UNIT 2 SOLUTION

Raoult’s Law:

pi = pio . Xi

pi – partial vapour pressure pi0 –

vapour pressure of the pure state

Xi – mole fraction of the solute

Raoult’s Law for a two component system:

Two liquids are volatile Mixing of

two liquids A and B pA – partial vapour

pressure of liquid A pB – partial vapour

pressure of liquid B

XA – mole fraction of liquid A XB – mole

fraction of liquid B pA0 – partial vapour
pressure of liquid A pB0 – partial vapour
pressure of liquid B p = pA + pB p =
pA0 . XA + pB0 . XB
0
PB

p – X diagram ( Vapour pressure Vs p = pA + pB

Mole fraction)
pB = pB0 . XB
XA + XB = 1 XA = 1 – XB p = vapour PA0
pA0 . ( 1 – XB ) + pB0 . XB p pressure
= pA0 – pA0 XB + pB0 . XB p pA = pA0 . XA
= (pB0 – pA0 ) XB + pA0

XA = 1 mole XA = 0
XB = 0 fraction XB = 1
Example 2.17:

Given data:

Liquid A – Ethanol Liquid B – Methanol

 PA0 = 44.5 mm Hg PB0 = 88.7 mm Hg
wA = 60 g wB = 40 g WA = C2H5OH = (2 X12) + ( 6 X 1) + ( 1 X 16) = 46
g/mol

WB = CH3OH = ( 1 X 12) + ( 4 X 1) + (1 X 16) = 32 g / mol Solution:

According to Raoult’s law, p

= p A + pB

p = pA0 . XA + pB0 . XB pA

= pA0 . XA

nA = 60 / 46 = 1.304

nB = 40 / 32 = 1.25

n = nA + nB = 1.304 + 1.25 = 2.554

XA = nA / n = 1.304 / 2.554 = 0.51

XB = nB / n = 1.25 / 2.554 = 0.49 X A + XB = 1

pA = pA0 . XA = 44.5 X 0.51 = 22.695 mm Hg pB = pB0 . XB
= 88.7 X 0.49 = 43.463 mm Hg

Total pressure p = pA + pB = 22.695 + 43.463 = 66.158 mm Hg.

XB of vapour = pB / p = 43.463 / 66.158 = 0.6569

Example 2.18:

Given data:

Liquid A = cyclohexane Liquid B = Ethanol pA0

= 280 mm Hg pB0 = 168 mm Hg

XA = 0.32 XB = 1 – XA = 1- 0.32 = 0.68

The total pressure of the mixing solution is 376 mm Hg.

Solution:

According to Raoult’s law,

p = pA0 . X A + pB0 . X B

= (280 X 0.32) + ( 168 X 0.68)

= ( 89.6 ) + ( 114.24 )

= 203.84 mm Hg

Observed value is 376 mm Hg and calculated value is 203.84 so the value is

less than that of observed value. From this, the above solution is non ideal
and exhibit positive deviation of Raoult’s law.

Page no 75 Review Exercises Problem no 2.35 Given

data:

Liquid A = methanol Liquid B = Ethanol

wA = 32 g wB = 23 g WA = 32 g/mol WB = 46 g/mol
0 0
pA = 90 mm Hg pB = 51 mm Hg

Solution:

nA = wA / WA = 32 / 32 = 1
nB = wB / WB = 23 / 46 = 0.5
n = nA + nB = 1 + 0.5 = 1.5

XA = 1 / 1.5 = 0.667

XB = 0.5 / 1.5 = 0.333

pA = pA0 . XA = ( 90 X 0.667 ) = 60.03 mm Hg pB

= pB0 . XB = ( 51 X 0.333) = 16.983 mm Hg

Total pressure p = 60.03 + 16.983 = 77.013 mm Hg.

Example 2.17 Page no 74:
Given data:

Liquid A = Ethanol Liquid B = Methanol

pA0 = 44.5 mm Hg pB0 = 88.7 mm Hg
wA = 60 g wB = 40 g

WA = C2H5OH = ( 2 X12 ) + ( 6 X 1 ) + ( 1 X 16 ) = 46 g /mol

WB = CH3OH = ( 1 X12 ) + ( 4 X 1 ) + ( 1 X 16 ) = 32 g /mol Solution:

According to Raoult’s law, nA = 60 /

46 = 1.304 nB = 40 / 32 = 1.25 n

= nA + nB = 1.304 + 1.25 = 2.554

X A = nA / n = 1.304 / 2.554 = 0.51 X

B = nB / n = 1.25 / 2.554 = 0.49

pA = pA0 . X A = ( 44.5 X 0.51 ) = 22.695 mm Hg

pB = pB0 . X B = ( 88.7 X 0.49) = 43.463 mm Hg

p = pA + pB = 22.695 + 43.463 = 66.158 mm Hg

X B in vapour = 43.463 / 66.158 = 0. 657

Example 2.18 Page No 74 Given

data:

Liquid A = cyclohexane Liquid B = ethanol

0 0
pA = 280mm Hg pB = 168 mm Hg

XA = 0.32 XB = 1 – 0.32 = 0.68 Solution:

According to Raoult’s law pA = pA0 . XA = 280 X

0.32 = 89.6 mm Hg pB = pB0 . X B = 168 X 0.68 =

114.24 mm Hg p = pA + pB = 89.6 + 114.24 =

203.84 mm Hg.

The calculated value is 203.84 mm Hg and the observed value is 376 mm Hg.
It is not an ideal solution. It is a non ideal solution exhibit the positive
deviation of Raoult’s law.

Page No 75 Review Exercises Problem No 2.35 Given

data:

Liquid A = methanol Liquid B = Ethanol wA = 32 g wB

= 23 g WA = 32 g /mol WB = 46 g / mol pA0 = 90 mm Hg
pB0 = 51 mm Hg Solution:

According to Raoult’s law, nA

= wA / WA = 32 / 32 = 1 nB = wB /

WB = 23 / 46 = 0.5 n = nA +

nB = 1 + 0.5 = 1.5

XA = nA / n = 1 / 1.5 = 0.667

XB = nB / n = 0.5 / 1.5 = 0.333

pA = pA0 . X A = ( 90 X 0.667 ) = 60.03 mm Hg pB =

pB0 . X B = ( 51 X 0.333) = 16.983 mm Hg p = pA + pB =

60.03 + 16.983 = 77.013 mm Hg

75 to 79 + or - 2 % error is acceptable
Total 3 marks Problem

Given data = ½ + ½ = 1

Formula = ½

Substitution = ½

Answer = ½

Unit = ½
Relative Lowering of Vapour Pressure:

p0 – p = wXM

p0 WXm

p0 = vapour pressure of the pure solvent mm Hg

p = vapour pressure of the solution mm Hg

w = given weight of the solute g

W = molecular weight of the solute g / mole

m = given weight of the solvent g

M = molecular weight of the solvent g / mole

Pg no 78 Example 2.22 Given

data:

p0 = 200 mm Hg solvent is Benzene if you add 2 g of non volatile solid

w=2g

m = 78 g M = C6H6 = (12X6) + (6X1) = 78 g /mole p

= 195 mm Hg W = ? (Molecular weight of the solute)
Solution:

Relative Lowering of Vapour Pressure:

p0 – p = wXM

p0 WXm

200 – 195 = 2 X 78

200 W X 78
 5 / 200 =2/W

W = 2 X 200 / 5

W = 2 X 40

W = 80 g /mol

A solution of lactose containing 8.45 g of lactose in 100 g water has a vapour

pressure of 4.559 mm Hg. If the vapour pressure of pure water is 4.579 mm
Hg. Calculate the molecular weight of lactose.

Given data:

p0 = 4.579 mm Hg

p = 4.559 mm Hg

w = 8.45 g W = ?

m = 100 g

M = 18 g /
mole
Solution:

p0 – p = wXM

p0 WXm

4.579 – 4.559 = 8.45 X 18

4.579 W X 100

4.36 X 10-3 = 1.521 / W

W = (1.521) / (4.36 X 10-3)

W = 348.23 g / mole = 348 g / mole

If the solution contains n moles of solute dissolved in N moles of solvent,

p0 – p = n

p0 N + n

Suppose, w – given weight of the solute, W – molecular weight of the solute

m – given weight of the solvent, M – molecular weight of the solvent

n=w/W
N=m/
M

p0 – p = w/W

p0 (w/W) + (m/M)

Ex 2.21 pg no 77

The vapour pressure of water at 298 K is 23.75 mm Hg. Calculate the vapour
pressure at the same temperature over 5 % aqueous solution of urea. (NH2)2
CO Given data:

p0 = 23.75 mm Hg p=? 5%

aqueous solution of urea 5 g of urea

dissolved in 95 g of water

w = 5 g W = (1X12)+(1X16) + (2X14) + (4X1) = 60 g/mol

m = 95 g M = 18 g/mol Solution:

p0 – p = w/W

p0 (w/W) + (m/M)
 23.75 – p = (5 / 60)

23.75 (5/60) + (95/18)

23.75 – p = (0.0833)

23.75 (0.0833) + (5.2777)

23.75 – p = (0.0833)

23.75 (5.361)

23.75 – p = 0.0155

23.75

23.75 – p = 0.0155 X 23.75

23.75 – p = 0.3681 p
= 23.75 - 0.3681 p
= 23.38 mm Hg.

pg no 78 eg 2.23 Given
data:

p0 = 23.76 mm Hg p = 22.98 mm Hg

n g of urea is dissolved in 1000 g of water m = 1000 g M = 18 g/mol Solution:

p0 – p = n
 p0 N + n

23.76 – 22.98 = n

23.76 (1000/18) + n

0.78 = n

23.76 (55.55) + n

0.03283 = n / 55.55+n (55.55+n)

0.03283 = n

(55.55 X 0.03283) + 0.03283 n = n

1.824 = n – 0.03283n

1.824 = n( 1-0.03283)

1.824 = n X 0.96717
n = 1.824 / 0.96717

n = 1.8859

Ex 2.24 Pg no 78 Given
data: w = 5 g W =?

m = 100 g M = 18 g /mole

Solution:

p0 – p / p0 = 0.02 / 0.78

= 0.025

p0 – p = wXM
 p0 W X m 0.025 = 5

X 18

W X 100

0.025 X W = 0.9

W = 0.9 / 0.025

W = 36 g /mol Elevation of Boiling Point:

When a solute is dissolved in a solvent, its boiling point is raised. The

increase in boiling point thus obtained is referred to as elevation of boiling
point.

ΔTb = Kb . m

ΔTb = change in the boiling point ΔTb = T2 – T1

T2 – temperature of the solvent when solute is added

T1 – boiling point of water (1000 C or 373 K)

Kb = molal elevation constant K Kg / mol m

= molality m = w / W X 1000 / V

w – given weight of the solute W – molecular weight of the solute

ΔTb = Kb . w X 1000

W X V (g)

Determination of Kb:

Kb = M R Tb2

1
X ΔHv

1
X Lv
ΔHv = molar enthalphy of vaporization of the solvent

Lv = latent heat of vaporization of the solvent

Lv = ΔHv / M

Kb = R Tb2

Page No 82 Example 2.25

A solution containing 12.5 g of a non-electrolyte substance in 175 g of water

gave boiling point elevation of 0.70 K. Calculate the molar mass of the
substance. (Kb for water = 0.52 K kg mol-1) Given data:

w = 12. 5 g V = 175 g ΔTb = 0.70 K W = ? Kb = 0.52 K kg /mol Solution:

ΔTb = Kb . w X 1000

W X V (g)

0.70 = 0.52 X ( 12.5 X 1000)

W X 175

0.70 X 175 X W = 0.52 X 12.5 X 1000

122.5 X W = 6500

W = 6500 / 122.5

W = 53.06 g/mol

Page no 82 Ex.2.26

10 grams of a non-volatile solute when dissolved in 100 grams of benzene

raise its boiling point by 10C. What is the molecular mass of the solute?
(Kb for benzene = 2.53 k kg mol-1) Given data: w = 10 g V = 100 g ΔTb
= 1 W = ? Kb = 2.53 K Kg /mol Solution:

ΔTb = Kb . w X 1000

W X V (g)

1 = 2.53 X 10 X 1000

W X 100

W = 2.53 X 10 X 10

W = 2.53 X 100

W = 253 g / mol

Page No 82 Ex 2.27 Given

data:

w = 0.5216 g W = 128.16 g / mole V = 50 g ΔTb = 0.402 K

Kb = ?

Solution :

1. Calculation Kb for CCl4:

ΔTb = Kb . w X 1000

W X V (g)
0.402 = Kb. 0.5216 X 1000
128.16 X 50
0.402 = Kb. 521.6
6408
0.402 = Kb . 0.08139
Kb = 0.402 / 0.08139

Kb = 4.939 K Kg / mol
Given data:

w = 0.6216 g V = 50 g ΔTb = 0.647 K Kb = 4.939 K

Kg/mol W=? 20

0.647 = 4.939 X 0.6216 X 1000

W X 50

0.647 = 61.4016 / W W

= 61.4016 / 0.647

W = 94.90 g/mol

Depression of Freezing Point:

The decrease in the freezing point of a solvent caused by the addition

of a non-volatile solute to it is termed as depression of freezing point.

ΔTf = Kf . m

ΔTf = change in the freezing point ΔTf = T2 – T1

T2 = Freezing point of the solvent 00C

T1 = Freezing point of the solvent with solute -ve

Kf = Molal depression constant K Kg / mol (or) cryoscopic constant m

= molality m = w / W X 1000 / V

w – Given weight of the solute W – molecular weight of the solute

V – Volume of the solvent

ΔTf = Kf . w X 1000

W X V (g)

Determination of Kf:

Kf = M R Tf2

1000 X ΔHfusion
ΔHfusion = molar enthalphy of fusion of frozen solvent

Lf = latent heat of fusion of the solvent

Lf = ΔHfusion / M

Kf = R Tf2

1000 X Lf

Page No 86 Example 2.29

The normal freezing point of nitrobenzene is 278.82 K. A 0.25 Molal solution

of a certain solute in nitrobenzene causes a freezing point depression of 2
degree. Calculate the value of Kf for nitrobenzene.

Given data:

m = 0.25 m ΔTf = 2 Kf = ?

Solution:

ΔTf = Kf X m

Kf = 2 / 0.25

= 8 K / molal

Page No 86 Ex 2.30

Addition of 0.643 g of a compound to 50 mL of benzene (density 0.879 g/mL)

lowers the freezing point from 5.510C to 5.030C. If Kf for benzene is 5.12 K
kg mol-1, calculate the molar mass of the compound.

Given data:

w = 0.643 g density = mass / volume

mass = density X vol = 0.879 x 50 = 43.95 g

V = 43.95 g
 T2 = 5.510C T1 = 5.030C ΔTf = 5.51 – 5.03 = 0.480C

Kf = 5.12 K Kg / mol W=?

Solution:

ΔTf = Kf . w X 1000

W X V (g)

0.48 = 5.12 X 0.643 X 1000

W X 43.95

0.48 X W X 43.95 = 5.12 X 0.643 X 1000

21.096 X W = 3292.16
W = 3292.16 / 21.096

W = 156.06 g/mol

Page No 86 Ex 2.31

Water is used in car radiator. In winter season ethylene glycol is added to

water so that water may not freeze. Assuming ethylene glycol to be
nonvolatile, calculate the minimum amount of ethylene glycol that must be
added to 6.0 kg of water to prevent it from freezing at -0.30C. The molal
depression constant of water is 1.86. The molecular weight of ethylene glycol
is 62 g /mol.

Given data:

w = ? W = CH2OH – CH2OH C2H6O2 = (2X12)+(1X6)+(2X16)=

24+6+32= 62 g/mol

V = 6 Kg = 6000 g ΔTf = 00C – ( - 0.30C) =0.30C Kf = 1.86 K Kg / mol.

Solution:

ΔTf = Kf . w X 1000

W X V (g)

0.3 = 1.86 X w X 1000

 62 X 6000

0.3 X 62 X 6 = 1.86 X w
111.6 = 1.86 X w w =
111.6 / 1.86 w = 60 g

Osmotic Pressure:

Laws of Osmotic Pressure and van’t Hoff’s Equation:

(i) Boyle – van’t Hoff law:

π α C ( at constant T)

π α 1 / V ( at constant T)
(ii) Charles’ – van’t Hoff
law: π α T (at constant C)

(iii) Avogadro – van’t Hoff law:

παn

Van’t Hoff Equation:

Normally C = 1 / V

We combine all the above equations

παnT1/V πVαnT

πV=nRT w.k.t no of moles n = w / W

πV=w/WRT

where, π = osmotic pressure (atm) V

= volume (litre) w = given weight of
the solute (g)
 W = Molecular weight of the solute ( g/mol)

T = temperature (K)

Determination of R value: R = PV / n T

P = 1 atm V = 22.4 L n = 1 mole T = 273 K

R = 1 * 22.4 / 1 * 273 = 0.0821 L atm / K mol

R = 0.0821 L atm / K mol

Sometimes Concentration C = n / V

Decimolar solution- 0.1 N in one litre

Centimolar solution – 0.01 N in one litre

Bimolar solution – 2 N in one litre Osmosis:

The spontaneous flow of the solvent through a semi permeable membrane

from a pure solvent to a solution or from a dilute solution to a concentrated
solution is called osmosis.

Isotonic Solution:

When two solutions are separated by a semi-permeable membrane and no

osmosis occurs, i.e., there is no net flow of water on either side through the
membrane, the solutions are said to be isotonic solutions.

For solution 1 πV1 = n1RT For solution 2 πV2 = n2RT

For isotonic condition both are equal

V1 / V2 = n1 / n2

Since n/V represents molar concentration, we may conclude that isotonic

solutions posses the same molar concentration.

Hypertonic solution:

When a solution has a higher osmotic pressure as compared to some other

solution, it is termed as a hypertonic solution.

Hypotonic solution:
 The solution having lower osmotic pressure as compared to some other
solution, it is referred to as hypotonic solution.

Page no 93 Ex 2.34

Calculate the osmotic pressure of an urea solution at 250C which contains 5

g of urea (molar mass = 60 g /mol) dissolved in 100 cm3 of solution.

Given data:

π=? T = 25 + 273 = 298 K w=5g W = 60 g/mol

3
V = 100 cm = 0.1 L R =0.0821 atm L / K mol Solution:

π V = w / W R T π X 0.1 =5/
60 X 0.0821 X 298 π = 5 * 0.0821 *

298 / 60 * 0.1 π = 122.329 / 6 π =

20.4 atm

Page no 93 Ex 2.35

Calculate the osmotic pressure of a decimolar solution of sucrose at 300 K.

Given data:

π = ? n = 0.1 V=1L T = 300K

Solution:

πV=nRT πX1=
0.1 X 0.0821 X 300 π = (0.1 X

0.0821 X 300 ) / 1 π = 2.463

atm

Page no 93 Ex 2.36

A 5 % solution of cane sugar ([Link] 342) is isotonic with 0.877% solution of

urea. Find the molecular weight of urea.
Given data:

5 % of cane sugar (sucrose) w1 = 5 g W1 = 342 g/mol w2 = 0.877 W2 = ?

Solution:

Isotonic solution , V1 = 100 mL =

0.1 L (sucrose) V2 = 100 mL =
0.1 L (urea)

V1 / V2 = n1 / n2

V1and V2 same volume

0.1 / 0.1 = n1/n2 1 = n1 / n2 n1 = n2

w1 / W1 = w2 / W2 5 / 342
= 0.877 / W2

W2 = 342 X 0.877 / 5

= 59.99 = 60 g/mol

The modified Van’t Hoff factor:

Observed value = experimental

Calculated value = Standard Reference value

The molecular weight of NaOH = 23X1 + 16X1 + 1X1 = 40 g / mol

The experimental value of NaOH in chemistry lab = 42.4 g/mol (student A)

The experimental value of NaOH in chemistry lab = 38.8 g/mol (student B)
van’t hoff factor i =observed value / calculated value Four colligative
properties:

For relative lowering of vapour pressure (P0-P) / P0 = i Xsolute

For elevation of Boiling point , ΔTb = i Kb . m

For depression of freezing point , ΔTf = i Kf . m

For osmotic pressure, πV=inRT

Association:
1. Acetic acid ( CH3COOH) M.W = 24+4+32 = 60 g / mol
2. Phenol ( C6H5OH) M.W = 72+6+16 = 94 g / mol
3. Benzoic acid (C6H5COOH) M.W = 84+6+32=122 g /mol Normally
for association the compound forms a dimer.

For association the degree of association is α

2 CH3COOH (CH3COOH)2
Initial 1 mole -----
At equl. (1 – α) α/2
Total number of moles = 1 – α +α / 2
= ( 2 - 2α +α ) / 2
= 1 – α/2
i= 1-α/2 for association

Page no 99 Ex 2.39

The freezing point of a solution containing 0.2 g of acetic acid in 20 g of

benzene is lowered by 0.450C. Calculate the degree of association of acetic
acid in benzene.

The major colligative property is Freezing Point Given

data:

w = 0.2 g W = CH3COOH = 24+4+32 = 60 g /mol V = 20 g

ΔTf = 0.450C Kf = 5.12 K Kg / mol

Solution:

ΔTf = iKf m i= ΔTf / ( Kf m) m = w / W X 1000

/V = (0.2/60) X (1000/20) = 0.167 i= (0.45) / ( 5.12 X

0.167)
 i=0.526

i= 1-α/2 for association

1-α/2 = 0.526

- α/2 = 0.526 – 1 -
α/2 = -0.474 α/2 =
0.474

α = 0.474 X 2 α= 0.948

Degree of association of acetic acid is 94.8%

Page no 100 Review exercise Problem no 2.86 & 2.89

2.0 g of benzoic acid is dissolved in 25 g of benzene shows a depression of

freezing point equal to 1.62 K. Molal depression constant (Kf) of benzene is

4.9 K Kg mol-1. What is the percentage association of the acid?

Dissociation:

Electrolytic solute - split up into ions and conduct electricity eg NaCl.

Non – electrolytic solute – Glucose soluble but it does not conduct

electricity

Volatile solute & Non-volatile solute

Consider the electrolytic solute

NaCl Na+ + Cl-

Initial 1 mole - -

At equ. (1-α) α α

Total number of moles = 1- α + α + α

 =1+α

Page No 99 Ex 2.40

A decinormal solution of NaCl exerts an osmotic pressure of 4.6 atm at 300

K. Calculate its degree of dissociation.

Given data:

decinormal = 0.1 N in 1 Litre π = 4.6 atm T = 300 K Solution:

the van’t hoff equation is π V = i n R T

R = 0.0821

4.6 X 1 = i X 0.1 X 0.0821 X 300

i= 4.6 / ( 0.1 X 0.0821 X 300)
i= 4.6 / 2.463
i=1.8676

1+α = 1.8676
α = 0.8676

The degree of dissociation is 86.76%

`Page no 99 Ex 2.41

Solute A = AgNO3 --------- Ag+ + NO3-

Solute B = Glucose Given data:

1.7 % meaning is 1.7 g of silver nitrate dissociated into 100 mL of

water.

3.4 % meaning is 3.4 g of glucose soluble into 100 mL of water.

For silver nitrate solution

AgNO3 --------- Ag+ + NO3-

Initial 1 mole - -

At equ. (1-α) α α

Total moles = 1-α+α+α = 1+α

 π V = in R T

π X 0.1 L = i (1.7 / 170) R T For

Glucose solution:

π V = nRT

π X 0.1 = (3.4 / 180) R T

Both solution are isotonic πsilver nitrate = π glucose

( 1 + α ) X 0.01 / 0.1 = 0.019 / 0.1

(1 + α ) = 0.019 / 0.01

1 + α = 1.9
α = 1.9 -1
α = 0.9
The degree of dissociation of silver nitrate is 0.9 i.e 90 %

Page no 100 Ex 2.42

A solution containing 1.23 g of calcium nitrate in 10 g of water boils at

100.9750C at 760 mmHg. Calculate the van’t hoff factor for the salt at this
concentration. ( Kb = 0.52 K kg mol-1) Given data:

The colligative property is elevation of boiling point

ΔTb = i X Kb X m

ΔTb = T2- T1 = 100.975 – 100

= 0.975

Kb = 0.52 w = 1.23 g

W = Ca (NO3)2 = ( 1 X 40 ) + ( 2 X 14 ) + ( 6 X 16) = 40 + 28 + 96

= 164 g /mole

V = 10 g
Solution:

m = ( w / W ) X (1000 / V) = ( 1.23 / 164 ) X ( 1000 / 10) = 0.75

0.975 = iX 0.52 X 0.75

i= ( 0.975 ) / ( 0.52 X 0.75)
i=2.5

The van’t hoff factor for the salt at this concentration is 2.5