Solution Chemistry OPTandon

322 , A.B.
PHYSICAL CHEMISTRY FOR COMPETITIONS
149.24 Example 15. Reaction,

No. of moles of H 2 S04
98 2.Br- (aq) + Cl z (aq) ---? 2Cl(aq) + Br2 (aq)
Total mass of water in solution =(85.26 + 48.30) is used for commercial preparation of bromine from its salts.
= 133.56 g
133.56 kg Suppose we' have. 50 mL of a 0.06 M solution of NaBr. What
1000 volume of a 0.05 M solution of Clz is needed to react completely
with the Br-? '
· No. of moles of Hz SO 4 149.24 1000
II
MoaIty= =--x-- Solution: 2Br- (aq) + Clz(aq) ---? 2Cl-(aq) + Br2 (aq)
Mass of water in kg 98, 133.56
M1V1 (Br- ) = M 2Vz (C1 2 )
=11.4 m
Example 12. The moleft-action ofCH3 0H in an aqueous
nl nz
solution is 0. 02 and its density is 0. 994 g cm-3. Determine' its where, nl and n 2 are corresponding coefficients.
- 0.06 x 50 = 0.05 X Vz
molarity and molality.
Solution: Let x mole of CH3 0H and y mole of water be 2 1
present in solution.
Example 16. Calculate the molarity, molality and mole
Mole fraction of CH3 OH =_x_ = 0.02
, x+ y fraction of ethyl alcohol in a solution of total volume 95 mL
. y x 1 prepared by adding 50 mL ofethyl alcohol (density = 0.789 mel)
So, - = 49 or - = to 50 mL water (density = 1.00 g m/:,-l ).
,x y 49
. x - 1000 Solution:
Molahty = - - x 1000= - - = 1.13 m Vol. x density
18xy 18x49 No. of moles of ethyl alcohol = - - - - -
. Total mass Mol. mass
Volume of solutIOn = mL
density = 50x 0.789 = 0.8576
- 46
32x+18y
' I'ltre=------~
32x+ ll'tre
0.994 x 1000 994' Vol. x density 50 x I
No. of moles of water =------ =
Mol. mass 18
Molarity --x--x994
32x+ 18y =2.7777
\
994 · ' No. of moles 1000
__9_94_ _ = 1.0875 M MoIartty = x
32+ 18xyl x 32+18x49 VoL of sol. in mL
, ,Example 13. Calculate the concentration of NaOH 0.8576 x 1000 = 9.0~~ 1f
solution in g/mL, whic:i has the same normality as that of a 95
solution ofHCI of concentration 0.04 g/mL. .
Molality = No. of moles of .ute x 1000
Solution: N Ws x 1000 0.04 x 1000 = 1.095 Mass of solvent "ams
HC1
Es xV 36.5x 1
== 0.8576 xIOOO= 52m
NNaOH ""N Rcl 50
1.095 = ws x 1000 · ==
MoI e f ractIOn 0.8576 0.8576 0236'
== - - = .
40x I 0.8576+ 2.7777 3.6353
Ws 0.0438g/mL
5.5' SOLUTIONS- OF GASES IN LIQUIDS
"Example 14. How many Na+ ions are present in 50mL of , (Solubility of Gases)
a 0. 5 M solution ofNaCl?
, MV All gases are soluble in water as well as in other liquids to a
Solution: Number of moles ofNaCI = - - greater or lesser extent. Solutions of gases in water play an
1000
important role in our daily life. The common examples are
0.5 x 50 = 0.025 carbo rated beverages, i.e., soft drinks, household cleaners
1000 containing aqueous solutions of ammonia, formalin-an aqueous
NaCI---? Na + + Cl- solution of , formaldehyde, etc. The natural waters contain
Number of moles of Na + = Number of moles of NaCI dissolved; 02 which is vital for the existence of aquatic life in sea,
! 0.025 ' . rivers and lakes.
The solubility of a gas in a liqui4 is expressed in terms of
'Number of ions of Na + 0.025 x 6.023 X 10 23
absorption coefficient. It is defined as the volume of the gas in
1.505 X 10 z2 mL that can be dissolved by 1 mL of a liquid solvent at the
SOLUTIONS 323
temperature of the experiment at one atmospheric pressure. The (y == rnx) passing through origin. Fig. 5.2 shows the variation of
volume of the gas is measured at STP. Thus, if v is the volume of solubility of some gases against equilibrium pressure. The
the gas dissolved, reduced to STP, V is the volume of the solvent straight line graphs show the validity of Henry's law.
and P is pressure of the gas in atmospheres, then the absorption
coefficient, a, Is given by . Slope of the line
'tan 0': K
v
i tan 01 = K(for N2)
VP
The following factors affect the solubilities of gases in liquids: .
(i) Nature ofthe gas and solvent: Generally, the gases which
can be easily liquefied are more soluble in common solvents. For·
yN'
.' ,,~.. ~\ 61 ~
tan 02 : K(for 02)
example, CO 2 is more soluble in water than oxygen or hydrogen. I;""" I •
The gases which react with the solvent posses higher solubility.
Pressure of gas ~
For example, HCI and NH3 are highly soluble in water. overtiquid .
Oxygen, nitrogen and carbon dioxide are much more soluble
Fig. 5.2 Variation of solubility of a gas with pressure
in ethyl alcohol than in' water. at the same temperature and
pressure. If solubility of the gas is known at one particular pressure.,
(ii) Temperature: The solubility of most of the gases'in then it can be calculated at other pressures using the followin!t
liquids decreases with increase of temperature as the dissolution relation,
is an exothermic process. When water is heated in a beaker, ~==PI ... (ii)
bubbles of air are formed on the sides of the glass before the m2 P2
water boils. As the temperature rises, the dissolved air molecules
begin to ."boil out" of the solution long before the water itself . where 'mI' is the solubility of the gas at pressure 'PI' and 'm2' is
boils. the solubility of the gas at pressure 'P2 '.· .
When a mixture of two or more non-reacting gases is brought
t in contact with a solvent, each constituent gas dissolves in
~0.003 proportion to its own partial pressure. Henry's law can be applied
is to each individual gas independent of the presence of other gas. If
gO.002
we use the mole fraction oftne gas in the solution as a measure of
a its solubility, then the law can be stated as, "molefraction of the
il 0.001
:l
'0
gas in a solution· is proportional to the partial pressure' of the
rJ)
'. 20 40 60 80 100120 . gas."
Temperature CC) ~ xocp
.Fig. 5.1 Temperature dependence of O2 gas where, x ==·mole fraction of the gas in solution
solubility in water and p == partial pressure of the gas.
The reduced solubility of molecular oxygen in hot water has a
or x=K' p
direCt bearing on thermal pollution~ i.e., the heating of the
environinent--:usually waterways-to temperatures that are 1
or p= K,x==KHx ( KH == },) .. :(iii)·
harmful to its living inhibitants.
(iii) Pressure : The most important factor which influences . K H is called Henry's law constant. Different gases havt::
the solubility of a gas in a liquid is the pressure. The .effect of diff~rent' values of KHat a defmite temperature for a given
pressure on the solubility of the gas in the liquid is given by solvent.
Henry's law, which states that the solubility of a gas in a liquid is
directly proportional to the pressure of the gas over the solution TableS.l Values ofHenry~s Law Constant (K H ) for Some
. at a definite temperature. The solubility is taken as the mass of Common Gases in Water
the gas dissolved per unit volume of the liquid ..Thus, if m is the
Gas Temperature (K) XJI
mass of the gas dissolved per unit volume of the solvent and P is
the pressure of the gas in equilibrium with the solution, then He 293 144.97
mocp Hz 293 69.16
... (i) N2 293 76.48

or m==KP
N2 ,]03 88.84·
wh~re, K is the proportionality constant. .
°2 293 34.86
When P == I, m == K, i. e., the solubility of the gas at unit
393 46.82
pressure is equal to constant K. The value of K is different for
each gas at a particular temperature. The magnitude ofK depends From equation (iii), it can be inferred that high"-' is the value
uponthe nature of the gas, nature of solvent, temperature and the of Henry's law constant, the lower is the solubility <l
the gas in
units of pressure. Equation (i) represents equation of straight line the l i q u i d . · · . . \ .
I
324 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Limitations of Henry's Law 6.56x 10-2

Henry's law holds good if the following conditions are 5x P2
fulfilled:
P2 = 0.762 bar
(i) The pressure is not too high,
(ii) The temperature is not very low,
(iii) The gas does not chemically combine with the solvent.
The gas molecules do not either dissociate or associate in the 1. 0.5 MH2 S04 is diluted from 1 litre to 10 litre, normality of the
solvent. In case the dissolved gas reacts with the solvent, higher resulting solution is: (AFMC 20(5)
solubilities can result. The solubility of ammonia in water is (a) IN (b)O.IN (c) ION (d) liN
much higher than expected because of the following reaction: [ADs. (b)]
NH3 +H20=NH40H~NH~ + OW . [Hint: M\V1 M 2V2
Carbon dioxide also reacts with water. 0.5 xl M2 X 10
CO 2 +H20~H2C03 M2 =0.05
Another interesting example concerns the dissolution of x
N = M basicity of acid = 0.05 x 2 0,1 N]
oxygen in blood. Normally, oxygen gas is only sparingly soluble 2. Molar solution means 1 mole of solute present in:
in water. However, its solubility in blood is abnormally high tReECE (Medical) 20051
because. of the high content of haemoglobin (Hb) molecules, (a) 1000 g of solvent (b) 1 litre of solvent
which are eventually delivered to the tissues for use in (c) 1 litre of solution (d) 1000 g of solution
metabolism. [Ans. (c)]
Hb+40 2 ~Hb(02)4 3. The molarity ofa solution containing 50 g ofNaCI in500 g of
Due to these processes, Henry's law is not strictly followed. a solution and having a density of 0.936 g/cm 3 is:
(a) 1.5M (b) 1.6M (e) 1.8M (d) 1.2M
Applications of Henry's Law [Ans. (b)]
1. Soft drink bottles are sealed at high pressure, to increase the [Hint: M = x x d x 10 ... (i)
solubility of CO 2 in the soft drink. . mB
2. At high altitude, partial pressure of oxygen is low, it leads to
x = 50 x 100 = 10
low concentration of oxygen in blood of people living there. Low 500
cont1~n'tration of oxygen develops anoxia, i.e., unable to think
x 10 = 1.6M]
M = 10 x 0.936
and act properly. 58.5
3. When scuba divers go deep in the sea, solubility of 4. 20 rnL of 0.5 M HCI is mixed with 30 rnL of 0.3 M HCI, the
. atmospheric gases increases in blood. When the divers come up, molarity ofthe resulting solution is:
there is release of dissolved gases and it leads to the formation of (a) 0.8 M (b) 0.53 M (e) 0.38 M (d) 0.83 M
bubbles of nitrogen in our blood capillaries and hence there is [Ans. (c)]
painful sensation caU:::-d bends. To avoid bends; the tanks of
[Hint: M1V\ + M 2V2 =MR(Vj +
scuba divers are filled with 11.7% 56.2% N2 and 32.1%
oxyge.n. 0.5 x 20 + 0.3 x 30 = M R X 51
LNote : (i:) Gases are less soluble in aqueous solutions of electrolytes M R =0.38M
than in pure water. It is called salting out effect. where, M R =resultant molarity 0 mixture.]
. (ii) Non-electrolytes such as sugar if present in a solution also 5. How many moles and how man) .:>.ams ofNaCI are present in
reduce the solubility of gases in water.] 250 rnL of a 0.5 MNaCI solution?
(a) 0.125 mol; 7.32 g (b) 7.32 niol; 0.125 g
ExalDple 17. Calculate the concentration ofCP2 in a soft
drink that is bottled at partial pressure ofCO2 of 4 atm' over the i (c) 0.125 mol; 0.125 g . (d) 7.32 mol; 7.32 g
[Ans. (a)]
liquid bt 25° C. The Henry s Law constant for CO 2 in water at ','
MV 0.5 x 250 .. .
25 0 C is 3.1 x 10-2 mol/litre-atm. . . [Hint: Number of moles = - - :: = 0.125
Solution: According to Henry's Law: I' i 1/ /' 1000 1000
f
: i s =KP 3.1 x lOt x 4 = 0.12 mol litre-I p Mass of NaCI = 58.5 x 0.125 = 7.32 g]
:. 6. Density of a 2.05 M solution of acetic acid in water is 1.02
ExampIe;l8./ The pdrtial pressure of ethane.: q~?r a ':"; glmL. The molality of the solution is: (AJEEE 20(6)
saturated soltiiiofo containing 6.56 x 10-2 g of ethane t~~ [. b~r. If (a) 1.14 mol kg- I (b) 3.28 mol kg- l
the solution conlains 5 x 10-2 g 'of ethane, th{!n wha{sh~tt bifhe (e) 2.28 mol kg:-l (d) 0.44 mol kg-I
partial pressuJ pf the gas? . • ....,,_ ... [ADs. (e)]
Solution: ~ = PI . [Hint: m= ¥xlOOO 2.05x 1000
S2 P2 1000d MmB 1000x 1.02- 2.05 x 60
=.2.28 mol kg-I]
I
SOLUTIONS
'" 325
7. The hardness of water sample containing 0.002 mol of (0.5 0.1) x = 0.4- 0.2
magnesium sulphate dissolved in a litre of water is expressed OAx = 0.2
as: ; -i-'F'f -:<":',,-;~,-,) 2-0n:; x = 0.5L
(a) 20 ppm (b) 200 ppm (c) 2000 ppm (d) 120 ppm :. 0,5 L of A and 1.5 L of B should be mixed.]
(e) 240 ppm
,[Ans. (b)] ~~6 SOLUTIONS OF LIQUIDS IN LIQUIDS
6
[Hint: 10 g water contains (0.002 x 1000) mol MgS04 When one liquid dissolves in another, the molecules of the
1 mol MgS04 1 mol CaC0 3 solvent are caused to move apart so as to accommodate the solute
2 mol MgS04 ;E 2 mol CaC0 3, i.e.,2 x 100 g CaC03 molecules. Similarly,the solute molecules must also be separated
so that they can take their places in the mixture. In both these
. . Hardness of water = 200 ppm]
processes, energy is required. Finally, as the solute and solvent
8. The density (in g mL-1) of a 3.6 M sulphuric acid solution, molecules are brought together, energy is released because ofthe
i.e., 29% H2 S04 (molar mass == 98g mor l ) by mass will be: attractive forces between them. When solute and solvent,
('>"IEEE 20()7) molecules are strongly attracted to each other, more energy is
(a) 1.45 (b) 1.64 (c) 1.88 (d) 1.22 released in the final step. Three cases may arise under these
[Ans. (d)] circumstances. The overall dissolution process results either in
evolution of heat or absorption of heat, or energy released in the
[Hint: M = x x d x 10 final step is the same as the energy absorbed in the first two, i. e. ,
ms
net change is zero.
3.6 x 98 '" 1.22 mL-l] Examples:
29 x 10 ' g 1. Benzene and carbon NO evolution or absorption
9. I litre solution containing 490 g of sulphuric acid is diluted to tetrachloride: of heat.
10 litre with water. What is the normality of the resulting 2. Acetone and water: Evolution of heat.
solution? (~';crt \~I;U7) 3. Ethyl alcohol and water: Absorption of heat.
(a) 0.5 N (b) 1.0 N (c) 5.0 N (d) 10.0 N A liquid mayor may nof be soluble in another liquid.
[Ans. (b)] Depending upon the relative solubility of a liquid in another, the
[Hint: N : : ; - 'xL1000
__
490 x 1000 10 following three cases are possible:
Es xV 49 x 1000 Liquid-Liquid Systems .'
N/V I =N Z V2
__________~I --------------1
IOxl N 2 xlO 1. Liquids that are 2. Liquids that 3. Liquids that
N z = 1] completely - are partially are practically
10. 250 mL ofa Na 1 C0 3 solution contains 2.65 g ofNa 1C03 . 10 miscible. miscible. immiscible,
mLofthis solution is added toxmL of water to obtain 0.001 M Examples: Examples: Examp!Js:
Na 2 C03 solution. The value of x is .... Benzene and Ether and wa- Benzene
toluene; ter; Phenol and water;
(Molecular mass ofNa 1 C03 = 106 amu) [SHe (Mains) 20081
Ethyl alcohol and water; Carbon tetra-
(a) 1000 (b) 990 (c) 9990 (d) 90
and water; Nicotine and chloride and
[Ans. (b)] Carbon tetra- water. water; Ben"
[Hint: Molarity of solution. chloride and zene and
M
Ws x 1000 = 2.65 x 1000 0.1 benzene. alcohol.
ms X V 106 x 250
M/V1 =M2 V2 Miscible liquids form three types of solutions, which can be
0.1 x 10 =0.001 (10 + x) ideal or non-ideal solutions.
x= 990mL] • > Ideal' solution:. An ideal solution is' one in which the '
H.The yolumes ohwo-HCI s{)lutions A (O:5N ) and B (0.1 N) to molecules attract one another with equal force irrespective of
their nature. Thus, a solution composed of two components
be mixed for preparing 2 L of 0.2 HfiC! are : , _, ____ _
A andB will bean ideal one if- the forces between
EAMCET (IVIed) 2(}o8!
A and A, Band B should be the same. An ideal solution
(a) 0.5 L of A + 1.5 L of B
(b) 1.5 L of A + 0.5 L of B
possesses the follOWIng characteristics:
(c) 1 L ofA + I L of B (i) Volume change of mixing should be zero.
(d) 0.75 L of A + 1.25 L ofB AVmix 0; Vsolvent + Vsolute = Vsol ...1ion
[ADs: (a)] (ii) Heat change on mixing should be zero.
[Hint: Let x L of A and (2 x) L of B are mixed. MI mix = o(Heat is neither absorbednor evolved.)
M1V/ + M 2V2 =MR(V/ + V2 ) (iii) There should be no chemical reaction between solvent
0.5 x x + 0.1 (2 - x) 0.2 x 2 and solute.
326 (7, R. B. PHYSICAL CHEMISTRY FOR COMPETITIONS '
Solvent+ Solute ~ Solution (vi) Ideal solutions must obey Raou!t's law at all
1Non-i~l
H2 0 + NH3 ~NH40H concentratious.
H 20 + CO 2 ~H2C03 The following are some of the binary mixtures which show the
H 2 0 + CaO ~Ca(OHh properties of ideal solutions:
(a) Benzene and toluene,
(iv) Solute molecules should not dissociate in the ideal (b) Carbon tetrachloride and silicon tetrachloride,
solution. (c) n-Hexane and n-heptane,
(d) Ethylene dibromide and ethylene dichloride.
NaCI Aqueous medi"n; Na + + CI- ) Raoult's Law
Non-ideal
Aqueous mediwn
H 2S04 )' 2H + + SO~- According to this law, the partial pressure of any volatile
constituent of a solution at a constant temperature is equal to
the vapour pr~ssure of pure constituent multiplied by the
(v) Solute moleculeS should not associate in ideal solution.
mole fraction of that constituent in the solution.
2
'0'
" eOOH Dissolved
benzeneIn
. . •
(ASS0711on)
err.
~
0-.+0
O---HO
,y
+0 0-
"'-
I """OH---OVC( ) 'I Non-Ideal
b
.
~.
Let a mixture (solution) be prepared by mixing n A mole ofo
liquid A and nB mole of liquid B. Let P A and PB be the partial
pressures of two constituents A and B in solution and P ~ and P ~
the vapour pressures in pure state respectively....
Table S.2 Comparison between Ideal and Non-ideal Solutions
Non-ideal solutions
Ideal solutions
Positive deviation from Raoult's law Negative deviation from Raoult's law
I. Obey Raoult's, law at every range of Do not obey Raoult's.law. Do not obey Raoult's law.
concentration.
=
2. IlH mix 0; neither heat is evolved nor IlH mix > O. Endothermic dissolution; heat IlH mix < O. Exothermic dissolution; heat
absorbed during dissolution. - is absorbed. is evolved.
3. AVmix 0; total volume of solution is AVmix > O. Volume is increased after AVmix < O. Volume is decreased during
equal to sum of volumes of the dissolution. dissolution.
co~ponents.
·4. P = PA + PB P~-XA + p~ X B PA ). p~ X A; PB > pZ X B PA <P~XA; PB <p~ X B

i·e.,PA = P~XA;PB'= pZ X B :·PA + PB > p~ X A + pZ X B :·PA + PB < p~ X A + p~ X B
5. A - A, A B, B - B interactions A - B attractive force should be weaker A B attractive force should be greater

should be same, i.e., 'A' and 'B' arei(!enti- than A - A and B - B attractive forces. than A - A and B - B attractive forces.
cal in shape, size and character. 'A' and 'B' have different shape, size and 'A' and 'B' have different shape, size and
• character. character.
6. Escaping tendency of 'A' and 'B' should 'A' and 'B' escape easily showing higher Escaping tendency of both components
be same in pure liquids and in the.solu- vapour pressure than the expected value. 'A' and 'B' is lowered showing lower
tion. vapour pressure than expected ideally.
Examples: Examples: Examples:

dilute solutions; acetone + ethanol; acetone + aniline;
benzene + toluene; acetone + CS 2; acetone + chloroform;
, n-hexane + n-heptane; water + methanol; CHpH + CI'I 3COOH;
chlorobenzene + bromobenzene; water + ethanol; H 2 0+HN0 3 ;
ethyl bromide + ethyl iodide; . CCl 4 + toluene; yhloroform + diethyl ether;
n-butyl chloride + n-butyl bromide. CCl 4 + CHCI 3 ; water + HCI;
acetone + benzene; acetic acid + pyridine;
CCl 4 +CHPH; chloroform + benzene.
cyclohexane + ethanol.
SOLUTIONS I 327
Thus, according to Raoult's law, =XAPJ+XBP:

p A :::
n A +nB
P ~ = mole fraction of Ax P ~ = X A P J This law, in fact, is the major deciding factor, whether
a solution will be ideal or non-ideal. Ideal solutions obey Raoult's
law at every range of concentration. Non-ideal solutions do
and PB nB pg = mole fraction of B x p~ X B PBD
not obey Raoult's law. They show either positive or negative
nA + nB
deviation from Raoult's law. For comparison between ideal
If the total pressure be P, then
and non-ideal solutions a table has been given below. (Only
P PA + PB binary combinations of miscible liquids have been considered.) .
Graphical Representation of Ideal and Non-ideal Solutions

Ideal deviation . Positive deviation Negative deviation
~ ~
:::l
tJ)
<Jl
pg :::l
<Jl
<Jl
~ ~
0. 0-
....
:::l
....
:::l
....
:::l
0
0.
0
0.
o
0.
~ ~ ~
Mole fraction XA = 1 Mole fraction Xs= 1 XA = 1 Mole fraction

Xs=O XB= 1 Xs=O XA=O Xs 0
Fig. 5.3
Relation between Dalton's Law and Raoult's Law: pressure of the solution and the mole fraction of methanol in the
The composition of the vapour in equilibrium with the vapour.
solution can be calculated applying Dalton's law of partial Solution: Mol. mass of ethyl alcohol == C zHs OH = 46
pressures. Let the mole fractions of vapours A and B be 60
f A arid f B respectively. Let P A and P B be the partial pressures No. of moles of ethyl alcohol = - 1.304
46
of vapours A and B respectively and total pressure P.
Mol. mass of methyl alcohol = CH 3 0H = 32
PA=fAP ... (i) . 40
PB == fB P ... (ii) No. of moles of methyl alcohol = = 1.25
32
PA X A p~ ... (iii)
~ X A' , mole fraction of ethyl alcohol ::: 1.304 = 0.5107
PB =X B pg .. , (iv) .. . 1.304 + 1.25
Equating eqs. (i) and (iii),
fA P=X A p~ ,X B', mole fraction of methyl alcohol 1.25
or
X A p~ PA 1.304+ 1.25
fA = 0.4893
P P
Similarly, equating eqs. (ii) and (iv), Partial pressure of ethyl alcohol X A .p~ ::: 0.5107x 44.5
. . 0
- X B PB =PB 22.73 mmHg
f B- -
P P Partial pressure of methyl alcohol = X B .p~ 0.4893 x 88.7 .
Thus, in case of ideal solution the vapour phase is richer with = 43.40 mmHg
more volatile component, i.e., the one having relatively greater Total vapour pressure of solution = 22.73 + 43.40
vapour pressure. = 66.13mmHg
Example 19. The vapour pressures of ethanol and, Mole fraction of methyl alcohol in the vapour
methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal Partial pressure of CH3 0H 43.40 :=c 0.6:":63
.solution is formed at the same temperature by mixing 60 g of
Total vapour pressUre' 66.13
ethanol with 40 g of methanol. Calculate the total vapour
Example 20. Two liquids A and B form an ideal solution. 25 = 0.25' n - 35 0.3
At 300K, the vapour pressure of a solution containing 1mole ofA 100 ' B - 114
and 3mole ofB is 550mm ofHg. At the same temperature, if one

0.25 0.3
mort! mole of B is added to this solution, the vapour pressure of xA = ; Xo=----
the solution increases by 10 mm of Hg. Determine the vapour 0.25+ 0.30 0.25+ 0.30
pressure ofA and B in their pure states. =0.45 =0.55
Solution: Let the vapour pressure of pure A be ::: p~; and o 0
p::: PAxA + POxB
the vapour pressure of pure B be p~ .
105.2x 0.45+ 46.8x 0.55
Total vapour pressure of solution (1 mole A + 3 mole B)
::: 47.34+ 25.74= 73.08 kPa
::: X A • p~ +X 0 • p2 [X A 11> mole fraction of
A and X 0 is more fraction of B]
1, 0 3 0
550 - PA + - Po 12. Mole fraction ofthe component A in vapour phase is Xl and the
4 4
mQle fraction of component A in liquid mixture is x" then
or 2200= p~ + 3PZ ... (i)
(p~ vapour pressure of pure A; p~ vapour pres;ure of
Total vapour pressure of solution (1 mole A + 4 mole B) pure B), the total vapour pressure of liquid mixture is:
1 0 4 0
::: PA + PE (a) p~ (b) p~ (c) P~ (d) P~ x2
5 5 XI X2 x2 XI
/ 1 0 4 0
560=- PA +- Po [Ans. (a)]
5 5 [Hint: PA = P~ x2' vapour pressure of ,A'
or 2800 p~+4p~ ... (ii) Mole fraction of A in vapour J!!L
Solving; eqs. (i) and (ii), Plotal
p~ =:= 600mm ofHg::: vapour pressure of pure B xt

P~ X
= - -z
p~ 400 mm ofHg ::: vapour pressure of pure A P
o
. Example 21. An aqueous solution containing 28% by P PA X2]
XI
mass ofa liquid A (mol. mass 140) has a vapour pressure of160
mm at 37°C. Find the vapour pressure of the pure liquid A (The 13. Vapour pressure of pure A (p~ )::: 100mm Hg
vapour pressure ofwater at 37°C is 150mm} . Vapour pressure of pure B (p~) 150mm Hg
Solution: For two miscible liquids, 2 mole ofliquid A and 3 mole ofliquid B are mixed to form an
P tolal Mole fraction of Ax p~ + Mole fraction of B x p~ ide!,1 solution. The vapour pressure of solution will be:
(a) 135 mm (b) 130 mm (c) 140 mm (d) 145 mm
- 28 [Ans. (b)]
No. of moles of A ::: - 0.2
140 2 3
[Hint: XA "5' XB =="5
Liquid B is water. Its mass is (100 - 28), i. e., 72.
No. of moles of B 72 ::: 4:0 P ::: P~ X A + P~ xB
18 2 3
== 100 x - + 150 x - =40 + 90 == 130]
Total no. of moles ::: 0.2+ 4.0= 4.2 5 5
Given, P tolal = 160 mm 14. The vapour pressure ofa certain pure liquid A at 298 K is 40 m
bar. When a solution of B is prepared in A at the same
pZ = 150mm temperature, the vapour pressure is found to be 32 m bar. The
- 0.2
So, 160 --xP1 0
+ 4.0 x 150 mole fraction of A in the solution is:
4.2 4.2 (a)05_.. . (b) 0.2 (c) 0.1 (d) 0.8
p~::: 17.15X4.2=360.l5mm [Ans. (d)]
0.2 . [Hint: P = pOxA
32 = 40xxA or xA =0.8]
Example 22. Heptane and octane form ideal solution. At
15. 100 mL of liquid A and 25 mL of liquid B are mixed to form a
373K, the vapour pressures of the two liquids are 105.2/cPa and
solution of volume 125 mL. Then the solution is:
46.8/cPa respectively. What will be the vapour pressure, in bar,of .
--(a) ideal
a mixture of25g olnepfaneand 35 gO! Delane? ~-.
(b) non-ideal with positive deviation
Solution: (A) Heptane C7 H 16 mA = 100 (c) non-ideal wit!). negative deviation
(B) Octane C 8 H I8 mE 114 (d) cannot be predicted
[Ans. (a)]
[Hint: ~ Vmix == 0, hence the solution is idea\.]
SOLUTIONS 329
16. The vapour pressure of pure benzene at 88°C is 957 mm and

that of toluene at the same temperature is 379.5 mm. Calculate Vapour
'the composition of benzerie-toluene mixture boiling at 88°C: , T Liquid
(a) xbenzene 0.66; Xtoluene 0.34
(b) xbenzene = 0.34;. Xtoluene =; 0.66 -c:
iT: --- ----------
II
(c) x benzene = X toluene = 0.5 '0

a. Tx
I
---+------~--!-.--,---'~
(d) x benzene 0.75; Xtoluene =; 0.25 2? Tz ---1-------+--
._ I :
[Ans. (a)] =0 I I
[Hint: p =pgenzene xbenzene + P~luene Xtoluene III :

I
I
:
I
I
760 = 957· xbenzene + 379.5(1- xbenzene) A 100% Y x Y1 XIZj B 100%
Xbenzene = 0.66
B 0% Composition A 0% •
and xtoluene I - 0.66 0.34 ] •
17. At 2S'C, the total pressure of an ideal solution obtained by
mixing 3 mole of A and 2 mole of B, is 184 torr. What is the Fig. 5.4 Liquid-vapour equilibrium diagram
vapour pressure (in torr) of pure B at the same temperature of a solution of type-I
(Vapour pressure of pure A at 25°C is 200 torr.)?
Suppose a solution of composition x is heated. When the
(CET (J&K) 20061
(a) 180 (b) ,160 (c) 16 (d) 100 temperature Tx is reached, the boiling will start. At this
[Ans. (b)] temperature, the vapour coming off from x will have the
3 3 composition Xl • Since, Xl is richer in B than X, the composition of
[Hint: XA 0.6 the residual liquid will become richer in A. Let the new
nA + nB 3+ 2 5
, composition be y. This liquid cannot boil at temperature Tx but
x B = 0.4 will require higher temperature Ty . The vapour coming off at
P = P~XA + P~XB temperature Ty will also be richer in B as represented by YI'
\ 184 200 x 0.6 + p~ x 0.4 Hence, the composition of the residue will again be enriched in
, 1,.'
pZ x 0.4
184 = 120 + A. Thus, if the process is allowed to continue, the boiling point of
solution will go on increasing towards TA , the boiling point of
o 64
PE =- = 160 torr] pure liquid A. At the same time the solution becomes more and
0.4
more rich in A. If the process is continued for a sufficiently long
18. The mass of glucose that would be dissolved in 50 g of water
time, pure liquid A can be obtained.
in order to produce the same lowering of vapour pressure as is
produced by dissolving 1 g of urea in the same quantity of Now, if the initial vapours are condensed, the solution
water is: (KCET 2006) obtained wilt"have the composition XI and boils at temperature
(a) 1 g (b) 3 g (c) 6 g (d) 18 g T z . Evidently, the distillate is richer in B than before. If the
[Ans. (b)] process of condensation and redistilling is continued, the final
distillate will be pure B component.
[Hint: . (~P)glucose =(~P)urea
Thus, the two liquids forming a solution of type-I can be
(XB )glueose = (xB )urea separated by fractional distiUa~on.
i.e, ( nE) (nE)
nA glucose \. nA urea
Solution of type-II (Positive deviations from Raoult's
law): The boiling temperature-composition curves for the
WE 18 1 X 18 liquid and vapour phases have been shown in Fig. 5.5. The
-x two curves meet at a minimum point C where the liquid and vapour
50 180 50 x 60
phases have the same composition. The liquid mIxture at point C
WE = 3 g]
will boil at ,constant temperature T without undergoing any
5!7 THEORY OF FRACTIONAL DISTILLATION
The process of separation oCone liquid from 'a"nother liquid
(binary mixture) having different boiJing points by distililltionis
termed ,fr.actional distillation. The information, whether a
partlcul;r solution of two liquids can be separated by distillation
or not, is provided by the study of liquid-vapour equilibrium
diagrams at· constant pressure, say atmospheric pressure. The
separation is possible only when the vapour phase has a A 100% X X1 Y1 Y B 100%
composition different from that ofthe boiling liquid mixture. B 0% Composition A 0%
Liquid pairs of type-I (Ideal solutions): The boiling
•
temperature composition curves for liquid and vapour phases in Fig. 5.5 Boiling point-composition curves
the case of binary solutions of first type are represented in Fig. in bil'!ary solution of type-II
5.4.
change in composition. snch a mixture which boils at constant It is never possible to separate a mixture completely into the
temperature and distils over completely at the same pure components A and B. It mainly gives a constant boiling
temperature without any change in composition, is called mixture (azeotropes) which can never be separated by
constant boiling mixture or azeotropic inixture. distillation. .
Consider the distillation of a mixture of composition x. , There are several liquid pairs which form maximum boiling
The vapour given off has the composition xl' The composition of point azeotrope. Some examples are tabulated below:
residual liquid will shift towards A. In the mean
% Composition Boiling point
time thecompositioRofthe distillate shifts towards C. Ultimately Mixture
of azeotrope (pressure .. 1 atm)
by repeated fractional distillation, the mixture of composition C ---.-~-----.~-----~---.~-'---
will be obtained as distillate and pure liquid A will be left as 1. Nitric acid-Water 68% Nitric acid 125.SoC
residue. It will never be possible to have pure B. 2. Acetic acid-Pyridine 65% Pyridine 139.0°C
When a mixture of composition y is distilled, th~pour given 3 .. Chlorofonn-Acetone 80% Chlorofonn 65.0°C
off has the coml?,osition Yl'j. e., the composition~ residual
liquid will Shifttowards R Ultimately the mixture of composition 4. Hydrogen chloride- 79.8% Water 108.6°e
Water
C will be obtained as distillate and pure liquid B will be left as
residue. It will nev~r be possible to have pure A.
There are several liquid pairs which form minnnum boiling 5.8 SOLUTIONS OF SOLIDS IN LIQUIDS
point azeotropes. Some examples are given in the table:
Solutions of this type are most common. In solutions of solids in
Table 5.3 Some Azeotropic,Mixtures liquids, the liquid is invariably referred to as a solvent and the
solid dissolved in it as the solute. If a solute is added in small'
% Composition of Boiling point
Mixture amounts at a time to a given amount of a solvent at a constant
azeotrope (pressure = 1 atm)
--..-- temperature, with vigorous stirring or the solvent after each
1. Water-Ethanol 95.97 Ethanol 78,15°C addition, a stage is reached when the added solute no more
2. Pyridine-Water 57.00 Pyridine 92.60°C disappears, i. e. ,goes into solution but remains undissolved. The
solution is then said to be saturated. A solution which remains in
3. . Ethanol-Benzene 32.40 Ethanol 67.80°C
contact with undissoived solute is termed as saturated. It can
4. Acetic acid-Toluene 28,00 Acetic acid 105.40°C also be defined as one which is in eqUilibrium with the excess
Solutions of type-UI (Negative deyiations from Raoult's of solid at a particular temperature.
law): The boillng temperature-composition curves for the The amount of solute dissolved in 100 g of a solvent to form a
liquid and vapour phases have been shown in Fig. 5.6. The curves saturated solution at a given temperature is termed the solubility
meet at point C. At this point, both liquid and vapour phases have of the solute in the given solvent at that temperature. Each
same composition, The constant-boiling mixture has maximum substance has a characteristic solubility in a given solvent at a
boiling point. de.finite temperature.
When a solid is added to the solvent, the particles from the
solid diffuse into it. The solute. and solvent molecules move
c
t constantly in the solution phase. Some of the particles of the
solute retJ,lm to the solid state due to collisions. Thus, two
e
'0
A
opposite processes operate simultaneously.
c.. k,.. :
Cl
.5 ! 9(qcy, (a) Dissolution: Particles of solute leaving the solid and
'5 ,, ,,
I ,
dissolving in the solvent.
co (b) Recrystallisation: Solute particles returning to the solid
'Y 'Y1
A 100% form. .
80% -
Composition 8 100%
AO% When these two processes move with same speed, an
equilibrium stag~ is reached,
Fig. 5.6 Boiling temperature-composition
. curves in binary solution of type-III Solute (solid) ~ Solute (dissolved)
Consider the distillation of a mixture of composition x. The Thus, a dynamic equilibrium exists in a saturated solution.
vapour coming off is richer in A as indicated by composition When a saturated solution prepared at a higher temperature is
Xl . The composition of the residual liquid shifts towards C. As the
cooled, it gives a solution which contains usually more of solute
distillation proceeds, the composition Of the distillate moves than required for the saturated solution at that temperature. Such
towards A and that of residue towards C. a solution is referred to as a supersaturated solution. It is
Similarly, a mixture of composition lying between Band C, usually unstable and changes to saturated solution when excess
say y, on distillation will give vapour richer in B as indicated by of solute comes out in solid state. '
composition Yl' The composition of residual liquid shifts The: following factors influence the solubility of a solute in a
towards C and di'stillate towards A on repeated distillation, liquid:
SOLUTIONS
(1) Nature of solute,

200 ~;o"'li
(2) Nature of solvent,
V
~Ii . /VI
(3) Temperature. 190 ~-'<:/ ~
180
i
I i
/"" I
f-~
1. Nature of solute: The solutes (solids) can be classified as II Vi
ionic and non-ionic solids. The ionic solids consist of positively 170
~V ~rr;
and negatively charged ions. It is the force of attraction between 160 r-
/ ./ V I i
the ions, L e., lattice energy which opposes the tendency of a 150
I /~ 1.0,
solute to dissolve. This force of attraction is different in different ~ 140
j/ ..:.-
f?1- t
V
~ 130
I ~l
ionic solids depending on the charges present on the ions and if I
C)
120 i d
distance between ions (ionic radii). The ionic solutes having high 0
~'"A / ' V
lattice energy like BaSO 4 are less soluble while those having less
0
Q;
110
100
~,. V L 'f:,.'O{ ____.....-
lattice energy have more solubility. The ions are solvated by the ,c. I. /1 / ....- ~
90
solvent molecules and in this process energy (known as hydration ~ ~f?/ J.:--
80
70 ~w~
energy) is released. When the hydration energy is high, the ionic :0
:::J --/ ,
~
~
~/1'
(5
s'olid is more soluble. CIl
60 V ' ...... ~a2so~ All
Many non-ionic substances dissolve in polar solvents due to
50
1<..,9.C =?
hydrogen bonding. Generally, if the solute and solvent have
__ ';c,rA. ~ .- ~ NaCI
/"
similar characteristics, i. e. , both are polar or both non-polar, the 40
30 1~~~2~O4- ,---
~ftf
solubility is high and if both are dissimilar, the solubility is found
low. 20 ,--,'"
Na~'e,oy
10
2. Nature of solvent: Ionic solids dissolve to a larger extent Ft-1
in a solvent having a high dielectric constant as compared to 10 20 30 40 50 60 70 80 ,90 100
solvents oflow dielectric constants. Dielectric constant of water Temperature in degree celsius
is 80 while that of methyl alcohol is 33.5. An ionic solid,
therefore, dissolves more readily in water than in methyl alcohol. Fig.5.7 Solubility curves of some compounds
Benzene has a very low dielectric constant of 2.3 and, hence, 1. Mass of empty dish w g
ionic solids do not dissolve in benzene. 2. Mass of dish + solution = WI g
For non-ionic solids, the guiding principle is 'like dissolves 3. So, Mass of solution (wI - W) g
like', Le., if the solvent is polar, it will dissolve the polar solutes 4. Mass of dish + residue ~ W2 g
and if it is non-polar, it will dissolve the non-polar solutes in it. So, Mass of residue = (w2 w) g x g
3. Temperature: The solubility of a solute in a given and Mass of solvent (Mass of solution
solvent varies appreciably with temperature. A few curves drawn - Mass of residue )
between solubility in water and temperature are given in Fig. 5.7. = (WI - W) - (W2 - W)
It is observed that the solubility of NaCI increases' very = (WI W2)= yg
slightly with an increase in temperature whereas those of
KN0 3 ' NaN0 3 , AgN03 and KI, etc., increase greatly. A Thus, the solubility of salt = x x 100 g per 100 g ~f solvent.
y
sharp break in a solubility curve indicates the formation of
a compound whose ~olubility is different from that of the Example 23: 50 g of a saturated aqueous solution of
substance from which it has been formed as in the case of potassium chloride at 30°C is evaporated to dryness. when 13.2 g'
N a 2 SO4 ·lOH2 O. It losses its water of crystallisation at ofdry KCf was obtained. Calculate the solubility ofKCf in water
32.3°C and is converted into anhydrous form. There are few at 30°C.
substances like calcium acetate, cerium sulphate, calcium Solution: ' Mass of water in solution (50-13.2) 36.8g
chromate, etc., which show a decrease in solubility with rise in
temperature. Solubility of KCl = Mass ofKCl x 100 13.2 x 100= 35.87
. Mass of water 36.8 g
Generally, solubility depends on heat of solution. If a
substance dissolves with absorption of heat, the, solubility Example 24. How much copper sulphate will be required.
increases with rise of temperature. On the other hand, if a to saturate 100 g of a dilute aqueous solution ofCuSO4 at 25° C
substance dissolves with evolution of heat, the solubility if 109 of the dilute solution leave on evaporation and dlying 1.2
decreases with rise of temperature. g of anhydrous CuSO4? The solubility ofCuSO4 in water at 25° C
Determination of solubilil); The solubility of salts is is 25.
generally determined by gravimetric method. First of all a Solution: 100 gof dilute solution of CUS04 contain
saturated solution is prepared. Some part of this saturated = 1.2 x 10= 12.0g CUS04
solution is weighed out in a porcelain dish. The solution is Mass of water present in dilute solution
evaporated slowly to dryness ona sand bath. The dish is cooled = (100-12) 88g
and weighed again. The observations are recorded as follows: To saturate 100 g of water, CuS0 4 required 25 g
So, to saturate 88 g of water, CuSO 4 required ~x88 termed lowering in vapour pressure and the ratio [ Po ~P S ] is
100
=22g
termed relative lowering in vapour pressure.
Thus, the mass of CuSO 4 to be added to 100 g of dilute
solution to saturate it (2212)=IOg Raoult, in 1886, established a relationship between relative
lowering in vapour pressure and composition of the solution after
5.9 COLLIGATIVEPROPERTIES OF a series of experiments in various solvents. The relationship is
DILUTE SOLUTIONS known as Raoult's law. It states that the relative lowering in
A dilute solution is one in which the amount of the solute is vapour pressure oCa dilute solution is equal to mole fraction
very small in comparison to the amount of the solvent. The of the solute present in the solution.
dilute solutions show more or less ideal behaviour as the heat and If n moles of solute be dissolved in N moles of the solvent, the
volume changes, accompanying the mixing of solute and solvent, mole fraction of the solute will be _n_ .
are negligible for all practical purposes. Dilute solutions obey n+N
Raoult's law, . Po - Ps n
Dilute solutions containing non-volatile solute exhibit some Accordmg to Raoult's law, = -'--
special properties which depend only upon the number of solute Po n+N
particles present in the solution irrespective of their nature. These This is the mathematical expression for Raoult's law.
properties are termed as colJigative properties. The colligative [Modified form of Raoult's law: The above relationship
properties are: can be written as,
(i) Lowering in the vapour pressure, n+N N
(ii) Elevation inthe boiling point, -=-=--=--=1+-
Po - P s n n
(iii) Depression in the freezing point and
(iv) Osmotic pressure. Po _ 1 =N or --""-"-_ == N .
or
Colligative ·properties are the properties of dilute solutions, Po Ps n Po - p, II
that is why these are termed as colligative properties of dilute
solutions. These properties are related to one another. Thus, if po-ps=n WAX~
or
one is measured, the other can be calculated. The importance of Ps N rnA wB
these properties lies in the fact that they provide methods for the
This equation gives accurate results and is easy to apply.]
determination of molecular masses of dissolved solutes. The
results are excellent if the following three conditions are Derivation of Raoult's Law for a Dilute Solution
satisfied: When a non-volatile solute is dissolved in a volatile solvent, a
(i) The solution should be very dilute. fraction of the surface of solvent is blocked by solute molecules
(ii) The solute should be non-volatile. where no evaporation occurs. Thus, under similar conditions, the
(iii) The solute does not dissociate or associate in sQlution. , vapour pressure is decreased. The vapour pressure of the
solution, thus, depends, upon the number of molecules of the
5~10 LOWERING IN .THE VAPOUR solvent present on the surface of the solution. The number of
PRESSURE such molecules is proportional to mole fraction of the solvent.
So, the vapour pr~ssure of solution,
When a non-volatile solute is added ,to a solvent, the vapoUr
pressure is lowered due to the following reasons: 'Ps'oc~
(i) Percentage surface area occupied by the solvent decreases. n+N
Thus, the rate of evaporation and vapour pressure decreases. The " N
solute molecules occupy the surface, and so the per cent surface or Ps k · - -
,area occupied by the solvent decreases. -n.¥N·
(ii) According to Graham's law-G}.evaporation, (k is proportionalityfaetor)
. 1 For pure solvent, n=0
Rate 0 f evaporatIOn oc ~
"density N
When a non-volatile solute is dissolved in a liquid, its density
and hence, Po =k == k '" (ii)
O+N
increases. Thus, both rate of evaporation and vapour pressure are Putting the value of kin eq. (i)
lowered. N
If Po is the vapour pressure of pure solvent and Psis the Ps =Po--
n+N
vapour pressure' of the solution, the 'difference (Po - P s ) is
Note: Isopiestic solutions: Two solutions having same vapour pressure at same temperature are known as isopiestic solutions.
SOLUTIONS 333
N Loss in mass in the solution bulbs oc P s

or :::--
Po n+N Loss in mass in the solvent bulbs ex: ( Po - P s )
Total loss in both sets of bulbs oc [ P s + ( Po Ps)]
or 1-.!!..£==1-~ oc Po
Po n+N
Total loss in mass of both sets of bulbs is equal to gain in mass
or Po Ps ==_n_ ... (iii) of guard tubes .
Po n+N Po -: P s Loss in mass in solvent bulbs
Thus == ---~-----~-------
This is Raoult's equation. 'Po Total loss in mass in both sets of bulbs
If a solution is made by dissolving WB g of solute (molecular Loss in mass in solvent bulbs
mass mB) in wAg of the solvent (molecular mass mA)' the mole :::--------------------
Gain in mass of guard tubes
fraction of the solute will be
Further, we know from Raoult's law,
Po Ps == ____-=:..~_"'____
Po WA / mA + WB / mB
WA + WB
Loss in mass of solvent bulbs
mA mB
Gain in mass of guard tubes WA /mA + W B / mB
If the solution is very dilute, wB can be neglected in the The above relationship is used for calculation of molecular
mB
. masses of non-volatile solutes.
denominator as compared to WA • The eq. (iii), thus, becomes For very dilute solutions, the following relationship can be
mA applied:
PO-Ps==WBxmA ... (iv) Po P s Loss in mass of solvent bulbs == WB xmA
Po mB XWA Po . Gain in mass of guard tubes mB x WA
This relationship is useful in the determination of the
molecular mass of dissolved solute by measuring relative Vapour Pressure of Liquid and Temperature
lowering of vapour pressure. Liquid ~ Vapour Mf yap. > 0
Vapour pressure of liquid increases with temperature. Here,
Measurement of Relative Lowerjng in Vapour Mf is enthalpy of vaporisation. A 'graphical representation of
Pressure (Ostwald and Walker Method) vapour pressure versus temperature is given below:
The apparatus used is shown in Fig. 5.8. It consists of two sets
of bulbs. The first set of three bulbs is filled with solution to half
of their capacity and second set of another three bulbs is filled
with the pure solvent. Each set is separately weighed accurately.
Both sets are connected to each other and then with the accurately
weighed set of guard tubes filled with anhydrous calcium r
chloride or some other dehydrating agents like P20S' conc.
H 2S04 etc. The bulbs of solution and pure solvent are kept in a
thermostat maintained at a constant temperature.
Dry air
Temperature - - 1/T - -
Fig. 5.9 Variation of vapour pressure with temperature
If vapour pressure of a liquid is known at a temperature; it can
be calculated at another temperature using Clausius-Clapeyron
equ'ation:
S91ution Solvent Weighed CaCl2 tubes
Fig. 5.8 Ostwald and Walker method

P2 )
loglo ( PI
[I 1]
Mf yap.
== 2.303R TI - T2
A current of pure dry air is bubbled through the series of bulbs Here, PI == Vapour pressure at temperature ~
as she'.'''' in Fig. 5.8. The air gets saturated with the vapours in
P2 == Vapour pressure at temperature T2
each set of bu:bs. The air takes up an amount of vapours
proportional to th.., vc.;Jour pressure of the solution first and then : :::::a_SOME SOLVED EXAMPLES\r.:::::
it takes up more amount of vapours from the solvent which is
proportional to the difference in the vapour pressure of the Example 25. Calculate the vapour pressure lowering
solvent and the vapour pressure of solution, i. e. , Po Ps' The caused by addition of 50 g of sucrose (molecular mass 342) to
two sets of bulbs are weighed again. The guard tubes are also 500 g ofwater if the vapour pressureofpure water at 25°C is 23.8
weighed. mmHg.
[Ans. (d)] vapour pressure of water at 25°C is 17.5 rnm, what is the
molecular mass of the solute? [EAMCET (Engg) 2008j
[Hint: nA = = 100 = 5.55 (a) 206 (b) 302 (c)318 (d) 276
rnA 18
[ADS. (c)]
n 34.2 0.1 [Hint:
B .342 100/18
(17.5 0.225)= 17.5 x----~
x = 5.55 = 5.55 0.982 100/18+ -
A
5.55 + 0.1 5.65
p= poxA 17.275 (100 +~) 100
23.75 x 0.982 23.33 rum] 17.5 18 mB 18
21. Lowering of vapour pressure due to a solute in I molal
aqueous solution at 1000e is: 0.987 ( 5.55 + !:) 5.55
(a) 13.44 mm Hg (b) 14.12 mm Hg 25
(c) 31.2 mm Hg (d) 35.2mmHg 5.55 + - = 5.628
mB
[Ans. (a)]
mB '" 318mm]
x 1000
[Hint: m XB = mole fraction of solute
(l-xB)m A
rnA molar mass of solvent
5~11 ELEVATION OF BOILING POINT
1= x 1000 (Ebullioscopy)
(I xB)xl8 The boiling point of a liquid is the temperature at which its
XB 0.0176 vapour pressure is equal to the atmospheric pressure. The
vapour pressure of a liquid is lowered when a non-volatile solute
xA = 1- 0.0176= 0.9824 is added to it. Hence, the temperature of the solution when its
P = poxA vapour pressure will be equal to atmospheric pressure will be
= 760 x 0.9824 = 746.62 higher than the temperature of the pure solvent. In other words,
the boiling point of the solvent is elevated by the addition of
tlp = Po P = 760 746.62
non-volatile solute. The difference in the boiling point of the
'" 13.4 ] solution and the boiling point of the pure solvent is termed
22. The mass of a non-volatile solute (molecular mass = 40) elevation of boiling point.
which should be dissolved in 114 g octane to reduce its vapour Elevation of boiling point,
pressure to 80% will be: (t1T) Boiling point of the solution - Boiling point of pure
(a)20g (b)30g (c) 109 (d)40g solvent
[ADS. (e)] This can be better understood by plotting a graph of vapour
[Hint: If Po 100, then P 80
. pressure against temperature for a pure solvent and two solutions
of different concentrations. The curves orthe solutions always lie
P= Po XA below the curve of th,e pure solvent. The line poe represents the
80 = 100 xXA atmospheric pressure. To', TI and T2 represent the boiling points
xA =0.80 of pure soJvent, solution I and solution II respectively. The
114/114 vapour pressure of pure solvent, solution I and solution II at'
1141114 + wB /40 temperature To are Po, p] and P2 respectively.
'0,8=---
1 + Ws /40
1 + Ws = 1 t
40 0.8
wB 10 g]
. 23. 3g urea is dissolved in 45g of water. The relative lowering of
vapour pressure is : IComed (Karnataka) 20081
(a) 0.05 (b) 0.04 (c) 0.02 (d) 0.01
[Ans. (c)]
3 To T1 T2
(HiDt: ns = 0.05; 45 = 2.5
60 18 Temperature :......-
Xs = 0.05 0.01 96 = 0,02 ]

Po 2.5+ 0.05 Fig. 5.10
24. When 25g of a non-volatile solute is dissolved in lOOg of
water, the vapour pressure is lowered by 0.225 mm. If the
I
SOLUTIONS 337
Assuming that the solutions are very dilute, these curves may K
Then, I1T=-==K b
, be approximately taken as straight lines near the boiling point. lOOO
Thus, AA CE and AABD are similar.
. AC AE K b is called molal elevation constant. II 'J:; defined as the
Therefore, --- elevation in boiling point produced when 1 mole of the solute
AB AD
T2 -To == is dissolved in 1000 g of the solvent.
or
T\ -To Po PI Thus, K 1000K b
I1T2 11P2
or Putting this value in eq. (i),
1111 I1Pj
or I1T ex: I1P I1T == 1000K b WA
... (iii)
From Raoult's law for dilute solution, mA WB.
Po - Ps _ WB xm A or I1T == Molality x K b
Po .,mB XWA
( P s == vapour pressure of solution)

WB xm A
(since
" mB
WB
x wA
x 1000 == molality I
or Po Ps == . Po
mB xWA
The elevation in boiling point of a solution o.
For the pure solvent, Po (its vapour pressure at the boiling non-electrolYte is propo!tional to its molality and equimolal
point) and mA (its molecular mass) are constant. Therefore, solutions of all the sUbs'tances in the same solvent will show
equal elevation in boiling points. These are known as Raou!t's.
Po - Ps ex: ''----'''---
mB xWA laws of elevation of boiling point.
Molal elevation constant is characteristic of a particular
or I1p ex: 11 T ex: - - - ' ' - - - - solvent and can be calculated from the thermodynamical
mB xW A
relationship.
RT2
or I1T K· ---"'-- ... (i) K - b
mB XWA b - 1000L
v
where K is a constant, called as elevation constant. where, R is molar gas constant, Tb is the boiling point of the
When, WB == 1, (one mole of solute) and WA == 1g, then solvent on kelvin scale and Lv the latent heat of vaporisation of
mB solvent in calories per gram. '
, ?
I1T==K For water K =- 2x(373t = 0.515
Thus, boiling point constant is equal to the elevation in boiling b lOOOx 540
point which would be theoretically produced when I mole of a
·The molal elevation constants for some common solvents are
non-volatile solute is dissolved in I g of the solvent.
given in the following table:
If WB == 1 and WA = 100 g,
mB
I1T=- K K l1IWII cIrtwiIdtiI C'tt" u-

Then, I
s.huIt 8fIt.{"q
lOO (K. . . . .-l)
K is called molecular elevation constant. It is defined as the
I Water 100.0 0.52
elevation in boiling point produ~ed whtn.l mole of the solute Acetone 56.0 1.70
is dissolved in 100 g of the solvent,·; Chloroform 61.2 3.67
Thus, K lOOK I. Carbon tetrachloride 76.8 5.02
B'enzene 80.0 2.70
Putting this value in eq. (i),
l'l::hyl alcohol 78.4 1.15
I1T== lOOK '.-~ ... (ii)
If K b' W A ,I1T. and W B are known, molecular mass of a
non~volatile solute can be determined.' The most convenient
WB
If - =1 and w A == 1000 g, method for the determination of I1T in the laboratory is the
mB t:nu{sberger method.
* This relation may also be written as:
/:iT 1000 xw
mXW
where, wand Ware masses of solute and solvent respectively and m = molecular mass of solute.
I
5.12 DEPRESSION OF FREEZING POINT or

(Cryoscopy)
Freezing point of a substance is defined as the temperature at For the pure solvent, Po and mB are constants. Therefore,
which the vapour pressure of its liquid is equal to the vapour
pressure of the corresponding solid. Since, the addition of a Po - Ps oc_....!O-_
mB w A
non-volatile solute always lowers the vapour pressure of a
solvent, therefore, it will be in equilibrium with solid phase at a or Apoc--=--
lower pressure and hence at a lower temperature. The difference mB w A
between the freezing points of the pure solvent and its solution is WB
called depression of freezing point. or Ap ex; AT oc - - " - -
mB wA
Depression of freezing point
or AT K ._"'-- ... (i)
(AT) == Freezing point of the solvent mB wA
Freezing point of the solution where, K is a constant, called depression constant.
This can be better understood by plotting a graph of vapour
pressure against temperature for a pure solvent and two solutions, When, WB I (one mole of solute) and W A == I g
mB
solution I and solution II. CFB is a curve for a solid solvent. The
solvent, solution I and solution II vapour pressure curves meet AT=K
CFB curve at points B, F and C respectively. Thus, To , Tl and T2 Thus, depression constant is equal to the depression of the
are the freezing points of pure solvent, solution I and solution II freezing point which would be theoretically produced when one
respectively. The vapour pressures at temperatures To ,~ and T2 mole of a non-volatile solute is dissolved in I g of the solvent.
for solvent, solution I and solution II are, thus, Po, PI and P2
respectively. If wB = land Ws = 100g,
For very dilute solutions, the curves FD and CE are almost , mB
straight lines and CB is also nearly a straight line. The ABEC and
K
ABDF are similar. AT
100
EC BE
So,
DF BD =K'
.or To T2 = Po P2 K' is called molecular depression constant.

To -Tl Po -PI It is defined as the depressiun of freezing point produced
when 1 mole of the solute is dissolved in 100 g of the solvent.
AT2 AP2
or --=--
,Thus, K == lOOK'
or Putting this value in eq. (i),
AT == lOOK' X
... (ii)
,mB xW A
WB
If - == I and W A = 1000 g
mB
K
AT
1000
Kf
Kf is called molal depression constant.
T Z T1 To
It is defined as the depression of freezing point produced
Temperature -
when 1 mole of solute is dissolved in 1000 g of the solvent.
Fig. 5.11 Thus, K == 1000Kr
. From Raoult's law for dilute solurions, Putting this value in eq. (i),
Po - Ps wB. mA
Po mB w A AT == 1000Kf -=-- ... (iii)
mB wA
* This relation may alsQ'be written as:
' W O O Kr x W
AT
ImxW
where W and Ware the masses of solute and sol ver:t respectively and m =molecular mass of solute.
SOLUTIONS
or AT = molality x K J (iv) Solute does not form a solid solution with solvent in frozen state,
i.e., only solvent separates in solid state on freezing the solution.
KJ is characteristic of a particular solvent and can be (v) Equimolal quantities of different substances dissolved in the
calculated from the thermodynamical relationship . same quantity of solvent bring out the same depression in
0.002 2 freezing point of the solvent under identical conditions.
: : ::::: SOME SOLVED EXAMPLES :::::::

where, TJ is the freezing point of solvent in absolute scale and LJ Example 35. On dissolving 1O.8g glucose (m. wt. =' 180) in
the latent heat of fusion in calories per gram of the solvent. For 240 g ofwater, its boiling point increases by 0.13° C. Calculate the
water, molecular elevation consta~t of water.
K _ 0.002 x
Solution: AT = lOOK I x w
J - 80 WXm -
= 1.86K kg mol- l
Dr K' = ATx Wx m
The molal depression constants for some common solvents are . 100 x w
given in theJollowing table:
Given, AT 0.13" C, W = 240g,m 180and w= 1O.8g
Table S.S Molal Depression Constants of Some Solvents K' = O.13x 240 x 180 = 5.20
.
; . Molal elevati,n eonstant 100 x 10.8
Solvent F.pt; (OC) . . (Kkg~orl) Example 36. A solution of 2.5 g of a non-volatile solid in
Water 0.0 . 1.86 100g benzene is boiled at 0.42°C higher than the boiling point of
pure benzene. Calculate the molecular mass of the substance.
Ethyl alcohol -114.6 1.99
Molal elevation constant ofbenzene is 2.67 K kg mo/- J •
Chloroform -{)3.5 4.70
1000K b x w
Carbon tetrachloride -22.8 29.80 Solution: In == ----"---
WxAT
Benzene 5.5 5.12.
Camphor 179.0 39.70 Given, K b == 2.67, w = 2.5g, W 100g, tlT == 0.42
m 1000 x 2.67x 2.5 = 158.9
If K J' w A ,AT and wB are known, molecular mass of a 100 x 0.42
non-volatile solute can be determined. AT is measured by
The molecular mass Df substance is 158.9.
Beckmann's method in the laboratory.
The molecular mass of non-volatile and non-ionisable solute Example 37. The molal elevation constant for water is
can be calculated using following formula: 0.56 K kg mol -1. Calculate the boiling point of a solution made
K J wB by dissolVing 6.0 g ~f urea (NH 2CONH 2) in 200g of water.
mB = - X - . x 1000
AT wA Solution: AT = 1OOOK b x w
where, WBand W A are the masses of solute and solvent· mxW
respectively. , Given, Kb =0.56Kkg mDI- J , w =6.0g, W 200g, m= 60
Anti-freeze solutions: Water is used in radiators of cars an!!
other automobiles. In cold countries where the atmosi$.erie.. AT = 1000 x 0.56 x 6.0 0.280 C
temperature becomes less than zero degree, the water: in 'he " 200x 60
radiators would freeze. Anti-freeze solutions are useful under
Thus, the bDiling point Df sDlutiDn . b.pt. Df water + AT
these conditiDns when the vehicles are used in the region~ Df
sub-zero temperature so. that the water dDes nDt fr~eze in =-; (l00° C+ 0.28° C) 100.28° C
radiators. Such solutiDns are made by dissolving ethylene glYCDl Example 38. By dissolving 13.6 g of a substance in 20 g oj
in water. Freezing pDint can be lowered to. the desired' extent by water, the freezing point decreased by 3.T'C. Calculate the
varying the cDncentratiDn Df ethylene glycoL Glycerol can also molecular mass of the substance 'Molal depression constantfar
be used as anti-freeze. wf?tcY" 1.863 K kg mol -1)
Freezing mixture : It is a mixture of ice and commDn salt
1000KJ x w
(Nact). It is used in the making Df ice-cream and in the Solution: m=------'----
labDratDries to. create low temperatures. With the help' Df this WxAT
mixture, a temperature as IDW as-33°C (240 K) can be achieved.
Given, KJ = 1.863 K kg mD: 1
Note: Ebullioscopic and cryoscopic methods are effective when.
(i) Solutions are dilute. Solutions obey Raoult's law. w == I3.6g, W 20g, AT -=: 3.7° C
(ii) The solute is non-volatile.
(iii) There is no association or dissociation of solute molecules in the m= 1000x 1.863 x 13.6 == 342.39
solution. 20x 3.7
(b) 0.512 (c) 0.512 (d) 0.0512 Difference between Osmosis and Diffusion
(a) 0.186
1.86 The two processes, diffusion and osmosis, can be
[Ans. (d)) distinguished in terms of the following aspects:
[Hint: llT = K j x m (i) In diffusion, solute as well as solvent molecules flow in
0.186 = 1.86 x m opposite directions while in osmosis the flow of solvent
m 0.1
molecules occurs in one direction only.
(ii) For osmosis, a semipermeable membrane* is required
llT = Kb x m =0.512 x 0.1 = 0.0512) while for diffusion it is not required.
30. The amount of urea to be dissolved in 500 cc of water
( K r 1.86) to produce a depression :::'" :JJ 86°C in the Semipermeable membrane
freezing point is: (UGET (ManipaJ) 2006) "A membrane which allows the solvent molecules to pass
(a)9g (b)6g (c)3g (d)O.3g through it but prevents the passage ofsolute molecules through it
[Ans. (c)] is called a semipermeable membrane." . . .
[Hint: '-'AT =-- K j x wB X 1000 Examples of semipermeable membranes are too many.
mB x WA Parchment paper, membranes covering the animal and plant cells
x 1000 and many gelatinous inorganic substances such as calcium
0.186 1.86 x
60x 500 phosphate and copper ferrocyanide, etc., act as semipermeable
WB = 3 g] membranes. Animal and plant membranes are not all completely
semipermeable. The best semipermeable membrane used is
31. What should be the freezing point of aqueous solution
. prepared by deposition of copper ferrocyanide, CU2[Fe(CN)6]'
containing 17 g ofC 2 H sOH in 1000 g of water (Kj for water
in the pores of a porous pot.
J.86deg kg mol-.1)?
Working of semipermeable membrane : Sev~ral theories
(a) 0.69°C (b) 0.34°C have been put forward to explain thewv,~...~ng Vi semIllt:rmeable
(c) O.O°C (d) 0.34°C membrane. These are :
[Ans. (a)]
(a) The sieve theory: The theory was suggested by Traube.
[Hint: llT =Kr x x 1000 = 1.86 x 17 x 1000 = 0.69 According to this theory, a semipermeable membrane contains a
mB x WA 46 x 1000 large number of small pores which eet like a sieve. The pores
Freezing point of solution =0 - 0.69; 0.69° C] allow the smaller molecules of solvent to pass through it but does
.not allow the larger molecules of solute to do so. However, this
5.13 OSMOSIS AND OSMOTIC PRESSURE theory fails in those cases of semipermeability where the solute
molecules' are smaller than the solvent molecules.
Osmosis: When a semipermeable membrane is placed between (b) The solution theory : According to this theory, a
a solution and a solvent, it is observed that solvent molecules membrane is permeable to those substances which dissolve in it
enter the60lution arid the volume of solution increases. It is also and is impermeable to those which are insoluble in it. Thus, a
observed that if two solutions of unequal concentrations are layer of phenol acts as a semipermeable membrane when placed
separated by a semipermeable membrane, the solvent molecules
between a solution of Ca(N03 h. Phenol allows water to pass
from a solution of lower concentration move towards a solution through it because water is soluble in phenol. It is impermeable to
of higher concentration. This phenomenon was first observed by
Ca(N03 h because Ca(N03 h is insoluble in phenol.
Abbe Nollet (1748) and termed as Osmosis (Greek, osmos to
(c) Vapour pressure theory : According to this theory, a
push). Osmosis is defined as the spontaneous flow of solvent
solvent can pass through a semipermeable membrane because the
molecules through semipermeable membrane from a pure
vapour pressure of the pure solvent is higher than the vapour
solvent to a solution or from a dilute to a concentrated
pressure ofthe solution. This theory is widely accepted because it
solution.
explains the phenomenon of osmosis.
The phenomenon of osmosis can be demonstrated by the
Osmotic pressure: A porous pot is taken and a
following experiment:
semipermeable membrane of copper ferrocyanide is deposited in
Two eggs of same size are taken and their outer hardshell is its walls. It is fitted with a long glass tube with the help of a
removed by dissolving in dilute hydrochloric acid. One of the rubber stopper. It is filled with concentrated aqueous sugar
eggs is placed in distilled water and the other in saturated salt solution and placed in distilled water. Osmosis occurs and the
solution. level· of the solution in glass tube rises over a period of time.
After sufficient time, it is noticed that the egg placed in water After a few days, the level becomes stationary. At this
swells up and that placed in salt solution shrinks. In the first case, eqUilibrium state the hydrostatic pressure of the liquid column
water enters the concentrated egg fluid while in the second case, exactly balances the tendency which enables the water molecules
water comes out of the egg as salt solution is more concentrated to pass through semipermeable membrane.
than the egg fluid. ,
* Membranes which allow the passage of only solvent molecules through them are called semipermeable membranes. Egg membrane, goat's bladder
and cell membranes can serve as semiperineable membranes but these are not perfect for laboratory measurements. Artificial membranes of gelatinous
inorganic substances such as copper ferrocyanide are used these days as semipermeable membranes.
I
SOLUT.IONS I 343
Maximum level solution in order to stop the flow of the solvent into the
- .
solution through semipermeable membrane is equal to
: I
. Hydrostatic
pressure
Initial level
0smotic pressure.
Determination of Osmotic Pressure: Berkeley and

Hartley's Method
Various methods are employed for the measurement of
osmotic pressure but the best known method was suggested by
Berkeley and Hartley. The apparatus used is shown in Fig. 5.14.
Semipermeable A porcelain tube having copper ferrocyanide membrane in: its
membrane walls is enclosed in a metallic jacket. The porcelain tube is fitted
with a reservoir of pure solvent at one end and a capillary tube at
Sugar solution
the other end. In a metallic jacket, there is an arrangement for
applying external pressure which is measured with the help of
~_ ~_ ~_ ~_ ~_~_~_~_ ~__~_ ~_ ~_ t-- Water pressure gauge.
Fig. 5.12 Hydrostatic pressure determination

The hydrostatic pressure developed as a result of osmosis Stopcock
Capillary
is a measure of osmotic pressure of the solution. Osmotic tube
pressure is also defined as the hydrostatic pressure built up on
the solution wbichjust stops the osmosis.
Osmotic pressure := hydrostatic pressure
1t = hdg Semipermeable
membrane
where, h = increase in level in the tube of unit cross section,
=
d density of solution and g acceleration due to gravity. Steel vessel
Actually, this will not be an exact measure of osmotic pressure Fig. 5.14 Berkeley and Hartley's method
of the solution originally taken because sufficient dilution has
taken place with time. Procedure: The porcelain tube is filled with pure solvent
If osmosis takes place due to concentration gradient i.e., when and the metallic jacket with solution. The level in the capillary
two solutions of different concentration are separated by tube will tend to move down as the solvent flows towards
semipermeable membrane then, solution due to osmosis. External pressure is now applied onthe
,solution by the piston so that level in capillary remains stationary.
1t = hdg := AeRT
The reading of pressure gauge is recorded. This is the osmotic
Alternative definition: An apparatus as shown in Fig. 5.13
pressure of the solution.
consists of a water-tight chamber which is divided into two
halves by a semipermeable membrane and fitted with a Advantages: (i) It is a quick and accurate method.
water-tight piston and a flow indicator in separate compartments. (ii) The concentration of the solution does. not change
The compartment having a piston is filled with solution and the because flow of solvent is not permitted into solution; so the
other compartment is filled with a pure solvent. Water (solvent) results obtained by this method are reliable ..
tries to flow into the solution side. To check this tendency, a (iii) As the osmotic pressure is balanced by external pressure,
certain pressure shall have to be applied by the piston. This there is no strain on membrane and the danger of itr bursting is
external pressure.is thus a measure of osmotic pressure of the eliminated. So, this method can be used to measure high osmotic
solution. The external pressure which must be applied on tbe pressures also.
External
Comparison of osmotic pressures: de-Vries developed an
pressure approximate method for comparing the relative osmotic
Flow
~ indicator
pressures of aqueous solutions. A solution of low osmotic
pressure is termed hypotonic and solution of high osmotic
pressure isterrned hypertonic. The,protoplasmic layer, lining the
cell walls of plant cells is easily penetrated by water but is almost
impermeable to the substances dissolved in' the cellular fluid.
When a plant cell is placed in hypotonic solution, the water is
drawn in and the cell swells. If the cell is placed in a hypertonic
solution, water will diffuse out of the cell flu:,i and partial
collapse of the cell will take place when hypotonic solution is
separated from hypertonic solution using semipermeable
Fig. 5.13 membrane, then osmosis takes place from hypotonic to
hypertonic because solvent concentration is greater in hypotonic 5.14 VAN'T HOFF THEORY OF DILUTE
solution. This phenomenon is known as plasmolysis. The change SOLUTIONS
in cell can be observed under a microscope. When the plant cell is.
van't Hoff realised that an analogy exists between gases and
placed in the solution of same osmotic pressure as that of the cell
solutions provided osmotic pressure of solutions is used in place
fluid, no change in the structure of the cell is observed. Such
of ordinary gas pressure. He showed that for dilute solutions of
solutions having same osmotic pressures are termed isotonic. By non-electrolytes the following laws hold good:
putting, therefore, cells of the same kind into solutions of
1. Boyle-van't Hoff law: The osmotic pressure (P or 1t)
different concentrations, it can be ascertained whether the
solution is hypertonic or hypotonic or isotonic. of a solution is directly proportional to its concentration (C )
when the temperature is kept constant. The concentration of the
<~..... " / ~~:I~~~e

solution containing one gram mole in V litre is equal to
f l,) ~(C=~).
cellUlose .. , .....)
cell wall ~.&_Plasma
Thus, Po<; C (when temperature is constant)
or poc_1
V
or PV constant or 1t V constant
(A) (8)
van't Hoff presumed that the osmotic pressure is due to the
Fig.5.15 Plasmolys,is' bombardment of solute molecules against the semipermeable
membrane as the gas pressure is due to hits recorded by gas
, Some biological explanation on the basis of osmosis are given molecules against the walls of its container.
below: . '
2. Pressure~Temperature law (Gay-Lussac-van't Hoff
(i) In animals, circulation of water to all parts of body takes
law): Concentration remaining same, the osmotic pressure of a
place due to osmosis. . .
dilute solution is directly proportional to its absolute temperature
(ii) Plant roots absorb water from soil due to osmosis. Concen- (T), i.e., .
tration of cell sap illside the root hair cells is higher than that of
water present in the soil. Water enters the root cells due to
endosmosis. P 1t
or - = constant or - := constant
(iii) Water absorbed by plant roots is circulated in the entire T T
. plant body and reaches to the top of a tall tree due to osmosis. Combining the two laws, i. e., when concentration and
(iv) Osmosis helps in plant growth and germination of s~eds. temperature both are changing, the osmotic pressure will be
(v) Red blood cells burst when placed in water; it is due to given by:
endosmosis. pocCT
(vi) Vari?us functions of plants are controlled by osmosis,
e.g., stretchmg of leaves and flowers, opening and closing of or p:= kCT
flowers.
(vii) Use of salt and sugar in pickles and jams acts as or
1
P=k·_·T
V
( ~ince, C == ~)
preser~atives. It prevents growth of bacteria and fungi by
osmOSIS. or PV STornV ST
(viii) Dead bodie3 swell under water due to endosmosis.
S is called molar solution constant.
(ix) When dried fruits and vegetables are placed in water, they
Here, V is the volume of solution containing one gram mole of
slowly swell and return to the original form. It is again due to
the solute. The value of S comes out to 0.082 litre atm K- 1 mol- 1
endosmosis of water into the fruits and vegetables.
'. Intravenous drip of saline water: Saline drip to the patients which is in agreement with the value of R, the molar gas constant.
IS also based on the principle of osmosis. In case, the solution contains n gram moles in V litre, the general
equation would become:
(i) A 0.91% solution of NaCI in water is isotonic to human
blood. Hence, in this solution red blood cells neither swell nor PV nST or1tV=nST
shrink. 3. Third law: Equimolecular solutions of different solutes
(ii) Aqueous solution of NaCI with concentration less than exert equal osmotic pressure under identical conditions of
0.91 % is hypotonic to blood. On placing red blood cells in this temperature. Such solutions which have the same osmotic
solution, endosmosis results into bursting ofRBCs. pressure are termed isotonic or iso-osmotic. When two isotonic
(iii) Aqueous solution ofNaCI with concentration more than solutions are separated by a semipermeable membrane, no flow
of solvent molecules is observed on either side.
0.91 % is hypertonic to blood. On placing red blood cells in it
exosmosis or plasmolysis results into shrinking of cells.
SOLUTIONS
The law is similar to Avogadro's hypothesis. It can be stated

or
as, "Equal volumes of dilute solutions of different solutes,
having the same temperature and osmotic pressure, contain
equal number of molecules". This is the condition for isotonic solutions.
If molecular mass of one solute is known, the molec,ular mass
For solution I, PV = n i ST of the other can be determined without using osmotic pressure
For solution II, values.
Thus, ni must be equal to n 2 when P, V and T are same. Osmotic pressure of mixture of two solutions:
The analogy of dilute solutions with gases is thus perfect. This Case I: Let two solutions of same substance having
led van't Hoff to suggest that a solute in dissolved state (Le., in different osmotic pressures 1t 1 and 1t2 are mixed. Osmotic
solution) behaves as a gas and the osmotic pressure of the pressure of the resultant solution can be calculated as, .
solution is equal to the pressure which the solute would exert 1t I VI + 1t 2V2 = 1tR (VI + V2 ) •
if it were a gas at the same temperature and occupying the where, VI and V2 are the volumes of two solutions and 1t R is the
same volume as that of the solution. This statement is known as resultant osmotic pressure.
van't Hoff theory of dilute solutions.
Case II: Let n l and n2 are the number of moles of two
different solutes present in VI and V2 volumes respectively.
5.15 DETERMINATION OF MOLECULAR Osmotic pressure of the mixture can be calculated as,
MASSES n l i l RT n2 i2RT
1t = 1t1 + 1t2 = + --='-=--
In the case of dilute solutions, it has been stated that the equation (~ + V2 ) (VI + V2 )
PV = nST holds good. Instead of one gram mole of the solute
present in V litre of solution, let wB gram of solute (mol. mass 1t= (nli l +n 2 i 2 ) RT
mB) be present in V' litre of solution; then , (VI + V2 )
n = WB and V V' Here, i l and i z are van't Hofffactor'for the two solutes.
mB
Thus, the equation PV = nST becomes: ······1
•••••• SoME SOLVED EXAMPLE51••••
•••···•.
PV ' = wB ·ST , Example 49. 200 em 3 ofan aqueous solution contains 1.26
me
g of a polymer. The osmotic pressure of such solution at 300 K is
wB xS xT found to be 2.57 x 19-3 bar., Calculate the molar mass of the
or me -
- --"PV-' - - polymer. .
Knowing the value of P experimentally, the value of mA ' i. e. , 1tV WB RT
Solution:
molecular mass of the solute can be determined. ma
Consider two solutions I and II having ni and n2 moles of the
,WB RT
solute in VI and V2 · litres of solution respectively. Let PI and P2 me=-x-
be their osmotic pressures at the same temperature (T). V 1t
From the equation PV nST, _1.26

- - x 0.083x300_61038
- gmo)-1
0.2 2.57 x
For solution I, l1VI = nlST
Example 50. A solution is prepared by dissolving 1.08 g oj
or PI =!!.L ST human serum albumin, a protein obtainedfrom blood plasma, in
~ 50cm 3 ofaqueous solution. The solution has an osmotic pressure
For solution IJ" P2V2 = n2 ST of5.85 mm Hg at 298K:
(a) What is molar mass of albumin?
or P2 =V ST (b) What is height of water column placed in solution?
2
d (H 2 0) 19 cm- 3
Ifboth solutions are isotonic, i. e., PI = P2 , obviously, Solution: (a) Molar mass of albumin can be calculated
!!.L ST =!!1. ST using following relation:
VI V2 xRT
me =--=-- .. :(i)
1tV
or !!.L =n2 Given, we 1.08g;R=0.0821litreatmK- I mol- 1
VI V2
5.85 50
Wilmi W2 1m2
T 298 K 1t = - atm' V = - - 0.05 litre
or --=--- .' 760 ' 1000
~ V2
356 I
solutiofi: We know Dividing eq. (i) by (ii)
I:!T = i x k f x m 0.465 .
--=l
0.201 = ix 1.86x 0.1 0.245
i 1.0806 1.897
The degree of dissociation HF may be calculated liS. i-I 1.897 - 1
We know, a=--
a i-I =1.0806-1' 0.0806 n-I 2- 1
n-I 2-1 . 0.897
Percentage dissociation = a x 100 0.0806 x 100 .. Percentage ionization = 0.897 x 100
. 8.06 =89.7
Example 23. There is K1 and sucrose solution with 0.1 M Example 24. 102% solution of glycerine .and 2% solution
COl .Jntration, if the osmotic pressure ofK1 and sucrose solution of glucose are isotonic. Molecular mass of glucose is 180 then
is 0.465 atm and 0.245 atm respectively. Thenfind the van i Hoff find out the molecular mass ofglycerine. ![Al1PMT,(M_ios):ZOO9J
factor ofK1 and its degree of dissociation.ilmm !(M~iDS} :Z'_l filoiutiofi : 'It glycerine == 'It glucose
soiution : For KI
C (glycerin~) =C (glucose)
= iCRT
'It
0.465 i x 0.1 x RT. ... (i) 120x 1000 2x 1000
For Sucrose mgIycerine xlOO 180x 100
'It = CRT mglycerine = 91. 8
0.245 = 0.1 x RT ... (ii)
1. SoiufioHi It is a homogeneous mixture .of two of more 4. Solutions of liquids In liquids! Miscib.1e liquids form
components· whose concentration can be varied within certain three types of solutions which may be ideal or non-ideal solutions.
limits. A solution containing only two components is termed a Ideal solution is that in which the attractive forces among the
. binary solution:. One component is called the solute while other solute and solvent molecules are of the same order as that of
as solvent. The component having the same physical state as the solute intramolecular and solvent intramolecular forces. The W
solution is called the solvent. In solutions, in which the two mix~g and I:!V mixing in such solutions is zero. Ideal solutions
components have the same physical state, the component present obey Raoult's law.
in larger proportion is termed the solvent and the other The solutions in which solute-solvent interactions are
componen:t is called solute. different from solute-solute and solvent-solvent interactions are
2. $()tubiUtyi A solution is said to· be saturated when it called non~ideal solutions. The non-ideal solutions do not obey
contains as much solute as it can dissolve at a particular Raoult's law for all concentrations.
temperature in presence of the undissolved solute. A super- W mix *" 0 and I:! V*"O in these solutions. There are two types
saturated solution contains more. quantity and an unsaturated of deviations from the ideal behaviour. .
solution contains less quantity of the solute than a saturated (i) If I:! Vmix > 0 and W mix > 0, then non-ideal solutions
solution. . . . show positive deviations, Such solutions form a constant boiling
The amount of the solute in grams which can dissolve at a mixture of defmite cOInposition (azeotropic mixture) having
particular temperature in 100 grams of the solvent when the . boiling point less than either of both the liquids. In these
solution is saturated is termed solubility of the solute. solutions . solvent-solvent and solute-solute interactions are
3. SolubUlty of a 11l8tH It liquid: Gases which can be stronger than solvent-solute interactions. Examples are:
.easily liquified are more soluble in common solvents. The gases H20+CH3 0H;H 2 0+ C2~OH; C6H6 + CH3 0H;
which form ions in water are highly soluble in water. The C 6H6 + CCI 4 ; (CH 3 hCO+ C 6H6; (CH 3 h CO+ C2~OH.
solu~ility of a gas generally decreases with rise in temperature (ii) If I:!Vmix < 0 and W mix < 0, then non-ideal solutions
and mcreases with increase in pressure. show negative deviations, In these solutions, solvent-solvent and
Mass of gas dissolved per unit volume of a solvent is directly solute-solute interactions are weaker than solvent-solute
proportional to the pressure of the gaS at a given temperature. interactions. Such solutions also form azeotropic mixture having
This is Henry's law. boiling point higher than either of the two solvents. Examples
m KP (at constant temperature)
where, m is the mass of gas dissolved per unit volume of solvent,
P is pressure of the gas in equilibrium with the solution and K is
proportionality constant.
357
CC'li!ame ~ .JIldfiditinn .'

•"1i1mDmtla --" -
}, Mass percentage %(WIW) Mass of solute Number of parts by mass of solute per hun- No effect
x 100
Mass of solution dred parts of the solution.
1.,. Gram per litre gIL Mass of solute in grams Amount of the solute in grams present in Changes' with change
Volume of solution in litres - one litre of solution. of temperature.
$, Parts per million ppm Mass of solute Number of parts by mass of solute per 1(f No effect
X 106
Mass of solution parts of solution.
4, Molarity M Number of moles of solute Number of moles of solute per litre of solu- Changes with challge
Number of litres of solution tion . of temperature. '
~. Molality m . Number' of moles of solute Number of moles of solute present in I kg No effect

Number of kilograms of the solvent of the solvent.
l), Normality N Number of gram equivalents of solute Number of gram equivalents of the solute Changes with change
<
Number of litres of solution present in one litre of the solution. of temperature.
1.. Mole fraction X ~ Ratio of number of moles of one component No effect

nA + nB . to the total number of moles of solution.
$. Formality F Number of formula mass Number of formula mass in grams present Changes with change
Number of litres of solution per litre of solution. of temperature.
-
(" ~"W§ mw~ The partial pressure of any volatile
constituent of a solution at a constant temperature is equal to the
pressure. (po ~ Ps J is called relative lowering in vapour
vapour pressure of pure constituent multiplied by mole fraction
pressure.
of that constituent in the solution.
The relativ~ lowering in vapour pressure of a solution
P A == mole fraction of A x p~ ~ X A X p~ containing non-volatile solute is equal to the mole fraction of the
In the case of binary solution of two volatile liquids, the total solute present in the solution. this is Raoult's law.
vapour pressure of such solution can be given as: Mathematically,
Total vapour pressure of solution == p~ x X A + p~ X X B Po - Ps X n
. Po == solute == n+N
== P A + PB
Mole fraction of component A in vapour phase, Let w g of the solute (mol. mass == m) be dissolved in W g of
i. e., YA ==~== p~ XA solvent (molecular mass == M).
P p~ X A + p~ XB Po-Ps .wlm
Po wlm+WIM
p~ XB
similarly, YB == --~--=-- If the solution is very dilute wi m in denominator can. be
p~ X A + p~ XB neglected.
7. etl~y~ "~~~} The properties of dilute Po - P s _ wi m_ wM !'l.p
solutions containing non-volatile solutes, which depend upon the Po - WI M - mW or Po m A wB
number of solute particles in solution are called colligative
properties. These properties do not depend upon the natUre of ' .. Eley!l;Cicm M Wi~~: The boiling point of a
solutes and solvents. The four colligative properties are: solution containing non-volatile solute is always higher than the
(i) Relative lowering in vapour pressure boiling point of a pure solvent. The increase in boiling point is
(ii). Elevation in the boiling point termed elevation and represented' as !'l.Tb'
(iii) Depression in the freezing point I1Tb oc Molality of the solution
(iv) Osmotic pressure.
or !'l.Tb == m x K b . (K b is a molal elevation constant)
All these properties are dependent on the concentration of
solutes in solution. lOOOxK b Xw IOOOxK b xW A
or !'l.Tb == or . !'l.Tb == -----"---.....:-::-
!S.• ~o/~ JMy~iJ.l t'qHf "~fg:: When' a Wxm wBxmA
non-volatile solute is dissolved' in a solvent, its vapour
pressure decreases. ( Po - P s )is known as lowering in vapour where, W == mass of solute; m ==. molecular mass of solute;
W == mass of solvent
RT? . osmotic pressure istenned hypotonic and the solution having

K b is equal to - - 9 - . higher osmotic pressure is termed hypertonic solution. The two
lOOOL
solutions having equal osmotic pressures are termed as isotonic .
.' whet"~.W"1);:: boiling point of solvent in.absolute scale; Condition for isotonic solutions is'' . •' .
L =latent heat of vaporization
3-=~
The units ofKb areK kg mol~l. miVI mVZ 2
10. Depression in freezing point: The freezing point of a
A 0.91% solution of pure NaCI is isotonic with human blood
solution containing non-volatile solute is always less than the
cells (RBC). An NaCI solution with concentration less than
freezing point of a pure solvent. The decrease in freezing point is
0.91% is called hypotonic and RBC will swell and burst in the
tenned depression and represented as AT, .
solution. An NaCI solution with concentration greater than
AT, Oc:: molality of the solution 0.91 % is called hypertonic and RBC will shrink in this solution,
i. e. , will "undergo plasmolysis or crenation.
or AT, =m x K, (K, is a molal depressionconstant)
12. van't Hoff fador: When the' solute undergoes
. l~x~xw lOOOx~x~ dissociation or association in solution, the number of particles
or AT, = or AT, =---..::..--- in solution increases or decreases and thus, the colligative
Wxm WB xmA
property changes accordingly. In 1886, van't Hoff introduced a
where, W= mass of solute; m = molecular mass of solute; factor' i' known as van't Hoff factor to express the extent of
dissociation or association of the solute in solution.
W = mass of solvent
van't Hoff factor, i
. . RT? .
K, is equal to __0_. . Observed colligativeproperty
. lOOOL . =------~-~-~~~~~-
Theoretical or nonnal colligative proPerty
where, To = freezing point Of solvent in absolute scale;
No. of particles atter dissociation or association
L =latent heat of fusion. =------~---------~-------------
No. of particles when there is no dissociation or association
The units of Kf are K kg mol-I .. Normal molecular mass of the solute
=
n. Osmosis and osmotic pressure: When a solution is Observed molecular mass of the solute
separated from the pure solvent with the help of a semipenneable
membrane, the solvent molecules from' the pure solvent move From the value of' i' it is possible to detefmine the degree of
towards· the solution: The movement of solvent molecules from dissociation or association.
low . concentration to higher concentration through In case of dissociation 'i' is greater than I.
semipenneable membrane is tenned as osmosis .. . I+(n-l)a
I =--'---'--
A.s a result of osmosis, a p~sure is developed which is 1
tenned as osmotic pressure, i. e. , the hydrostatic pressure
where, n is the number of particles per molecule and (l is the
which develops oil account of osmosis is called osmotic pressure.
. degree of dissociation. ,
It is equal to h· d . g. It is also found that if an equal and opposite
force is applied on the solution, the osmosis stops. Thus, the i-I
or a=---
excess pressure that .must be applied on the solution as to prevent· (n -1)
osmosis is also the measure of osmotic pressure.
Similarly, in case of association~ , i' is less than I.
Osmotic pressure of a dilute solution is given by van't Hoff
equation, P = CRT, where C = concentration, R = solution
constant and T =absolute temperature.
1+(;-1) a
i=-------
C=!!.=~ 1
V mxV.
where, n is the number of molecules which are associated to fonn
where, w= mass of solute in grams one giant molecule and IX is the degree of association.
V = volume of solution in Htres i-I
or
m =molecular mass of solute
i.e., P=~.RT
mxV
Molecular masses of electrolytes observed by the methods
Best method for the determination of osmotic pressure is based on colligative properties are always leSs than nonnal
Berkeley and Hartley's method. molecular masses.
The tenn hypertonic and hypotonic are applied to compare the
osmotic pressures of two solutions. The solution having lower
SOLUTIONS
13. Calculation of osmotic pressure from lowering of . To

,t7~_ avoid the freezing of water in ~(lar rildi~tor, in the
vapour pressure: - su~~o weather, ethylene glycol is adde,ftOiowc:r the freezing
Po -P fUnB point of water.' .
--=-- 18. Freezing point is same as melting point. Hence, instead of
Po RdT
depression in freezing point, depression in melting point can be
where, Po =vapour pressure of pure solvent determined. For this purpose camphor is used as solvent because
P =vapour pressure of solution it has high molal depression constant, i. e. , 40 K m -I . .
7t = osmotic pressure
mB =molecular mass of solvent 19. Relationship between different colUgative properties:
d-= density of solution in gmV I (i) Osmotic pressure 7t and boiling point elevation I1Tb:
= dRT
R gas constant in attn mL I deg I mol, i. e. , 82.1 . 7t =I1Tb X - --
lOOOK
14. Variation of vapour pressure with temperature b
(Clausius-ClapeyrOli equation): (ii) Osmotic pressure 7t and freezing point depression I1T, :
log 10 (PPr
2
) =~ [..!.. - ..!.]
2.303R 7j T2 7t =I1T, x - dRT
--
lOOOK ,
where, ~ =vapour pressure at7j (iii) Elevation in boiling point and relative lowering of
P2 =vapour pressure at T2 vapour pressure:
fjJ[ = latent heat of vaporization per mole
15. Variation of vapour pressure of a liquid with external
I1Tb =tOOOK b X -l1P ; mA =molar mass ofsolvent
mA Po
pressure:
(iv) Depression in freezing point and relative lowering of
IOglO(P2)=
PI 2.303RT
(P2-~) vapour pressure:
where, PI =vapour pressure at external pressure PI

P2 =vapour pressure at external pressure P2
20. Hygroscopic and deliquescent substances both absorb
V, =molar volume of liquid. moisture from the air. The former do not change their state, e.g. ,
16. Molecular masses of polymers are best determined by glycerol, whereas the latter dissolve into it, e.g., NaOH. They
osmotic pressure method because other colligative properties absorb moisture because the vapour pressure of their saturated
give so low value that they cannot be measured accurately. solution is'iess thantbat of water vapours present in surroUndings
at that temperature.
The substances like Na 2COl ·1 OH 2o which lose their water or
crystallisation are called emorescent.

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322 , A.B.

PHYSICAL CHEMISTRY FOR COMPETITIONS

149.24 Example 15. Reaction,

example, CO 2 is more soluble in water than oxygen or hydrogen. I;""" I •

... (i) N2 293 76.48

Limitations of Henry's Law 6.56x 10-2

Table S.2 Comparison between Ideal and Non-ideal Solutions

·4. P = PA + PB P~-XA + p~ X B PA ). p~ X A; PB > pZ X B PA <P~XA; PB <p~ X B

5. A - A, A B, B - B interactions A - B attractive force should be weaker A B attractive force should be greater

Examples: Examples: Examples:

Thus, according to Raoult's law, =XAPJ+XBP:

Graphical Representation of Ideal and Non-ideal Solutions

Mole fraction XA = 1 Mole fraction Xs= 1 XA = 1 Mole fraction

and 3mole ofB is 550mm ofHg. At the same temperature, if one

p~ =:= 600mm ofHg::: vapour pressure of pure B xt

16. The vapour pressure of pure benzene at 88°C is 957 mm and

(c) x benzene = X toluene = 0.5 '0

[Hint: p =pgenzene xbenzene + P~luene Xtoluene III :

(1) Nature of solute,

N Loss in mass in the solution bulbs oc P s

Fig. 5.8 Ostwald and Walker method

Xs = 0.05 0.01 96 = 0,02 ]

( P s == vapour pressure of solution)

I1T=- K K l1IWII cIrtwiIdtiI C'tt" u-

5.12 DEPRESSION OF FREEZING POINT or

.or To T2 = Po P2 K' is called molecular depression constant.

: : ::::: SOME SOLVED EXAMPLES :::::::

Determination of Osmotic Pressure: Berkeley and

~_ ~_ ~_ ~_ ~_~_~_~_ ~__~_ ~_ ~_ t-- Water pressure gauge.

Fig. 5.12 Hydrostatic pressure determination

<~..... " / ~~:I~~~e

The law is similar to Avogadro's hypothesis. It can be stated

From the equation PV nST, _1.26

CC'li!ame ~ .JIldfiditinn .'

~. Molality m . Number' of moles of solute Number of moles of solute present in I kg No effect

1.. Mole fraction X ~ Ratio of number of moles of one component No effect

RT? . osmotic pressure istenned hypotonic and the solution having

13. Calculation of osmotic pressure from lowering of . To

where, PI =vapour pressure at external pressure PI

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