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SOLUTIONS

• TYPES OF SOLUTIONS
• EXPRESSING CONCENTRATION OF
SOLUTIONS
INTRODUCTION
• A solution is a homogeneous mixture of two or more chemically non- reacting

substances whose composition can be varied within certain limits .

• Their utility or importance in life depends on their composition :

Brass Bronze German Silver 1ppm Fluoride 1.5ppm fluoride High conc. Of
ions ions Fluoride ions
Cu + Zn Cu + Sn Cu+ Zn + Ni Prevents tooth Tooth become Used in rat
decay mottled poison

• Intravenous injections are mixed with salt solution at particular ionic concentrations
that match with blood plasma concentrations .
Types of solutions
Expressing concentration of solutions
Concentration

Mass Volume Mass by Parts per Mole Molarity Molality


Percentage Percentage volume million Fraction
w/W v/V percentage
w/ V
PERCENTAGE
MASS % VOLUME % MASS BY VOLUME %

10% ethanol means 10g of 10% ethanol means 10ml of 10% ethanol means 10g of
ethanol on 100 g of solution ethanol on 100 ml of solution ethanol on 100 ml of solution
N- 1 : Calculate the mass percentage of benzene (C6H6) and carbon
tetrachloride (CCl4) if 22 g of benzene is dissolved in 122 g of carbon
tetrachloride
N-2: A solution is prepared by dissolving 90 mL of hydrogen peroxide in
enough water to make 3000 mL of solution. Identify the concentration of
the hydrogen peroxide solution.

• Volume percent = volume of solute x 100


volume of solution
= 90 mL x 100
3000mL
Volume percent = 3 %
N- 3: Many people uses a solution of Na3PO4 to clean walls before putting
the wall paper . The recommended concentration is 1.7% (w/v). What mass
of Na3PO4 is needed to make 2L of the solution
N-4: A solution is obtained by mixing 300 g of 25% solution and 400 g of 40
% solution by mass . Calculate the mass percentage of the resulting solution
.

• Mass % of solute = (235 / 700)x 100 = 33.57 %


• Mass % of solvent = 100- 33.7 = 66.43%
SELF ASSESsMENT
P-1 : What is the mass of the sodium hypochlorite present in commercial bleaching
solution which contains 3.62 mass percentage of sodium hypochlorite in water

P-2 : Calcium chloride can be used instead of road salt to melt the ice road during
the winter . To determine how much CaCl 2 had been used on a nearby road , a
student took a sample of slush to analyze. The sample had a mass of 23.47 g . When
the solution was evaporated , the residue had a mass of 4.58 g (assume that no
other solutes are present) . What was the mass /mass percent of CaCl 2 in the slush ?
PREPARATION OF SOLUTION
VOLUMETRIC ANALYSIS

• https://youtu.be/uZM4zTCByg8
• https://youtu.be/IAp13NCa8qo
• https://youtu.be/hvEUta68ymE
PARTS PER MILLION ,mole fraction
• Parts per million (ppm)

• Mole fraction of component (X) =

• Suppose a solution is made of two components A and B


X A = nA as XA + X B = 1 so XB = 1- XA
nA + nB
N-5 : An aqueous solution has 0.0070 gram of oxygen dissolved in
1000 grams of water. Calculate the dissolved oxygen concentration of
this solution in parts per million.

• ppm = 0.0070 x 106


1000 + 0.0070
= 7 ppm
N- 6 : Calculate the mole fraction of benzene in solution containing
30% by mass in carbon tetrachloride .
30% means 30 g of Benzene is dissolved in 100g of CCL4.
Weight of Benzene = 30 g , Weight of CCl 4 = 70 g
Molar mass of benzene = 78 g mol -1 , Molar mass of CCL4 = 154 g mol-1,
No. of moles of CCl4 = 70 / 154 = 0.4545mol
No. of moles of benzene = 30 / 78 = 0.3846mol
XBenzene = nBenzene = 0.3845/ 0.3846 + 0.4545 = 0.458
n Benzene + n CCl4
X CCl4 = 1- 0.458 = 0.542
SELF ASSESsMENT
P- 3: A fungus that grows on peanuts is a deadly toxin . When ingested
in large amount , this toxin destroys liver . Any shipment of peanuts
that contains more than 25 ppm of this fungus is rejected . A company
receives 20 tonnes (20 x 106g) of peanuts to make peanut butter .
What is maximum mass in grams of fungus that is allowed ?
P- 4: Calculate the mole fraction of ethylene glycol (C 2H6O2) in a
solution containing 20% of C2H6O2 by mass.
MOLARITY , MOLALITY
Molarity: Molarity (M) is defined as number of moles of solute dissolved in one litre of solution

0.25 mol L–1 (or 0.25 M) solution of NaOH means that 0.25 mol of NaOH has been dissolved in
one litre

Molality: Molality (m) is defined as the number of moles of the solute per kilogram (kg) of the
solvent .

1.00 mol kg–1 (or 1.00 m) solution of KCl means that 1 mol (74.5 g) of KCl is dissolved in 1 kg of
water.
N- 7 : Calculate the molarity of a solution containing 5 g of NaOH in
450 mL solution.
N-8:Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of
benzene.
N – 9 : Calculate the molarity of each of the following solutions:
(a) 30 g of Co(NO3)2. 6H2O in 4.3 L of solution (b) 30 mL of 0.5 M H2SO4
diluted to 500 mL.

(b) M1 V1 = M2V2 , 30 x 0.5 = M2 x 500 , M2 = 0.03 M


N – 10: Calculate the mass of urea (NH2CONH2) required in making 2.5
kg of 0.25 molal aqueous solution.
N –11: Calculate (a) molality (b) molarity and (c) mole fraction of KI if
the density of 20% (mass/mass) aqueous KI is 1.202 g mL -1.
N –11: Calculate (a) molality (b) molarity and (c) mole fraction of KI if
the density of 20% (mass/mass) aqueous KI is 1.202 g mL -1.
N –11: Calculate (a) molality (b) molarity and (c) mole fraction of KI if
the density of 20% (mass/mass) aqueous KI is 1.202 g mL -1.
N-12: A sample of drinking water was found to be severally contaminated with
chloroform supposed to be carcinogenic . The level of contamination was 15 ppm (
by mass) (i) Express this is percent by mass
(ii) Determine the molality of chloroform in the water sample.
15 ppm means 15 g of chlorofom in 106 g of solution
% by mass = 15 x 100
106 = 15 x 10-4 %

Molality = no. of moles of solute / mass of solvent in kg


MCHCl3 = 119.5 g mol-1 , n CHCl3 = 15 / 119.5 = 0.1255
Molality = 0.1255 x 1000
106 = 0.1255x 10-3 M
SELF ASSESsMENT
P-5: A solution of glucose in water is labelled as 10% (w/w) , what would be
the molality and mole fraction of each component in the solution ? If the
density of solution is 1.2 g ml-1 , then what would be the molarity of the
solution ?
P-6: An antifreeze solution is prepared from 222.6 g of ethylene glycol
(C2H6O2) and 200 g of water .Calculate the molality of the solution . If the
density of the solution is 1.072 g ml-1 then what shall be the molarity of the
solution ?
SELF Assessment
P-7 : Nalorphene (C19H21NO3), similar to morphine, is used to combat
withdrawal symptoms in narcotic users. Dose of nalorphene generally
given is 1.5 mg. Calculate the mass of 1.5 × 10−3m aqueous solution
required for the above dose.
SOLUBILITY of solids in liquids
• The solubility of a solid at any temperature is defined as the
maximum amount of solute in grams which can dissolve in 100g of
the solvent to form a saturated solution at that particular
temperature
• Factors on which solubility depends:
– Nature of solute and solvent
– Temperature
– Pressure
NATURE OF SOLUTE AND THE SOLVENT
• Like dissolves like

• Polar compounds like NaCl dissolves


in polar solvents like water

• Non-polar solvents like Napthalene


and Anthracene are soluble in non
polar solvents like Benzene , Ether ,
CCl4 etc.
TEMPERATURE
• When a solute is dissolved in a solvent, the
following dynamic equilibrium is
established.
Solute + Solvent ⇌ Solution
According to Le Chatelier’s principle
• Endothermic (ΔsolH > 0), then the solubility
will increase with the increase in
temperature
• Exothermic (ΔsolH < 0), then the solubility
will decrease with the increase in
temperature
Pressure
• Pressure has no significant effect on the solubility of solids in
liquids.

• Reason − Solids and liquids are negligibly affected by pressure as


they are highly incompressible.
SOLUBILITY OF A GAS IN A LIQUID
• The solubility of any gas in a particular liquid is the volume of the gas in cc that
can dissolve in a unit volume (1cc) of the liquid to form a saturated solution at a
particular temperature and under a pressure of one atmosphere .

• Factors on which solubility depends:

– Nature of gas and solvent

– Temperature

– Pressure
NATURE OF gas AND THE SOLVENT

• Like dissolves like

• Oxygen dissolves only to a small extent in water.

• Hydrogen chloride gas (HCl) is highly soluble in


water.
Pressure
• The solubility of gases in liquids increases with the increase in
pressure.
Henry’s Law
• Henry’s law − The solubility of a gas in a liquid is

directly proportional to the pressure of the gas.

Or

• The partial pressure of a gas in vapour phase (p) is

directly proportional to the mole fraction of the

gas (x) in the solution,

p = KHx

Where, KH = Henry’s law constant


appLications of Henry’s Law
• Production of carbonated beverages

• Bends to scuba divers

• To avoid bends, the tanks used by scuba divers are filled with air
diluted with helium (11.7% helium, 56.2% nitrogen and 32.1%
oxygen).

• Anoxia to climbers or people living at high altitudes


Henry’s Law
• Higher the value of KH , lower is the solubility .
TEMPERATURE
• The solubility of the gas decreases
with increase in temperature .

• Gas + Solvent ⇌ Solution + Heat

• Aquatic species is more


comfortable in cold water than hot
water.
N-1 : If N2 gas is bubbled through water at 293 K, how many millimoles of N2 gas
would dissolve in 1 litre of water. Assume that N2 exerts a partial pressure of 0.987
bar. KH N2 at 293 K is 76.48 kbar

Target : To cal. millimoles of N2


Given :PN2 = 0.987 , KH N2 =76.48Kbar
Henry’s Law , P N2 = KH x XN2
XN2 = 0.987 / 76480 = 1.29 x 10-5
As XN2 = nN2 , 1.29 x 10-5 = nN2
nN2 +nH2O nN2 + (1000/18)

nN2 = 71.59 x 10-5 moles = 0.716 millimoles


N-2: The partial pressure of ethane over a solution containing 6.56 × 10–3 g of
ethane is 1 bar. If the solution contains 5.00 × 10–2 g of ethane, then what shall be
the partial pressure of the gas?
N-3 : Henry’s law constant for the molality of methane in benzene at 298 K is
4.27 × 105 mm Hg. Calculate the solubility of methane in benzene at 298 K
under 760 mm Hg.

Acc. To Henry’s law


P = KH x X
X = 760 / 4.27 x 105
= 1.78 x 10-3
N-4: The air is a mixture of a number of gases. The major components are oxygen and
nitrogen with approximate proportion of 20% is to 79% by volume at 298 K. The water is
in equilibrium with air at a pressure of 10 atm. At 298 K if the Henry’s law constants for
oxygen and nitrogen are 3.30 × 107 mm and 6.51 × 107 mm respectively, calculate the
composition of these gases in water.
Total pressure : 10 x 760 = 7600mm
Acc- to Henry’s Law : P = KH x X
SELF Assessment
N- 1: H2S, a toxic gas with rotten egg like smell, is used for the
qualitative analysis. If the solubility of H 2S in water at STP is 0.195 m,
calculate Henry’s law constant.

N -2 : Henry’s law constant for CO 2 in water is 1.67x108 Pa at 298 K.


Calculate the quantity of CO 2 in 500 mL of soda water when packed
under 2.5 atm CO2 pressure at 298 K.
VAPOUR PRESSURE
Vapour Pressure of a liquid or a solution is the pressure exerted by the vapours in
equilibrium with the liquid / solution at a particular temperature .
FACTORS AFFECTING VAPOUR PRESSURE
• Nature of the
liquid

• Temperature
raouLt’s Law for volatile solutions
For a solution of volatile liquids, the partial vapour
pressure of each component in the solution is
directly proportional to its mole fraction.
For component 1 : p1∝ x1 , p1= p10 x1
For component 2: p2∝ x2, , p2= p20 x2
According to Dalton’s law of partial pressures,
raouLt’s Law for volatile solutions
• Let y1 , y2 = Mole fractions of the components 1 and 2 respectively
in the vapour phase.

• According to Dalton’s law of partial pressures,


raouLt’s Law - speciaL case of Henry’s Law

• Acc. to Raoult’s Law : p1 = p10x1


• Acc. to Henry’s Law : p1 = KH x1
• So the partial pressure of the volatile component or gas is
directly proportional to its mole fraction in solution. Only the
proportionality constant KH differs from p10.
• Thus, Raoult’s law becomes a special case of Henry’s law in
which KH becomes equal to p10.
raouLt’s Law for non-volatile solutes
When a non-volatile solute is added to a
solvent, the vapour pressure of the
liquid decreases.
Reason: The number of solvent
molecules on the surface decreases and
as a result, number of solvent molecules
escaping from the surface decreases.
raouLt’s Law for non-volatile solutes
Raoult’s law : For any solution, the partial vapour
pressure of each volatile component in the solution
is directly proportional to its mole fraction.
Binary solution (non-volatile solute (Urea , Glucose )
& volatile solvent ) Since the solute is non-volatile,
only the solvent molecules contribute to vapour
pressure.

• Then, according to Raoult’s law,

p1∝ x1 , p1= p10 x1


N-1 Vapour pressure of chloroform (CHCl3)& dichloromethane (CH2Cl2)
at 298 K are 200 mm Hg and 415 mm Hg respectively. (i) Calculate
the vapour pressure of the solution prepared by mixing 25.5 g of
CHCl3 and 40 g of CH2Cl2 at 298 K and, (ii) mole fractions of each
component in vapour phase.
N-1 Vapour pressure of chloroform (CHCl3)& dichloromethane (CH2Cl2)
at 298 K are 200 mm Hg and 415 mm Hg respectively. (i) Calculate
the vapour pressure of the solution prepared by mixing 25.5 g of
CHCl3 and 40 g of CH2Cl2 at 298 K and, (ii) mole fractions of each
component in vapour phase.
N-2: The vapour pressure of pure liquids A and B are 450 and 700 mm Hg
respectively, at 350 K . Find out the composition of the liquid mixture if total
vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.
N-2: The vapour pressure of pure liquids A and B are 450 and 700 mm Hg
respectively, at 350 K . Find out the composition of the liquid mixture if total
vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.
SELF Assessment
P1: Heptane and octane form an ideal solution. At 373 K, the vapour pressures of
the two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be
the vapour pressure of a mixture of 26.0 g of heptane and 35 g of octane?

P-2: 100 g of liquid A (molar mass 140 g mol–1) was dissolved in 1000 g of liquid B
(molar mass 180 g mol–1). The vapour pressure of pure liquid B was found to be
500 torr. Calculate the vapour pressure of pure liquid A and its vapour pressure
in the solution if the total vapour pressure of the solution is 475 Torr.
Ideal and non ideal solutions
Ideal solutions Non ideal solutions
Solutions in which A-A and B-B interactions Solutions in which A-A and B-B interactions
are similar to A-B interactions. are not similar to A-B interactions.

It obeys Raoult’s Law under all conditions of It does not obeys Raoult’s Law
temperature and pressure .
No change in volume Δ V = 0 Change in volume Δ V ≠ 0

No change in Enthalpy ΔH = 0 Change in enthalpy ΔH≠ 0


n-Hexane and n-heptane, Ethanol + Acetone ,
Bromoethane and Chloroethane, Chloroform + Acetone
Benzene and Toluene
Non ideal solutions
• A-A , B-B > A-B
Solutions showing
• ΔV = + ve , ΔH = + ve
Positive deviations
• PA>pAoxA , pB > pBoxB

• A-A , B-B < A-B


Solutions showing • ΔV = -ve , ΔH = - ve
Negative deviation
• PA< pAoxA , pB < pBoxB
Solutions showing positive deviations
• The intermolecular forces of attraction
between solute-solvent molecules are
weaker than those between solute-
solute molecules and solvent-solvent
molecules. Therefore, solvent molecules
can easily escape, resulting in increase in
vapour pressure.

• Example: Ethanol and acetone mixture.


Solutions showing negative deviations
• The intermolecular forces of attraction
between solute-solute molecules and
solvent-solvent molecules are weaker
than those between solute-solvent
molecules. This results in the
decreasing of vapour pressure.

• Example − Chloroform and acetone


mixture
Azeotropes
Binary mixtures which have the same composition in liquid and vapour phase, and have
constant boiling points. Not possible to separate the components by fractional
distillation
Minimum boiling Azeotropes Maximum boiling Azeotropes

Solutions showing large positive deviation Solutions showing large negative deviation
from Raoult’s Law from Raoult’s Law

Ethanol(351.3K) -water (373K) mixture HNO3(359K)- H2O (373K) mixture containing


containing ethanol approximately 95% by 68% nitric acid and 32% water by mass
volume . Azeotrope(351.15K) azeotrope is 393.5 K.
COLLIGATIVE PROPERTIES
• Properties which depend upon the number of solute particles
present in the solution irrespective of their nature, relative to
the total number of particles present in the solution
• Relative lowering of vapour pressure of the solvent
• Depression of freezing point of the solvent,
• Elevation of boiling point of the solvent
• Osmotic pressure of the solution
Relative Lowering of Vapour Pressure
The vapour pressure of solution decreases when a non-volatile solute is
added to a volatile solvent.
V.P of solution = Mole fraction of solvent x V.P of the pure solvent
Ps = x1 x p1o or ps = n1 , 1- ps = 1 - n1
p1o n1 + n2 p1o n1 + n2
or p1o –ps = n1 + n2 – n1 , p1o –ps = n2 or p1o –ps = x2
p1o n1 + n2 p1o n1 + n2 p1o
The relative lowering of vapour pressure of a solution containing non-
volatile solute is equal to the mole fraction of the solute in the solution
p1o – ps = n2
p1o n1 + n2
For dilute solutions n2 <<< n1 so neglect n2
p1o – ps = w2 x M1
p1o M2 x w 1

As relative lowering of vapour pressure depends upon no. of moles of


non volatile solute so it is a colligative property .
N- 1 : The vapour pressure of pure benzene at a certain temperature is 0.850
bar. A non-volatile, non-electrolyte solid weighing 0.5 g when added to
39.0 g of benzene (molar mass 78 g mol-1). Vapour pressure of the solution,
then, is 0.845 bar. What is the molar mass of the solid substance?
N-2: Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea
(NH2CONH2) is dissolved in 850 g of water. Calculate the vapour pressure
of water for this solution and its relative lowering.
Molecular wt. of urea = 60 g mol-1
N-3: The vapour pressure of water is 12.3 kPa at 300 K. Calculate
vapour pressure of 1 molal solution of a non-volatile solute in it.
1 molal solution means 1 mol of the solute is present in 1000 g of the solvent (water).

nH2O = 1000/18 = 55.56 mol

Therefore, mole fraction of the solute in the solution is

x2 = 1 / (1+55.56) = 0.0177.

Vapour pressure of water, p10 = 12.3 kPa

Applying the relation, (P10 - P) / P10 = X2

(12.3 - p1) / 12.3 =0.0177 , 12.3 - P1 = 0.2177

p1 = 12.0823

Hence, the vapour pressure of the solution is 12.08 kPa.


Elevation in the boiling point
• The boiling point of a liquid is the
temperature at which the vapour
pressure of the liquid becomes equal to
the atmospheric pressure .
• With addition of non-volatile solute,
vapour pressure decreases and hence,
boiling point increases
• ΔTb = Tb - Tbo
Elevation in the boiling point
Δ Tb = Kb x m (Kb = molal elevation constant or ebullioscopic constant )

Molal elevation Constant : is defined as elevation in the boiling point


when the molality of the solution is taken as unity means 1 mole of the
solute dissolved in 1 Kg of the solvent )
Units of Kb = K/m or oC / m or K Kg mol-1
N-4: 18 g of glucose, C6H12O6, is dissolved in 1 kg of water in a saucepan.
At what temperature will water boil at 1.013 bar? Kb for water is 0.52
K kg mol-1.

Moles of glucose = 18 g/ 180 g mol –1 = 0.1 mol

Number of kilograms of solvent = 1 kg

Thus molality of glucose solution = 0.1 mol kg-1

ΔTb = Kb × m = 0.52 K kg mol–1 × 0.1 mol kg–1 = 0.052 K

Boiling point of solution will be 373.15 + 0.052 = 373.202 K.


N-5: The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile
solute was dissolved in 90 g of benzene, the boiling point is raised to
354.11 K. Calculate the molar mass of the solute. Kb for benzene is 2.53
K kg mol–1 o
ΔTb = Tb – Tb = 354.11 K – 353. 23 K = 0.88 K
Depression in the freezing point
• F.Pt of a substance Is the temperature at which
the solid and the liquid forms of the substance
are in equilibrium i.e solid and liquid form of the
substance has the same vapour pressure .

• With addition of non-volatile solute, vapour


pressure decreases, which leads to a decrease in
freezing point.

• ΔTf = Tfo- Tf
Depression in the freezing point

• Molal depression constant or Cryoscopic constant : is defined as


depression in f.pt when molality is taken as unity
• Units K / m or K Kg mol-1
N-6: 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate
(a) the freezing point depression and (b) the freezing point of the solution.
N-7: 1.00 g of a non-electrolyte solute dissolved in 50 g of benzene lowered
the freezing point of benzene by 0.40 K. The freezing point depression
constant of benzene is 5.12 K kg mol–1. Find the molar mass of the solute.
N-8: A 5% solution (by mass) of cane sugar in water has freezing point of 271K.
Calculate the freezing point of 5% glucose in water if freezing point of pure
water is 273.15 K.
5% solution of cane sugar in water means 5 g of cane sugar is present in (100 - 5)g = 95 g of water.
M(C12H22O11) = 12 × 12 + 22 × 1 + 11 × 16 = 342 g mol - 1. ΔTf = (273.15 - 271) K = 2.15 K
ΔTf = Kf x W2 x 1000 , 2.15 = Kf x 5 x 1000 , Kf = 13.99 K Kg mol-1
W1 x M2 95 x 342
5% glucose in water means 5 g of glucose is present in (100 - 5) g = 95 g of water.
M(C6H12O6) = 6 × 12 + 12 × 1 + 6 × 16 = 180 g mol - 1
ΔTf = Kf x W2 x 1000 , ΔTf = 13.99 x 5 x 1000 , ΔTf = 4.09K
W1 x M2 95 x 180

f.Pt of glucose solution 273.15 – 4.09 = 269.06 K


SELF Assessment
P-1 : Cal. the mass of a non-volatile solute (molar mass 40 g mol–1)
which should be dissolved in 114 g octane to reduce its vapour
pressure to 80%.

P-2 : A solution containing 30 g of non-volatile solute exactly in 90 g of


water has a vapour pressure of 2.8 kPa at 298 K. Further, 18 g of water
is then added to the solution and the new vapour pressure becomes
2.9 kPa at 298 K. Calculate:
(i) molar mass of the solute (ii) vapour pressure of water at 298 K.
SELF Assessment
P-3: Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to
be added to 500 g of water such that it boils at 100°C. Kb = 0.52 K Kg mol-1

P-4 : Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in


75 g of acetic acid to lower its melting point by 1.5°C. Kf = 3.9 K kg mol-1.

P-5: Two elements A and B form compounds having formula AB 2 and AB4.
When dissolved in 20 g of benzene (C6H6), 1 g of AB2 lowers the freezing point
by 2.3 K whereas 1.0 g of AB4 lowers it by 1.3 K. The molar depression
constant for benzene is 5.1 K kg mol–1. Calculate atomic masses of A and B.
SOLUTIONS –5

OSMOTIC PRESSURE
VAN’T HOFF FACTOR
OSMOSIS
The process of flow of solvent

molecules from pure solvent to

solution or from solution of lower

concentration to solution of higher

concentration through a semi-

permeable membrane is called

osmosis.
SEMIPERMEABLE MEMBRANE
• The membranes which appear to be continuous sheets or films, yet they contain
a network of submicroscopic holes or pores.

• Small solvent molecules, like water, can pass through these holes but the
passage of bigger molecules like solute is hindered

Natural SPM Artificial SPM


Vegetable membrane and animal Man made membrane
membrane which are found under the
outer skin of the animals and the plants
Pig’s Bladder Parchment membrane , Cellophane
,Copper ferrocyanide
OSMOTIC PRESSURE
• The pressure required to just stop the flow
of solvent due to osmosis is called osmotic
pressure (π) of the solution.
• The osmotic pressure π has to be applied to
the solution to prevent osmosis.
• π = CRT (R = Gas constant)
π = (n/V) RT
n = no. of moles of solute and R is gas
constant
OSMOTIC PRESSURE
• O.P method is widely used to determine molar masses of proteins, polymers and
other macromolecules.
• The osmotic pressure method has the advantage over other methods for determining
molecular masses .
• Osmotic pressure measurement is done around the room temperature so it is very
useful to determine molar masses of biomolecules because they are not stable at
high temperature
• As compared to other colligative properties, its magnitude is large even for very dilute
solutions.
Isotonic Solutions Hypotonic Solutions Hypertonic solutions
Solutions having same Solution having a low Solution having a high
concentration of solute concentration of solute relative concentration of solute relative
to another to another

Same osmotic pressure Lower osmotic pressure Higher osmotic pressure


0.9 % soln of NaCl is isotonic NaCl solution with NaCl solution with
with RBC concentration less than 0.9% concentration high than 0.9%

During intravenous injections During intravenous injections During intravenous injections


with Isotonic solution ,RBC with Hypotonic solution , RBC with Hypertonic solution , RBC
neither swell nor shrink. will swell . will shrink .

No change in egg , raisins Egg or raisins will swell Egg or raisins will shrink
placed in isotonic solution
BIOLOGICAL IMPORTANCE OF OSMOSIS
• A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle.

• Wilted flowers revive when placed in fresh water.

• The blood cells collapsed when placed in water containing less than 0.9% salt.

• People taking a lot of salt or salty food experience water retention in tissue cells and intercellular
spaces because of osmosis. The resulting puffiness or swelling is called edema.

• Water movement from soil into plant roots and subsequently into upper portion of the plant is
partly due to osmosis.

• The preservation of meat by salting and of fruits by adding sugar protects against bacterial
action. Through the process of osmosis, a bacterium on salted meat or candid fruit loses water,
shrivels and dies.
REVERSE OSMOSIS
• If the pressure applied on the solution is greater
than its osmotic pressure, then the direction of
osmosis is reversed i.e., the solvent starts passing
from solution to solvent. The phenomenon is called
reverse osmosis.

• This phenomenon is used in purification


(desalination) of sea water.

• The pressure required for the reverse osmosis is


quite high. A workable porous membrane is a film
of cellulose acetate placed over a suitable support
N-1: 200 cm3 of an aqueous solution of a protein contains 1.26 g of the
protein. The osmotic pressure of such a solution at 300 K is found to
be 2.57 × 10-3 bar. Calculate the molar mass of the protein.

π = CRT , π = (n/V) RT , π = (W2 / M2V)RT ,

M2 = W2RT/ π V

Given V = 200 x 10-3 L , m = 1.26 g , T = 300 K , π = 2.57 x 10-3 bar


R = 0.083 LbarK-1mol-1

M2 = 1.26 x 0.083 x 300 / 2.57 x 10-3 x 0.200 = 61,022 g mol-1


N- 2: At 300 K, 36 g of glucose present in a litre of its solution has an osmotic
pressure of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at
the same temperature, what would be its concentration?

π = CRT , π = (n/V) RT

First case : 4.98 = (36/180) x R x 300 = 60 R

Second case : 1.52 = CR x 300

Dividing 2 by 1 we get C = 0.061 M


Abnormal molecular masses
• The molar mass of some of the substance calculated from its colligative property is
either lower or higher than the expected or normal value. Such molar mass is called
abnormal molar mass.

Example Urea Glucose KCl (g mol-1) CH3COOH in CH3COOH in


(g mol-1) (g mol-1) water(g mol-1) Benzene
(g mol-1)
Normal M.M 60 180 74.5 60 60
Calculated 60 180 37.25 30 120
M.M
Reason No change No change Dissociated Dissociated Associated
C.P remains C.P remains C.P inc . So C.P inc . So C.P dec. So
same same MM dec MM dec MM inc.
Van’t hoff factor

CONCEPTUAL QUESTIONS
Q1: Will Elevation in boiling point be same for 0.1M NaCl and 0.1 M sucrose ?Explain
Ans : No, For NaCl , i = 2 , so ΔTb = 2 Kbm whereas in sucrose i=1 so ΔTb = Kbm i.e
Elevation in B.Pt for NaCl is double than sucrose .
Q-2: Which of the following solutions have maximum depression in f.pt
(a) 0.5 M Li2SO4 (b) 0.5 M NaCl (c) 0.5 M Al2(SO4)3 (d) 0.5 M BaCl2
Ans: C
Q-3: What is Van’t Hoff factor for a compound which undergoes teramerisation
Ans : i= Moles of compound after assocoation / moles before association
(a) 4 x →(x)4 so i=1/4 = 0.25
CONCEPTUAL QUESTIONS
Q-4: The depression in freezing point of water observed for the same
amount of acetic acid, trichloroacetic acid and trifluoroacetic acid
increases in the order given above. Explain briefly.
Sol : CH3COOH < CCl3COOH < CF3COOH
As F is most electronegative in nature so it is having strong electron
withdrawing effect i.e –I effect because of this dissociation in
CF3COOH is maximum and CH3COOH is minimum .so greater the ions
produced more is colligative property
N-3: Determine the osmotic pressure of a solution prepared by dissolving 25 mg of
K2SO4 in 2 litre of water at 25° C, assuming that it is completely dissociated.

As it is completely dissociated so i= 3 for K 2SO4

π = iCRT , π = i (n/V) RT

n = W2 / M2 = 25 x 10-3 / 174 = 0.1436 x 10-3


= 3 x 0.1436 x 0.0821 x (25+ 273)
2
= 5.27 x 10-3 atm
N-4: Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of
water such that its osmotic pressure is 0.75 atm at 27° C.
π = iCRT , π = i (n/V) RT

π = i W2RT , 0.75 = 2.47 x W2 x 0.0821 x (27+273)


M2 V 111 x 2.5

W2 = 3.418 g
N- 5 : 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a
depression in freezing point equal to 1.62 K. Molal depression constant
for benzene is 4.9 K kg mol–1. What is the percentage association of acid
if it forms dimer in solution?
Formula used : α = i – 1 / (1/n)-1 , ΔTf = i Kf m
Step-1 : Calculate molality , m = n solute / W1(Kg) = (2/122) / 25 x 10 -3 = 0.655m
Step -2: Cal Van’t Hoff factor i = ΔTf / Kf m = 1.62 / 4.9 x 0.655 = 0.504

Step -3: Cal. α , α = i – 1 , 0.504 – 1 = 0.992


1/n – 1 (1/2) – 1

Step -4: % association 99.2 %


N-6: 0.6 mL of acetic acid (CH3COOH), having density 1.06 g mL–1, is
dissolved in 1 litre of water. The depression in freezing point
observed for this strength of acid was 0.0205°C. Calculate the van’t
Hoff factor and the dissociation constant of acid. Kf = 1.86 K Kg mol-1
Formula : ΔTf = i Kf m , α = i – 1 / n -1 , Ka = cα2 / 1-α
Step-1 : Calculate molality , m = n solute / W1(Kg)
n solute = (0.6 x 1.06 )/ 60 = 0.0106 , m = 0.0106 / 1 = 0.0106 moles / Kg

Step -2: Cal Van’t Hoff factor i = ΔTf / Kf m = 0.0205 / 1.86x 0.0106 = 1.04

Step -3: Cal. α , α = i – 1 , 1.04 – 1 = 0.04


n–1 2–1

Step-4: Ka = 0.0106 x (0.04)2 / 1- 0.04 = 1.76 x 10 -5


Self assessment
P1:Calculate the freezing point of an aqueous solution containing 10.5 mg of MgBr 2 in 200g
of water .(Molecular mass MgBr 2 = 184 g mol-1, Kf = 1.86 K Kg mol-1)

P2: Calculate the depression in the freezing point of water when 10 g of CH 3CH2CHClCOOH
is added to 250 g of water. Ka = 1.4 × 10–3, Kf = 1.86 K kg mol–1

P-3:19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point
of water observed is 1.0 0 C. Calculate the van’t Hoff factor and dissociation constant of
fluoroacetic acid.

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