••

ll
I\ It T r \ 0f) \ - \- c. )_\' Rt-')'-, l_,' j ~ T1-\. L
I
- ,) ~ -\
.,
\ \, \ 1
- I
I l

(i_ 1'.J,- ~1 ~ IK 8 , l 0 I~ C ;- 1--\ ~S:• l U \ I CJ f\} _ rclo \,;\,1--sj ' ( f\ ~ , :..o\ .r" ,, '•'I- .......
I) ~
,, l
j
1J ,1

r f\,-, ~ s ol :c\1,•.,-J '""' '!t1-

f"\ ,.J_~,, o: ~Cl u+ ~•'x loo IJ
f"'I O \ ,.-J _; \:\ LM) :. ~o l u~ ; 1; 1:';J ,._ \u 111
Mo.ts d - ~olu~ lYI{_.,,.;\
II
M~ ., of Sol v-b :x. IO 1.J I'""\ ,)\t'I r- u\ C. l ' '"'-~-,!.;. 0 f ".,,
0
J \ -

M~,; or 'i.ofu\-t' + Mo..\s oC So\LO.,J

Mc:-4<:, of ~ol\)-\ ~{•...J' ~ l Ow
v~1,,,_'-'- of- ':,o\.,\-io" )( t er.s1~ ot ~cl

\Jo\u,""--0 a~ S.o I\l-\-e. " \() o

.t,
vl.)1,_h'--u, 0 ~ .So l\J~D"' f~ : '!' Sc.I ,,11 =
\J'oolv~o,, (;~ L'\
"/ G.,Yv :: /w\0tcl.b~ 0~ ~olu~(" ~M) ;<. lou
n \Jo 10~,,i, o~ &o Iv ~<:>ri(,·" "'1 Q
) I

,, ~\J )
0
S,\~'0•3 \--h o.r (OV1c_l(y"'l\ru1ov-1

C -:: ""~ ~·,,)o t- scl v½. ;" 1 "(YI

L~""'/L,) ' f.
I
M,v, = 1'~1.. \J 2.. '

\h luMD o ~ ~Ok)"h..01"'1 L
M ~ Vs :.. f"\ fl l
i11
("V ..1 , (~ \J "I.. 1 \J I i.. \J 1 -\ \) l)
-:: MD-.,!,iwb .t <;o(\Jh ;" ?{" x /uuo "
\JL, lu Y'"\.:i 0 \- f:.olu~-.i" ;,,., "'{_
t' '°'r r H- > i---""' f..l\ \' _\ \.-,-\ ' r, J

.~ t ,o~ ( vr,<VIJ:
_ \ _ -:: . fo lvf-->r - ~ !;olvte.__
0 ) ?a.l) \-s. ~o 1
f""\o\,Jj ~ M:,\o)l+-;j IOO 0 I

~PM -::. MQ.t,fpf <:a lute x. \ O(., v~\·,\,L\'\ 1..___-h.~_.J v'1 a.J -1 -,,..._
/
Mrt,>;, cJ,~of <; o /0t , 011 '
fv\ -:: Xsoi..n. -,.__ \oa a x. f so,.,.:..-,,.,. \;
x~,vw M!,0\--.. + y iol ...t¼-;, - f'ri ~-;,..,_h

(~x) Nu~~ rv\~~ (N j ·

14..p .. Y (I -=- L N, ('o . of ~°1s"vv"'"I :½tu.i u~~;,.,lJ of' S ")I u~
\/o 1uf'-'I., of Sc.\uh0"1
(Y la lu.frt?3 G) :
() Solu ½

W scLil::,
Vsc1..,'t,"o, ,

~ - - n~ =
~
~~ x. Me 8:: S c. k_,\p
f'\A M e" l,.') (')
X" ~ : So\v.:.r.t
1 ~
M -- 1<.g,.,..\ O -- V0'.!. X, \ () (v, ,,.. 0,'6°1);Y\_~)
Xp X {V\~ fvle A L,)-1)
 Solut ions (Gen 377
I
era 1and Colllgative Properties)
ill, ol l'l.pn•"i" I! lhl' co11 n •11t rutlo 11 uf H ,01 I'
.. \ Id III II IOn :
Some of tl11: mcthocb ,ire given in the tabk·

Symbol Formula
Dennltlon Effect of temperature
0
o ( JI'. 11) Ma~~L>f ,ulutc
X I()() No effect
M ,I\, ul , olu11011 Number of parls by ma,s of , olutc per hun-
died flJm o f the ,olut1on
(_jr;\11\ pl•r htrl" gL M ,i" nl ~olutc 111 gr,1111,
J\moun1 of the ~olutl· 111 gram, prc,cnl rn Chungc~ v. 1th change
Ynlumc o l \olut1on in litre,
one lure <•t ,olut1on o f temperature
ppm I\ la" ol ,nlu1c
p.,rt, per m1llwn X 10''
M,1" ol , olution Numbn 0f pJn~ by ma,~ o f ~,,lute per Io' No clkt l
pJrh of solu1111n
\,f
,. ~lt)I Jn l )'
Nur11h.:r of moll:~ ul ,olutc
Number of lu re~ o f ,ulutmn
"lumber uf mules of ,olulc per l11rc ol , o lu- Ch,lngc, \\ 1th change
lrnn of 1empcraturt
/ II Number ol mole, of ,olutc
~-MolJhty Number of k1lu!!r,11m ol thi· ,ohcnt
Number ol rnnk, of solute prr,cnt rn 1 kg
,,rthe ,,,I\ cnt
"1l> d k l 1

.V Number ot gmm e4lll\alc11ts of , olutc

~-Normaht) Number uf litrr, ol , ~ 100- -
Number uf i:r.im cqu1\·alcnL, c,f the "'luk
prc,cnt 1n one l11rr 11f 1hc ,olut111n
( h,rn~e, with change
o f 1empi:r.1turc

, \hilc trn.:t1,1n ,\' II ◄

RJllo o f numhcr of mules of 11nc u,rnp<•m:nl Nn cllc:U
II I + II II
111 the 101.11 n11rnner 111 mr,lc, <11 ~olntmn
F N11111'1c:r of fnnu11IJ ma"
~
hmnali1y N11n1bcr of f11rmul.1 ma" rn KJ.1m, prl·,cnt Ch.,ngc:~ \\ 1th change
N11mhc:r ,if liin:~ of , 0!11111111 pc, ht1 c: ,,t ,olut1on 111 temper Jturc

/1. R.ioul! \l1rn : The partial pn:s,url' ol any , olatilc

,,,ns ·ruent
ll of a ,oluti,m
· at a l:lll\stanl temperature
. . 1s equal to the: pn:~~urc ( P o -
fl u
11
-J 1, c..ilkJ rclatl\oC lowcrmg 111 \ :.ipour
iJJ)l.lUr pn:ssurc of pure: const_,tucnt mult1pl1e<l by mole fraction
pTC!,~Uf\: .
ofthJl constituent m the sol1111011
. . o f I I x p II = X ◄ x p 0◄ The rclattVl: lowcr1ng ,n \ Jpour prc" urc o l :.i <;olut1on
p 4 = moIe lrar..:11on 1
contammg non-, ola11k -.olutc 1, c4ual 10 the mole fra1.: 11on orthe
In ,be c,1se of binary solution of two \'Olatik liquids, the total solute present in the ,oluuon Th,.-, ,., Ranult·-; law
,Jrour pressure of such solution c:an be given as· Mathema1tcal ly,
Total l'apour pres~urc o l. ,o Iut1011
. = p 0◄ x , V1 .◄ + p (I x "V
8 8 Pn - P n
= 'I;' """le = - - v
= p4+fJ R Pn n+
~tole frJction of component A in \'apour phase. Let \\ g of the !>Olute ( rnol rnJ"- = m) be dis~oh cJ in W g o r
(I X
solvent (molecular ma~-,= \I ).
I e., y =!!...:i.= PA A
◄ (J O \/ Po -P , _ \\·I m
P p4X,1+ Pa"H
Po 11 m + Ii \I
pi X 11
similarly, Y11 = o o, If thc ~otut1on 1s \ cry d1lute ,,· m in denominator can be
PA x,, + P11 ,\ 8 neglected
i . Colligative propertir,: The properties of dilute Po -P , w'm \\ ,\I 6p I I' ◄ f1I R
- - - = -- - = - - or =
solutions containing non-volatile solutes. wh ,ch depend upon the Po W .\ I m lr Po
nwnber of solute particles in solution are called CC\lhgative 9, ~ ll', 1tion nf ho1 ling point·The boiling point of a
properties. These properties do not depend upon the nature of
solution containing non-,·olatik solute 1s al\\ a:, s hi gher than the
1olutes and solvents. The four colli gatiYe properties are:
boiling pomt of a pun~ soh ent. The increase m bo1!tng pomt 1s
(1) Relative lowering m \'apour pressure trnned ele\ at ion and repre~entcd as uT1
(11 ) Ek vation in the boi ling point
~T,. oc Molalit~ of the ,;,,lutirm
1111) Depression in the free7ing point
(i,) Osmot1c pressure. or ~ T" = 111 x K ,. (K ,, 1, a nwlal ck, at ion c:onsLant)
All these properties are dependent on the concentration of I 000 x K ,. x iv I 000 x K ,. x \\ ~
~ 1lutes m solution.
~ T,. = ------ 0r e1T,. = - -- - - --
11 X III 11
8
X m
1
8. Relathe IO\Hrini,: 111 , ,1po 11 r p1-r~,urt : \\'hen a
non-,olatile solute i., dis'iolvcd in J solvent. it:- vapour where, 11· = ma~, of !solute: 111 = m,1kcul.1r ma,, 0f ._,,lute: .
prc~sure decrea-.es. ( p 11 - p , I i~ knm"n a, lowcnng tn \'apour II' = ma,, of snlvcnt

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I
378 . f compet itions
G. R.B. Physical Chemistry or
-monc pressure 1:. tcnn..:d hypotooic ,..,._1
K 1, ts equal h> -RT 2 IO\\er 0 ) . ...,u the
L 111."hcr osmotic pressure 1s termed h1mert So"'11,.
having e- Jt' on1c "'VQ
IOUO/. The I\\O sulu11ons h~ving equal o:-rn?t1c ~rcssurcs ar1: / oluU(in
where r -
· o-
bo1I
tng point of s11h ent m ab~ulute ~c:ik. ,soton1c Co
nditt0n tor 1,otonic solutions 1s e~ ~
II I IV 2
L = latent heat of VJponLJti0n -- =--
The units or K. t, are K kg 11101 I
1
ti. lh prt ,,i1111 in rrel'Jinl! point : The freezing po111t of a A 0_9 111 0 c;olution of pure NaCl ,~ 1c;oton1c with hulllln
solution containing 1101H ola11k :.olute is ,1lways b s than the celb (R.UC) An NaCl .solu11on \\tlh concentration '11~
1
freezmg Pulllt of a pure Sl1lvc n1. The decrease 1n freen ng point 15
tr nn~-1
1.:,
d
rpre:-sion and rcpn:,entcd as ..'iT 0_91 ~0 is callcJ hypotoml.' and RBC will swell and burst 1~
1 ,oluuon. An NaCl solut10n v. 1th concentration b'Teaier II tbt
..\T r °" molahty or the , lllut1on 0.9 I% ,s callrd hypertontc a_nd RBC w1~I shrink in this Solu~
r .. \\ ill unJcrgo plasmol~•s1s or crcnat1on. ~
(1T
..\Tr = 111 >< A. r ( K1 " amolal deprc:,~1011 rnnstant) 1

~ \en ' t ll off f:.irtor: When the solute

I-·
• I 000 x ,; , x 11• t ooo x K x 11• 1 • unrt.....
or I
j, 7 J = - - -- - - ur ~T = - - - - - - <l1~-Sociation or association in solution, the number of -•~Oti
II' x III I \\ 8 X Ill I . , • • • Pillttcici
n mcrea!.cs nr dt:crcascs and thus. the c .
111 \U lutlo . 0 11 l&ili

"here, 11 = m~s L't ~olute; 111 = molecular ma,s of solute; roperty changes accordingly. In 1886, van 't Hoff lntrod Ve
P
he tor •1 • known a~ \ an .t II oIT 1·actor to express the ex lleeda
II' = ma,~ of ~oh cn1 ' ' . ten, or
<l,~,oc iation or assoc1atJOn of the solute 111 solution.
K , 1s equal to __
RTo_
1
van· t Hoff f.ictor. 1
IOOOL Ob,crvcJ colligative propcr1y
where. T0 = l~e,.ing point of ,olvem 111 at.."1lu1e ~l·alc: = Thcun.:ucal or normal coll1gative pro~r1}
L = latent heat of lus1on No. ol par1iclc~ after dbsociat1on or a~,ociation
The units of KI arc K kg mot 1 = No. of particles when there i, no di%ociation or assoc-;;;
11 . Chmu~i, and o,mot1c 1m·,~11rc: \\'hen a solution 1s Normal molecular ma\, of the ~olute
separated from the pure solvent wnh the help of a semipermeable = Ob,cn·cd molecular ma,, of the ~olutc
membrane. the solvent molecules from the pure solvent move
towards the solution. The mo\'ement of soh ent molecules from f rom the value or ' , · 1t is pos,1ble to detennine the dcgret of
low concentration to higher concentration through dissociation or assoc1auon.
scm1penneable membrane is tenned as osmosis. In case of dissoc1at10n •i' i~ grcater than I.
As a result of osmosis. a pressure is developed which is
1+(11- l) a
termed as osmotic pressure. i.e.. the hydrostatic pressure 1 =
which de,·elops on account of osmosis is called osmouc pressure. I

It is equal to Ji · d · g. It is also found that if an equal and opposite where. 11 is the number of particles per molei:ule and a is the
force is applied on the solution, the osmm,1s stops. Thus. the degree of dissoc1at1on.
excess pn:s:.ure that must be applied on the ~olut1on as to pre,·ent I - I
osmosis 1s also the measure of osmotic pressure. or 0 . = --
(11 - I)
Osmotic pressure of a dilute solution i~ given by , an 't Hoff
equation. P =CRT. where C = concentration, R = ~olullon Similarly, in ca~c of assoc1at1011. · i · i:. les~ than I .
conc;tant and T = absolute temperature.
C=.!!_ =_11_,_ 1+ (f- 1) a
V mxV i= - - -- -
where. 11• = ma,s of ~olute m gram~
where, 11 is the number or mok cuk ~ \\'lm:h arc associated to fonn
1' = volume of solution in litre,
one giant molecule and a is the degree or a)sociat1on
m = molel.'ular mas~ of ,olute
I - I
II' or fl. = - - -
i e., P= - - · RT
Ill X V
(~- 1)
II ,
Best method ror the detennmation of osmotic pre~sure 1s
Berkeley and Hartley's method. Molecular mas,cs of elel:trolytes ob~crvcd by the m~thod1
The terms hypertonic and hypotonic are applied to compare based on colligative propertic) arc always less than normal
the osmotic pressure~ of two solutions. The solution having molecular masses.

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 ol 11\lllOt ir
Solutions (General
pn \\llrl' f'ru111 I .
fl\\ Hin~ of
and Colligative Properties)

17• T1o a\
. d tor• in rhc
379
-
01d the frci:,mg of waler ,n a car rJ IJ
f'o - p - nm a i.u~-uro 11 earbcr, ethylene glycol 1s added 10 lo wer lhl' freezing
- Pi, - --
Rdr Jl01nt of 1-1 nter
IX. Freezing point,~ same as melting poml. Hence, ,n~read of
_ vapour prc!-~urc of pure ,olvcnt
dcprc~~1on in frcc✓.ing po int , dcprcsswn rn mcl11ng point can be
~~· f11 : vap<>ur prrs,ure of :-olution dctcm11ncd. For th,~ purpose camphor I!> usc:d a~ solvent bccau~c
P - ,m,1tic pn'ssurc
It:: 0 - ' 1 h.ts high molal dcprcs~Hln con~Lalll, , t' . 40 I< m _,
- molecular ma,~ of ,oln.·nt
m;; (kn,it) of ,olu11on in gmL
1 l'I lhfJl11111 , hip ht IIHl'O diffr,rnl c 11fl l,:11IIH rru plrlll , :
(H O~moc,c prcs~urc 11 and boiling pornr d c:\'al1on oTh
R == fJ~ cons1an1 maim ml / deg / rnnl, 1 c., 82 . 1
dRT
uf \ .1~111ur prn,u n · "It h ln11pl
• (1111 1t =J.T x - - -
1'- \JrfJ' 'nin l'11u,11ion) n1 11rr(· h IOOOK ~
\ (IJPl'.
{f•P'
111
( p~ ) _ Mf I l r l (II) O~rnutu.. prc\surc n and frcczrng porn! dcprc!>SHlO ~ T f
log,o Pi /- 2.303R p:;- - r 2 j n = or
t!R f
x- - -
1 IOOOK 1
P, :: I ap<>Uf prcs~ure al r,
( tll) £:lcq1t10n 111 boilrng po101 llnd rda l1\ c lo~ cnng o f
~/l(!t- p.' == 1 apaur pressure a, ~2 vupour pre\\urc.
)II :: latent hc<1! of vaponLat,on per ~olc
lion uf u1pour prl'\\ltrl' of u liquid ,,, 11t nl a:\rh - IOOOK h )( -
.11' m 4
= molar ma.~s of solvent
I~ \ ,r11l 1'11111 1
,iul'\':
"'"
In·> Dcpre,;~1on in fre,Ling point and rclati, c lowering of
p v, (p p) vapour prc.,surc.
Jogio ( Pi - 2.303RT
1] -
2 - 1
IOOOK I uP
:: , apour pres~ure al external pressure p 1 or, = - - - - x -
Jhlft· Pi mA Po
_ rapour pres~ure at external pressure P, 211· Hygroscopic and deliquescent substanc.cs both absorb
p, - -
= molar volume of liquid. moisture from the air The fonner do not change their ~,acc. e. g ,
11
\fofecular masses of polymers are best detenmncd by glycerol, whereas the lauer d1ssoh e mco 1L, e.g .. NaOH. They
Jo..
ric pressure method because other colhgative
· properties absorb moisture because the I apour pressure of their sarurated
-~ 1011 ralue that they cannot be measured accurately. solution 1s less than lhac of v. ater, apours present m surro undings
fl'• so at that temperature.
The ~ubstances like 1\.i 2 CO 1 IOH 20 wh,cb lose their v. awr of
Cf)Stalhsattonare called efflorescent.

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