Solutions & Numericals
Solutions & Numericals
1
1
* Units of molarity : Mol. lit
* Molarity depends upon the temperature because the molarity expression contains
volume term.
* Molarity (M) = n/V
n Number of moles of solute
V Volume of solution in lit.
w 1000
Molarity (M) =
* GMW V
W weight of the solute in grams
GMW gram molecular weight of the solute
V Volume of the solution in ml.
* For dilution :
M1V1 = M2V2
M1 Molarity of concentrated solution
V1 Volume of concentrated solution
M2 Molarity of dilute solution
V2 Volume of dilute solution
Volume of water to be added V2 – V1.
f) Molality (m) :
* The number of moles of the solute dissolved in one kg of the solvent is called molality.
1
* Units of molality : Mol. kg
* Molality is independent of temperature because the expression of molality does not
contain volume term.
W1 1000
GMw W2
W1 weight of solute in grams
W2 weight of solvent in grams
GMw gram molecular weight of solute.
g) Mole fraction :
* The ratio of the number of moles of a component to the total number of moles of all
the components of solution is called mole fraction of that component.
Let n1 is the number of moles of solute and n2 is the number of mole of solvent.
Then,
n1
X1
mole fraction of solute n1 n2
2
and,
n2
X2
mole fraction of solvent n1 n2
* Sum of the mole fractions of solute and solvent is equal to one.
* Mole fraction has no units.
* Mole fraction is independent of temperature because its expression contains only weight
terms.
Solubility :
* The maximum amount of substance that can be dissolved in a specified amount of
solvent at a specified temperature is called solubility.
Solubility of a solid in a liquid :
1) Polar compounds are soluble in polar solvents while non-polar solutes are soluble
in non-polar solvents.
2) The solution which cannot dissolve some more solute at a given temperature is
called saturated solution.
3) The solution which is capable of dissolving some more solute at a given temperature
is called unsaturated solution.
4) The solution which contains more solute than that required for saturated at a given
temperature is called supersaturated solution.
Supersaturated solutions are meta stable.
5) (i) If the lattice energy of a substance is higher than its hydration energy, then the
dissolution process is endothermic and the solubility of that compound increases with raise in
temperature.
(ii) If the lattice energy of a substance is lower than its hydration energy, then the
dissolution process is exothermic and the solubility of that compound decreases with raise in
temperature.
6) Pressure does not affect the solubility of a solid in a liquid.
Solubility of a gas in a liquid :
1) The solubility of gases increases with increase of pressure.
2) According to Henry’s law, at a constant temperature the solubility of a gas in a
liquid is directly proportional to the pressure of the gas.
(OR)
The partial pressure of the gas in vapour phase (P) is directly proportional to the
mole fraction of the gas (X) in the solution.
P ∝X
(OR) P = KH.X
Where KH is called Henry’s law constant.
3
* A plot of partial pressure of the gas versus mole fraction of the gas in solution gives a
straight line passing through the origin. Slope is equal to Henry’s law constant.
* Higher the value of KH at a given pressure, the lower is the solubility of the gas in the
liquid.
* As temperature increases, the KH value increases, ie, the solubility of a gas decreases
with increase in temperature.
Applications of Henry’s law :
1. The soda water bottles are sealed under high pressure to increase the solubility of CO2
in soda water.
2. When scuba divers go into the deep sea, due to increase in pressure the solubility of
the gases in blood increases. When divers come out towards surface, the pressure
gradually decreases and dissolved gases release from blood by forming bubbles of
nitrogen in blood. This blocks capillaries and creates a medical condition called bends.
Because of this divers feel more pain and dangerous to life.
To avoid bends, the tanks used by scuba divers are filled with air and helium because helium
is less soluble in blood.
3. At higher altitudes, the partial pressure of oxygen is low. Due to this the people living
there will have low concentration of oxygen in blood. Because of this they suffer with
anoxia by which they cannot think and work properly.
* Vapour pressure of liquid-liquid solutions :
1. The pressure exerted by the vapour over the surface of the liquid when the liquid is
in equilibrium with its vapour at a given temperature is called vapour pressure of the
liquid P .
o
(or) PA PAo . X A o
where PA is the vapour pressure of the pure liquid ‘A’.
similarly,
PB ∝ XA
(or) PB PBo . X B o
where PB is the vapour pressure of the pure liquid ‘B’.
PTotal PA PB
4
PA
* Mole fraction of ‘A’ in vapour phase PT
PB
Mole fraction ‘B’ in vapour phase PT .
* The solution which obeys Raoult’s law over the entire range of concentrations is called ideal
solution.
i) If the intermolecular attractive forces between the A – A and B – B are nearly equal to those
between A – B, then an ideal solution forms.
ii) For an ideal solution,
Vmixing 0
iii) For an ideal solution,
H mix 0
ie., no heat is absorbed or liberated during the formation of solution.
iv) This type of solution boils at an expected temperature.
Eg. (1) n-hexane + n-haptane
(2) Benzene + toluene
(3) Bromo ethane and chloroethane
Non-ideal solutions :
* The solution which does not follow over the entire range of concentration is called
non-deal solution.
For the non-ideal solution with +ve deviation from Roult’s law :
1) It the A-B interactions are weaker than those between A-A and B-B, then this type of
solutions results.
2) For this solution,
Vmix ve
3) For this solution,
H mix ve
i.e., the solution is formed with the absorption of heat.
4) The solution shows more vapour pressure than expected and boils at a lower temperature
than expected.
PA PAo . X A , PB PBo . X B
PT PAo . X A PBo . X B
and
Eg. (1) Ethanol + Acetone
(2) Water + Ethanol etc.,
For the non-ideal solution with –ve deviation from Raoult’s law :
5
1) If the A – B interactions are stronger than those between A – A and B – B, then this type of
solution result’s.
2) For this type of solution,
Vmix ve
3) For this type of solution,
H mix ve
i.e., the solution is formed with the liberation of heat.
4) The solution shows less vapour pressure than expected and boils at an higher temperature
than expected.
o o
i.e., PA PA . X A ; PB PB . X B
o o
and PT PA . X A PB . X B
Eg. (i) Chloroform + acetone
(ii) Phenol + Aniline
(iii) Water + HNO3
Azeotropes :
* The binary mixture of two liquids having same composition in liquid and vapour phase and
boil at a constant temperature without change in the composition is called azeotrope (or)
constant boiling mixture.
* The solution of two liquids which show a large positive deviation form Raoult’s law form
minimum boiling azeotrope at a specific composition.
Eg. Ethanol + Water [95.6% ethanol + 4.4% water]
with boiling point
* The solution of two liquids which show a large negative deviation from Raoult’s law form
maximum boiling azeotrope at a specific composition.
Eg. HNO3 + H2O [68% HNO3 + 32% water]
with boiling point 393.5 K.
Colligative properties:
The property of a dilute solution which depends upon the number of particles of the
solute, irrestpective of their nature, present in the solution is called colligative property.
Lowering of vapour pressure, elevation of boiling point, depression of freezing point and
Osmatic pressure are the colligative properties.
1) When a non volatile solute is dissolved in a pure liquid, then the vapour pressure of the
liquid decreases. This decrease in vapour pressure is called lowering of vapour pressure
2) According to Raoult’s law, vapour pressure of the solution depends upon the mole fraction
of the solvent
6
PA X A (or ) PA PA0 . X A
P PA0 PA PA0 PA0 . X A
PA0 1 X A PA0 . X B
P
XB
PA0
PA0 PA
or 0 X B
PA
0
Here PA PA = lowering of the vapour pressure
PA0 PA
PA0 = Relative lowering of vapour pressure
Relative lowering of vapour pressure is equal to the mole fraction of the non-volatile
solute present in the solution
PA0 PA nB
0
XB
PA nA nB
PA0 PA nB
PA0 nA
PA0 PA wM
or
PA0 mW
To calculate the molar mass of given unknown solute (m) accurately following
expression can be used
PA0 PA wM
PA mW
When a non-volatile solute is added, then the boiling point of the liquid increases. This
increase in boiling point is termed as elevation of boiling point.
7
Reason: When a non-volatile solute is added, the vapour pressure of the liquid
decreases. To make the vapour pressure of the solution as 1 atm, higher temperature is
required where the solution boils. Hence boiling point elevates.
Tb B.P of solution
Tb Tb0
Tb Tb Tb0
or Tb Kb . molality
where Kb is the molal boiling point elevation constant (or) Ebullioscopic constant.
Kb is given by
2
R.Tb0
Kb
1000.lv
0
Where Tb is the boiling point of pure liquid and lv is the latent heat of vapourisation
For water,
2 373 373
Kb
1000 540
0.515 K .mol 1.kg
0.52 K .mol 1.kg
1
* units of Kb= K .mol .kg
* When a non-volatile solute is added, then the freezing point of the solvent decreases. This
decrease in freezing point is termed as depression of freezing point.
Reason: When anon-volatile solute is added then the vapour pressure of the solvent
decreases and now it would become equal to that of solid solvent at lower temperature. Thus
the freezing point of the solvent decreases.
8
T f0 F.P of pure solvent
T f F.P of solution
T f T f0 T f
* For a dilute solution, the depression of freezing point is directly proportional to the
molality of the solution
T f molality
(or) T f K f .molality
where Kf is called molal freezing point depression constant (or) cryoscopic constant.
w 1000
T f K f .
m W
The depression in the freezing point observed when one mole of non-volatile non-
electrolyte solute is dissolved in one kg solvent is called Kf.
Kf is given by
2
R.T f0
Kf
1000.l f
Where
T f0 is freezing point of pure solvent
2 273 273
Kf
For water, 1000 80
units of
K f K .mol 1.kg
Osmotic pressure:
9
The minimum pressure that must be applied on solution to stop the osmotic flow of
solvent molecules is called osmotic pressure.
V nRT
n
or RT
V
or CRT
w 1000
or R T
m V
Where c molarity of the solution
T Absolute temperature
The solutions having same osmotic pressure at a given temperature are called isotonic
solutions.
1 c1.RT
& 2 c2 RT
If 1 2 then c1 c2
Among two solutions, the solution with higher osmotic pressure is called hypertonic
while the solution with lower osmotic pressure is called hopotonic.
When blood cells are placed in 0.9% (w/v) aq.NaCl solution, then blood cells
collapse due to loss of water by osmosis. People taking a lot of salt experience water retention
in tissue cells and intercellular spaces because of osmosis. The resulting puffiness or swelling
is called edema.
10
When the solute undergoes association then the experimentally determined
molar mass is always higher than the true value.
To account for the degree of association or degree of dissociation, van’t Hoff introduced
a factor (i), known as Vant Hoff factor.
i>1
i 1
n 1
Where n is the number of ions per molecule obtained due to dissociation.
i<1; Normal molar mass < experimental molar mass and observed colligative property <
normal colligative property.
1 i
1 1/ n
Where ‘n’ is the number of molecules undergoing association.
PA0 PA n
0
i B
PA nA
Tb Kb .molality.i
11
iii) Depression of freezing point
T f K f .molality.i
C.RT .i
As dilution increases, i value increases i.e., the degree of dissociation increases.
NUMERICALS
Mass of component
Mass percentage of benzene = 100
* Total mass
22
100
22 122
= 15.28%.
122
Mass percentage of CCl4 = 100
144
= 84.72%.
2. Calculate the mole fraction of benzene in solution containing 30% by mass in CCl4.
* Mass of benzene = 30g
Mass of CCl4 = 100 – 30 = 70g
Mass
Number of moles of benzene =
gram molar mass
30
0.3846
78
Mass
Number of moles of CCl4
gram molar mass
= 70/154 = 0.4545.
n Benzene
Mole fraction of benzene =
Total moles
0.3846
0.3846 0.4545
= 0.4583.
w 1000
M
(a) m V (ml )
w = 30g, m = 291, V = 4300ml
30 1000
Molarity = 0.024M
291 4300
12
(b) M 1V1 M 2V 2
0.5 30 M 2 500
(or) M 2 0.03M
4. Calculate the mass of urea [MW = 60] required in making 2.5 kg of 0.25 molal aqueous
solution.
w 1000
Molality (m) =
* GMW W
w = weight of solute = ?
GMW = 60, W = weight of solvate = 2500 g
Molality = 0.25 m
w 1000 20 1000
molality (m) =
GMW W 166 80
1.506 mol.kg 1
Mass 100
w 20 g , GMW 166, V
(b) density 1.202
w 1000
molarity (M) =
GMW V (ml )
20 1000
1.202
166 100
= 1.448 M.
Mass of KI
Number of moles of KI =
(c) Molar mass of KI
20
0.12
166
80
Number of moles of H 2O 4.444
18
Number of moles of KI
Mole fraction of KI =
Total moles
0.12
0.0263
4.444 0.12 .
6. Concentrated nitric acid is 68% by mass. Density of the solution is 1.504 g/ml. Calculate
the molarity of the acid.
* w = 68g, GMW = 63,
13
w 1000
Molarity (M) =
GMW V (ml )
68 1000
1.504
63 100
= 16.234 M.
7. A glucose solution in water is 10% (w/w). Its density is 1.2 g/ml. Calculate (a) molality and
(b) mole fraction of each component.
* (a) w = 10, W = 90, GMW = 180
w 1000 10 1000
Molality (m) =
GMW × W 180 90
= 0.617 m.
Mass of glucose
Number of moles of glucose =
(b) Molar mass
10
0.0555
180
Mass of water
Number of moles of water =
Molar mass
90
5
18
Number of moles of glucose
Mole fraction of glucose =
Total moles
0.0555
5.0555
= 0.011.
X N2 ?
P K H .X
P 0.987
X N2
(or) K H 76.48 103
1.28 105
14
nN2 nN 2
X N2
nN2 nH 2O nH 2O
n N 2 X N 2 nH 2 O
1000
1.29 105 7.17 104
18
= 0.717 milli mole.
9. If the solubility of H2S in water at STP is 0.195m, calculate Henry’s law constant.
* 0.195 m = 0.195 mole H2S in 1 kg water.
1000
nH 2 S 0.195, nH 2O 55.55
18
P kH .X H2S
1
k H P / X H2S
0.195(0.195 55.55)
= 285.87 atm.
8
10. Henry’s law constant for CO2 in water is 1.67 10 Pa at 298K. Calculate the quantity of
CO2 in 500 ml of soda water when packed under 2.5atm CO2 pressure at 298K.
* K H 1.67 108 Pa
PCO2 2.5 1.013 105 2.5325 105
X CO2 ?
PCO2 k H . X CO2
PCO2 2.5325 105
X CO2
(OR) kH 1.67 108
1.5164 103
nCO2
X CO2
nCO2 nH 2O
nCO2
1.5164 103
(500 /18)
nCO2 1.5164 103 500 /18
= 0.042
S1 P1
S2 P2
15
P1.S 2 1 5 102
P2
(or) S1 6.56 103
= 7.62 bar.
12. An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the
normal boiling point of the solvent. What is the molar mass of the solute?
P o Ps w M
* Pso m W
1.013 1.004 2 18
1.004 m 98
m = 40.98 g/mol.
13. Heptane and octane form ideal solution. At 372K, the vapour pressure of the two liquids
are 104.2k Pa and 46.8k Pa respectively. What will be the vapour pressure of a mixture of
26 g of heptane and 35 g of octane.
Mass
No. of moles of heptane =
* Molar mass
26
0.260
100
35
Number of moles of octane = 0.307
114
No. of moles of heptane
Mole fraction of heptane =
Total moles
0.26
0.458
0.26 0.307
No. of moles of octane
Mole fraction of octane =
Total moles
0.307
0.542
0.26 0.507
Vapour pressure of the solution (PS ) PAo . X A PBo . X B
= 105.2 (0.458) + 46.8(0.542)
= 48.287 + 25.319
= 73.606k Pa.
14. The vapour pressure of two liquids A and B are 450mm of Hg and 700 mm of Hg
respectively at 350K. Find out the composition of the liquid mixture if total vapour
pressure is 600 mm of Hg. Also find the composition in the vapour phase.
o o
* PS PA ( X A ) PB ( X B )
but X A X B 1
(or) X B 1 X A
600 450( X A ) 700(1 X A )
450 X A 700 700 X A
(or) 250 X A 700 600 100
100
XA 0.4
250
16
and X B 1 0.4 0.6
In liquid phase A and B are in 4 : 6 mole ratio.
Tb Tbo Tb
= 373 + 0.052 = 373.052 K.
17. The boiling point of benzene is 353.23 K. When 1.8g of a non-volatile solute was dissolved
in 90g of benzene, the boiling point is raised to 354.11K. Calculate the molar mass of
1
solute. Kb for benzene is 2.53K. Kg. mol .
1
* w = 1.8 g, W = 90 g, K b 2.53 K. Kg. mol
17
Tb Kb . molality. i
w 1000
=K b i
m W
1.8 1000
0.88 2.53 1
m 90
2.53 1.8 1000
m 58 g/mol
0.88 90
18. Calculate the weight of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75g of acetic
1
acid to lower its melting point by 1.5 C . K f 3.9 K . Kg . mol
o
* w ?, W 75 g , m 12 6 1 8 16 6 176
T f 1.5, K f 3.9 K. Kg. mol1
T f K f . molality
w 1000
=K f .
m W
T f m W 1.5 176 75
w
(or) K f 1000 3.9 1000
= 5.0769g.
19. Calculate the osmotic pressure in Pascals exerted by a solution prepared by dissolving 1.0
o
g of polymer of molar mass 185000 in 450ml of water at 37 C .
* CRT
w 1000
R T
m V (ml )
11000
0.0821 310
18500 450
0.003057 atm
=0.003057 1.013 105 Pa
=309.69 Pa .
20. At 300K, 36g of glucose is present in a litre of its solution has an osmotic pressure of 4.98
bar. If the osmotic pressure of the solution is 1.52bar at the same temperature, what
would be its concentration?
* 1 C1 RT
2 C2 RT
1 C1
2 C2
4.98 36 1000
C2
1.52 180 1000
1 4.98 180
C2 1.52 36
1.52 36
C2 0.061 mol. lit 1
(or) 4.98 180
18
21. 19.5 g of CH2(F)COOH is dissolved in 500 g of water. The depression in the freezing point
o
of water observed is 1.0 C . Calculate the of fluoroactic acid.
* T f K f molality i
w 1000
T f K f i
m W
19.5 1000
1.0 1.86 i
(or) 78 500
i 1.0753
i 1 1.0753 1
0.0753
n 1 2 1
K a C. 2 /(1 )
19.5 1000 (0.0753) 2
78 500 (1 0.0753)
3.066 103 .
22. Calculate the depression in the freezing point of water when 10g of CH3CH2CHClCOOH is
3 1
added to 250 g of water. K a 1.4 10 & K f 1.86 K. Kg. mol .
2
* K a C.
10 1000
1.4 103 2
122.5 250
2 0.0042875
(or) 0.0655
i 1 i 1
(or) 0.0655 =
n 1 2 1
(or) i 1.0655
T f K f . molality. i
10 1000
1.86 1.0655
122.5 250
0.647 0.65K .
23. Determine the amount of CaCl2 (i = 2.47) dissolved din 2.5 lit of water such that its
0
osmotic pressure is 0.75 atm at 27 C .
* 0.75 atm, T = 27 + 273 = 300 K
Molar mass (m) = 40 + 71 = 111
V = 2.5 lit, R = 0.0821 lit. atm. K 1. mol1
CRT . i
w 1000
R T. i
m V
.mV
.
w
1000 R T i
0.75 111 2500
1000 0.0821 300 2.47
3.421g .
19
24. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4
o
in 2 lit of water at 25 C . Assume that K2SO4 dissociates completely.
* CRT i
****
20