(l3 ] MAF , aniline -ives offensive smell formin- iso yanide ompound whereas ?!methyle aniline not. +hy yanide ion a t as ambident nu leophile I 1ns.!!!! (yanide ion an lin0 throu-h either arbon or nitro-en, therefore it is an ambident nu lophile. Fow would you remove nonpolar impurities from an amine I 1ns.!!! 1ddin- F(l , amine will form salt whereas nonpolar impurities will not rea t . 1mines an be re-enerated by addin- ?aAF . +hy tert. 1mines donot under-o a ylation rea tion I 1ns.!! &ert. 1mines donot under-o a ylation rea tion be ause they donot have ?! atta hed to F! atom. Fow will you onvert the followin-. (a) 1niline to a etanilide (b) 2enEene to aniline

J.3.

J.#.

J.6.

J9.

J8.

J$.

1nsH! (a) (9F6?F"B(F3(A(l (b) (9F9BF?A3 (on

?aAF
(oneF /o# " 333M

(9F6?F(A(F3 BF(4 (9F6?A"

3F "

(9F6?F"
/n7F l

JD. +hy does the boilin- point of (F3?F" less than F(AAFI 1nsH! F(AAF is asso iated with intermole ular F!bondin- in -reater extent then (F3?F" and therefore F(AAF has hi-her boilin- point than (F3?F" . J1@. +hat is Lwitter ionI +rite the formula of Lwitter ion of alanine. 1nsH! &he ion of a mole ule havin- Bve han-e at one end and :ve har-e at other is alled Ewitter ion. (F3 :(F!(AAF (F" J11. (F3!(F!(AA! ?F"

Fow will you prepare aniline from nitrobenEene industriallyI 1D6

1nsH! 1niline is prepared industrially by redu tion of nitrobenEene in presen e o of 'e7F l. ?A" B 9%F) J1".
'e7F l

F"

and

?F" B "F"A

1romati primary amines are not prepared by -abrial phthalimide synthesis. +hyI 1nsH! 2e ause aryl halides donot under-o nu leophili substitution rea tion. J13. (onvert the followin-! (i) 1 etamide to ethanamine (ii) 2enEene to autophenone (iii) 1nitine to #! bromo aniline (iv) 3ethanamine to ethanamine (v) Chenol to aniline (vi) Gthyl al ohol ( ethanol) to ethanamine

?a7( F AF 1nsH! (i) (F"(A?F" (F3(F"?F" " 6 1l l3 (ii) (9F6 B (F3(A(l (9F6(A(F3 F"A7FB (iii) (9F6?F" B (F3 o l (9F6?F(A(F3 2r (9F#?F(A(F3 F"A7F 2r(9F#?F"

(F (AAF 3

?F"

AP
2r (iv) (F3?F" (F3AF (F3(F"?F" ?F (v) AF or (9F9AF 3
Ln l "

(F3(l (9F6?F"

(F3(?

(vi) 1#.

(9F6AF B ?F3

1l A " 3 Feat

(9F6?F"

1 ount for the followin-! (i) ?itration of toluene is easier than benEene (ii) Gthylanmine is soluble in water where as aniline is not. (iii) pMh of aniline is more than that of methylamine. (iv) .iaEonium salts of aromati amines are more stable than these of aliphati amines. (v)3ethylami e in water rea ts with ferri hloride to pre ipitate hydrated ferri oxide. (vi) Crimary amires have hi-her boilin- point then tertiary amines. (vii) /ilver hloride dissolves in aqeous methylamine solution. (viii) 1niline readily rea ts with bromine to -ive ",#,9 tribromo!aniline.

1nsH! (i) &he methyl -roup of toluene is ele tron releasin- -roup and releases eleases ele tron density to the benEene rin- and hen e ma0es the Noinin- of ele trophile ?A"B more easier and faster. (ii) Gthylamine has more ele tron density on the ?!atam with ele tron releasin- nature of ethyl -roup while aniline has ele tron -ainer benEene rin- ] deereaus ele tron density on the ?!atom ] hemee formation of F!bond with water be omes diffi ult and hen e not soluble. 1D9

(iii) 1niline is less basi than methylamine due to ele tron releasin- benEene rin- and hen e pMb value is more ] Mb value is less. (iv) .iaEonium salt of aromati amines have dipolar ?"! l -roup whi h shows more intermole ular attra tion than those of aliphati amines and hemee more stable. (v) 3ethylamine is basi in nature and have attra ts to the l -roup of 'e l 3 in presen e of F of water and hen e pre ipitate the 'erri oxide hydrated. (vi) Crimary amires have less surfa e and less spheri al shape and hen e experi n e -reate varder waal=s for e of attra tion and hen e -reater boilin- point (vii) /ilver hloride has tenden y to form omplex ompound with aqeous methyl amine and hen e dissolves. (vii) 1niline has ele tron releasin- amine -roup, ?F" and in reases ele tron density on the ortho! and para! positions of the benEene rin- and hen e form ",#,9 tribromo!aniline.

1mines are basi even more basi than ammonia amon- amines, al0yl amines are more basi than aryl amines. Explanati!n2; &he basi nature of amines is be ause of lone pair of ele trons on the ?!atom whi h an be donated to other. .. P : ?F" .. ?F"

1l0yl amines have ele tron donor al0yl -roup ( P ) that in reases the ele tron density on the ?! atem and ma0es the al0yl amines more basi while aryl amines the al0yl amines more basi while aryl amines have ele tron -ainer benEene rin-. 2enEene is ri h in ele trons but havintenden y to -ain ele trons instead of donatin- to the ?!atom ] hen e the ele ton density on the ?! atom be omes less and hen e less basi . &he low basi ity of aryl amines may be explained broadly by ellustratin- resonatin- stru tures of anyl amines ie aniline. &he low basi ity of anylamires is with resonan e stabiliEation of the ompound i.e

.. ?F" I

B ?F" II

B ?F" III

B ?F" I*

.. ?F" *

Aut of I!!* resonatin- stru tures the fi-ures II ,III and I* are involved in the har-e separation. &he fi-. II ele trons are always rotatin- between 9 arbon atoms and not available permanently to the ?!atom for stron- basi nature. In omparision to the aryl amires the al0yl amines have no su h type of resonan e and hen e the movement of ele trons is always al0yl -roup to the ?!atom of the fun tional -roup amino -roup (?F"). P : ?F" &his phenomena ma0es the permanent displa ement of the ele trons towards ?!atom ma0es it more basi . 1D8

DOR 9E<O+ A5ERA7E

?1 Ma&/ Que ti!n
1. ". 3. #. 6. 9. 8. $. D. 1@. 11. 1". 13. 1#. 16. +rite IOC1( ?ame ! ((F3)"(F?F" +rite IOC1( ?ame ! (F3?F(F((F3)" +rite IOC1( ?ame ! (F3(F"?( (F3)" (lassify the -iven amines into primary, se ondary] tertiary. ((F3 )"(F?F" ,( (F3 )" (F?F", (F3(F"?((F3)" 1rran-e the followin- in de reasin- order of CMb valuesY ((F3 )" (F?F" ,( (F3 )" (F ?F(F3, (F3(F"?((F3)" 1rran-e the followin- in in reasin- order of basi stren-th 1niline, .imethylaniline, .iethyl amine ]3ethyl amine +hi h of the ompounds is most basi : 1niline, p!?itroaniline ] p!&oludine +hi h of the followin- ompounds is more soluble in water! 1niline, .iethyl aniline ] Gthyl amine +rite the hybridiEed state of amines. +hat is the -eometry of aminesI +hat is the stru tural formula of Lwitter ion of /ulphanili a id (omplete the followin- : (u(? 1r?"BK! B(?! !!!!!!!!!!!!! !!!!!!!!B?" B K : (onvert : 1niline to benEonitrile (onvert : 1niline to sulphanili a id. +hat do you mean by ambident ?u leophiles I Give an example.

?" Ma&/ Que ti!n

1. ". 3. #. 6. 9. 8. $. Give reasons !!! a. 1mines are basi in nature. b. 1ryl amines are less basi than ethyl amines. Fow would you distin-uish between Crimary ] se ondary aminesI Aut of ethyl al ohol ] ethyl amine, whi h has hi-her boilin- point and whyI Illustrate ea h of the followin- with an example : a /andmayer rea tion b. .iaEotiEation rea tion. Fow will you onvert !!! a. ?itrobenEene to phenol b. 1niline to hlorobenEene 1 ount for the followin-!!! (i) Crimary amines are hi-her boiln- points than omparable tertiary amines. (ii) (on . /ulphuri a id used in nitration of 2enEene. +rite the hemi al equations for one example of ea h the followin-!!! (i) (ouplin- rea tion (ii) Foffmann bromamide rea tion. Fow will you onvert!!! 1D$

(i) 3ethanamine to ethanamine (ii) Gthanamine to methanamine. D. (omplete the followin- : ?a(? AF! ?aAF7 2r" (i) (F3(F"I!!!!!!!!! 1!!!!!!!!!!!!2!!!!!!!!!!!!!!!!!!!!! ( (ii) 1@. 11. 1". 13. 1#. 16. ?F3 ?aA2r ?a?A"7 F(l (F3(AAF!!!!!!!!!!!! 1!!!!!!!!!!!!! 2 !!!!!!!!!!!!!!!!!! (
heat

Fow will you onvert !!! (i) Gthanoi a id into methanamine (ii) 3ethanol to ethanoi a id +rite short notes on the followin-! (i) (arbylamine rea tion (ii) 1 etylation rea tion +hy annot aromati primary amine be prepared by Gabrial phthalimide synthesisI Gxplain, +hy it diffi ult to prepare pure amines by ammonolysis of al0yl halidesI /ilver hloride dissolve in methylamine solution, Give reason. +rite the stru ture of the followin- ompounds :(i) &?& (ii) pi ri a id

?*. Ma&/ Que ti!n

1. 7i4e &ea !n ! a. 1niline is wea0er base than y lohexaamine. b. 1l0ylamines have less CMb value than arylamines. . 3ethylamine in water rea ts with ferri hloride to pre ipitate ferri hydroxide. +hat happen when a. 1liphati 7aromati amines rea t with hloroform in al oholi potash. b. 1niline ombines with bromine water at room temperature. . 1rene diaEonium hloride ombines with fluorobori a id. B&edict the p&!duct Y (i) 1rene diaEonium hlorides rea t with phenol in presen e of al0ali. (ii) #!?itrotoluene ombines with bromine ] further redu ed by tin in Cresen e of a id. (iii) 1niline is treated with 1 etyl hloride in presen e of pyridine. 7i4e !ne chemical te t t! di tin1ui h %etween them! (i) Gthylamine and aniline (ii) Gthylamine and dimethylamine (iii) 1niline and benEylamine. Identif$ the c!mp!und A, 9, 3 in the f!ll!win1 &eacti!n ! (i) 2r"7?aAF F?A" 1!!!!!!!!!!!!!!!!! 2 !!!!!!!!!!!!!!!( /n7 F(l ?a?A"7 F(l 1DD

".

3.

#.

6.

(ii) 1!!!!!!!!!!!!!!!! 2 !!!!!!!!!!!!!!!!!!!!!!! ( (iii) 9. 2r"7 MAF 1!!!!!!!!!!!!!!!!!! 2 !!!!!!!!!!!!!!!!!!!! ( Feat

3!mment !n the f!ll!win1! a. Foffmann=s bromamide rea tion. b. (arbylamine rea tion . .iaEotiEation rea tion +&ite the chemical &eacti!n ! a. Finsber-=s test for all amines. b. &est to distin-uish aliphati amines ] aromati amines. +&ite the &eacti!n E menti!n the p&!duct with IUBA3 nameY (i) 1niline ombines with nitri a id in presen e of sulphuri a id. (ii) 1niline ombines with sulphuri a id at #63Y#83M. (iii) 1rene diaEonium hloride ombines with ethanol. 7i4e &ea !n ! (i) /ilver hloride dissolves in aqeous methyl amine solution. (ii) &ertiary amines do not under-o a ylation rea tion. (iii) 1niline readily rea ts with bromine to -ive ",#,9!tribromoaniline. +hat is the Gabrial phthalamide synthesis I (ondensation of aniline and benEaldehyde -ives ompound 1 that is hydro-enated to -ive ompound 2 .Identify 1 and 2 . +hat happens when (i) ?itropropane redu ed with 4i1lF# (ii) Gthyl iso yanide under-oes hydrolysis (iii) 2enEene diaEonium hloride rea ts with phenol in basi medium.

8.

$.

D.

1@. 11. 1".

DOR A5ERA7E
?1. Ma&/ Que ti!n
1 ". 3. +hy do amines rea t as ?u leophilesI Fow is m!nitroaniline obtained from nitroareneI +rite IOC1( name of the ompoundY

F"?

A(F3

#. 6. 9. 8. $. D.

Give hemi al test to distin-uish between benEyl amine ] aniline . (omplete the followin- rea tionsY (on . F"/A# 1r?F" !!!!!!!!!!!!!!!!!!!!! !!!!!!!!!!!!!!!!!!! Fow would onvert, aniline to benEonitrileI +hat is 3endius rea tionI +hy does ammonolysis of al0yl halides not -ive pure 1minesI Fow will you onvert aniline to phenolI "@@

?" Ma&/ Que ti!n

1. ". Acc!mpali h the f!ll!win1 c!n4e& i!n : a. (hlorobenEene to p! hloroaniline b. ?itromethane to dimethyl amine 7i4e &ea !n ! a. 1liphati amines are stron-er base than aromati amines. b. .iaEonium salts of aromati amines are more stable than aliphati amines. +&ite the chemical &eacti!n f!& the f!ll!win1 with !ne example. a. (ouplin- rea tion b. /andmeyer rea tion. #!w will $!u ca&&$ the f!ll!win1 c!n4e& i!n Y a. 1niline to benEonitrile b. 1niline to ", #, 9!tribromo aniline =e c&i%e the te t !f p&ima&$ amine E ec!nda&$ amine with chemical equati!n .

3. #. 6.

?*. Ma&/ Que ti!n

1. ". 3. /tartin- the ne essary hemi al rea tions, onditions write the hemi al Gquations to obtained hlorobenEene from aniline. Identify K ] V. ?F3 F"7?i P(AP !!!!!!!!!!!!!! K !!!!!!!!!!!!!! V +rite short notes on the followin-!!! a. (arbylamine rea tion. b. .iaEotisation rea tion. . Foffmann 2romamide rea tion. .es ribe a hemi al test to identify pr. 1mines, se , amines and tert. 1mines= 1n aromati ompound 1 on treatment with aq. 1mmonia ] heatin- forms ompound 2 whi h on further heatin- with bromine and MAF forms another ompound, 'ormula (9F8?. Identify the ompounds 1, 2 and (. 1 ount for the followin-!!! a. pMb value of aniline is more than that of methyl amine b. Gthylamine is soluble in water but aniline is not. a. 1queous methyl amine rea ts with 'erri hloride to -ive pre ipitate hydrated ferri oxide.

#. 6. 9.

DOR A9O5E A5ERA7E ?1. Ma&/ Que ti!n .

1. ". 3. #. 6. 1n or-ani ompound K havin- mole ular formula ( "F8? An treatment nitrous a id -ives an oily yellow substan e. Identify K= ?ame the produ t obtained by a tion of aniline with 2romine. +hat happens when ethyl amine dissolves in liq. 1mmoniaI Fow would you prepare Aran-e .yeI Give the rea-ents used in Gatterman rea tion.

?" Ma&/ Que ti!n .

1. ". 7i4e &ea !n Y a. &ert. 1mines do not under-o a ylation rea tion. b. 1niline annot be prepared by Gabrial synthesis= Acc!mpli h the c!n4e& i!n Y "@1

3. #. 6.

b. 2enEoi a id to aniline . Cropanoi a id to ethanoi a id +hat happen when! b. 1romati amines rea t with nitrous a id. . 1ryl diaEonium hloride rea ts with phenoli in basi medium. =i tin1ui h %etween the pai& !f the c!mp!und Y a. Gthanamine ] diethylamine b. Chenol ] aniline. +&ite the p&!duct f!& the f!ll!win1 &eacti!n ! a. ?itroethane is treated with lithium 1luminium Fydride. b. Gthyl!isonitrile is hydrolysed in the presen e of a id=

?*. Ma&/ Que ti!n .

1. +&ite h!&t !n the f!ll!win1Y a. Gattermann rea tion. b. Foffman bromamide rea tion . Gabrial phthalamide rea tion. 1n or-ani ompound 1 with mole ular formula ( "F6?A" , rea ts with nitrous a id to -ive ("F#A3?, 2. An redu tion 1 Gives another ompound ( with mole ular formula ("F8? An treatment with nitrous a id -ives . whi h shows iodoform test, Identify 1. =i tin1ui h %etween. (1) 1liphati amines ] aromati amines. (2) 1niline ] phenol (() .iethylamine ] triethylamine Acc!mpli h the c!n4e& i!n Y a. b. . 6. ?itrobenEene to benEoi a id. 2enEene diaEonium hloride to p!hydroxy aEobenEene. (hlorobenEene to p! hloroaniline.

".

3.

#.

1n aliphati ompound K, mole ular formula (3F8?A, rea ts with bromine in presen e of MAF to produ e another ompound V . &he ompound V further rea ts with nitrous a id to form Gthanol ] nitro-en -as. Identify K ] V and write hemi al rea tions involved. 7i4e uita%le &ea !n Y (1) (2) (() Gthylamine dissolves in liquid ammonia. 1niline does not under-o 'riedel (rafts rea tion Gabriel phthalamide synthesis is preferred for synthesiEinCrimary amines.

9.

LLLLLLLLLLLL

"@"

UNIT ;1. 9IOMO<E3U<ES

1 %i!m!lecule is a mole ule that naturally o urs in livin- or-anisms. 2iomole ules onsist primarily of arbon and hydro-en, alon- with nitro-en, oxy-en, phosphorus and sulfur. Ather elements sometimes are in orporated but are mu h less ommon. 1 diverse ran-e of biomole ules exist, in ludin-H

/mall mole ulesH o 4ipid, Chospholipid, Gly olipid, /terol o *itamin o Formone, ?eurotransmitter o (arbohydrate, /u-ar o .isa haride 3onomersH o 1mino a id o ?u leotide o Chosphate o 3onosa haride ColymersH o Ceptide, Ali-opeptide, Colypeptide, Crotein o ?u lei a id, i.e. .?1, P?1 o Ali-osa haride, Colysa haride

Saccha&ide
3onosa harides are arbohydrates in the form of simple su-ars. Gxamples of monosa harides are the hexoses -lu ose, fru tose, and -ala tose and pentoses, ribose, and deoxyribose =i accha&ide are formed from two monosa harides Noined to-ether. Gxamples of disa harides in lude su rose, maltose, and la tose 3onosa harides and disa harides are sweet, water soluble, and rystalline. Colysa harides are polymeriEed monosa harides, omplex, unsweet arbohydrates. Gxamples are star h, ellulose, and -ly o-en. &hey are -enerally lar-e and often have a omplex, bran hed, onne tivity. &hey are insoluble in water and do not form rystals. /horter polysa harides, with "!16 monomers, are sometimes 0nown as oli-osa harides.

Amin! acid
1mino a ids are mole ules that ontain both amino and arboxyli a id fun tional -roups. (In bio hemistry, the term amino a id is used when referrin- to those amino a ids in whi h the "@3

amino and arboxylate fun tionalities are atta hed to the same arbon, plus proline whi h is not a tually an amino a id). 1mino a ids are the buildin- blo 0s of lon- polymer hains. +ith "!1@ amino a ids su h hains are alled peptides, with 1@!1@@ they are often alled polypeptides, and lon-er hains are 0nown as proteins. &hese protein stru tures have many stru tural and fun tional roles in or-anisms. &here are twenty amino a ids that are en oded by the standard -eneti ode, but there are more than 6@@ natural amino a ids. +hen amino a ids other than the set of twenty are observed in proteins, this is usually the result of modifi ation after translation (protein synthesis). Anly two amino a ids other than the standard twenty are 0nown to be in orporated into proteins durin- translation, in ertain or-anismsH

/eleno ysteine is in orporated into some proteins at a OG1 odon, whi h is normally a stop odon. Cyrrolysine is in orporated into some proteins at a O1G odon. 'or instan e, in some methano-ens in enEymes that are used to produ e methane.

2esides those used in protein synthesis, other biolo-i ally important amino a ids in lude arnitine (used in lipid transport within a ell), ornithine, G121 and taurine.

B&!tein t&uctu&e
&he parti ular series of amino a ids that form a protein is 0nown as that proteinus primary stru ture. Croteins have several, well! lassified, elements of lo al stru ture and these are termed se ondary stru ture. &he overall 3. stru ture of a protein is termed its tertiary stru ture. Croteins often a--re-ate into ma romole ular stru tures, or quaternary stru ture.

Metall!p&!tein
1 metalloprotein is a mole ule that ontains a metal ofa tor. &he metal atta hed to the protein may be an isolated ion or may be a omplex or-anometalli ompound or or-ani ompound, su h as the porphyrin -roup found in hemoproteins. In some ases, the metal is oordinated with both a side hain of the protein and an inor-ani nonmetalli ion. &his type of protein!metal!nonmetal stru ture is found in iron!sulfur lusters.

5itamin
1 vitamin is a ompound that annot be synthesiEed by a -iven or-anism but is nonetheless vital to its survival or health (for example oenEymes). &hese ompounds must be absorbed, or eaten, but typi ally only in tra e quantities. +hen ori-inally dis overed by a Colish do tor, he believed them to all be basi . Fe therefore named them vital amines. &he l was dropped to form the word vitamines. 1. 3a&%!h$d&ate : (arbohydrate is a lass of ompounds that in lude polyhydroxy aldehyde, polyhydroxy 0etone and lar-e polymeri mole ules that an be bro0en down to polyhydroxy aldehyde and 0etones. GxampleH su-ar, -lu ose, star h, -ums et . &hey are derived mainly from plants. ". M!n! accha&ide : &hese in lude non!hydrolysable soluble in water e.-. -lu ose, fru tose, et . "@# arbohydrates. &hese are

3. Ald! e : &he monosa harides GxampleH -lu ose.

ontanin- a aldehydi

-roup are

alled aldose.

#. Ket! e ! &he monosa harides ontanin- a 0etoni -roup are alled 0etose. GxampleH fru tose. 6. =i accha&ide : &hese arbohydrates, whi h on hydrolyses yield two mole ules of monosa harides are alled disa haides. &hey are rystalline solid. /oluble in water and sweet in taste. GxampleH ane su-ar, maltose, la tose. 9. Oli1! accha&ide : &hose arbohydrates whi h yields " to 1@ monosa harides mole ules on hydrolysis are alled oli-osa harides. GxampleH Paffinose. An hydrolysis it -ives -lu ose, fru tose and -ala tose. 8. B!l$ accha&ide ! &hose arbohydrates, whi h produ e lar-e no, of monosa harides units are alled polysa harides. &hey are formed by lin0in- to-ether a lar-e no. of monosa haride units throu-h -ly osidi lin0a-e. e.- : star h, amylose, -ly o-en, ellulose, et . $. Su1a& ! In -eneral, monosa harides and oli-osa harides are rystalline solids, soluble in water and sweet in taste. &hese are olle tively alled su-ars. e.- -lu ose, su rose. D. N!n; u1a& : &he polysa harides are amorphous, insoluble in water and tasteless are 0nown as non!su-ars e.-ss star h and ellulose. 1@. Reducin1 u1a& : &hose arbohydrates whi h ontains free aldehydi or 0etoni -roup and redu es 'ehlin-=s solution and &ollen=s rea-ent are alled redu in- su-ars. e.-. all monosa harides, maltose and la tose. 11. N!n;&educin1 u1a& : &hose su-ars whi h do not have free aldehydi or 0etoni -roup and do not redu e 'ehlin-=s solution and &ollen=s rea-ent are alled non! redu in- su-ars. e.-. su rose. 1". 7luc! e : Glu ose has one aldehydi -roup, one primary al oholi ( ! (F "AF ) and four se ondary al oholi -roup ( ! (FAF ) and -ives rea tion with (i) F(? : Glu ose rea ts with hydro-en yanide to -ive -lu ose yanohydrin (F"AF : ((FAF)# : (FA B F(? (F"AF ! ((FAF)# : (F(AF)((?) (ii) &ollen=s rea-ent : Glu ose redu es &ollen=s rea-ent to metalli silver. (F"AF : ((FAF)# : (FA B 1-"A (F"AF ! ((FAF)# : (AAF B "1(iii) Glu ose on prolon- heatin- with FI forms n!hexane. /u--estin- all the six arbon atoms in -lu ose are lin0ed linearly. FI (F"AF : ((FAF)# : (FA (F3! ((F")# : (F3 Ped C n!hexane 13. B&!tein : Croteins are omplex ployamides formed from amino a ids. &hey are essential for proper -rowth and maintenan e of body. &hey are lon- polymers of amino a ids lin0ed by peptide bonds.

"@6

1#. M$!1l!%in : It is a protein whi h stores oxy-en in mus le tissue. It onsists of only sin-le polypeptide hain asso iated with heme unit. 16. Amin! acid : &he ompounds, whi h ontain arboxyli a id -roup and amino -roup, are alled amino a id. It forms proteins. 19. E ential amin! acid : &hose amino a id whi h are not synthesiEed by our body alled essential amino a id. GxampleH valine, lysine, et . 18. N!n; E ential amin! acid : &hose amino a id whi h are synthesiEed by our body alled non!essential amino a id. It is also alled dispersible amino a ids. GxampleH -ly ine, alanine, et . 1$. En'$me : &hey are essential biolo-i al atalysts, whi h are needed to atalyse bio hemi al rea tion. GxampleH maltase, la tase. 1lmost all enEymes are -lobular proteins. &hey are hi-hly spe ifi for a parti ular rea tion and for a parti ular substrate.

1 MARK QUESTIONS Q. 1. +hich ca&%!h$d&ate i called 1&ape; u1a& - 7i4e it c!nden ed t&uctu&al f!&mula. An . Glu ose is alled -rape!su-ar I Its ondensed stru tural formula is H (FA f ((FAF)# f (F"AF

Q. ". +hich !f the f!ll!win1 i n!t an ;amin! acid #i tidine, t&$p in, c$ teine, p&!line An . &rypsin, it is a protein made from amino a ids.

Q. *. +&ite the t&uctu&e !f Fwitte& i!n f!&med f&!m Alanine. An . (AA: f (F3 Y ( Y F f ?F3B Q. .. +&eite the name and t&uctu&e !f the imple t amin! acid which can h!w !ptical acti4it$. An (AAF f (F3 Y ( Y F f ?F" 1lanine

"@9

Q. 0. #!w man$ h$d&!1en %!nd a&e p&e ent %etween (i) A and T (ii) 3 and 7 in a d!u%le helix t&uctu&e An . (i) between 1 and & there exist two hydro-en bonds H 1!!!!!!!!!!& !!!!!!!!!! between ( and G there exist three hydro-en bonds H !!!!!!!!!! (!!!!!!!!!! G !!!!!!!!!! Q. 6. +hen RNA in h$d&!l$ ed the&e i n! &elati!n hip am!n1 the quantitie !f f!u& %a e !%tained li/e =NA. +hat d!e thi fact indicate a%!ut t&uctu&e !f RNA An . &his indi ate that P?1 has a sin-le strand stru ture.

(ii)

Q. 8. +he&e d!e the wate& p&e ent in the e11 1! afte& %!ilin1 the e11 An . 1fter boilin-, the water soluble -lobular protein of e-- while -et denatured and it o-ulates into hard and rubbery insoluble mass. Q. :. +hich 4itamin i helpful in healin1 w!und and cut - +hat i the chemical name !f thi 4itamin An . *itamin!( is helpful in healin- wounds and uts, its hemi al name is 1s orbi a id.

" MARKS QUESTIONS Q. 1. +hat t$pe !f %!ndin1 help in ta%ili in1 the ;helix t&uctu&e !f p&!tein An . In a !helix stru ture, polypeptide hain of amino a ids oils as a ri-ht handed s rew be ause of the formation of all possible Fydro-en bonds between Y ?F -roup at ea h amino residue and S ( 5 @ -roup of adNa ent turn of helix. Q. ". Name the wate& in !lu%le f&acti!n !f Sta&ch. Name the m!n!me& !f thi . An . 1mylope tin is water insoluble fra tion of star h. It is a polymer of !-lu ose. en'$me u ed f!& &eacti!n. 4a tase (i) (1"F""A11 B F"A YYYYZ (9F1"A9 B (9F1"A9 4a tose -lu ose -la tose Invertase (ii) (1"F""A11 B F"A YYYYZ (9F1"A9 B (9F1"A9 /u rose -lu ose fru tose Q. .. #!w will $!u p&!4e that all the ca&%!n at!m !f 1luc! e a&e in t&ai1ht chain "@8

Q. *. +hat a&e the p&!duct !f h$d&!l$ i !f (i) lact! e (ii) uc&! e. Al ! name the

An .

An .

&he rea tion of -lu ose with FI -ives n!hexane and it proves that all sin! arbon!atom are in strai-ht hain. FI Fo (F" Y ((FAF)# Y (FA YYYZ (F3 Y ((F")# Y (F3 Feat n!hexane

Q. 0. Enume&ate tw! &eacti!n !f 1luc! e which cann!t %e explained %$ it !pen chain t&uctu&e. An . (i) Glu ose does not -ive / hiff\s &est althou-h it ontains aldehyde -roup. (ii) Glu ose does not form rystaline produ t with ?aF/A3. Q. 6. 9;c!mplex i an !ften p&e c&i%ed 5itamin. +hat i c!mplex a%!ut it - +hat i it u efulne An . It is a type of *itamin whi h ontains 21, 2", 29 and 21". It required to release ener-y from food and to promote healthy s0in and mus les. Its defi ien y auses beri!beri (*itamin 21) and 1naemia (*itamin 21"). Q. 8. +hat a&e an!me& - 7i4e tw! p!int !f diffe&ence %etween tw! an!me& !f 1luc! e. An . &he pair of opti al Isomers whi h differ in the orientation of F and AF -p only at ( 1 (arbon atom are alled anomers. .ifferen e between two anomers of -lu ose H !. (B) -lu ose (1) &he spe ifi rotation is B 111X. 1D."X. (") &he : AF -p at (1 is below the plane. plane. (") &he : AF -p at (:1 is above the !. (B) -lu ose (1) &he spe ifi rotation is B

Q1. +hat monosa harides ould be obtained from the hydrolysis of ea h of the followin-H

(a) /u rose (b) (ellulose ( ) /tar h (d) Gly o-en (" ma&/ )

Q". +hy is 1&C an ener-y ri h mole ulesI (" ma&/ )

Q*. /hown below is a mole ule of 1&C. 1&C on hydrolysis form 1.C. Indi ate the point of leava-e in 1&C mole ule when it forms 1.C on hydrolysis. (" ma&/ ) "@$

Q.. +hy is su rose a non!redu in- su-arI (" ma&/ )

Q0. +hy are maltose and la tose redu in- su-arsI (" ma&/ )

Q.1 +hat monosa harides ould be obtained from the hydrolysis of ea h of the followin-H (a) /u rose (b) (ellulose ( ) /tar h (d) Gly o-en (" ma&/ ) 1. (a) Glu ose and fru tose (b) Glu ose ( ) Glu ose (d) Glu ose Q." +hy is ATB an ener-y ri h mole ulesI (" ma&/ ) ". ATB is ener-y ri h mole ule be ause of the presen e of four ne1ati4el$ cha&1ed !x$1en at!m very lose to ea h other. &hese four ne-atively har-ed oxy-en atoms experien e very hi-h repulsive ener-y. +hen ATB is hydrolysed, the hydrolysis of bonds results in de rease in repulsive for es and onsequently a lar-e amount of ener-y is released. Q.* /hown below is a mole ule of 1&C. 1&C on hydrolysis form A=B. Indi ate the point of leava-e in ATB "@D

mole ule when it forms 1.C on hydrolysis.

(" ma&/ ) *. .urin- hydrolysis, the bond between se ond and third phosphate an be easily bro0en to form 1.C the point of leava-e is shown in dia-ram below. Coint of leava-eto form 1.C.

Q.. +hy is su rose a non!redu in- su-arI (" ma&/ ) .. /u rose is a non!redu in- su-ar be ause an!me&ic

arbon of both monosa harides are involved in -ly oside or a etal formation. Q.0 +hy are maltose and la tose redu in- su-arsI (" ma&/ ) 0. 3altose and la tose are redu in- su-ars be ause in one of the monosa haride units there is a homia etal -roup that an be opened to -ive free :(FA -roup.

DOR 9E<O+ A5ERA7E Que ti!n !f !ne ma&/ J 1. +hat are biomole ules I ". Give two examples of monosa haries. 3. Give name the monomers whi h onstitutes la tose . #. Give the name of lin0a-e whi h found between the monomer units of su rose 6. ?ame the two essential amino a ids. 9. ?ame the sour e of vit. G. 8. +ho proposed the double heli al stru ture of .?1 I

DOR A5ERA7E
1. +hat are monosa harides I "1@

". Give an example of bran hed polysa haride . 3. +hat are non!redu in- su-ars I #. +hat happen when -lu ose is treated with FI I 6. .raw the pyranose stru ture of alpha!.!-lu ose 9. ?ame the omponents of star h . 8. +here -ly o-en is present in human body I $. ?ame the primary onstituents of proteins. D. +hat are the expe ted produ ts of hydrolysis of maltoses1@.+hi h type of proteins onstitute enEymes I

DOR A9O5E A5ERA7E

1. +hy is maltose a redu in- su-arI ". Give the name of most abundant arbohydrate present on the earth. 3. +rite down the rea tion between a eti anhydride and -lu ose. #. Give the formula of -ly ine . 6. +hat is the fun tion of -ly o-en in human body. 9. .raw the stru ture of Ewitter ion. 8. +hat do you mean by denaturation of proteins I $. +hat is the a tivation ener-y for a idi hydrolysis of su rose I

DOR 9E<O+ A5ERA7E

Que ti!n !f tw! ma&/ 1. +hat are main fun tions of hexose su-arsI ". Give two appli ations of arbohydrates in plants. 3. Give the fun tions of ellulose. #. Fow we lassify the amino a ids a ordin- to the need in the body I 6. +hat happen when denaturation of proteins ta0es pla eI Gxplain with examples 9. Give importan e and sour e of vit. 2. 8. Gxplain peptide lin0a-e

DOR A5ERA7E
1. .raw the furanose and pyranose stru ture of hexose su-ar. ". Gxplain a idi and basi amino a ids with examples 3. .ifferentiate between fibrous and -lobular proteins. #. +hat is the differen e between nu leoside and nu leotide. 6. Fow an we lassify the vitamins .Give sour e of vit 1 ] (.

"11

DOR A9O5E A5ERA7E

1. .raw the hawarth proNe tion formula for maltose. ". .ifferentiate between tertiary and quaternary stru ture of proteins 3. .ifferentiate amylase and amylope tin #. +hat are fun tional differen e between .?1 and P?1. 6. ?ame the fa tors affe tin- enEymati a tivity.

DOR 9E<O+ A5ERA7E

Que ti!n !f th&ee ma&/ 1. Fow arbohydrates are lassified a ordin- to monomer units present in them I ". Give two hemi al rea tion for preparation of -lu ose. 3 .Fow star h is different from ellulose I #. +hat do you mean by se ondary stru ture of proteins I Gxplain. 6. Give main sour e of and fun tion of vit. 2 ] vit. .

DOR A5ERA7E
1. ". 3. #. Give the rea tion of -lu ose with (i) 2r" (ii) ?F"AF (iii) F?A3. Fow an you show that -lu ose have y li stru tureI Gxplain the alpha :heli al and beta pleated stru ture of proteins. Gxplain the me hanism of enEyme atalysis.

6. Give differen e between .?1 ] P?1. Give appli ations of P?1

DOR A9O5E A5ERA7E

1. ". 3. #. 6. +hat do you mean by .?1 fin-er!printin- I Gnlist their uses. Fow do you explain the amphoteri nature of amino a ids I Give biolo-i al appli ation of .?1. &wo strands of .?1 are not identi al but omplimentary. Gxplain. /upply of vit. ( needs ontinue for human body. +hy I S!me Imp!&tant Que ti!n with An we& 1. ". 7i4e !ne example !f %&anched p!l$ accha&ide. 1ns. ! /tar h +h$ uc&! e i /n!wn a in4e&t u1a& 1ns! 2e ause after hydrolysis opti al rotation is han-ed. "1"

3.

+hat = E< den!te I 1ns! Pelative onfi-uration of parti ular hydro arbon with respe t to -ly eraldehydes. ..Amin! acid ha4e &elati4el$ hi1h meltin1 p!int a c!mpa&ed t! c!&&e p!ndin1 hal!acid . Explain. 1nsH 1mino a ids have relatively hi-her m.p as ompared to orrespondin- haloa ids. +e 0now that amino a ids have amino (basi ) -roup and arboxyli (a id) -roup. 1 proton whi h omes from arboxyli -roup is a epted by amino -roup. &hus amino a id exists in the form of dipolar ion i.e. Ewitter ion. .ue to this ioni form amino a ids be ome rystalline solids and due to this salt li0e stru ture show hi-her meltinpoint. 0 1nsH 6 1nsH Amin! acid a&e amph!te&ic in natu&eJ%eha4i!&. Explain. .ue to presen e of dipolar ion i.e. Ewitter ion, amino a id an rea ts with a id and bases. +h$ canWt 4itamin 3 %e t!&ed in !u& %!d$- O& +h$ except 91" !& 4itamin 9 and 3 canWt %e t!&ed in !u& %!d$*itamin 2 ex ept 21" ] ( are water soluble vitamins. &herefore these vitamins are re-ularly supplied from outside be ause they are readily ex reted in urine and an=t be store in our body. +hat i 1l$c!1en- +h$ 1l$c!1en i al ! /n!wn a animal ta&chGly o-en is polysa haride of -lu ose. (arbohydrates are stored in animal body as -ly o-en. It is found in liver, brain. It is also 0nown as animal star h be ause its stru ture is similar to amylope tin and is hi-hly branded. +hat i =NA fin1e&p&intin1- Enli t thei& u e . It is well 0nown fa t that every individual has unique fin-erprints. &hese o ur at the tips of the fin-ers and have been used for identifi ation for a lon- time. 2ut these an be altered by sur-ery. 1 sequen e of base on .?1 is also unique for a person and information re-ardin- this is alled .?1 fin-erprintin-. 'ollowin- are the uses of .?1 printin-. in forensi laboratories for identifi ation of riminals. &o determine paternity of an individual. &o identify the dead bodies in any a ident by omparin- the .?1=s of parent or hildren. &o identify ra ial -roups to rewrite biolo-i al evolution.

8 1nsH

:. 1nsH

a) b) ) d)

"13

UNIT I 10
BO<MMER

B!l$me&2 ; Colymer ompounds are very hi-h mole ular masses formed by the
ombination of /imple mole ules by ovalent bonds. Gx. n(F"5(F" Yc (Y (F"Y (F"Y)n Gthene ( 3onomer) Gx. Colythene. 3!p!l$me& 2; 1 polymer from two or more type of monomers is alled opolymer Gx. &erylene or de ron, ?ylon 99. 3la ificati!n !f p!l$me& H! Colymer are lassified in number of ways des ribed as follows (1) Natu&al p!l$me& 2; &he polymers obtained from nature (plants ] animals ) are alled natural polymers. G-. /trar h, (ellulose, ?atural rubber and Croteins et . (2) S$nthetic B!l$me& 2; &he polymers whi h are prepared in laboratory are alled /yntheti or man made polymers. G-. Colythene, C*(, ?ylon, &eflon. Colythene ( Colymer)

#!m!p!l$me& H! 1 polymer from one type of monomers is alled homopolymer

3la ificati!n !f p!l$me& !n the %a i !f t&uctu&e

(a) 4inear polymer H! &hese are polymers in whi h monomeri units are lin0ed to-ether to form linear hains. G-. Colythene, C*(, &eflon (b) (ross lin0ed polymersH! &hese are polymers in whi h the monomers unites are ross! lin0ed to-ether to form a three! dimensional networ0. Gx. 2a0elite, /yntheti rubber. ( ) 2ran h hain polymersH! &he polymers in whi h monomers are Noined to form lonhains with side hains. Gx. 4ow density polythene.

3la ificati!n !f p!l$me& !n the %a i !f m!lecula& f!&ce .

"1#

(a) GlastomersH! &he polymers that have elasti elastomers. Gx. ?atural rubber

hara ter li0e rubber are alled

(b) 'ibersH! &hey have stron- intermole ular for es between the hains. &hese for es are either F!bondin- or dipole intera tions. Gx. ?ylon!99, da ron, sil0 et . ( ) &hermoplasti s H! &hese are the polymers whi h an be easily softened repeatedly heated and hardened when ooled with little han-e in their properties. Gx. Colythene, C*(. (d) &hermosittin- Colymers H! &hese are the polymers whi h under-o permanent han-e on heatin-. &hey be ome hard and infusible on heatin-. Gx. 2a0elite. Gt .

3la ificati!n !f p!l$me& !n the %a i !f m!de !f $nthe i .

(a) 1ddition polymersH! 1 polymers formed by dire t addition of repeated monomers without the elimination of by produ t mole ule is alled addition polymers. Gx. Colythene, C*(,C&'G, et (b) (ondensation polymers H! 1 polymer formed by the ondensation of two or more than two monomers with the elimination of simple mole ules li0e water, ammonia, hydro-en sulphide, al ohol, et . is alled ondensation polymer. In this ea h ase monomer -enerally ontains two fun tional -roups. Gx. ?ylon 99 and ?ylon 9, 2a0elite, .ae ron, et . #i1h den it$ p!l$thene (Fei1la& Natta catal$ t) It is prepared by heatin- of about 333! 3#3M under a pressure of 9!8 atm in the presen e of Lei-lar ?atta atalyst ( &ri ethyel aluminium &itenium tetra hloride ) 333!3#3M, 9!8 atam n (F" 5 (F" YYYYYYYYYYc Lei-lar ?atta atalyst OsesH! It is used in manufa ture of ontainers ( bu 0ets , .ust bin, et ) It is used in manufa ture of different house wares pipes et . (Y (F"Y (F")n

"16

Colymer (ori-ion Gree0) poly means many, mers means part =efinati!n2 *ery lar-e mole ules havin- hi-h mole ular mass (1@3!1@8 u) 3a romole uleH other name for polymer ColymeriEationH the pro ess of formation of polymer (lassifi ation of polymerH 1. 2ased on sour esH
"19

a. ?aturalH from plants and animal sour es for example star h ellulose rubber et . b. /emi syntheti H polymer with modifi ation of natural polymer for example rayon. . /yntheti prepared in laboratory for example nylon, ethylene et . ". 2ased on stru ture of polymerH a. 4inearH lon- and strai-ht han-e for example C*(

b. 2ran hedH linear polymer with bran hes for example low density plasti

. (ross lin0ed or networ0H ontains stron- ovalent bond between various linear polymer for example 2a0elite, melamine .

3. 2ased on mode of polymeriEationH a. 1ddition polymeriEationH repeated unit of monomers havinunsaturation in its stru ture
"18

i. ii.

Fomo!polymerH when monomer is of same 0ind for e.-. polyether, C*( (opolymer polymer havin- two different monomers for e.-. 2una!/, 2una! ?

b. (ondensation polymeriEationH repeated ondensation rea tion between mostly two different bi!fun tional monomer unit with the elimination of water al ohol et . for e.-. nylon 99, .a ron #. 2ased on mole ular for es a. GlastomersH rubber li0e solid with stret hable property up to some extant for e.-. 2una!/, 2una ?. &he for e between hains is wea0 *anderwall for e. b. 'iberH thread li0e solid with hi-h tensile stren-th 'or e between hain is hydro-en bondin- for e.-. polyester, nylon 9, 9 . &hermo plasti H linear or sli-htly bran hed lon- hain mole ule, soften on heatin-. 'or example polyethylene C*(. Gt . d. &hermosettin-H ross lin0ed mole ule on e setup an=t not be soften on heatin-. for example 2a0elite, melamine .e reasin- order of for e of attra tion between the hains
&hermosettin- S 'iberS &hermoplasti S Glastomers

=iffe&ence %etween the&m!pla tic and the&m! ettin1

T$pe !f p!l$me&i'ati!n &eacti!nH 1ddition polymeriEation or hain -rowthH
.ue to in rease in the len-th of hain .ue to addition of similar monomer it is addition polymeriEation e.-. polythene

/teps of addition polymeriEation with free radi al me hanismH (hain initiation Hby mole ules li0e 2enEoyl peroxide((9F6A(AA(A(9F6) (hain propa-ation H throu-h free radi al (hain terminalisation H ombination of free radi als. J .whi h atalyst is used in F.C li0e polytheneI 1. Lei-ler!?atta atalyst. J. what is Lei-ler!?atta atalystI 1. &riethylaluminium (("F6)31l and titanium tetra hloride(&i(l#) (ondensation polymeriEation or step -rowthH /in e ea h step produ es a fun tionaliEed spe ies and is independent of ea h other,this is alled step -roth. 1s,monomers with different fun tional -roups are ondensed,so, it is (ondensation polymeriEation. "1$

e.-. (ondensation between Fexamethylene!di!amine% ?F"!((F")9!?F") and 1dipi a id%FAA(!((F")#!(AAF in ?ylon!9,9. J.why nylon is named as su hI 1.It is 1 roname of ?ew!Vor0 and 4ondon. J .why is it alled 9,9I 1. 1s the monomers ontain six arbon ea h i.e. Fexamethylene! di ! amine% ?F"!((F")9! ?F") and 1dipi a id %FAA(!((F")#!(AAF. J. what is the monomer of nylon!9I 1. (aprola tum %?F"!((F")6!(AAF). J. +hi h properties of polyester ma0e it more usable fibre I 1. (rease resistant, .ip dry, 2lendin- with other natural fibre li0e otton, wool et . J. what are different 0inds of blended polyesterI 1. &ere!(ot (&erelene with (otton) &ere!+ool (&erelene with +ool) &ere!/il0 (&erelene with sil0) J.1 &ere!(ot shirt is mar0ed as 9@!#@.+hat does it meanI 1. It ontains 9@% terelene and #@% otton. J. +hat is the sour e of natural rubberI 1. 3il0y latex from rubber tree. J. +hi h ountries are the -reater produ er of rubber I 1. /ri :4an0a, 3alaysia, Indonesia, /outh 1meri a. J. +hat is the monomer of natural rubberI 1. Isoprene ("!3ethylbut!1,3!diene). J. +hat is a vul aniEed rubberI 1. +hen natural rubber is heated with sulphur, it forms ross!lin0a-e of sulphur between linear polymers. /u h rubber is alled vul aniEed rubber. J. Fow is vul aniEed rubber than natural rubberI 1. vul aniEed rubber ?atural rubber 1. ?on sti 0y 1./ti 0y ". 4in0a-e of sulphur ".4inear hain 3. 4ess absorbent of water 3. 1bsorbs water #. Gasily oxidiEed #. 4ess oxidiEed 6. +or0in- temp. !#@ to 1"@ @( 6. +or0in- temp. #@ to 1"@ @( 9. &ou-h and hard 9. /oft J. +hat is ?eoprene rubberI 1."!(hlorobut !1,3!diene J. +hy is ?eoprene rubber non :inflammable I 1. .ue to presen e of hloro -roup . J. +hat is 2io!de-radable polymerI 1. &he polymers whi h an be de-raded by mi robes. e.-. CF2* and ?ylon!" ,?ylon!9. J. Give full form of C*(, C&'G,CF2*I 1. C*(H Coly *inyl (hloride C&'G H Colytetrafluoroethene CF2* H poly!q!hydroxybutyrate! o!q!hydroxy valerate. ?ame of polymer 3onomer stru ture Oses 1ddition polymer Colythene Gthene (F"5(F" (arry ba-s,toys,bu 0ets C&'G(&eflon) &etraflouroetene ('"5('" ?on !sti 0 oo0ware,Ailseals,-as0et Colya rylonitrile 1 ronitrile (F"5(F(? /ubstitute for wool(min0) Colypropene Cropene (F"5(F(F3 ropes,pipes Colystyrene /tyrene (F"5(F(9F6 Insulator,+rappin- material C*( *inyl (hloride (F"5(F(l Pain oats,floorin-,water pipes (&hermo ol) "1D

(ondensation polymer ?ylon 9,9 1dpi 1 id (AAF!((F")#(AAF Cara hute Pope, /o 0s, /to 0in-s Fexamethylene! di : amine % ?F"!((F")9!?F") ?ylon 9 (aprola tum %?F"!((F")6!(AAF) Cara hute Pope, /o 0s, /to 0in-s .a ron Gthylerne Gly ol AF!((F")"AF &erephthali 1 id (AAF!(9F#!(AAF 2lended 'ibers, /o 0s, /to 0in-s 2a0alite 'ormaldehyde F(FA Gle tri swit hes, Fandel of pressure oo0er Chenol (9F6AF 3elamine 'ormaldehyde F(FA Onbrea0able (ro 0ery 3elamine (3?9F9

1 MARK QUESTIONS Q. 1. +&ite an equati!n f!& the 3hemi t&$ in4!l4ed when a d&!p !f h$d&!chl!&ic acid ma/e a h!le in n$l!n t!c/in1 . An . &he (Y (A Y ?F Y) amide bond in nylon -ets hydrolysed.

Q. ". Di%&e a&e !f c&$ talline t&uctu&e. +h$ An . 'ibres have stron- intermole ular for es of attra tion whi h leads to lose pa 0in- of their hains and impart rystalline stru ture. Q. *. +hich a&tificial p!l$me& i p&e ent in %u%%le 1um !& chewin1 1um An . 2ubble -um or hewin- -um ontains syntheti /tyrene!butadiene rubber.

Q. .. Name the p!l$me& u ed f!& ma/in1 medicinal 3ap ule. An . CF2*O( Colyhydroxy butyrate!(A!!hydroxy valerated.

Q. 0. +hich p!l$me& i u ed in ma/in1 elect&ical 1!!d and wh$ An . 2a0elite be ause of its ele tri al insulator property.

Q. 6. I (3#" Q 3# Q 36#0)n a h!m! p!l$me& !& a c!p!l$me&. An . It is a homo polymer and the monomer from whi h it is obtained in styrene ( 9F6 (F 5 (F". Q. 8. +hich c!lli1ati4e p&!pe&t$ i u ed t! dete&mine the m!lecula& ma e !f the p!l$me& An . Asmoti pressure is the olli-ative property used to determine the mole ular masses of polymer. ""@

" MARKS QUESTIONS Q. :. +&ite the name !f m!n!me& and t&uctu&e u ed f!& 1ettin1 the f!ll!win1 p!l$me& BmmA, B53, Tefl!n An . (i) (ii) (iii) C*( Y monomer Y *inyl hloride, (F" 5 (F Y (l &eflen Y monomer Y &etrafluoro ethylene, '"( 5 ('" C331 Y monomer Y 3ethyl metha rylate, (F3 f (F" 5 ( Y (AA(F3

Q. >. Identif$ the m!n!me& in the f!ll!win1 p!l$me& t&uctu&e 2

An .

(i)

FA(F" Y (F"AF ethane!1, "!dial 3elamine

- 2N N NN N
2

and

FAA( Y

Y (AAF

(ii)

2enEene!1, #!di arboxyli a id 'ormaldehyde

2

N-

and

F(FA

Q. 1?. #!w d! d!u%le %!nd in the &u%%e& m!lecule influence thei& t&uctu&e and &eacti4it$ An . .ue to presen e of double bond the rubber mole ule show is! onfi-uration be ause whi h the polymer hains an not ome lose to ea h other and -et boiled but as they have their hindran e problem. &his or-ani solvents et . Q. 11. +h$ a&e the N!. !f 6, 6 and 6 put in the name !f n$l!n;6, 6 and n$l!n;6 An . &he no. of 9, 9 in nylon!9, 9 implies that both the monomers of nylon!9, 9 namely hexamethylene diamine and adipi a id ontain six arbon atom ea h. &he no. of 9 in auses them to have wea0 *ander +aals intra tion between the mole ules onsequently they -et elasti property, solubility in

""1

nylon!9 ontains six arbon atom ea h. &he no. of 9 in nylon!9 indi ates that its monomer (aprole tum has six arbon atom in its mole ule. Q. 1". 3!uld a c!p!l$me& %e f!&med in %!th additi!n and c!nden ati!n p!l$me&i ati!n !& n!t - Explain. 1ns. Ves, thou-h opolymers are mostly addition polymers li0e styr ue butadiene rubber and butyl rubber, the term an be used for ondensation polymers also e-. for example. (i) 1ddition polymerisation of styrene and butadiene form opolymer styrene butadiene rubber. n (F" 5 (F Y (F 5 (F" B n (9F6(F 5 (F" YYYS (9F6 (Y (F" Y (F 5 (F Y (F")n Y (F" Y (F Y)n (ii) 9. n FAA( Y ((F")# Y (AAF B n F"? Y ((F9) Y ?F" YYYZ adipi a id hexamethylene Y n F"A diamien (Y ?F ((F")9 Y ?F Y (A Y ((F")# Y (A Y)n (ondensation polymer be ame thylene diamine and adipi a id form nylon!9,

Q. 1*. A&&an1e the f!ll!win1 p!l$me& in inc&ea in1 !&de& !f thei& m!lecula& f!&ce 2 (a) (%) 1ns. (a) (b) 1ns. n$l!n;6, 6, 9una;S, p!l$thene. n$l!n;6, Ne!p&ene, p!l$4in$l chl!&ide. 2una / , Colythene , ?ylon!9, 9. ?eoprene , Colyvinyl (hloride , ?ylon!9.

Q. 1.. Explain the diffe&ence %etween 9unaQ S and 9una Q N. 2una Y ? is a opolymer of 1, 3!butadiene and a rylo nitrile, 2una Y / is a opolymer of 1, 3!butadiene and styrene. Q. 10. +h$ h!uld we alwa$ u e pu&e t m!n!me& in f&ee &adical mechani m 1ns. 3onomer has to be as pure as possible be ause the presen e of any other mole ule durin- free radi al polymerisation an a t hain initiator or inhibitor whi h will interfere with the normal polymerisation rea tion.

9E<O+ A5ERA7E
?1 Ma&/ Que ti!n J1H +rite the monomer of Colyvinyl hloride. 1nsH *inyl hloride. J"H +rite the polymer of phenol and formaldehyde that is used for ma0in- ombs. 1nsH 2a0elite, (a) Chenol (b) 'ormaldehyde """

J3H +rite the monomer of Glyptal polymer. 1nsH (a) Gthylene -ly ol (b) Chthali a id J#H +hat is /yntheti polymer I Give one example. 1nsH 3an made polymers are alled /yntheti polymers. Colyethene, C*(. J6H +hat is approximate mole ular mass of Colymer I 1nsH It is approximate mole ular mass 1@3!1@8u. J9H +hat are monomers of ?ylon 9.9 1nsH (a) Fexamethylene diamine and adaipi a id. J8H +rite the 3nomers of 2una!s. 1ns. 1, 3 butadine and styrene J$H +hat are arben fibers I Give two examples. 1nsH 1 lon- thread solid posses hi-h tensile stren-th. G-. &errylen and ?ylon. JDH +hat is addition polymeriEation I 1nsH 1 hemi al rea tion in whi h monomer unit is repeated to produ e a mole ule without losin- of mole ule li0e water or ammonia. Gx. Colythene, Colyvinyl hloride J1@H Give one example of ea h for low density polythene and hi-h density polthene. 1nsH 4.C. /queEe bottle and toys F.C. 2u 0ets, dustbin, bottles. ?" Ma&/ Que ti!n J1. .ifferentiate between thermo plasti and thermo settin- Clasti . 1nsH The&m! Bla tic B!l$me& 1. 4iner or sli-htly bran hed lonhan-e mole ules ". Cosses intermediate inter mole ular for e of attra tion. The&m! ettin1 B!l$me& 1. (ross lin0ed or heavy bran hed mole ule ". &his an not be reused 3. Gx. 2a0elite, Orea!'ormal dehyde

3. Gx. Colythene, Colystyrene resins J"H Give two Colymerisation rea tionds for ea h. (a) 1ddition polymers and (b) (ondensation Colymers 1nsH 1ddition Colymers H! n(F"5( (ondensation Colymers n F"?((F")9 ?F" B n FAA(((F") (AAF %?F((F")"?F(A((F")#(A))nBnF"A J3H +hat are elastomers I Give one example. 1nsH &he rubber li0e material whi h are elasti in nature. G-. ?atural rubber. ""3 ( (F" (F")n

J#H +rite the hemi al stru ture of Glyptal 1nsH Gthylene Gly ol!AF(F"(F"AF Chthali a id (AAF

(AAF J6 H .efine (opolymers.Give two examples. 1nsH &he Colymer in whi h repeatin- units are ombined with two or more differents types of monomers G-. Colyster and terrylene(.a ron) J9H +hat is ?eopreneI 3ention any two uses. 1nsH 1 syntheti rubber made by hloroprene. It is a syntheti rubbers. OsesH (onveyor belts in oal mines ] -as0ets. J8H .efine /yntheti rubbers. +hether it is homopolymer or o!polymerI 1nsH 1ny *u lanised rubbers li0e polymers. +hi h is -ettin- stret hed to about twi e len-ths and returns to the ori-inal shape and siEe as the external for e is released. G-. Fomopolymers. J$H Gxplain the differen e between 2una!? and 2una!/. 1nsH 2una!?H! 1. It is obtained by the opolymeriEation of 1,3 : butadiene and a rylonitrile in the presen e of a Ceroxide (atalyst. ". It is resistant to a tion of Cetrol. 3. It is used in ma0in- in oil seals tan0 linin- et 2una!/H! 1. It is obtained by the (opolymerisation of buta diene and styrene. ". It is used for automobile tyres. JDH +hat do you understand by *ul anised PubbersI 1nsH +hen natural rubber is heated with sulpher at 383M to #16M. &he vul aniEed rubber has ex ellent elasti ity with low water absorption tenden y. &he probable stru ture of vul aniEed rubber mole ule as followsR (F3 (F" ( / (F / ""# (F"

(F" J1@H Gxplain the termsH! (a) C.I (b) C331

( (F3

(F

(F"

1nsH C.I H! Colydispersity IndexH &he ratio of the mass avera-e mole ular mass is alled C.I C331H! It is polymer of ethyl methyla rylate. A5ERA7E STU=ENT 5e&$ Sh!&t An we& ?1 Ma&/ J1H +rite the monomer of ColystyreneI 1nsH /tyrene. J"H +rite the stru ture of monomer of ColystyreneI 1nsH 1r (F 5 (F" J3H +rite the monomer of ?eopreneI 1nsH (hloroprene. J#. +rite the name of monomers of 3elamine!'ormaldehyde. 1nsH 3elamine and 'ormaldehyde. J6H +hat is the monomer of Colya rylonitrileI 1nsH 1 rylonitrile J9. +rite the polymer of &etrafluoro ethane. 1nsH &eflon. J8H .efine (opolymersI 1nsH &he polymer is obtained by two or more different monomers. J$H Is ( ?F (FP (A )n is a homopolymer or a opolymerI 1nsH It is a (opolymer. JDH +hy should one always use purest monomer in free radi al polymeriEationI 1nsH &he impurities present in monomer may ombine with free radi al that slow the rate of polymeriEation. J1@H +hat is meant by C&GG I Give its popular name. 1nsH Colytetra fluoroethylene. &eflon. ?" Ma&/ Que ti!n J1H .ifferntiate between addition polymer and ondensation polymer. ""6

1nsH 1ddition Colymer 1. 4ar-e no. of unsaturated monomers ombine to-ether to form polymers G-. Colythene and polystyrene (ondensation Colymer 1. 4ar-e no. of monomers havin- different fun tional -roup with release of small mole ule li0e water ombine to form polymers. G-. ?ylon and &eflon

J"H .istin-uish between thermoplasti and thermo settin- polymers. &hermo plasti polymer 1. &he inter moli uler for es are intermediate. ". there are no ross lin0a-e bond 3. G-. Colythene and polystyrene &hermo settin- plasti 1. &he inter mole ular for e are maximum. ". &hey are ross lin0a-ed. 3. G-. 2a0elite

J3H .istin-uish between Fomopolymers and (opolymers. Fomopolymers 1. &he polymers whi h are form by only one type of monomers G-. &eflon ] C*( (opolymers 1. &he polymers whi h are form by two or more types of monomers .G-. &errylene ] 2una!/

J6H .epi t a free radi al me hanism of addition polymeriEation of isoprene. . P^ B (F" 5 (Y(F 5 (F" tf (F3 Yc P Y (F"Y (Y(F 5 (F" tf (F3 v t t w t (F3 (F" !!!!! ""9 tf (F3 . P Y (F"Y (5(FY (F"

and (5( P YY (F" t &rans 1, # stru ture t (F3 (5( P YY (F" t (is 1, # stru ture J9H +hy are the numbers 9, 9 and 9 put in the name of ?ylon 99 and ?ylon 9I 1nsH ?ylon 99 means that it is formed by two monomers ea h ontainin- six arbon atoms. +hile in ?ylon 9 means that it is formed by a monomer ontainin- six arbon atoms. J8H Gxplain the stru tural differen e between polya rylats and polyesters 1nsH Colya rylate! (F" 5 (YP f (AAP 1nd Colyster : Y (YAY ff A J$H +hat is CF2* I 1nsH It is a poly hydroxyl butyrate. (o!q! hydroxyl *alerate. It is opolymer of 3! hydroxyl butanoi a id and 3! hydroxyl pentanoi a id in whi h monomer units lin0ed by ester lin0a-e. JDH Gxplain the differen e between 2una!? and 2una!/. 1nsH 9una;N2; ""8 (F" !!! F F

1. ".

It is optained by the opolymeriEation of 1,3 : butadiene and a rylonitrile in the presen e of a Ceroxide (xtalyst. It is resistant to a tion of Cetrol. 9una;S2;

3. It is used in ma0in- in oil seals tan0 linin- et 1. It is obtained by the (opolymerisation of buta diene and styrene. ". It is used for automobile tyres. J1@. 1rran-e the followin- Colymers in in reasin- order of inter mole ular for es. (a) ?ylon 99, 2una!/ and Colythene (b) ?ylon 9, ?eoprene and C*( 1nsH (a) 2una!/, Colythene and ?ylon 99. (b) ?eoprene, C*( and ?ylon 9. 9RI7#T STU=ENT 5e&$ Sh!&t An we& Que ti!n2 ?1 Ma&/ J1. +hat does stand for C.I 1nsH Colydispersity Index. J". +rite the name of neoprene polymerI 1nsH (hloroprene J3H +rite the name of rea-ent use for initatin- a free radi al hain rea tion. 1nsH &ertiary 2utyle peroxaide. J#H +hat are arbon fiberI 1nsH 1 lon- thread solid posses hi-h tensile stren-th. G-. &errylen and ?ylon J6H 1 polymer is use for ma0in- ombs, name the polymer. 1ns H 2a0lite J9H 1 polymer is used for ma0in- paints and la quers, name it. 1nsH Glyptal. J8H ?ame the monomer of polyvinyl hloride. 1nsH *inyl loride. J$H 1rran-e in in reasin- order of inter mole ular for es. ?ylon 99, 2una!/ and polyethene. 1nsH ?ylon 99 S polyetheneS 2una!/ J1@. 1rran-e the followin- Colymers in in reasin- order of inter mole ular for es ?ylon 9, ?eoprene and C*( 1ns H ?ylon 9, C*( and. ?eop S#ORT ANS+ER ?" Ma&/ J1H +rite the stru ture of monomer of polystyrene. ""$

1nsH /tyrene. 1rY (F5(F" J"H (lasify the polymers as addition and ondenstation polymers. ?ylon 99, 2una!/, Colythene. 1nsH ?ylon 99 ondensation polymer. 2una!/ and polytheneY1ddition polymer. J3H (lassify the polymers as addition and ondensation polymerY ?ylon 9, ?eoprene and C*(. 1nsH ?ylon 9 Y(ondensation polymer ?eoprene and C*(Y 1ddition polymer. J#H +hat is 2iode-radble polymerI 1nsH &he polymers whi h are 2iode-rable and not auses any environmental population is alled 2iode-rable . G-. CF2* and ?ylon " ?ylon 9. J6. +ho do double bonds in rubber mole ules influen e there stru ture and rea tivity. 1nsH Greater the number of double bound the rubber will be less rea tive be ause of -reater inter mole ular for es of attra tion amon- the monomers. J9H +hat is CF2*I Give its one use. 1nsH It is a poly q hydroxybutyrateY o q hydroxyl valerate . It is obtain by the opolirisation of 3Y hydroxyl butanoi a id and 3Y hydroxy pentanoi a id.It is used in spe iality pa 0a-in- , orthopaedi devi es.

""D

UNIT ;16 3#EMISTRM IN E5ERM=AM <IDE

STU=M MATERIA<
1. ". 3. #. 6. 9. 8. $. &ranquiliEers! they are hemi als whi h are used for treatment of mental diseases .they a t on hi-her enters of entral nervous system. Gxample Gquanil , /e onal ,luminal or 2arbituri a id et . 1ntibioti s! (hemi al substan es whi h are produ ed by mi ro!or-anisms(su h as moulds and ba teria) and are apable of destroyin- other mi ro or-anism are alled antibioti s .Gxample peni illin ,1mpi iline. 2road spe trum 1ntibioti s! 1ntibioti s whi h are effe tive a-ainst several different types of harmful mi ro!or-anisms and thus, apable of urin- several infe tions are alled broad spe trum antibioti s Gxample hloromy etin, &etra y line . 1ntihistamins H! 1ntihistamins are amines whi h are used as dru-s to ontrol the aller-y effe ts produ ed by histamines. Gxample diphenyl hydraEine or promethaEine . 1ntipyriti s H! (hemi al substan es whi h are used to brin- down the body temperature in hi-h fevers are alled antipyreti . Gxample 1spirin, para etamole or 1nal-in et . .isinfe tants H! (hemi al substan es whi h 0ill mi ro :or-anism or stop their -rowth but are harmful to human tissue are alled disinfe tants .example 1.% solution of phenol (")/A" in very low on entration. 1nal-esi sH! hemi al substan e used for relievin- pain are alled anal-esi s . Gxample noval-in, profanes et . 1nta idsH! &hese substan es rea t with hydro hlori a id present in the stoma h neutraliEe it partially. Gxample ma-nesium hydroxide , 1luminum hydroxide et . it an be used as tablet or in aqueous suspension . 1ntifertility dru- &hose dru- whi h ontrol the birth of the hild are alled antifertility dru-s. /teroids are the a tive in-redients of the pill fun tionin- as an antifertility a-ents. some ommonly used pills ontains a ombination of ethynlestradiol and norethindrone. 1nti an er a-ents &hose dru-s whi h are used in treatment of an er are used as anti an er a-ents e.- is!platin. 1ntimi robials .isease in man and animal whi h may be aused by ba teria, virus and other mi ro!or-anisms mi robes. 1ny or-anism that auses diseases is alled a patho-en. 3any body se retions either 0ill the mi robes or inhibit their -rowth. Gxamples are lysoEyme in tears, nasal se retion and saliva, fatty a ids and la ti a id in sweat and seba eous se retions and hydro hlori a id in stoma h. &he ontrol of mi robial diseases an a hieved in three ways by (1)1 dru- whi h 0ills the or-anisms in the body(ba teria) e.- peni illin "3@

D.

1@. 11.

1". 13.

(2a tri idal). (") 1 dru- whi h inhibits or arrests the -rowth of the or-anism (ba teriostati ) (3) In reasin- immunity and resistan e to infe tion of the body. 1ntibioti s are the lass of dru-s used as antimi robials. (hemi als in food H! 3any hemi als are added to food for their preservation and enhan in- their appeal. &hese in lude flavourin- , sweetness, dyes, antioxidants, et . CreservativesY&hose hemi als whi h prevent undesirable han-es in flavour, olour, texture, appetiti appeal durin- a stora-e are alled preservative. &hey delay these han-es and prevent spoila-e of food due to mi rovial -rowth. &he most ommon preservative is sodium benEoate((9F6(AA?a) . (lass 1 preservatives!in ludes table salts, su-ar , ve-etable oil. (lass " preservativeYsodium benEoate ,salts of sorbi a ids and propanoi a id. 1ntioxidants!!! 1ntioxidants are the important lass of ompounds whi h prevent oxidation of food materials. &hese ompounds retard the a tion of oxy-en on the food and thereby help in preservation. &hese a t as sa rifi ial materials i.e. they are more rea tive towards oxy-en than the materials they are prote tin-. Gxample (1) 2utylated hydroxyl anisole (2F1) (") 2utylated hydroxyl toluene (2F&) 1rtifi ial sweetness sweetness are another type of food additives e.- ortho sulphobenEimide (sa harin) is mar0eted as soluble sodium or al ium salt. It is 3@@ times sweeter than ane su-ar. It is lifesaver for diabeti patients and is to ontrol inta0e of alories

1#.

16.

19.

/oapY&hey are sodium or potassium salts of hi-her fatty a ids li0e steri a ids, olei a id and palmiti a id. /oaps are formed by heatin- fat with aqueous sodium hydroxide solution the rea tion is alled saponifi ation. A x (F"!A!(!(18F36 A (F"!AF x f (F!A ! (!(18F36 B3?aAF 5c (F!AFB3(18F36(AA?a A f x (F"!AF /odium stearate (F"!A!(!(18F36 Gly eryl stearate Gly erol 18. .eter-entsH &hey are sodium or potassium salts of sulphoni a ids e.- sodium al0yl benEene sulphonate. &ypes of .eter-entsH! (i) 1nioni deter-entsH! +hen deter-ents bears an anion at the soluble end of the hain, it is alled anioni deter-ents.ex. It is used in toothpastes and house hold wor0.
(F3((F")19(F"AFBF"/A# ! F"A 4auryl al ohol 4auryl hydro-en sulphate /odium lauryl sulphate (1nioni deter-ents) (F3((F")19(F"A/A3F ?aAF(aq) ! B (F3((F")19(F"A/A3 ?a

"31

1$.

1dvanta-e of deter-entsH (a) &hey wor0 well even with hard water. (b) &hey are more effe tive than soaps. ( ) &hey an wor0 well even with a idi water.

1. ". 3. #. 6. 9. 8. $. D.

(d) &hey an wor0 well with woolen -arments. (hemotherapy H &reatment of diseases with the help of suitable dru-s. 1ntipyreti H Pedu e body temperature. G-H 1spirin, 1nal-in. 1nal-esi H Cain Miller. G- H 1spirin, 3orphin, Feroin, 1nal-in. &ranquiliser H .e reases anxiety. G-H 4uminal, /e onal. 1ntibioti H (ure (hloroampheni ol. infe tions. G-H Ceni ilin, &etra y lin,

1ntimalarial H G-H Juinine, (hloroquinine. 1ntifertility .ru- H 2irth ontrol. G-H 1 pill ontainin- estro-en and pro-esterone. Creservatives H (hemi als used for preventin- spoila-e of food materials. G-H /odium 2enEoate. 1rtifi ial sweetenin- a-ent H G-H /a harin, 1spartame (methyl ester).

1@. (ationi .eter-ents H G-H &rimethylstearylammonium hloride. 11. 1nioni .eter-ents H G-H /odiumdode ylsulphate.
"3"

1". ?on!ioni .eter-ents H G-H Centaa rythritolmonostearate.

5,$ Biodegrada" e 6etergents : 6etergents having straight h!drocar"on chain and easi ! decomposed "! microorganisms$ 7g: Sodium aur! su phate4 sodiumdodec! "en8enesu phonate$ Important Juestions H 19. +hat is understood by (hemotharepy. 18. a) b) ) d) e) 1$. a) b) ) d) 1D. a) b) ) d) "@. "1. "". "3. "#. "6. "9. Gxplain the terms with an example H 1ntibioti . &ranquilliEers. 1ntihistamin. 1ntipirati s. .isinfa tant. .es ribe the followin- substan es with one suitable examples H 'ood Creservatives. /weetnin- a-ent. GnEymes. 1ntioxident. Gxplain the followin- terms with one examples H 2iode-radable deter-ents. ?on!biode-radable deter-ents. 1nioni deter-ents. ?on! ioni deter-ents. +hat are anal-esi dru-s. Fow are they lassified and when are they usually re ommended for use. 1spirin dru-s help in preventin- of heart atta 0, explain. .iabeti patient are advised to ta0e artifi ial sweeteners instead of natural sweetener. +hyI +hi h type of deter-ent produ e less foam. +hi h type of deter-ent would you use to formulate toilet leaner and +hyI ?ame the antisepti you will add to soap to ma0e it useful for ontrol of pimples. .is uss two ways in whi h dru-s prevent atta hment of natural substrate on a tive site of enEymes. "33

"8. a) b) ) d) e) f) -) h)

+rite one use of followin-s H Lenta . C(3. Panitidine. Gquanil. ?ovestrol. 3orphin. (hloroamCheni ol. 2ithional.

Fints H 6. 1nal-esi s : Cain Miller (lassifi ation : ?ar oti : 3orphin (to relief post operative pain) ?on ?ar oti : 1spirin, C(3 (to redu e fever , to prevent blood platelets oa-ulation) 9. 1spirin a t as blood thiner and auses no oa-ulation. 8. &he artifi ial sweetners are either non metaboliEed by body or do not produ e arbohydrate li0e -lu ose when metaboliEed. $. ?onioni deter-ents D. (ationi deter-ents 1@. 2ithional 1". Lenta : 1nta id C(3 : 1ntipyreti s, 1nal-esi s Panitidin : 1nta ids Gquanil : &ranquilliEer ?on*estrol : 1ntifertility dru-s 3orphine : 1nal-esi s (hloroamCheni ol : 1ntibioti s 2ithional : 1nti epti s

1 MARK QUESTIONS Q. 1. 7i4e an example !f a chemical u% tance which can act %!th a an anti eptic and di infectant. An . Chenol.

Q. ". +hat i the chemical name !f anti eptic chl!&!x$len!l An . #!(hloro!3, 6!dimethyl phenol.

Q. *. +hich al/al!id i u ed t! c!nt&!l h$pe&ten i!n An . Peserpine. "3#

Q. .. +hich al/al!id i u ed t! t&eat mala&ia An . Juinine.

Q. 0. Identif$ the f!ll!win1 2

#O Q An . Cara etamol.

Q N#3O3#*

Q. 6. +hat i the u e !f the f!ll!win1 c!mp!und 2

)C) C-

C)) -

An .

1nal-esi . 4alue -

Q. 8. +hich a&tificial weetne& ha the l!we t weetne An . 1spartame.

Q. :. +hich a&tificial weetne& ha the hi1he t weetne An . 1litame.

4alue -

Q. >. +hat /ind !f a d&u1 i 3hl!&pheni&amine maleate An . 1nti histamine dru-.

Q. 1?. +hat i the chemical name !f a pi&in An . "!1 etoxy benEoi a id.

Q. 11. Name the anti%acte&ial p&e ent in t!!thpa te. An . &ri losan.

Q. 1". Identif$ the d&u1 2

An .

Ceni illin G. NO" 1&!up attached t! a&!matic nucleu in it

Q. 1*. +hich anti%i!tic c!ntain An . t&uctu&e (hlorampheni ol.

"36

Q. 1.. +hat i the u e !f %a&%itu&ic acid An . &ranquiliEer. Q. 10. Name !ne anal1e ic d&u1 which i al ! u ed t! p&e4ent hea&t attac/ . An . 1spirin. Q. 16. +hat i the applicati!n !f the f!ll!win1 m!lecule in e4e&$da$ life 3#* (3#")11 3#" Q An . It is a deter-ent.

Q SO*INaC

Q. 18. 7i4e an example !f a d&u1 that i antip$&etic a well a anal1e ic. An . Cara etamol. Q. 1:. Out !f m!&phine, N;Acet$l;pa&a;amin!phen!l, =ia'epam and tet&ah$d&!caten!l, An . which can %e u ed a anal1e ic with!ut cau in1 addicti!n ?!1 etyl!para!aminophenol. weet a u&c&! e.

Q. 1>. Name a u1a& u% titute which i 16? time a An . 1spartame. " MARKS QUESTIONS

Q. 1. +hen a mixtu&e !f alic$lic acid, acetic anh$d&ide and acetic acid i &efluxed, An . what i the p&!duct !%tained and what i it u e in e4e&$da$ life 1spirin used as anal-esi .

Q. ". =i tin1ui h %etween a na&&!w pect&um and %&!ad pect&um anti%i!tic. An . 1 narrow spe trum antibioti wor0s a-ainst a limited ran-e of mi robes whereas a broad spe trum antibioti wor0s a-ainst a lar-e variety of mi robes. Q. *. +hat i Sal4a& !n - T! which cla An . it u ed 1ntimi robial a-ent. Osed for the treatment of /&. alled /yphilis. Q. .. #!w d!e api&in act a an anal1e ic An . It inhibits the synthesis of prosta-landins whi h stimulates inflammation of the tissue and ause pain. Q. 0. +hat a&e %a&%itu&ate - T! which cla !f d&u1 d! the$ %el!n1 An . 6, 6!derivatives of barbituri a id are alled barbiturates. &hey belon- to the lass of tranquiliEers. &hey also a t as sleep produ in- a-ents. G-. 4uminal, *eronal. Q. 6. +hat i tinctu&e i!dine - +hat i it u e An . 1l oholi /olution of I". Osed as an antisepti . "39 !f d&u1 d!e it %el!n1 - D!& what di tance i

Q. 8. T! what cla it %e u ed An .

!f medicine d!e chl!&amphe&ic!l %el!n1 - D!& what di ea e can

2road spe trum antibioti Osed to ure typhoid, dysentry, a ute fever.

Q. :. Bic/ the !dd !ne am!n1 t the f!ll!win1 !n the %a i !f thei& medicinal p&!pe&tie menti!nin1 the &ea !n. (i) (ii) An . (i) (ii) <uminal, ec!nal, phenacetin, equanil 3hl!&!x$len!l, phen!l, chl!&amphe&ical, %ithi!nal Chena etin is an antipyreti while all the rest are tranquilisers. (hlorampheri al is an antibioti while all the remainin- are antisepti s.

Q. >. +h$ i %ithi!nal added t! !ap An . 1 ts as an antisepti and redu es the odours produ ed by ba terial de omposition of or-ani matter on the s0in. Q. 1?. +h$ a&e cimetidine !& &anitidine %ette& antacid than !dium %ica&%!nate !& ma1ne ium !& aluminium h$d&!xide An . If ex ess of ?aF(A3 or 3- (AF)" or 1l (AF)3 is used, it ma0es the stoma h al0aline and thus tri--ers the release of even more F(l. In ontrast, imetidine or ranitidine prevent the intera tion of histamine with the re eptor ells in the stoma h wall and thus release lesser amount of F(l. Q. 11. +h$ i the u e !f a pa&tame limited t! c!ld f!!d and d&in/ An . It de omposes at ba0in- or oo0in- temperatures and hen e an be used only in old foods and drin0s. Q. 1". +hat p&!%lem a&i e in u in1 alitane a a&tificial weetene& An . It is a hi-h poten y artifi ial sweetener. &herefore it is diffi ult to ontrol the sweetness of the food to whi h it is added. Q. 1*. +hat i the pu&p! e !f addin1 anti!xidant t! f!!d - 7i4e tw! example !f anti!xidant . An . &hey are added to prevent oxidation of fats and oils present in food thus preventinfood from be omin- ran id. G-. 2F1 (2utylated hydroxy anisole) 2F& (2utylated hydroxy toluene)

DOR 9E<O+ A5ERA7E ?1 Ma&/ Que ti!n

1. ". 3. #. .efine the term hemotherapy .efine the term &ranquiliEers and -ive one example. .efine the term 1nti Axidants and -ive one example. ?ame a food preservative whi h is most ommonly used by food produ ts. "38

6. 9. 8. $. D. 1@. 11. 1". 13. 1#. 16. 19. 18. 1$. 1D. "@.

4ist two maNor lasses of antibioti s and -ive one example of ea h lass. +hy is bithional added to the toilet soapI Give an example of a nar oti whi h is used as an anal-esi . .efine antisepti and -ive one example. ?ame one medi al ompound ea h that is used to treat (1) hypertension (") -eneral body pain. +hat is fun tion of wide spe trum antibioti s and -ive one example. Fow are antisepti different from disinfe tantI Give one example of ea h of them. /oap is a wea0 antisepti itself. +hat may be added to soap to improve its antisepti a tionI +hat type of dru- is hlorampheni olI +hy ethanol is added to soapI ?ame the medi ine whi h an a t as anal-esi as well as antipyreti . Give its hemi al name. Give one example of ba teri idal antibioti and ba teriostati antibioti . +hy is use of aspartame limited to old foods and drin0s +hat type of dru- is Chena etinI Fow are syntheti deter-ents better than soapsI +hat is tin ture of IodineI

DOR 9E<O+ A5ERA7E STU=ENTS

11.
1". 13. 1#. 16. 19. 18. 1$. 1D. 11@. 111. 11". 113. 11#. 116. 118. 11$.

&he bran h of s ien e whi h deals with the treatment of diseases usin- suitable hemi als is 0nown as hemotherapy.
&hey are hemi als whi h are used for treatment of mental diseases. Gxample : Gquanil. 1ntioxidants are the ompounds whi h prevent oxidation of food materials. Gxamples, 2F1 (2utylated hydroxy anisol) and 2F&( 2utylated hydroxy toluene. (lass I! preservatives : &able salt, su-ar and ve-etable oil. (lass II : preservatives : /odium benEoate (a) /imple antibioti s! Cen iline, 1mpi iline (b) 2road spe trum antibioti s : (hloromy etin. 2ithional is added to soaps to impart them antisepti properties. /u h soaps are used to redu e odor due to ba terial a tion on s0in surfa e. 3orphine or heroin. &hey are hemi als whi h 0ill or prevent the -rowth of mi roor-anisms. &hey are applied to livin- tissues. Gxample! M3nA# /olution, @." % solution of phenol et . (i) Gquanil (ii) ?oval-in 1ntibioti s whi h are effe tive a-ainst several different types of harmful mi ro or-anisms and apable of urin- several infe tions are alled broad spe trum antibioti s. Gxample! (hloromy etin, tetra y line. 1ntisepti is used in livin- tissue where as disinfe tants are used in nonlivin- thin-s. Gxample of 1nti epti ! &in ture of iodine ( "!3 % iodine in al ohol : water solution) and iodoform a t as antisepti . Gxample of disinfe tants : "% solution of phenols. 2ithional. 2road spe trum antibioti s. &o ma0e transparent the soap. 1spirin. It is unstable at oo0in- temperature. 1ntipyreti s. "3$

119. Afloxa in and hlorampheni ol respe tively.

11D. 1"@.

2road spe trum antibioti s. "!3% Iodine in ethanol is alled tin ture of iodne.

DOR A5ERA7E
?1 Ma&/ Que ti!n
1. ". 3. #. 6. 9. 8. $. D. 1@. +hat are main onstituents of .ettolI +hat are food preservativesI ?ame the sweetenin- a-ent used in the preparation of sweet for a diabeti patient. +hy do soaps not wor0 in hard waterI If water ontains dissolve al ium hydro-en arbonate, out of soaps and syntheti deter-ents whi h one will you use for leansin- lothsI +hy should not medi ine be ta0en without onsultin- do torsI ?ame two nar oti s whi h are used as anal-esi sI +hat is an antipyreti s I Give an example. +hat are anta-onists and a-onists I Ci 0 out the odd amon-st the followin- ompounds on the basis of there medi inal properties. 4uminal, /e onal, Chena etin, Gquanil.

DOR A9O5E A5ERA7E

?1 Ma&/ Que ti!n
1. ". 3. #. 6. 9. +rite the hemi al formula of (i) /odium stearate (ii) /odium palmitate +rite hemi al equation of soaponifi ation. +hat is biode-radable deter-entsI +rite hemi al formula of (i) /odium dode yl benEene sulphonate and (ii) /odium lauryl sulphate. +hat are patho-ens I +hat is the hemi al formula of ataioni deter-ents I

DOR 9E<O+ A5ERA7E

?" Ma&/ Que ti!n
1. ". 3. #. 6. 9. 8. $. D. 3ention one important use of ea h of the followin(i) Gquanil (ii) su ralose ?ame a broad spe trum antibioti s and state two diseases for whi h it is pres ribed. /tate the fun tion alon- with one example ea h of (i) 1ntihistamines (ii) 1ntioxidents. .es ribe the followin- with an example. (i) 1ntimi robials (ii) 1nal-esi s ?ame the medi ines used for the treatment of the followin- diseases (i) &uber ulosis (ii) &yphoid .es ribe the followin- with example. (i) Creservatives (ii) 2iode-radable deter-ents .es ribe the followin- with -ivin- examples (i) Gdible olours (ii) 1ntifertility dru-s .efine the followin-s and -ive one examples. (i) 1ntipyrites (ii) 1ntibioti s Give one important use of ea h of the followin- H (i) 2ithional (ii) (hlorampheni ol (iii) /treptomy ine (iv) Cara etamol "3D

DOR A5ERA7E
?" Ma&/ Que ti!n
1. ". 3. #. 6. +hy do we require artifi ial sweetenin- a-entsI +hi h pro ess is involved in holdin- the dru-s to the a tive site of enEymesI +hat are different types of syntheti deter-ents I Gxplain with sutable Gxamples. Fow are syntheti deter-ents better than soapI .es ribe the leansin- a tion of deter-ents.

DOR A9O5E A5ERA7E

?" Ma&/ Que ti!n
1. ". 3. #. 6. +hat are biode-radable and non biode-radable deter-entsI Gxplain the followin- terms with suitable examples. (a) (ationi deter-ents (b) anioni deter-ents. +hy are deter-ents usually preferred to soap for washin- lothsI +hy biode-radable deter-ents are more prefer now a days. .efine the followin- terms with suitable examples. (i) 1nta ids (ii) 1ntihistamines (iii) 1ntibioti s (v) 'oodpreservatives. (iv) 1ntifertility dru-s

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