CHEMISTRY

SOLUTION & COLLIGATIVE PROPERTIES

Concentration Terms :

% Concentration
% w/w =

weight of solute (g)

weight of solution (g) 100

It does not change on changing temperature .

Ex.

10% w/w urea solution = 10 gm of urea is present in 100 gm of solution.

= 10 gm of urea is present in 90 gm of water.

% wt/vol. (w/v)

% w/v = wt. of solute/100 mL of solution

gram of solutes
% w/v = volume of solution in mL 100
It changes on changing temperature .

Ex.

10% (w/v) urea solution. = 10 gm of urea is present in 100 mL of solution.

But not 10 gm of urea present in 90 ml of water
for dilute solution : volume solution = volume solvent.

% v/v

If both solute & solvent are liquids = volume in (mL) of solute per 100 mL of solution.
Ex.

10% v/v alcohol ethanol aq solution = 10 ml of ethanol in 100 ml of solution.

10 ml of C2H5OH in 90 ml of H2O

Strength of solution in g/L

Weight of solute (in gram) per litre (1000 mL) of solution.
Ex.

10% (w/v) sucrose solution, then specify its concentration in g/L

100 mL .......... 10 g

1000 mL ........

10
1000 = 100 g/L
100

Ex-1

If we have 6% w/w urea solution with density 1.060 g/mL, then calculate its strength in g/L ?

Solution

6 g urea is present in 100 gm solution.

6 g in

100
mL
1.060

100
mL 6 gm.
1.060
6

1000 mL = 100 1.060 1000 = 10.6 6 = 63.6

Molarity = No. of moles of solute per litre of solution.

Let
n = No. of moles of solute
N = No. of moles of solvent
V = volume of solution

1000
n
W
M = V (in L) = M x V (in mL )

no. of moles of solute = molarity x volume ( in L)
no. of m. moles of solute = molarity x volume ( in mL)
If V1mL of C1 molarity solution is mixed with V2 mL of C2 molarity solution (same substance or solute)
Cf (V1+V2) = C1V1 + C2V2
Total moles
C1V1 C 2 V2
=
Total volume
V1 V2

Cf =

It changes on changing temperature .

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Molality = No. of moles of solute per kg(1000 g) of solvent.

Let w gram of solute (Molar mass = Mg/mole) is dissolved in 'W' gram of solvent.
1000
w
molality = x W ( g )
M

moles 1000
molality = W (g)of solvent
It does not change on changing temperature .

Ex-2

If 20 ml of 0.5 M Na2SO4 is mixed with 50 ml of 0.2 M H2SO4 & 30 ml of 0.4 M Al2(SO4)3

solution. Calculate [Na+], [H+], [SO42], [Al3+]. [Assuming 100% dissociation]

Solution

Molarity =

moles
= 10 m. moles of Na2SO4
volume
20 m. moles of Na+

[Na+] =

(ii)

[H+] = ?
10 m. moles H2SO4
20 m. moles H+
[H+] =

20
= 0.2 M
100

(i)

20
= 0.2 M
100

(iii)

[SO 42] =

(iv)

[Al3+] =

10 10 36
56
=
= 0.56 M
100
100

24
= 0.24 M
100

Derive a relationship between molality & molarity of a solution in which w gm of solute of molar
mass M g/mol is dissolved in W g solvent & density of resulting solution = 'd' g/ml.
say 1 L solution taken,
mass of 1 lit solution = (1000 d) g
moles of solute = (molarity)
mass of solute = (molarity) x m
mass of solvent = W
= 1000 d (molarity) m

(molarity ) 1000
molality = 1000 d molarity M.Wt [Where no.of moles of solute = molarity]
Ex-3

Calculate molality of 1.2 M H2SO4 solution ? If its = 1.4 g/mL

Soluiton

1.2 1000
Molality = 1000 1.4 1.2 98 = 0.936

Normality
No. of equivalents per litre of solution =

no. of equivalent s of solute

volume of solution (in L )

No. of equivalents = normality volume (in L)

(Normality = n-factor molarity)

Equivalent mass =

Molar mass
n factor

No. of equivalent =

Mass of the species

Mass of the species
=
Molar mass
equivalent mass
n factor

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'n' - factor
(i) For oxidizing/reducing agents :
no. of e involved in oxidation/reduction half reaction per mole of oxidising agent /reducing
agent .
e.g. : 5e + 8H+ + MnO4 Mn2+ + H2O

n- factor = 5

(ii) For acid/ base reactions :

no. of H+ ions displaced/ OH ions displaced per mole of acid/ base.
e.g. : NaOH

n - factor = 1

H2SO4 n - factor = 2

(iii) For salt:

n = Total charge on cations.
or
total charge on anions
e.g. : Al2(SO4)3
n - factor = charge on the cation = 2 x 3 = 6

Mole Fraction :
For binary mixture
moles of solute
n
Xsolute = total moles in solutions =
nN
moles of solvent

XSolvent = Total moles in solutions =

nN
Xsolute + XSolvent = 1

ppm (Parts Per Million).

(a)

wt. of solute (in g)

ppm (w/w) = wt. of solution (in g) 106 = 1 million

(b)

wt. of solute (in g)

ppm (w/v) = vol. of solution (in mL ) 106

(c)

ppm (moles/moles) = moles of solution 106

moles of solute

Table : 1

Ex-4

If we have 10 molal urea solution, Calculate mole fraction of urea in this solution & also calculate
% w/w of urea (MW = 60).

Solution

10 moles urea in 1000 g of water

X urea =

10
10
1000 = 65.55 = 0.1526
10
18

% w/w weight of urea =

10 60
x 100 = 37.5%
10 60 1000

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* Note : For dil. aq. solution molality molarity

molarity 1000
molality = 1000 d molarity m (1 g/ml)
Ex-5

Calculate molarity of CaCO 3(aq.) solution which has concentration of CaCO 3 = 200 ppm.

Solution

200 g of CaCO 3 in 106 g of water.

200
2 moles of CaCO 3 in 103 liters of water. (density =1g/mL)
100

So molarity =

2
103

= 2 103 M.

Colligative properties & constitutional properties :

Colligative properties :

The properties of the solution which are dependent only on the total no. of particles or total concentration
of particles in the solution & are not dependent on the nature of particle i.e. shape, size, neutral /
charge etc. of the particles.
Constitutional Properties :

Properties which are dependent on nature of particles are constitutional properties like electrical
conductance.
There are 4 colligative properties of solution.

Osmotic pressure
P

lowering in vapour pressure P

Elevation in boiling point (T b)

Relative

Depression in freezing point (T f)

Osmosis & Osmotic pressure :

Osmosis & Diffusion

Diffusion : Spontaneous flow of particles from high concentration region to lower concentration region
is known as diffusion.

H2O
Blue

2+

Cu

Ex.

CuSO4

Saturated
(Solution)blue

Uniform

Figure
Osmosis :
The spontaneous flow of solvent particles from solvent side to solution side or from solution of low
concentration side to solution of high concentration side through a semipermeable membrane (SPM) is
known as osmosis.
SPM : A membrane which allows only solvent particles to move across it.
(a)

Natural : Semi permeable membrane

Animal/plant cell membrane formed just below the outer skins.

(b)

Artificial membranes also : A copper ferrocyanide.

Cu2[Fe(CN)6] & Silicate of Ni, Fe, Co can act as SPM.

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Ex.

Figure
Conclusion : After some time in (A) grape or egg will shrink and in (B) grape or egg will swell.
Ex-6

In which soluton side complex [Cu(NH3)4]2+ will form and deep blue colour will obtain.

Solution

In neither of side colour complex will form. No solute particle passes through SPM.

Osmotic Pressure :

h
--------------------------Solvent
Solution
SPM

Figure
The equilibrium hydrostatic pressure developed by solution column when it is seperated from solvent
by semipermeable membrane is called osmotic pressure of the solution.
= gh
;
= density of solution
g = acceleration due to gravity ;
h = eq. height
1 atm = 1.013 x 105 N/m 2

Figure

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Definition : The external pressure which must be applied on solution side to stop the process of
osmosis is called osmotic pressure of the solution.
C1 > C2 particle movement.
Pext. = (1 2)
Pext. must be applied on the higher concentration side.
Reverse Osmosis :
If the pressure applied on the solution side is more than osmotic pressure of the solution then the
solvent particles will move from solution to solvent side. This process is known as reverse osmosis.
Berkely : Hartely device/method uses the above pressure to measure osmotic pressure.
Vant Hoff Formula (For calculation of osmotic pressure)
concentration (molarity)
T
= CST
S = ideal solution constant
= 8.314 J mol1 K1 (exp value)
= R (ideal gas) constant

= atm.

C mol/lit.
R 0.082 lit.atm. mol 1 K1
T kelvin

n
RT (just like ideal gas equation)
V
In ideal solution solute particles can be assumed to be moving randomly without any interactions.
C = total concentration of all types of particles.
= C1 + C2 + C3 + s.................
= CRT =

(n1 n 2 n3 .........)
V

Ex-7

If V1 mL of C1 solution + V2 mL of C2 solution are mixed together then calculate final concentration

of solution and final osmotic pressure. It initial osmotic pressure of two solutions are 1 and 2
respectively ?

Solution

Cf =

C1V1 C 2 V2
V1 V2

1
1 = C1RT, C1 = RT

2
2 = C2RT, C2 = RT

C1V1 C 2 V2
RT
= V V
1
2

1V1 2 V2
= V V

Type of solutions :
(a) Isotonic solution : Two solutions having same osmotic pressure are consider as isotonic solution.
1 = 2 (at same temperature)
(b) Hypertonic : If 1 > 2 , Ist solution is hypertonic solution w.r.t. 2nd solution
(c) Hypotonic : 2nd solution is hypotonic w.r.t. Ist solution.

Figure

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Conclusion :
Pressure is applied on the hypertonic solution to stop the flow of solvent partices, this pressure become
equal to (2 1) and if hypotonic solution is replaced by pure solvent then pressure becomes equal to
2.
Note : Osmotic pressure of very dilute solutions is also quite significant. So, its measurement in lab
is very easy.

Ex-8
Solution

Calculate osmotic pressure of 0.1 M urea aqueous solution at 300 K ,

R = 0.082 lit atm K1
= CRT
= 0.1 x 0.082 x 300
= 2.46 atm.

Ex-9

If 10 gm of an unknown substance (non-electrolytic) is dissolved to make 500 mL of solution,

then osmotic pressure at 300 K is observed to be 1.23 atm find molecular weight ?
10 1000
1.23 =
x 0.082 x 300
M 500

Solution

20
0.082
400 gm/mol
x
x 300
100
1.23
If 6 gm of urea, 18 gm glucose & 34.2 gm sucrose is dissolved to make 500 mL of a solution at
300 K calculate osmotic pressure ?
molecular weight of urea = 60 gm , Glucose = 180gm , SUcrose = 342 gm
= C x 0.082 x 300

M=
Ex-10
Solution

0.3 1000 0.082 300

500
14.76 atm

Ex-11
Solution

If 200 mL of 0.1 M urea solution is mixed with 300 mL of 0.2 M glucose solution at 300 K,
Calculate osmotic pressure
0.02 moles urea
0.06 moles glucose
0.08

= 0.5 0.082 300 = 3.94 atm.

Ex-12

If urea (aq) solution at 500K has O.P. = 2.05 atm. & glucose solution at 300 K has OP = 1.23
atm. If 200 ml of Ist solutions & 400 ml of 2nd soln are mixed at 400 K then cal. O.P. of resulting
solution as 400 K (assume molarity is not dependent on temp.)

Solution

Curea =

2.05
= 0.05
R 500

Cglucose =
Ctotal =

1.23
= 0.05
R 300

Vurea = 200 mL

Vglucose = 400 mL

C1V1 C2V2
0.05 200 0.05 400
=
= 0.05
V1 V2
600

= CRT = 0.05 0.082 400

= 1.64 atm

Abnormal Colligative Properties :

Vant Hoff correction
For electrolytic solutes the No. of particles would be different then the No. of particles actually
added, due to dissociation or association of solute.
The actual extent of dissociation/association can be expressed as a correction factor known as

vant Haff factor (i).

Vant Hoff factor : i =

moles of particles in solution after dissociation / association

moles of solute dissolved

If solute gets associated or dissociated in solution then experimentable / observed / actual value of

colligative property will be different from theoretically predicted value so it is also known as abnormal
colligative property.

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This abnornality can be calculated in terms of Vant-Hoff factor.

i=

exp/ observed / actual / abnormal value of colligative property

Theoretical value of colligative property

exp . / observed no. of particles or concentration

Theoritical no. of particles or concentration

Theoretica l mass of subs tan ce

= exp erimental molar mass of the subs tan ce

i > 1 dissociation
i < 1 association
exp .

i=
theor .
Modified formula = iCRT

= (i1C1 + i2C2 + i3C3.....) RT

Case - I

: Electrolyte dissociates

Relation between i & (degree of dissociation) :

Let the electrolyte be AxBy
t=0
teq

AxBy (aq.)
C
C(1 )

xAy+ + yBx
0
0
xC yC

Net concentration = C C + xC + yC
= C [1 + ( x+y 1) ].
= C [1 + ( n 1) ].
n=x+y
= no. of particles in which 1 molecules of electrolyte dissociates
C [1 (n 1) ]
C
i = 1 + ( n 1)

i=

e.g.

NaCl (100% ionised), i = 2. ; BaCl2 (100% ionised), i = 3. ; K4[Fe(CN)6] (75% ionised), i = 4.

Case - II : Electrolyte associates

Relation between degree of association & i.

nA
A n.
t=0
C
0
teq

C ( 1 )

C C +

C
n
C
n

1
C [ 1 + 1 ]
n
1
i = 1 + 1
n

dimerise n = 2 ; trimerise n = 3 ; tetramerise n = 4.

e.g.

CH3COOH 100% dimerise in benzene, i =

1
1
; C6H5COOH 100% dimerise in benzene, i =
2
2

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(1) When reaction is not taking place :
Ex-13

Calculate osmotic pressure of a solutions having 0.1 M NaCl & 0.2 M Na2SO4 and 0.5 MHA.
(Given : Weak acid is 20% dissociated at 300 K).

Soluiton

= NaCl + Na SO + HA
2
4
= 0.1 RT 2 + 0.2 RT 3 + 0.5 RT 1.2
= 0.0821 300 (0.2 + 0.6 + 0.6)
= 34.482 atm.

Ex-14

If 0.04 M Na 2SO 4 solutions at 300 K is found to be isotonic with 0.05 M NaCl (100 %
disscociation) solutions. Calculate degree of disscociation of sodium sulphate ?

Soluiton

i1 C1 RT = i2 C2 RT
i1 C1 = i2 C2
0.04 (1 + 2) = 0.05 2
= 0.75
= 75%.

Ex-15

If 6 gm of CH3 COOH is dissolved in benzene to make 1 litre at 300 K. Osmotic pressure of

solutions is found to be 1.64 atm. If it is known that CH3COOH in benzene forms a dimer.
Calculate degree of association of acetic acid in benzene ?

Soluiton

1
i = 1 + 1 .
n
1
1.64 = 0.0821 300 [ 1 + 1 ] 0.1
n

1.64 = 0.0821 300 [1

] 0.1
2

1.64
2-
=
00.821 30
2
1.64
2-
=
2.46
2
3 = 2

4 = 6 3

2
3

(2) When reaction is taking place :

Ex-16

Solution

If 200 ml of 0.2 M BaCl2 solution is mixed with 500 ml of 0.1 M Na2SO4 solution. Calculate osmotic
pressure of resulting solutions ?
BaCl2 + Na2SO4 BaSO4 + 2 NaCl
0.04 moles
0.05
0
0
0
0.01
Not effect
0.08
0.01
0 .7

Not effect

0.08
0 .7

= (i1C1 + i2C2) RT.

= (3

0.01
0.08
+2
) 0.082 300. = 6.685 atm.
0 .7
0 .7

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Ex-17

Solution

If 200 ml of 0.2 M HgCl2 solution is added to 800 ml of 0.5 M KI (100% dissociated) solution.
Assuming that the following complex formation taken place to 100% extent.
Hg 2++ 4
[HgI4 ] 2
(Complexes are always soluble)
0.04 0.4
Calculate osmotic pressure of resulting initially solution at 300K ?
HgCl2 + 4KI
K[HgI4] + 2KCl.
40
400
0
0
0
400 160
40
80
240
1000

40
1000

80
1000

= (i1C1 + i2C2 + i3C3) RT.

= (0.24 2 + 3 0.04 + 0.08 2) 0.082 300. = 18.69 atm.

Relative lowering in vapour pressure ( RLVP) :

Vapour Pressure :

The conversion of a liquid to a vapour takes place in a visible way when the liquid boils, it takes place under
all conditions.

Figure
say 5 gm liquid left at teq
At eq. :

the rate of evaporation = rate of condense

H2 O ()
H2 O (g)

Kp = PH2O(g) eq.
finally

Figure

Although individual molecules are constantly passing back from one phase to the other, the total
number of molecules in both liquid vapour phases remain constant.
The pressure exerted by vapours of the liquid when equilibrium is established between vapours & its
liquid. is known as vapour pressure.
Vapour pressure is an equilibrium constant (KP) of the reaction.
liquid
vapours.
Since vapour pressure is an equilibrium constant so its value is dependent only on temperature for
a particular liquid
It does not depends on the amount of liquid taken or surface area of the liquid or on volume or shape
of the container. It is a characteristic constant for a given liquid.
The numerical value of a liquid's vapour pressure depends on the magnitude of the intermolecular
forces present and on the temperature. The smaller the intermolecular forces, the higher vapour
pressure because loosely held molecules escape more easily.
The higher the temperature, the higher the vapour pressure because a larger fraction of molecules
have sufficient kinetic energy to escape.

Hvap 1
ln Pvap = R T C Clausius-Clapeyron Equation

where
Hvap = the heat of vapourization of the liquid
R = gas constant
C = a characteristic constant of a liquid

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Ex-18

The vapor pressure of water at 80 C is 355 torr. A 100 ml vessel contained watersaturated oxygen
at 80 C, the total gas pressure being 760 torr. The contents of the vessel were pumped into a 50.0
ml, vessel at the same temperature. What were the partial pressures of oxygen and of water vapor,
what was the total pressure in the final equilibrated state ? Neglect the volume of any water which
might condense.

Ans.

PO2 = 810mm Hg, PH2O = 355 mm Hg , Ptotalal = 1165 mm Hg

Solution

100 ml volume vessel,

PH2O = 355

PTotal = 760

PO2 = 760 355 = 405

50 ml volume vessel,

PH2O = 355

PO2 =

405 100
50

PO2 = 810
PTotal = 355 + 810 = 1165.
Vapour Pressure of a solution

Vapour Pressure of a solutions of a non volatile solute ( solid solute ) is always found to be less than
the vapour pressure of pure solvent .
Reason :

Some of the solute molecules will occupy some surface area of the solutions so tendency of the
solvent particles to go into the vapour phase is slightly decreased hence

Ps

solvent

solution

Ps < P

PS < P
Figure

Lowering in Vapoure pressure = P PS

= P

P
P
Raoult's law : ( For non volatile solutes )
Relative lowering in Vapoure pressure =

Experimentally relative lowering in Vapoure pressure = mole fraction of the non volatile solute in
solutions.
RLVP

P - Ps
n
= XSolute =
P
nN

P
nN
N
P - Ps = n = 1+ n
N
=
n

P - P Ps
Ps
P
= P -P
P - Ps 1 = P - Ps
s

P - Ps
n
Ps = N

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P - Ps
w
M
Ps = m W
=

M
w
M
w
1000

1000 =

1000
m
W
m
W
1000

P - Ps
M
=
(
molality
)

Ps
1000

(M = molar mass of solvent)

If solute gets associated or dissociated

P - Ps
Ps

i.n
N

P - Ps
M
=
i

(molality)

Ps
1000

Ex-19

Calculate wt. of urea which must be dissolved in 400 g of water. So, final solutions has vapour
pressure 2% less than vapour pressure of pure water ?

Solution

Let vapour pressure be V of water

P0 Ps = 0.02 V
Ps = 0.98 V

0.02
0.98

w=
Ex-20

m
18

60
400

2 60 400
= 27.21 g.
18 98

10 gm of a solute is dissolved in 80 gm of acetone, vapour pressure of this solution = 271 mm of Hg.

If vapour pressure of pure acetone is 283 mm of Hg. Calculate molar mass of solute ?

Solution

P - Ps
w
M
Ps = m W
58
283 - 271
10
=

80
271
m

m = 163 g/mol.
Ex-21

Solution

Vapour pressure of solution containing 6 gm of non volatile solute in 180 gm of water is 20 Torr/mm
of Hg. If 1 mole of water is further added in to the vapour pressure increses by 0.02 Torr. Calculate
vapour pressure of pure water & molecular weight of non volatile solute ?

P - Ps
w
M
Ps = m W

P - 20
18
6
=

20
180
m
P - 20.02
18
6
=

20.02
198
m

P = 20.22 Torr.
m = 54 gm/mol.

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Ex-22

Solution

What is the final volume of both container ?

i1C1 = i2C2
0.1 2
0.1 1
=
.
100 x
100 x

200 2x = 100 + x.
x = 33.3 ml.
Ex-23

If 0.1 M solution of K4 [ Fe ( CN ) 6 ] is prepared at 300 K then its density = 1.2 gm/mL . If solute is
50% dissociated. Calculate P of solution if vapour pressure of pure water = 25 mm of Hg. (K = 39,
Fe = 56)

Solution

P - Ps
w
M
Ps = i m W
P - Ps
im M
Ps = 1000
3 0.1 1000

18

=
1000

1
.
2

1
.
2

368

1000

P
3
Ps = 1 + 7.12 10
Ps = 24.82 mm of Hg
p = 25 24.82 = 0.18 mm of Hg
Ex-24

Solution

Ba2+ ions, CN & Co2+ ions from a water soluble complex with Ba2+ ions as free cations for a 0.01 M
solution of this complex, osmotic pressure = 0.984 atm & degree of dissociation = 75%. Then find
coordination number of Co2+ ion in this complex (T = 300 K, R = 0.082 L atm. mol1 k1)
Say
C.N. = x
0.984 = i CRT
0.984 = i 0.01 0.082 300 = i 0.246
i = 4 = 1 + (n 1)
n=5
Ba[Co(CN)x ](x 2)
Ba(x 2) [Co(CN)x)2
x2+2=5
x=5
CN = 5
Ba3[Co(CN)5)2
can also have Ans. as Ba4[Co(CN)5].

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OstwaldWalker Method :
Experimental or lab determination of

P
P
or P
P
s

Figure
Initially note down the weights of the solution set, solvent set containers & of dehydrating agent
before start of experiment.
Loss of wt of solution containers Ps.
Loss of in wt of solvent containers (P Ps)
gain in wt of dehydriating agent P.

P Ps
loss in weight of solvent
Ps = loss in weight of solution
loss in weight of solvent
P Ps
= gain in weight of dehydratin g agent
P

Ex-25

Dry air was passed through a solution of 5 gm of a solute in 80 gm of water & then it is passed
through pure water loss in wt. of solution was 2.50 gm & that of pure solvent was 0.04 gm. Calculate
M.W. of solute ?

Solution

P Ps loss in weight of solvent

Ps = loss in weight of solution

P Ps
0.04
5 18

Ps = 2.50 = M 80

M = 70 g mole1

Ex-26

If same volume solution of different solute is used then what is order of (a) vapour pressure (b) moles
of solute (c) molar mass of solute.
Solution

PA 1 gm.
;
PC PB 1 gm ;
PC > PA > PB
;

PA PB 0.5 gm, PB 0.5 gm.

PC 1.5 gm.
nC < nA < nB .
;
MC > MA > MB.

Elevation in Boiling point (Tb)

Boiling point of a Liquid :

The temperature at which vapour pressure of a liquid becomes equal to the external pressure present
at the surface of the liquid is called boiling point of liquid at that pressure.
Normal boiling point :

The temperature at which boiling ocuurs when the external pressure is exactly 1 atm is called the
normal boiling point of the liquid. (Tb)
H2O()

H2O(g)

H = +ve

Kp = PH2O( g)/ eq.

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K p2

ln K
p1

H 1
1

R T1 T2

P2
ln =
P1

P
ln
P0

H vap. 1
1

R T T
2

(Claussius Clapeyron equation)

H 1 1
=
R T T
0

H H

lnP = ln P0
RT0 RT

lnP1

P
1/T

Figure
Boiling point of any solution :
Since vapour pressure of solution is smaller than vapour pressure of pure solvent at any temperature,

hence to make it equal to Pext. we have to increase the temperature of solution by greater amount in comparision
to pure solvent.
Pext.

P
Ps

Hvapour of solvent =Hvapour solution

Figure

As only solvent particles are going into vapours.

Ts > T

Figure
S =

H
T

Svapour =

Hvapour
Tbp

Svapour solvent =

H
Tb,solvent

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CHEMISTRY
Svapour solution =

H
Tb, solution

Svapour of solvent > Svapour of solution.

Tb, solvent Tb, solution

Figure
Graphical :

A B C

t
E
en 1
v
l
n
so utio 2 D
l
so tion
lu
so

Tb Tb1 Tb2

Figure
If solution are dilute then BE & CD can be approximated as straight lines.

ABE & ACD will be similar.

AB AE

AC AD

Tb1 P1

Tb 2 P2

Tb P

Using Raoults law :

P
n

.P
P
nN

or

P =

w M
. .P =
m W
Tb = Kb molality
Tb

w /m
.P
W /M

w 1000

W
m

.P

1000

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CHEMISTRY

Kb is dependent on property of solvent and known as molal elevation constant of solvent.

It is also known as ebullioscopic constant.

Kb = elevation in boiling point of 1 molal solution.

Units :

Tb
K

molality mol / kg

= K kg mol1
Using thermodynamics
2

RTb
1000 L vap

Kb =

LVap is latent heat of vapourisation in cal/g or J/g

R = 2 cal mol1 K1 or 8.314 J mol1 K1.
Tb = boiling point of liquid (in kelvin)
Kb = K kg mol1
2

RTb M
1000 Hvap

Also Kb =

Hvap molar enthalpy of vapourisation in cal/mole or J/mole

Here

M mole wt. of solvent

Hvap

Lvap =

If solute gets associated/dissociated.

Tb = i Kb molality

Ex-27

Calculate Kb of water if Lvap = 540 Cal/gm, Tb = 100C ?

Solution

Kb =

Ex-28

A solution of 122 gm of benzoic acid in 1000 gm of benzene shows a boiling point elevation of 1.4.
Assuming that solute is dimerized to the extent of 80 percent (80C). Calculate normal boiling point
of benzene. [Given : Molar enthalpy of vap. of benzene = 7.8 Kcal/mole]

Solution

Tb Ti =

2 373 373
= 0.52 K kg mol1
1000 540

1
122 1000
Kb 1 n 10.8
122 1000

H
H

Kb 2 0.8

Tb Ti = Kb 0.4

............. (i)

Kb =

RTb
1000 L vap.

Kb =

2 Tb 78
1000 7.8 1000

Now from eq (i)

1.4 = 0.4 20 106 Tb2
so
Tb = 418.33 K.

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CHEMISTRY
Ex-29

Solution.

1 Lit. of aq. solution containing 60 g urea having density = 1.060 gm/mL is found to have Tb = 0.5C,
If temperature of this solution increase to 101.5C, then calculate amount of water which must have
gone in vapour state upto this point. [Given Kb = 0.5 K kg mol1 for water]
mass of solution = 1.060 103 = 1060 gm
Tb = (molality) i Kb
1.5 =

60
1000 0.5 1
60(1000 w )

W water =

2000
= 666.67 g
3

Depression in freezing point (Tf)

Freezing point : Temperature at which vapour pressure of solid becomes equal to vapour pressure of liquid
is called freezing point of liquid or melting point of solid.

Hsub > Hvap.

Figure

Hsub = Hfusion + Hvap.

H2O(s)

H2O (g)

Kp = PH2O (g) /eq.

= vapour pressure of solid
for ice at 0C

H sub

ln P

Kp = Vp of ice 4 mm of Hg.

Hvap

P2
Hsub 1 1

ln P =
R T1 T2
1
0C 1/T

Figure

t)
lven
(so
d
i
u
Liq

P
A

solution 1
solution 2

d
soli E
D

0C

Figure

For - dil. solutions BE & CD can be assumed to be straight lines.

using similar triangles

Tf P

Tf = Kf . Molality

Kf = molal depression constant = cryoscopic constant

2

Kf =

RTf
RTf M
=
1000 L fusion
1000 Hfusion

for water Tf = 273 K & LFusion = 80 cal / gm

Kf =

2 273 273
= 1.86 K kg mol1
1000 80

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At freezing point or below it only solvent molecules will

freeze not solute molecules (solid will be of pure solvent)

Hfusion
Tf
SSolution > Ssolvent
SFusion =

freezing point of solution < freezing point of solvent

Figure
These 4 colligative properties are calculated only for solution containing non volatile solutes.

Ex-30

0.1M urea 0.1M NaCl 0.1M BaCl2

,
,
(A)
(B)
( C)

Solution

order of
order of R.L.V.P
order of V.P
order of TB
order of TB of solution
order of TF
order of TF of solution

Ex-31

1000 gm H2O have 0.1 mole urea and its freezing point is 0.2C and now it is freezed upto 2C
then how much amount of ice will form.

Solution

TF = 0.2 = Kf 0.1 1000

C > B > A.
C > B > A.
A > B > C.
C > B > A.
C > B > A.
C > B > A.
A > B > C.

.......(i)

1000

TF = 2 = Kf

0 .1
1000
wt. of solvent

.......(ii)

on dividing

wt. of solvent
0 .2
=
.
1000
2

weight of remaining H2O is 100 gm and weight of ice is 900 gm.

Ex-32
Solution

If boiling point of an aqueous solution is 100.1C. What is its freezing point? Given latent heat of
fusion and vapourization of water are 80 cal g1 and 540 cal g1 respectively.
For a given aqueous solution
Tb = Kb molality
Tf = Kf molality

1000 L f
Tb
K b'
RTb2
=
=

Tf
RTf2
1000Lv
K f'
2

Tb Lf
Tb
=
Tf
Tf2 Lv
Tb = 100 + 273 = 373 K.
Tf = 0 + 273 = 273 K.
Lf = 80 cal g1.
Lv = 540 cal g1.

0. 1
373 373 80
Tf = 273 273 540 .

Tf = 0.362.

Tf = 0.0 0.362.= 0.362C.

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CHEMISTRY
Ex-33

A 0.001 molal solution of a complex represented as Pt(NH3)4Cl4 in water had a freezing point depression of 0.0054C. Given K for H2O = 1.86 molality1. Assuming 100% ionisation of the complex,
write the ionisation nature and formula of complex.
Let n atoms of Cl be the acting as ligand. Then formula of complex and its ionisation is :

Solution

[Pt(NH3)4Cln]Cl(4 n) [Pt(NH3)4Cln]+(4 n) + (4 n) Cl
1
0
0
0
1
(4 n)
Thus particles after dissocation = 4 n + 1 = 5 n
and
therefore, van't Hoff factor (i) = 5 n
Now
T = K' molality van't Hoff factor
0.0054 = 1.86 0.001 (5 n)

n = 2.1 2 (integer value)

Thus complex and its ionisation is :
[Pt(NH3)4Cl2]Cl2 [Pt(NH3)4Cl2]2+ + 2Cl
VOLATILE SOLVENT Liq. solution

VOLATILE SOLUTE Liq. solution

SOLUTIONS CONTAINING

Mixture of 2 volatile liquids

Raoult's law ( for volatile Liq. Mixture )

A
x

x
x
x

A+ B
XA {mole fractions of A & B in liquid solution}
XB
Figure
let A, B be two volatile liquid
Partial pressure of A = PA
According to Raoult's law (experimentally )
PA XA
PA = XAPA
PA = vapour pressure of pure liquid A = constant (at a particular temperarure)
PB XB.

Similarly.

if P > P

PB = XBPB (vapoure pressure of pure liquid B)

A is more volatile than B

boiling point of A < boiling point of B

According to Dalton's law

PT = PA + PB = XAPA0 + XBPB0
xA' = mole fraction of A in vapour above the liquid / solution.
xB' = mole fraction of B
Dalton's law for gaseous mixture
PA = XA' PT
Raoult's law when liquid & vapour in equilibrium
PA = XAPA
XA' PT

= XA PA

PB = XB' PT = XBPB
XA + XB = 1 =

X A ' PT
PA0

XB ' PT
PB0

xA '
xB '
1
=
+
PT
PA
PB

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Graphical Representation :
PA= XAPA

&

PB = XB PB

PT = XAPA + XB PB
PT = XAPA + (1 XA) PB = ( PA PB ) XA + PB0
PT = (1 XB) PA + XBPB = ( PB PA ) XB + PA0
eg. PT = 150 + 200Xben.
PT

PA

PA

PB,

PB,

A is more volatile than B PA > PB

XA= 0
XB= 1

XA= 1
XB= 0

Figure
PT = PA + PB.
Ideal solutions (mixtures) :

The mixtures which follow Raoult's law at all temperature & at all compositions will be known as
ideal mixtures / ideal solution.
Characteristic of an ideal solution

Ideal solution will be obtained only when the forces of attraction between the liquid
molecules are exactly of same nature & almost of same magnitude
A ------ A
A -------- B,
B ----- B

Hmix = 0

Vmix = 0

Smix = + ve as for process to proceed

Gmix = ve

eg.

(1 ) Benzene + Toluene.
(2) Hexane + heptane.
(3) C2H5Br + C2H5.

Ex-34

An equimolar mixture of benzene & toluene is prepared the total vapour pressure of this mix as a
function of mole fraction of benzene is found to be
PT = 200 + 400 Xben.
(i)

(ii)

Calculate composition of vapours of this mixture [ Assume that the no. of moles going into vapour
phase is negligible in comparsion to no. of moles present in liquid phase].
P0Benzene= 600 mm of Hg
P0Toluene = 200 mm of Hg
f the vapour above liquid in part A are collected & are condensed into a new liqiuid, calculate
composition of vapours of this new liquid.

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CHEMISTRY
Solution

1
1
600 +
200 = 400 mm of Hg
2
2
Pbenz =Xben ' Pben = X'benPT.
(i) PT =

x'benzene =

1/ 2 600
3
=
400
4

x'Toluene =

1
4

(ii) PT =

3
1
600 +
200 = 500
4
4

3 / 4 600
= 0.9
500
X'Tol = 0.1

x1ben =

This process is known as fractional distillation.

Non - deal solutions :

The mixtures which do not follow Raoult's law will be known as non ideal mixtures/solution.

Non ideal solution can be of two types :

Non ideal solutions showing positive deviation
Non ideal solutions showing negative deviation
+ ve deviation

ve deviation

PT,exp > ( XAPA + XBPB )

A A
B B > A ---- B

Weaker force of attraction

eg.

PT exp < xAp + xBpB

A A
B B < A ------ B.

strong force of altraction.

Hmix = +ve

energy absorbed

Hmix = ve

Vmix = +ve

( 1L + 1L > 2L )

Vmix = ve

Smix = +ve

Smix = +ve

Gmix = ve

Gmix = ve

eg.

H2O + HCOOH
H2O + CH3COOH
H2O + HNO3
CHCl3 + CH3OCH3

H2O + CH3OH.
H2O + C2H5OH
C2H5OH + hexane
C2H5OH + cyclohexane.

( 1L + 1L < 2L )

CH3
CHCl3 + CCl4

C=O

CH3

Cl
C Cl
Cl

dipole-dipole interaction becomes weak

P0A > P0B

P0A > P0B

Figure

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Azeo tropic mixture

Azeo tropic mixture

Figure

azeotropic
(constant boiling mix/Composition)
Minimum boiling azeotropic mix.

Figure

Immiscible Liquids :

It is used to purify an organic liquid from impurity.

When two liquids are mixed in such a way that they do not mix at all then
Ptotal = PA + PB
PA = PA0 XA
XA = 1
PA0

PA =
PB = PB0 XB
XB = 1
PB = PB0
Ptotal = PA0 + PB0

PA0
PB0

nA
= n
B

PA0

PB0

PA0 =

WA MB
M A WB
n A RT
nBRT
; PB0 =
V
V

TA

TB

Tsoln.
Figure
B.P. of solution is less than the individual boiling points of both the liquids.

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Henry Law :
Henry law deal with effect of pressure on the solubility of gas.
Statement :
The solubility of a gas in a liquid at a given temperature is directly proportional to the pressure at which it is
dissolved.
Let
X = Mole fraction of gas at a given temperature as a measure of its solubility.
p = Partial pressure gas in equilibrium with the solution.
Then according to Henry's law.
Xp
or
pX
or
p = KH X
where KH = Henry law constant.
Note : (i) If a mixture of gases is brought in contact with solvent each constituent gas dissolves in proportion to its
partial pressure. It means Henry's law applies to each gas independent of the pressure of other gas.
(ii) Henry's law can also apply by expression the solubility of the gas in terms of mass per unit volume.
Mass of the gas dissolved per unit volume of a solvent at a given temperature is directly proportional to the
pressure of a gas in equilibrium with the solution.
m p, m = K p
where,
m = mass of gas dissolved in unit volume of solvent.
p = pressure of gas in equilibrium with solution.
Where K is the constant of proportional that depends on nature of gas, temperature & unit of pressure.
Characteristics of Henry law constant (KH).
(i) unit same as those of pressure torr or Kbar.
(ii) Different gas have different value of KH .
(iii) The KH value of a gas is different in different solvents and it increase with the increase in temperature.
(iv) Higher the value of KH of a gas lower will be its solubility.
Plot of p Vs X is a straight line passing through the origin with slop equal to KH

Figure
Plot of p Vs X for solution of HCl in cyclohexane.
Limitation of Henry's law :
Henry law valid only following condition.
(i) The pressure of gas is not too high.
(ii) The temperature is not too low.
(iii) The gas should not go any chemical reaction with the solvent.
(iv) The gas should not undergo dissociation in solution.

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Application of Henry's law :
Several application in biological and industrial phenomena.
(i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed under high pressure.
(ii) Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure
underwater. Increased pressure increases the solubility of atmosphere gases in blood. When the divers
come towards surface, the pressure gradually decreased. The release the dissolved gases and leads to the
formation of bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition known
as bends, which are painful and dangerous to life. To avoid bends, as well as, the toxic effects of high
concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium
(11.7% helium, 56.2% nitrogen and 32.1% oxygen).
(iii) At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low blood
oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition known as
anoxia.
Effect of temperature :
Solubility of gases in liquids decreases with rise in temperature. When dissolved, the gas molecules are
present in liquid phase and the process of dissolution can be considered similar to condensation and heat is
evolved in this process. We have learnt that dissolution process involves dynamic equilibrium and thus must
follow Le Chatelier's principle. As dissolution is an exothermic process, the solubility should decrease with
increase of temperature.
Note : KH values for both N2 and O2 increase with increase of temperature indicating that the solubility of gases
increases with decrease of temperature. It is due to this reason that aquatic spcies are more comfortable in
cold water rather than warm water.

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Summary
Solutions are homogeneous mixtures and they contain particles like ion or small molecule. There are seven
possible kinds of solutions. For solutions in which a gas or solid is dissolved in a liquid, the dissolved
substance is called the solute and the liquid is called the solvent.
The dissolution of a solute in a solvent has associated with it a free-energy change, G = H - TS. The
enthalpy change is the heat of solution (Hsoln ), and the entropy change is the entropy of solution
(Ssoln). Heats of solution can be either positive or negative, depending on the relative strengths of solventsolvent, solute-solute, and solvent-solute, Intermolecular forces. Entropies of solution are usually positive
because disorder increases when a pure solute dissolves in a pure solvent.
The concentration of a solution can be expressed in many ways, like molarity, mole fraction, % by mass,
and molality etc. When equilibrium is reached and no further solute dissolves in a given amount of solvent, a
solution is said to be saturated. The concentration at this point represents the solubility of the solute.
Solubilities are usually temperature dependent. Gas solubility usually decrease with increasing temperature,
but solubilities of solids can either increase or decrease with respect to temperature. The solubilities of
gases also depend on pressure. According to Henrys law, the solubility of a gas in a liquid at a given
temperature is proportional to the partial pressure of the gas.
In comparison with a pure solvent, a solution has lower vapor pressure at a given temperature, lower freezing
point and higher boiling point. In addition, a solution that is separated from solvent by a semipermeable
membrane gives the phenomenon of osmosis. All four of these properties solutions depend only on the
concentration of dissolved particles rather than on the chemical identity of the solute and consider as colligative
properties. The fundamental cause colligative properties is the same: the higher entropy of solvent in a
solution relative to that of the pure solvent.
Colligative properties have many practical uses, in the melting of snow by salt, the desalination of sea-water
reverse osmosis, the separation and purification of votalite component by fractional distillation, and the
determination of molecular mass by osmotic pressure measurement.

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MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1.
Sol.

A 6.90 M solution of KOH in water has 30% by weight of KOH. Calculate density of solution.
Let V = 1 lt , then moles of solute = 6.9
wt of solute = 6.9 56 gm

Msolute
%= M
100
solution
So, =

6.9 56
100 = 30
d 1000

d = 1.288 gm/litre
2.

10 ml of sulphuric acid solution (sp. gr. = 1.84) contains 98% by weight of pure acid. Calculate the volume of
2.5 M NaOH solution required to just neutralise the acid.

Sol.

Wt of solute = 10 1.84

So moles of solute =

98
gm
100

18.4
98

= 0.184
98
100

= 2 0.184

2 0.184 =

2.5 V
1000

V = 147.2
3.
Sol.

A sample of H2SO4 (density 1.8 g mL1) is labelled as 74.66% by weight. What is molarity of acid ? (Give
answer in rounded digits)
Let V = 1lt = 1000 ml
So mass of solution = 1800 gm
So mass of solute = 1800

74.66
gm
100

So molarity = moles of solute in 1lt =

4.

Ans.
Sol.

18 74 .66
= 13.71 M
98

Ans.

The density of 3M solution of Na2S2O3 is 1.25 g mL1. Calculate.

(a) the % by weight of Na2S2O3
(b) mole fraction of Na2S2O3
(a) 37.92 (b) 0.065
(a) msolution = 1000 1.25 = 1250 gm
mass of Na2S2O3 = 3 158 = 474
% (w/w) =

474
100 = 37.92
1250

(b) XNa2S2O3 =

3
= 0.065.
3 43.11

5.

Calculate Molality of aqueous urea solution which has X urea = 0.2

Sol.

molality = (1 X )m =
1 2

1000 X1

1000 0.2
= 13.88.
0.8 18

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6.
Ans.

If 200 mL of 0.1 M urea solution is mixed with 300 mL of 0.2 M Glucose solutions at 300 K calculate
osmotic pressure
3.94 atm

Sol.

Cnet =

C1V1 C 2 V2
V1 V2

Now
= Cnet RT
p = (0.04 + 0.12) 0.0821 300 = 3.94 atm.
7.
Ans.
Sol.

A 500 gm liquid consist of 15 gm ethane at any temp. T, at a pressure = 2 atm. Find Pressure of gas required
to dissolve 30 gm gas in 300 gm liquid.
P2 = 6.66 atm.
15 / 500
2
=
30 / 300
P
3
2
=
10
P

P = 6.66 atm.

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