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(2097) Lecture Notes Solutions and Colligative Proerties e
(2097) Lecture Notes Solutions and Colligative Proerties e
(2014-15)
(LECTURE No. 1 TO 6)
Lecture # 2
Section (C) :
4. Solutions of solids in liquids
4.1 Solubility of solids in liquids
4.2 Factors affecting the solubility of solids in liquids
4.2.1 Nature of solute
4.2.2 Nature of solvent
4.2.3 Effect of temperature (solubility curves)
4.2.4 Effect of pressure (no effect)
5. Solutions of gases in liquids
5.1 Solubility of gases in liquids
5.2 Factors affecting the solubility of a gas in liquids
5.2.1 Nature of gas.
5.2.2 Nature of solvent.
5.2.3 Effect of temperature
5.2.4 Effect of pressure (Henry’s law)
Section (D) :
6. Vapour pressure of a pure liquid or pure solid
6.1 Origin of saturated vapour pressure: Evaporation and condensation
6.2 Important points regarding vapour pressure
6.2.1 Definition of vapoure pressure
6.2.2 Factors affecting vapour pressure
6.2.3 Effect of Temperature on vapour pressure (Clausius-clapeyron equation)
6.2.4 Boiling point and Vapour pressure
6.2.5 Vapour pressure does not depend on
(i) amount of liquid (ii) surface area of liquid (iii) volume or shape of the container
6.3 Phase diagram of pure substance and Triple point (For Olympiad, Not for Boards)
Lecture # 3
7.1 Vapour pressure of liquid-liquid solutions (volatile solute + volatile solvent)
7.1.1 Staement of Raoult’s law for volatile solutes.
7.1.2 Derivation of total pressure over solution using Raoult’s law and Dalton’s law
y1P = x1p1º ; PT = x1 p1º + x2p2º
SOLUTION & COLLIGATIVE PROPERTIES # 2
1 1 y2
7.1.3 Determining compostion of vapour phase: = + 0
PT PT p2
7.1.4 Graphical representation of Raoult’s law
Section (E) :
7.2 Application of Raoult’s law for volatile solute
7.2.1 Phase diagram (Bubble and dew points)
7.2.2 Fractional
7.3 Limitations of Raoult’s Law
7.3.1 Molecular structure: Ideal & non-ideal solution
7.3.2 Positive deviation from Raoult’s law.
7.3.3 Negative deviation from Raoult’s law.
7.4 Azeotropic or constant boiling mixture.
7.4.1 Azeotropes (Maximum & minimum boiling azeotropic mixture).
7.4.2 Explanation of azeotropes with graphs.
7.5 Vapour pressure of completely immiscible liquids and steam distillation
Lecture # 4
Section (F) :
8.1 Introduction to colligative properties.
8.1.1 Types of colligative properties.
8.1.2 Van’t Hoff’s factor
(a) When electrolyte dissociates.
(b) Electrolyte associates.
Lecture # 5
Section (G) :
8.3 Elevation of boiling point.
8.3.1 Concept of boiling point.
8.3.2 Expression for the elevation in boiling point.
8.3.3 Determination of molecular mass of solute.
8.3.4 Calculation of molal elevation constant from enthalpy of vaporisation.
8.4 Depression in freezing point.
8.4.1 General discussion.
8.4.2 Expression for the depression in freezing point.
8.4.3 Calculation of molecualr mass of solute.
8.4.4 Calculation of molal depression constant from enthalpy of fusion.
8.4.5 Application of depression in freezing point.
8.4.6 Rast method.
Lecture # 6
Section (H) :
8.5 Osmotic pressure.
8.5.1 Definition of osmosis.
8.5.2 Osmotic pressure.
8.5.3 Expression for the osmotic pressure.
8.5.4 Experimental measurement of osmotic pressure.
8.5.5 Isotonic solution.
8.5.6 Determination of molecular mass (polymer and colloidal solution).
8.5.7 Explanation of some phenomena (biological) on the basis of osmosis.
8.5.8 Osmotic pressure of mixture of two or more than two solution.
Concentration Terms :
3.1. % Concentration
weight of solute (gm)
(a) % w/w = weight of solution (gm)
= wt of solute/100 gm of solution.
% wt/wt (w/w) does not depends on temp.
(c) % v/v : If both solute & solvent are liquids = volume in (mL) of solute per 100 mL of soln.
3.3. Molarity (Depends on temp.) = No. of moles of solute per litre of soln.
Soluite moles = n
Solvent moles = N
n W 1000
M = V (in L ) = x V in (mL )
M
no. of moles of solute = molarity x volume ( in L)
no. of m. moles of solute = molarity x volume ( in mL)
If V1mL of C1M solution is mixed with V2 mL of C2M solution (same substance or solute)
Cf (V1+V2) = C1V1 + C2V2
Ex. 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
moles
= = 10 m. moles of Na2SO4
volume
20 m. moles of Na+
20
(P) [Na+] = = 0.2 M
100
(ii) [H+] = ?
10 m. moles H2SO4
20 m. moles H+
20
[H+] = = 0.2 M
100
10 10 36 56
(iii) SO42– = = = 0.56 M
100 100
24
(iv) Al3+ = = 0.24 M
100
3.4. Molality (Does not depends on temp.) = No. of moles of solute per 1 kg(1000 gm). If solvent of w gm
of solute (Molar mass = m gm/mole) is dissolved in 'W' of solvent.
w 1000
molality = x W (gm)
M
moles 1000
molality = solvent W (gm)
Derive a relationship between moalaity & molarity of a solution in which w gm of solute of molar mass
m gm/mol is dissolved in W gm solvent & density of resulting solution = 'd' gm/ml.
say 1 L solution taken,
mass of 1 lit solution = (1000 d) gm
moles of solute = (molarity)
mass of solute = (molarity) x m
mass of solvent = W
= 1000 d – (molarity) x m
(molarity ) 1000
molality = (no. of moles of solte) 1000 d molarity M.Wt
moles of solute
(c) ppm (moles/moles) = moles of solution x 106
Ex. Calculate molarity of CaCO3(aq.) soln which has conc of CaCO3 = 200 ppm.
Ex. Molality of urea soln. which has X urea = 0.2
n
= 0.2
nN
0.2 moles of urea in 0.8 moles water
0 .2 250 125
x 1000 = =
0.8 18 18 9
Dissolution : When a solid solute is added to the solvent, some solute dissolves and its concentration
increases in solution. This process is known as dissolution.
Crystallisation : Some solute particles in solution collide with the solid solute particles and get separated
out of solution. This process is known as crystallisation.
A stage is reached when the two processes occur at the same rate. Under such conditions, number of solute
particles going into solution will be equal to the solute particles separating out and a state of dynamic
equilibrium is reached.
Solute + Solvent Solution
At this stage the concentration of solute in solution will remain constant under the given conditions, i.e.,
temperature and pressure. Similar process is followed when gases are dissolved in liquid solvents. Such a
solution in which no more solute can be dissolved at the same temperature and pressure is called a saturated
solution. An unsaturated solution is one in which more solute can be dissolved at the same temperature. The
solution which is in dynamic equilibrium with undissolved solute is the saturated solution and contains the
maximum amount of solute dissolved in a given amount of solvent. Thus, the concentration of solute in such
a solution is its solubility. Earlier we have observed that solubility of one substance into
another depends on the nature of the substances. In addition to these variables, two other parameters, i.e.,
temperature and pressure also control this phenomenon.
Saturated solution : A solution in which no more solute can be dissolved at the same temperature is called
saturated solution.
Solubility : It is defined as amount of solute dissolved in 100 g of solvent to form saturated solution.
Unsaturated solution : It is a solution in which more amount of solute can be dissolved at the same
temperature.
Supersaturated solution : It is a solution which contains more mass of the dissolved solute than the
saturated solution at the same temperature and pressure. It should be prepared in a dust-free vessel and at
a higher temperature. It is metastable. Mechanical stress, such as shaking or addition of solute, causes
deposition of solute.
Supersaturation : - Refers to a solution that contains more of the dissolved material than could
be dissolved by the solvent under normal circumstances. It can also refer to a vapour of a compound
that has a higher partial pressure than the vapour pressure of that compound. Super saturated
solution of water and sugar commonly used to make rock candy as shown in figure.
Supercooling :- is also known as undercooling. It is a process of lowering the temperature of a liquid or gas below
its freezing point without it becoming a solid. A liquid below its standard freezing point will crystallize in the
presence of nucleation around the crystal structure can form creating a solid. In supercooling, creation of a nucleation
means the formation of an interface at the boundaries of a new phase.Creation of liquid droplets in saturated vapor
is characterized by nucleation. Some plants are able to supercool the fluid in their cells cytosol and vacuole and
they survive temperatures down to –40°C.
Superheating :- is phenomenon in which a liquid is heated to a temperature higher than its boiling point, without
boiling. Superheating is achieved by heating a homogenous substance free of nucleation sites.
For boiling to occur, the vapor pressure must exceed the ambient pressure plus a small amount of of pressure
induced by surface tension
Memorize this theory as soon as you get the DPP. Revise it regularly and master this concept by practice.
vapour pressure of the compound.
1. Which of the following is correct statement (B) Surface tension suppress the superheating
(A) Carbonated water is a supersaturated due to additional forces of surface tension ,
solution of CO2 gas in water. that decrease the growth of bubbles.
(B) In supersaturation the solution contains more (C) Adding sand or gases to the liquid provides
than the dissolved material than it could nucleation sites which minimize the super
dissolved. heating.
(C*) Both (A) & (B) are correct (D*) Both B & C are correct
(D) None of these.
4. Which of the following is correctly matched.
2. Which of the following in correct statement. (A) Supersaturation – The vapour of a compound
(A*) Refrigeration is an example of super cooling that has higher partial pressure than the
process in which freezer cools drinks to a vapour pressure of the compound.
super cooled level. (B) Super cooling – The process of lowering the
(B) Supercooling is process of lowering the temperature of liquid or gas below freezing
temperature of a liquid below its freezing point without it become solid
point with becoming a solid. (C) Super heating – The process of liquid is
(C) Both (A) & (B) are correct heated to temperature higher than its boiling
(D) None of these point without boiling
3. Which of the following is correct option related (D*) All are correctly matched
to superheating
(A) Superheating refers to vapour of a compound
that has lower partial pressure than the
SOLUTION & COLLIGATIVE PROPERTIES # 9
represented by equation. Solute + Solvent Solution.This, being dynamic equilibrium, must follow Le
Chateliers Principle. In general, if in a nearly saturated solution, the dissolution process is endothermic (sol
H > 0), the solubility should increase with rise in temperature and if it is exothermic (sol H > 0) the solubility
should decrease. These trends are also observed experimentally.
If above process is exothermic i.e. H < 0, then as T increases, solubility decreases.
If above process is endothermic i.e. H > 0, then as T increases, solubility increases.
p
(iv) Higher the value of KH of a gas, lower will be its solubility. Since, X = K .
H
Plot of p Vs X is a straight line passing through the origin with slope equal to KH .
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 be applied by expressing 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.
Ex. The Henry's law constant for the solubility of N2 gas in water at 298 K is 1.0 × 105 atm. The mole fraction of
N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water of 298 K and 5 atm pressure
is : [JEE - 2009]
(A*) 4 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–6
Sol. PN = KH × x N2
2
1
x N2 = × 0.8 × 5 = 4 × 10–5 per mole
105
In 10 mole solubility is 4 × 10–4 .
Section : (D)
. Henry’s Law
When a gas is dissolved in a solvent the following equilibrium is established.
Gas + Solvent solution
The relationship between solubility of gas and its pressure is expressed in terms of Henry’s law, which states that
the amount of gas dissolved in the given amount of a solvent at any temperature is proportional to pressure of the
gas above solvent. It may also be stated as, at constant temperature the mole fraction of gas dissolved in a solvent
is directly proportional to the partial pressure of gas.
Let x be the mole fraction of a gas dissolved in a definate amount of liquid at temperature T.
If the partial pressure of gas over the solvent patm then
x P ; x = KHP or P = KH' X
KH = Proportionality constant or Henry constant.
Characteristics of Henry law constant (KH)
(i) Unit same as those of pressure (mol/ L atm, L atm/mole)
Gases KH(mol/l.atm)
O2 1.3 × 10 –3
N2 7 × 10 –4
(ii) Different gas have different value of KH
CO2 2.3 × 10 –2
H2 8.5 × 10 –4
(iii) The KH values of a gas is different in different solvent and it increase with the
increase in temperature.
(iv) Higher the value of KH of a gas lower will be its solubility
Application of Henry’s law
(i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed under high pressure.
(ii) At high altitude the partial pressure of oxygen is less than that at the ground level. This leads to low concentration
of oxygen in the blood and tissue 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.
Memorize this theory as soon as you get the DPP. Revise it regularly and master this concept by practice.
1. At 298 K and 1 atm pressure solubility of N2 in atm.
water was found to be 6.8 × 10–4 mol/L. If partial (A) H2 (B) O2
pressure of N2 is 0.78 atm, then what is the (C*) CO2 (D) None of these
concentration of N2 dissolved in water under
atmospheric conditions. 4. The Henry’s law constant for the solubility of N2
(A) 2.4 × 10–3 m (B*) 5.3 × 10–4 m gas in water at 298 K is 2.0 × 105 atm. The mole
(C) 9 × 10–4 m (D) 16.5 × 10–4 m fraction of N2 in air is 0.8. The no. of moles of N2
from air dissolved in 5 moles of water of 298 K
2. Solubility curves of four ionic salts X, Y, Z, W and 3 atm pressure is
are given below : (A) 2 × 10–5 (B*) 6 × 10–5
(C) 9 × 10 –4 (D) 9 × 10–5
Note: evaporation only takes place on the surface of the liquid. That's quite different from boiling which
happens when there is enough energy to disrupt the attractive forces throughout the liquid. That's why, if you
look at boiling water, you see bubbles of gas being formed all the way through the liquid.
If you look at water which is just evaporating in the sun, you don't see any bubbles. Water molecules are
simply breaking away from the surface layer. Eventually, the water will all evaporate in this way.
As the gaseous particles bounce around, some of them will hit the surface of the liquid again, and be trapped
there. This is called as condensation. There will rapidly be an equilibrium set up in which the number of
particles leaving the surface is exactly balanced by the number rejoining it. At equilibrium, rate of
evaporation becomes equal to the rate of condensation.
In this equilibrium, there will be a fixed number of the gaseous particles in the space above the liquid. When
these particles hit the walls of the container, they exert a pressure. This pressure is called the saturated
vapour pressure (or just vapour pressure) of the liquid.
Suppose,we take 10 gram liquid in a chamber. Initially, there are no molecules in the gaseous phase. Thus,
SOLUTION & COLLIGATIVE PROPERTIES # 14
no pressure is exerted on the mercury and the level of mercury in both columns is equal. Suppose, after
vapourization of 5 gram of the liquid vapour-liquid equillibrium is established. Now, molecules in the gaseous
phase exert pressure on the mercury and level of mercury in the column attached to the chamber decreases.
Note: From the figure, we can see that, Vapour Pressure of the liquid = h mm Hg.
Note: Volatile solids (like Iodine) also evaporate and have a vapour pressure at any given tempratre, just like
liquids.
Vapourization (liquid to vapour) is always endothermic. It needs heat to convert the liquid into the vapour.
According to Le Chatelier, increasing the temperature of a system in a dynamic equilibrium favours the
endothermic change. That means that increasing the temperature increases the amount of vapour present,
and so increases the saturated vapour pressure.
p Hv 1 1
ln 2 , where Hv = molar enthalpy of vapourisation of the given liquid,
p1 R T2 T1
" If you have this equilibrium and increase the pressure on it, according to Le Chatelier's Principle the
equilibrium will move to reduce the pressure again. That means that it will move to the side with the
smaller volume. Liquid water is produced.
" To make the liquid water freeze again at this higher pressure, you will have to reduce the temperature.
Higher pressures mean lower melting (freezing) points.
" Notice that the triple point for water occurs at a very low pressure. Notice also that the critical temperature
is 374°C. It would be impossible to convert water from a gas to a liquid by compressing it above this
temperature.
Comprehension
A phase is the form of the matter that is homogeneous in chemical and physical composition. Phases are solid
liquid and gases. Two immiscible liquids constituent two different phases. Two miscible liquids constituent only one
phase. Two differents solids constituent two different phases. Alltropes and polymorphes also consitutent two
different phases. For ex. Red phosphorus and White phosphorus are different phases, Diamond and Graphite are
different phases.
Phase diagram is the summary of the phases that are present at any given temperature and pressure. The phases
will simply be solid, liquid or gas states of a pure substance moving from one phase to another by changing the
temperature and pressure.
The three lines which meet at point T on the diagram is called the triple point. At triple point you must have unique
combination of temperature and pressure where all three phases are in equilibrium together.
At the top of limit of liquid–vapour equilibrium curve, labelled as C is known as critical point. The temperature and
pressure at point C is known as critical temperature and critical pressure. Above the critical temperature it is
impossible to condense a gas in liquid just by increasing the pressure. All you get is highly compressed gas.
79 B
C
76 x5
solid Liquid
P re ss u re (a tm )
x1 x2 x3
5.2 x4 ;
T
Vapour
1
0.5 A
4. 0
194 216 298 304.2
Temp (K)
Memorize this theory as soon as you get the DPP. Revise it regularly and master this concept by practice.
Give the answer of following question by using above phase diagram of CO2.
1. What kind of phase change will take place if solid
4. If the pressure is increased, the melting
S is kept in the open under normal condition ?
temperature of solid S will
(A*) Sublimation (B) Melting
(A) Not change (B*) Increase
(C) Evaporation (D) No change
(C) Decrease (D) Can’t say
2. Under which condition, are all the three phases
5. What happens to the system at X5 if pressure is
of the system S in equilibrium ?
changed slowly keeping temperature constant ?
(A) T > 304.2k and P > 72.9 atm
(A) At a higher pressure, the system will become
(B*) T = 216 K and P = 5.2 atm
liquid
(C) T > 304.2 K
(B) At a lower pressure, the system will become
(D) P > 72.9 atm
liquid.
(C*) The system will be in the same phase
3. Temperature of the system at X1 is increased at
(D) None of these
constant pressure to reach X4. Which of the
following is incorrect about the phases of the
system at different state.
(A) At X1 solid phase exists.
(B) At X2 solid liquid equilibrium phase exists
(C*) At X3 solid-liquid gas equilibrium phase exists.
(D) At X4 vapour phase exists.
A
x x
x
x
x B
x x
x
A+B
XA
XB
pA xA
pA = xAPAº
Similarly, for liquid B we have,
pB xB
pB = xBPBº
Total pressure over the solution PT , according to Dalton's law is
PT = pA + pB = xAPA0 + xBPB0
7.1.3 Determinig composition of vapour phase:
Let, yA = mole fraction of A in vapour phase above the solution and
yB = mole fraction of B in vapour phase above the solution
Now, we have
pA = yA PT .....Daltion's law of partial pressure for a gaseous mixture
pA = xAPAº ...........Raoult's law
Thus, pA = yA PT = xA PAº
Also, pB = yBPT = xBPBº
y A PT y bPT
xA + xB = 1 =
PA0 PB0
1 y A yB
Thus, P = 0 0
T PA PB
7.1.4 Graphical Representation :
pA= xAPAº & pB = xB PBº
PT = xAPAº + xB PBº
1 y A yB y 1 yA
= 0
0 = A0
PT PA PB PA PB0
PA0 PB0
PT
PA0 ( PB0 PA0 ) y A
From the above equation, the plot of PT with respect to y is a curve instead of a straight line. We can
superimpose this curve on the diagram for graphical representation of Raoult’s Law to get following phase
diagrams.
(A) Pressure versus Composition Phase Diagram (At constant T): P vs. x and y
In this kind of phase diagram the temperature has a fixed value. The mole fraction of one component is
plotted on the horizontal axis and the pressure is plotted on the vertical axis. If A is more volatile than B,
then we get following diagram.
Explaination:
(i) On horizontal-axis we have plotted both x and y that is both liquid composition and vapour
composition.
(ii) The lower curve (Dew Point Curve) represents the total pressure as a function of the composition i.e.
mole fraction in the vapor phase at equilibrium with the liquid phase. It is plotted using PT vs. yA equation:
PA0 PB0
PT 0
PA ( PB0 PA0 ) y A
(iii) The upper curve i.e. Bubble Point Curve (a straight line in the case of an ideal solution) represents the
total pressure as a function of composition i.e. mole fraction in the liquid. It is plotted using PT vs. xA
equation: PT = ( PAº – PBº ) xA + PB0
(iv) The area between these two curves is vapour-liquid equilibrium region. Vapours cannot exist
above the bubble point curve and liquid can not exist below the dew point curve.
(v) Suppose, initially the pressure over the solution is very high so that no vapour exist above the
liquid. As we gradually decrease the pressure, a point (Bubble point) comes when we cross the
Bubble-Point curve and first bubble of vapour starts forming. Hence, the name bubble point curve.
Now we have entered the vapour-liquid equilibrium region. On further decreasing the pressure, a
point (Dew Point) comes when we cross the Dew-Point curve when almost all the liquid has evaporated
into vapour i.e. only the last drop of liquid (Dew) remains. Beyond this point no liquid exists in the
system.
1 YA YB 0 .5 0 .5
= 0 + 0 = +
P PA PB 40 100
400
P=
7
YA PA0 X A 40 5 2
(d) YA = 0.5 = XA = XB =
P 400 / 7 7 7
(e) Let x mole of B be present in liquid phase.
Mole of A Mole of B
Liquid 1-x x
Vapour x 1-x
P = 40 (1 – x) + 100 x
1 YA YA 1 x 1 x 100 x (1 x )40
= 0 + P = + = 40 x 100
P PA B P 40 100
So p2 = 40 x 100
p = 20 10
20 10 = 40 (1 – x) + 100x = 40 + 60x
20 10 10 10 2
x= =
60 3
(B) Temperature versus Composition Phase Diagrams i.e. T vs x and y diagram
(i) In this type of phase diagram the pressure is held fixed. The mole fraction of one component is plotted on
the horizontal axis and the boiling temperature is plotted on the vertical axis.
(ii) The upper curve (Dew-Point curve) gives the boiling temperature at the given pressure as a function of
the mole fraction in the vapor phase, and the lower curve (Bubble-Point curve) gives the boiling tempera ture
at the given pressure as a function of the mole fraction in the liquid phase.
Note: If a liquid has a high vapour pressure at a particular temperature, it means that its molecules
can escape easily from the surface. The liquid with the higher vapour pressure at a particular
temperature is the one with the lower boiling point. If A is more volatile than B, then we get
following diagram.
(i) The compositions of the liquid and vapour that are in mutual equilibrium are not necessarily the same.
Common sense suggests that the vapour should be richer in the more volatile component.
(ii) In a simple distillation, the vapour over a boiling mixture is withdrawn and condensed in a separate
container. The liquid collected in the new container is called condensate and the liquid remaining in the
original container is called distillate. The condensate has higher mole fraction of the more volatile component
than the original mixture. The distillate has higher mole fraction of the less volatile component than the
original mixture. This is the principle of distillation and is used to separate a more volatile liquid from a less
volatile liquid.
(iii) In fractional distillation, the boiling and condensation cycle is repeated successively to get a condensate
which gets richer in the more volatile component after each cycle.
Ex. An equimolar mix of benzene & toluene is prepared the total V.P. of this mix as a fraction of mole
fraction of benzene is found to be
PT = 200 + 400 Xben.
(a) Calculate composition of vapours of this mix. [ Assume that the no. of moles going into vapour phase
is negligible in comparsion to no. of moles present in liq. phase ].
(b) f the vapour above liq in part A are collected & are condensed into a new liqiuid calculate composition
of vapours of this new liq.
Sol. (a) P0Beazene= 600 mm of Hg
P0Toloune = 200 mm of Hg
1 1
PT = × 600 + × 200 = 400 mm of Hg
2 2
Pbenz = xben ' Pºben = ybenPT.
1/ 2 600 3
ybenzene = = = 75%
400 4
1
yToloune = = 25%
4
condensate
( Liq. formed after
(b) condensation of
vapours. distillate ( rem. liq.)
3 1 3 / 4 600
PT = × 600 + × 200 = 500 yben = = 0.9 = 90%
4 4 500
yToluene = 0.1 = 10%
Non-ideal solutions:
Those solutions which do not obey Raoult's law are called non-ideal solutions.
When the forces of attraction between A — A, B — B is different from A — B then 'A' and 'B' form non-ideal
solutions. For these solutions :
(i) Raoult's law is not obeyed. (ii) Hmix 0 ; (iii) Vmix 0.
Note: Dashed lines represent vapour pressures and total pressure corresponding to ideal solution
Examples: water and ethanol, chloroform and water, ethanol and CCI4, methanol and chloroform,
benzene and methanol, acetic acid and toluene, acetone and ethanol, methanol and H2O,
C2H5OH + cyclohexane.
Explaination: The fact that the vapour pressure is higher than ideal in these mixtures means that molecules
are breaking away more easily than they do in the pure liquids. That is because the intermolecular forces
between molecules of A and B are less than they are in the pure liquids.
You can see this when you mix the liquids. Less heat is evolved when the new attractions are set up than
was absorbed to break the original ones. Heat will therefore be absorbed when the liquids mix. The enthalpy
change of mixing is endothermic.
Note: Dashed lines represent vapour pressures and total pressure corresponding to ideal solution
Examples: chloroform and acetone, chloroform and methyl acetate, H2O and HCI, H2O and HNO3, acetic
acid and pyridine, chloroform and benzene.
Explaination:These are cases where the molecules break away from the mixture less easily than they do
from the pure liquids. New stronger forces must exist in the mixture than in the original liquids.
You can recognise this happening because heat is evolved when you mix the liquids - more heat is given out
when the new stronger bonds are made than was used in breaking the original weaker ones.
A non-ideal solution is defined as the one which does not obey Raoult’s law. These are divided into two types.
1. Non-ideal positive deviation solution
2. Non-ideal negative deviation solution.
Positive deviation solution Negative deviation solution
A............A
molecular interaction
A.............B
is Stronger than
B............B
(iii) There is decrease in volume on mixing and
(iii) There is increase in volume on mixing and
evolution of heat takes place on mixing
absorption of heat.
Vmix ve Hmix ive
Vmix positive Hmix positive
S mix ive Gmix ive
S mix ive Gmix ive
Ex. H2O + HCOOH, H2O + CH3COOH
Ex. H2O + CH3OH, C2H5OH + Hexane
H2O + HNO3, CHCl3 + CH3OCH3
C2H5OH + Cyclohexane, CHCl3 + CCl4
Memorize this theory as soon as you get the DPP. Revise it regularly and master this concept by practice.
1. Identify the mixture that shows negative deviation 3. Total vapour pressure of mixture of 1 mole of A
solutions 0
PA 150 mm and 2 mole of B PB0 240 mm is
(A) Benzene + (CH3)2CO
(B*) (CH3)2CO+ C6H5NH2 200 mm. In this case :
(C) CHCl3 + C6H6 (A) There is a positive deviation from Raoult’s
(D) (CH3)2CO + CS2 law.
(B*) There is a negative deviation from Raoult’s
2. At 550C, ethanol has a vapour pressure of 168 law
mm, and the vapour pressure of methyl (C) There is no deviation from Raoult’s law.
cyclohexane is 280 mm. A solution of the two in (D) Molecular masses of A & B are also required
which the mole fraction of ethanol is 0.68, has a for calculating deviation.
total vapour pressure of 376 mm. This solution is
formed from its components with 4. Identify the mixture showing positive deviation of
(A) The evolution of heat non-ideal solution.
(B*) The absorption of heat.
(C) Neither absorption nor evolution of heat (A*) CH3COCH3 + CS2
(D) Nothing can be predicted on the basis of given (B) Hexane + Heptane
information (C) Chlorobenzene + Bromo benzene
(D) Acetone + Chloroform
The characteristic of such mixture is that the total pressure goes through a maximum ( in constant temperature
phase diagram), and therefore the temperature goes through a minimum (in constant pressure phase diagram).
At the lowest point in the temperature vs. composition phase diagram, the concentration in the vapour phase
is the same as the concentration in the liquid phase (y = x ). This concentration is known as the azeotropic
composition. At this point, the mixture boils at a constant temperature and without change in composition.
7.4.2 Maximum Boiling Azeotropes : Non-ideal solutions showing large negative deviation from Raoult's law
form maximum boiling azeotropes which boil at temperature higher than the boiling point of its components
A and B respectively, e.g., a mixture of HCl and H2O containing 20.2% HCl by weight boils at 108.5ºC higher
than either pure HCI (– 85°C) or water (100°C).
On left side, temprature versus composition phase diagram is shown. On right side, pressure versus
compostion diagram is shown for maximum boiling azeotrope.
(vi) To express the ratio of A to B in the vapor in terms of the actual weights wA and wB, the numbers of
moles must be multiplied by the respective molecular weights MA and MB ; hence,
(3)
Note: The boling point of a solution of two immiscible liquids is less than the individual boiling points of both
the liquids. This concept is used in steam distillation.
(2) Steam DIstillation: The boling point of a solution of two immiscible liquids is less than the individual boiling
points of both the liquids. This concept is used in steam distillation.
(i) A system of two immiscible liquids will boil when the total vapor pressure P is equal to the atmospheric
pressure. The boiling point of the mixture is thus lower than that of either constituent.
(ii) Further, since the total vapor pressure is independent of the relative amounts of the two liquids, the
boiling point, and hence the composition of the vapor and distillate, will remain constant as long as the
two layers are present.
A liquid (generally organic) that is immiscible with water, and that has a higher boiling point than water
can be boiled (distilled) at a much lower temperature by passing steam through it. In this way, the
organic liquid can be purified from impurities using steam distillation.
Phase (P) : A phase is defined as any homogeneous and physically distinct part of a system which is
separated from other parts of the system by definite bounding surface ; the term homogeneous means that
the system has identical physical properties and chemical composition throughout the whole of the system.
Number of Components (C) : It is the smallest number of independent chemical constituents by means of
which the composition of each and every phase can be expressed.
Degree of Freedom (F) : The degree of freedom or variance of the system is the minimum number of
independent variables such as temperature, pressure and concentration, that must be ascertained so that a
given system in equilibrium is completely defined.
Phase rule is a general rule which is applicable to all types of reactive and nonreactive systems.
Nonreactive system : Consider a heterogeneous system of P phases at equilibrium containing in all C
components
F= C – P +2 ; F + P = C +2
Example : Let us verify the rule by calculating the variance of a one- component system :
One phase only P =1, F = C – P + 2 = 1 – 1 + 2 = 2
Two phase in equilibrium P =2, F = C – P + 2 = 1 – 2 + 2 = 1
Three phase in equilibrium P =3, F = C – P + 2 = 1 – 3 + 2 = 0
Reactive system : Let us consider a heterogenous system composed of arbitrary amount of C constituents
For the sake of simplicity we assume that four of the constituents are chemically active, capable of undergo-
ing the reaction.
1A1 + 2A2 3A3 + 4A4
We have F = (C –2) –P + 2
where ‘r’ is the number of independent reactions that are taking place in the system.
Some Typical Example to Compute The Number of Components
For nonreactive system : Number components = Number of constituents
For reactive system : Number components = Number of constituents - (Number of chemical
reactions) - (Number of restricting conditions)
P
1. Relative lowering in vapour pressere P
2. Elevation in b.p. (T b)
3. Depression in freezing pt. (T f)
4. Osmotic pressure
i > 1 dissociation
i < 1 association
\ 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)]
i=
c
i = 1 + ( n – 1)
e.g. NaCl (100% ionise), i = 2. ; BaCl2 (100% ionise), i = 3. ; K4[Fe(CN)6] (75% ionise), i = 4.
1
i = 1 + 1 .
n
0 Ps
P
Lowering in VP = P 0 – PS = P and
P
Relative lowering in Vapour Pressure =
P0
Raoult's law (For non–volatile solutes): T he vapour pressure of a solution of a non-volatile solute is
equal to the vapour pressure of the pure solvent at that tem perature m ultiplied by its m ole fraction.
O R Relative Lowering in Vapour Pressure = mole fraction of the non volatile solute in solutions.
PS x solvent P 0 (1 x solute )P 0
P 0 - Ps n
RLVP = 0 = xSolute =
P n N
where n = number of moles of non-volatile solute and N = number of moles of solvent in the solution.
N P 0 - Ps Ps
= –1= 0
n P 0 P - Ps
P 0 - Ps n
0 =
P N
P 0 - Ps w M w M w 1000 M
= × = × × 1000 = × ×
Ps m W m W 1000 m W 1000
P 0 - Ps M
= ( molality ) ×
Ps 1000
where w and W = mass of non-volatile solute and volatile solvent respectively
m and M = molar mass of non-volatile solute and volatile solvent respectively
P 0 - Ps i.n P 0 - Ps M
If solute gets associated or dissociated ; = that is = i × (molality) ×
Ps N Ps 1000
Ex. Calculate wt of urea which must be dissolved in 400 gm of water so final solutions has V.P. 2% less than V.P.
of pure water :
let V.P be V. of water
P0 – Ps = .02 V
Ps = 0.98 V
0.02 w 18
= × ; where w = weight of urea.
0.98 60 400
2 60 400
w= gm.
18 98
Ex. 10 gm of a solute is dissolved in 80 gm of acctone V.P. of this sol = 271 mm of Hg. If V.P. of pure acctone is
283 mm of Hg. Calculate molar mass of solute.
P 0 - Ps w M
= ×
Ps m W
283 - 271 10 58
= ×
271 m 80
m = 163 gm/mol.
Ex. V.P. of solute 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 V.P. increses by 0.02. Torr calculate V.P of pure water & molecular wt. of non
volatile solute.
P 0 - Ps w M
= ×
Ps m W
P - 20 6 18
= ×
20 m 180
P - 20.02 6 18
= ×
20.02 m 198
P = 20.22 Torr.
m = 54 gm/mol.
Ex. If 0.1 M solutions 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 solutions if P of pure water = 25 mm of Hg. (K = 39, Fe = 56)
P 0 - Ps w M
=i ×
Ps m W
P 0 - Ps im M
=
Ps 1000
3 0.1 1000 18
=
1000 1 . 2 – 1 . 2 368 1000
P0
= 1 + 7.12 × 10–3
Ps
Ps = 24.82 mm of Hg
p = 25 – 24.82 = 0.18 mm of Hg
Ostwald–Walker Method :
P
Experimental or lab determination of relative lowering of vapour pressure or P
s
dry air
Ps P
anhydrous CaCl2
(dehydrating agent)
solution solvent
(i) Initially note down the weights of the solution set, solvent set containers & of dehydrating agent before start of
experiment.
(ii) Note down the same weights after the experiment is complete.
Loss of wt of solution containers Ps.
Loss of in wt of solvent containers (P – Ps)
gain in wt of dehydriating agent P.
Ex. 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 weight of solution was 2.50 g & loss in weight of pure water was 0.04 g. Find molecular weight
of the solute.
P 0 - Ps 0.04 w M 5 18
= = × = . Thus. m = molecular weight of the solute = 70 g/mol.
Ps 2.50 m W m 80
Ex.
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.
Ans. PA 1 gm. ; PA – PB 0.5 gm, PB 0.5 gm.
PC – PB 1 gm ; PC 1.5 gm.
PC > PA > PB ; nC < nA < nB . ; MC > MA > MB.
K p2 H 1 1
ln K
R T1 T2
p1
P2 H vap. 1 1
ln = (Claussius – Clapeyron equation)
R T T
P1 1 2
lnP1 P
1/T
T
Figure
Boiling point of any solution :
Since V.P. of solution is smaller than V.P. of pure solvent at any temp. hence to make it equal to Pext. we have
to increase the temp. of solution by greater amount in comparision to pure solvent.
Pext.
P
Ps
As only solvent particles are going into vapours, we haveHvapourisation of solvent = Hvapourisation of solution
Tsolution > Tpure solvent
ÄH vapourisat ion
Svapourisation =
Tbp
H
Svapourisation of solution
= T
b, solution
Thus, Svapourisation of pure solvent > Svapourisation of solution ; because Tb, solvent Tb, solution.
Due to presence of solute, it is difficult to vapourise the solution (so R.L.V.P occur), it is difficult to
boil (so elevation in boiling point occur), it is difficult to freeze (so depression in freezing point
occur).
This diagram is related to boiling point elevation and freezing point depression of solutions is
taken from 'MCMURRY FAY CHEMISTRY' for details see chapter -11 page no. 450.
1 atm
Liquid
Psolv
Pressure (atm)
Solid
Psoln
Gas
fpsolv
fpsoln bpsolv bpsoln
Tf Tb
Temperature (ºC)
Phase diagram for a pure solvent (red line) and a solution of a nonvolatile solute (green line). Because the
vapor pressure of the solution is lower than that of the pure solvent at a given temperature, the temperature
at which the vapor pressure reaches atmospheric pressure is higher for the solution than for the solvent.
Thus, the boiling point of the solution is higher point of the solution is higher by an amount Tb . Further more,
because the liquid / vapor phase transition line is lower for the solution than for the solvent, the triple point
temperature Tt is lower and the solid/ liquid phase transition line is shifted to a lower temperature. As a result,
the freezing point of the solution is lower than that of the pure solvent by an amount Tf .
Derivation of formula Tb = Kb × molality by Graphical Method:
A B C
P
t E
lv en 1
n
so utio 2 D
l
so tion
lu
so
T Tb Tb1 Tb2
H H
122 1000 1
Tb – Ti = × Kb 1 1 0.8
122 1000 n
H H
1
Kb 0.8
2
Tb – Ti = Kb × 0.6
2
2 Tb 78
Kb =
1000 7.8 1000
0.4 2 2
1.4 = 5
Tb
10
Tb = 418.33 K
Ex. 1 Lit. of aq. solution of urea having density = 1.060 gm/mL is found to have Tb = 0.5ºC, If temp. of this
solution increase to 101.5ºC then calculate amount of water which must have gone is vapour state upto this
pt. given Kb = 0.5 K kg mol–1 for water
Sol. mass of solution = 1.060 × 103 = 1060 gm
1060 M
0.5 = 0.5 ×
1060 60
1060 × 60 = M
1 Lit solution = 1060 gm
(Mass of water) i = 1000 gm
urea = 60 gm
Tb = (molality)i × Kb
60 1000
(Molality)i 3 = 60 W
water
1000
W water = gm.
3
1000 2000
mass of water vaporised = 1000 – = gm = 666.67 gm
3 3
vacuum
Hsub = + ve
ice cube
Hsub = Hfusion + Hvap.
d B
soli E
D
C
0ºC T
Hfusion
Lfusion =
M
2 273 273
For water Tf = 273 K & LFusion = 80 cal/g. Thus, Kf = = 1.86 K kg mol–1
1000 80
Note: (i) Depression in freezing point is proprtional to the lowering of vapoure pressure i.e. Tf P
(i) If solute gets associated/dissociated then Tf = i × Kf × molality
ÄTf K
(iii) Units of Kf: Thus units of Kf = K kg mol–1
molality mol/kg
(iv) At freezing pt or below it only solvent molecules will freeze not solute molecules (solid will be of pure solvent)
(v) Kf = depression in freezing point of 1 molal solution.
H fusion
(vi) SFusion =
T f . p.
Ssolution
[More entropy
Spure solvent more randomness]
Ssolid
Solution is only pure solvent.
SSoution > Ssolvent because freezing point of solution < freezing point of solvent
Ex. 1000 gm H2O have 0.1 mole urea and its freezing point is – 0.2ºC and now it is freezed upto – 2ºC then how
much amount of ice will form.
Tb Tb2 lf
Tf = T 2 lv
f
Tb = 100 + 273 = 373 K.
Tf = 0 + 273 = 273 K.
lf = 80 cal g–1.
lv = 540 cal g–1.
0. 1 373 373 80
Tf = 273 273 540 .
Tf = 0.362.
Tf = 0.0 – 0.362.= – 0.362ºC.
LECTURE # 6
8.5 Osmosis & Osmotic pressure :
Osmosis & Diffusion
Diffusion : Spontaneous flow of particles from high conc. region to lower conc. region.
H2O
Cu2+ Blue
Ex.
Saturated Uniform
CuSO4 (Solution)blue
Conclusion : After some time in (A) grape or egg will shrink and in (B) grape or egg will swell.
Ex. In which soluton side complex [Cu(NH3)4]2+ will form and deep blue colour will obtain.
h
---------------------------
Solvent
Solution
SPM
The equilibrium hydrostatic pressure developed by solution column when it is seperated from solvent
by semipermeable membrane is called O.P. of the solution.
= gh
= density of soln.
g = acc. due to gravity
h = eq. height
1 atm = 1.013 x 105 N/m 2
Solution Solvent
C1 SPM C2
Definition :
The ext pressure which must be applied on solution side to stop the process of osmosis is called
osmotic pressure of the of the solution.
C1 > C2 particle movement.
Pext. = (1 – 2)
Pext. must be applied on the higher conc. side.
Remarks :
If the pressure applied on the soln side is more than osmotic pressure of the solution then the solvent
particles will move from solution to solvent side. This process is reverse osmosis.
Berkely : Hartely device/method uses the above pr. to measure O.P.
Vont – Hoff Formula (For calculation of O.P.)
concentration (molarity)
T
= CST
C – mol/lit.
S = ideal soln. constant = atm. R – 0.082 lit.atm. mol–1 K–1
T – kelvin
1
1 = C1RT, C1 = RT
2
2 = C2RT, C2 = RT
C1V1 C 2 V2
= V V RT
1 2
1V1 2 V2
= V V
1 2
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.
Ex.1 Calculate osmotic pressure of 0.1 M urea aq. solution at 300 K ,
R = 0.082 lit atm K–1
= CRT
= 0.1 x 0.082 x 300
= 2.46 atm
Osmotic pressure of very dilute solns is also quite significant so its measurement in lab is very
easy.
Ex.4 If 200 mL of 0.1 M urea soln is mixed with 300 mL of 0.2 M Glucose soln. at 300 K calculate
0.02 moles urea
0.06 moles Glucose
0.08 C1V1 C 2 V2
= 0.083 300 or = V V RT
0. 5 1 2
= 3.94 atm
Ex.5 If an 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.)
2.05
Curea = = 0.05 200 mL
R 500
Ex. Calculate of a solutions having 0.1 M NaCl & 0.2 M Na2SO4 and 0.5 HA (weak acid which is 20%
dissociation solutions at 300 K)
= ( 0.2 + 0.6 ) RT + i3 C3 RT
i3 = 1+(1).2 =1.2
[ 0.8 + 0.6 ] RT
= ( 1.4 × 0.083 × 300 )
= 1.162 × 30
= 34.86 atm
Ex. If 0.04 M Na2SO4 solutions at 300 K is found to be isotonic with 0.05 M NaCl (100 % disscociation)
solutions calculate degree of disscociation of sodium sulphate.
i C1 RT = i2 C2 RT
0.05
[ 1+(2) ] 0.042 = 2 ×
2
5
1+2 = –1
2
3
2 =
2
3
= × 100 = 75 %.
4
Ex. If 6 gm of CH3 COOH is dissolved in benzene to make 1 litre at 300 K of solutions is found to be 1.64
atm. If it is known that CH3COOH in benzene forms a dimer.
O O
CH3 C C CH3
O H O
O H O
O C C
O H O
1
1.64 = 0.0823 × 300 × [ 1 + 1 ]
n
1.64 = 0.0823 × 300 [1 – ] 0.1
2
m moles of Ba +2 = 40
Cl – = 80
So42– = 50
Na+ = 100
+2 2–
Ba + SO4 BaSO4
40 50 0
Ba2+ SO42– BaSO4 not affect Colligative properties
0 10 40
(80 10 100 )
= × 0.082 × 300 atm.
700
= 6.685 atm.
Other method :
BaCl2 + Na2SO4 BaSO4 + 2 NaCl
0.04 moles 0.05 0 0
0 0.01 Not effect 0.08
0.01 0.08
Not effect
0 .7 0 .7
= (i1C1 + i2C2) RT.
0.01 0.08
= (3 × +2× ) 0.082 × 300. = 6.685 atm.
0 .7 0 .7
Ex. If 200 ml of 0.2 m HgCl2 solution is added to 800 ml of 0.5 M KI (100% dissciated) 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 O.P. of resulting initially solution at 300K
initially
K+ 400 millimoles
I+ 400 millimoles
Hg2+ 40 millimoles
Cl – 80 millimoles
Hg2+ + 4I – [ HgI4 ]2–
t 40 400 0
tf 0 240 40