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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 1

Solution
A solution is a homogenous mixture of two or more substances whose composition may be
different within certain limits. Though the solution is homogenous in nature but it retains the properties of it's
constituents.
The substances, making up the solutions are called components of the solution. If NaCl is dissolved in water, then
NaCl and H2O are the components of solution. If two components are there in the solution it is called binary solution.
Similarly for three components it is called tertiary solution and for four components we say quaternary solution.
The two components of binary solution are called Solute and Solvent.
Solvent is that component in the solution whose physical state is the same as that of the resulting solution while
the other component is called Solute. eg. Suppose sugar is dissolved in water and solution is in liquid state, then
solution and water are in the same physical state (liquid state), then water is solvent and sugar is solute.
For the solutions in which both the components have same physical state as that of solution, then the component
which is in less amount is called solute and other is called solvent.
In solutions, the components are of molecular size (about 1000 pm) and the components cannot be separated by
any of the physical methods such as filtration, settling, centrifugation etc.

Types of solution
Depending upon the physical state of the solvent and solute, solution can be classified into nine types.

Types of solutions
Solvent Solute Example
Gas Gas Mixture of gas, air
Gas Liquid Water vapour in air
Gas Solid Sublimation of a solid into gas
Liquid Gas CO2 gas dissolved in water
Liquid Liquid Mixture of miscible liquids
Liquid Solid Salt in water
Absorption of gases over metal,
Solid Gas
H2 gas over palladium
Mercury in copper, mercury in
solid Liquid
gold
Alloys, coloured stones, gems
Solid Solid
etc.

Among these solution, the most significant type of solutions are those which are in liquid phase.
They are:
1. Solid in liquid solution
2. Liquid in liquid solution
3. Gas in liquid solution
The solution in which water is the solvent are called aqueous solution and solution in which water is not the
solvent are called non aqueous solution
The common non-aqueous solvents are ether, Benzene, Carbon Tetrachloride.

1. Solid in liquid solution


Here solid is solute and liquid is solvent. The amount of solute dissolved in 100gm of solvent to make
a saturated solution at a particular temperature is called Solubility.
Solubility depends upon
(i) Temperature
(ii) Nature of solute and solvent

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 2

Cause of solubility
We know that like dissolve like, meaning of this is polar solvents dissolve polar solutes and non polar
solvents dissolve non polar solutes. For example ionic compounds like NaCl, KCl etc. are very soluble in
water but insoluble in solvents like CCl4 , CS2. Non Polar compds. I2 , S8 are soluble in CCl4 but insoluble
in water.
The solubility of ionic solution depends upon ion dipole interactions. Due to ion-dipole interaction solvation
energy (Hydration energy if water is solvent) is released which is responsible for the dissolution of solute in
the solvent.

2. Liquid in liquid solutions


When two liquids are mixed which may be completely miscible, partially miscible or immiscible.
Causes of miscibility of liquids
Chemically alike liquids mix with in one another as compared to others. Alkanes are miscible in all
proportions with one another because they are non-polar.
If there is dipole-dipole interaction, then two liquids are miscible. Molecular size of liquids which are
naturally soluble, are also same.

3. Gas in liquid solution


Most of the gases are soluble in water and their solubility depends upon the nature of the gas,
temperature and pressure. Oxygen gas is sufficiently soluble in water to permit the survival of aquatic
life in oceans, rivers and lakes.

Methods of expressing the concentration of a solution


The concentration of solution may be expressed in many ways. They are as under.

o Mass percentage
It is defined as the amount of solute present in 100gm of solution. Suppose sugar is dissolved in water
and concentration of sugar is 15% by mass. It means 15 gm of sugar is dissolved in 100gm of
solution,
Similarly, suppose WA gram is the mass of the solute A dissolved in WB gram of solvent B, then total
mass of solution = WA +WB gm and
Mass Percentage of A = WA / ( WA + WB ) X 100

o Volume percentage
It is defined as the volume of solute present in 100 volume of solution.
Suppose VA is the volume of solute A dissolved in solvent B having Volume VB
Then, total volume solution = VA + VB
Therefore Volume percentage of A = VA / ( VA + VB ) X 100

o Molarity
It is defined as the number of moles of solute dissolved in one litre of solution It is represented by M.

Therefore
Molarity = number of moles of solute / volume of solution (in 1 litre)
= w /m X V ( litres)

=wX1000/mXV(ml.)
If we want to prepare 1 molar solution of NaOH, then we should take one mole NaOH (40gm)
and dissolve it in water and make the solution one litre in volume. Molarity is expressed in
moles/litre. Molarity of solution can be changed due to increase in temperature because by

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 3

increasing the temperature volume of solution will increase but number of moles in solution will be
same.

o Normality
It is defined as the number of grams equivalent of solute dissolved in one litre solution. It is expressed
by N.

Normality (N) = number of grams equivalent of solute / volume of solution in litre


or, = w / E X V ( litres)

=w X 1000 / E X V(ml.)

Normality of solution can be changed due to increase in temperature because by increasing the
temperature volume of solution will increase but number of gm. Equivalents in solution will be same.
A solution having normality one is called normal solution
N / 10 solution is called deci normal solution
N / 2 solution is called semi normal solution

o Molality
It is defined as the number of moles of solute dissolved in one kg of solvent. It is represented by m.

Molality (m) = number of moles of solute / mass of solvent in kg


= w / E X W ( K.g)

=w X 1000 / E X W(gm.)

It is expressed in units of moles kg-1. The molality of solution does not change with temperature.

o Mole fraction
Suppose A and B two components have been mixed to make a solution, then mole fraction of A will be
equal to the ratio of Number of moles of A to the total number of moles of A and B. Mole fraction is
denoted by X (Shi).
Here, XA =no. of moles of A / (no. of moles of A + no. of moles of B)

And XB =no. of moles of B / (no. of moles of A + no. of moles of B)

And XA + XB = 1
In a binary solution, if we know the mole fraction of one component, the mole fraction of other can be
calculated.

o Formality
It is defined as the number of grams formula mass of ionic solute dissolved in one litre of solution. It
is represented by F.

Formality (F) = no. of gram formula mass of ionic solute / volume of solution in litre

A solution containing one gram formula mass of ionic solute in one litre solution is called one formal
solution or formal solution.

o Parts Per Million (PPM)


When a solute present in a very small amount in solution, then concentration is expressed in
PPM. It is defined as the number of parts by mass of solute per million parts by mass of the solution.
We know O2 is dissolved in sea water. Suppose, a litre of sea water (litre of sea water = 1030 gm)
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 4

contains 6 x 10-3 gm of dissolved oxygen.


Since, 1030 gm of sea water contains 6 x 10-3 gm O2
Therefore 1 gm of sea water contain 6 x 10-3 / 1030 gm O2
Therefore 106 gm of sea water contain = 6 x 10-3 / 1030 x 106 gm O2
= 5.8 gm O2 per 106 gm sea water.
Where 5.8 gm O2 is dissolved in 106 gm sea water or one million grams of sea water.
Therefore 5.8 PPM is the concentration of O2 in seawater.
Atmospheric pollution in cities due to harmful gases is generally given in PPM though in this case the
values refer to volumes rather than masses. eg. Suppose it is found that SO2 in the air is 10 PPM. It
means that 10cc of SO2 is present in 106 cc or 1000 litre of air.

Some numerical problems


Q No. 1 Calculate the concentration of solution which is obtained by mixing 200 gm of 25 %
solution of NH4 NO3 with 150 gm of a 40% solution of NH4 NO3 (ammonium nitrate).

Solu.
Total mass of sol. = 200 +150 = 350 gm
Amount of NH4 NO3 in 200 gm 25 % sol. = 200 x 25 / 100 = 50 gm.
Amount of NH4 NO3 in 150 gm of 40 % sol. = 150 x 40 / 100 = 60 gm.
Therefore, total mass of solute = 50 + 60 = 110 gm
Therefore, Conc. of sol. = mass of the solute / mass of the sol. x 100
= 100 x 110 / 350
= 31.4 %
Q No. 2 HNO3 contain 69 % by mass. Calculate the volume of this solution which contain 19.9
gm of NHO3. (Density of solution = 1.41 gm/cc)
Solu.
69 gm HNO3 is present in 100 gm sol.
Therefore, 19.9 gm HNO3 is present in 100 / 69 x 19.9 gm solution
= 28.8 gm.
We will determine volume of solu. whose mass is 28.8 gm and density is 1.41 gm/cc
We know D = M / V
Therefore V = M / D
= 28.8 / 1.41 cc
= 20.4 cc Ans.
Q No. 3 The concentration H2SO4 in a bottle labelled as 49 % H2SO4 by mass and its density is
1.5 gm/c.
Calculate
(i) Molarity (ii) Normality (iii) Molality of H2SO4
Sol.
49 % H2SO4 by mass means 49 gm H2SO4 in 100 gm solution

(i) Calculation of molarity


Molecular mass of H2SO4 = 98
Volume of 100 gm of H2SO4 = Mass / Density
= 100 / 1.5
= 66.6 cc
here, 49 gm H2SO4 is dissolved in 66.6 cc of solution
therefore, Molarity = No. of moles of H2SO4 / Volume of solu. In litre
= (49/98) / (66.6/1000)
= 49 / 98 x 1000 / 66.6
= 7.5 M

(ii) Calculation of normality


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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 5

here, equivalent weight of H2SO4 = Molecular Mass / Basicity


= 98 / 2
= 49

Therefore Normality of solution


= No. of equivalent weight of H2SO4 / Volume of solution in water
= (49/49) / (66.6/1000)
= 49 / 49 x 1000 / 66.6
= 15 N.

(iii) Calculation of molality of H2SO4 solu.


Here mass of H2SO4 in 100 gm solutions = 49 gm
Therefore number of moles of H2SO4 = 49 / 98 = 0.5
Mass of water in the solution = 100 - 49 gm
= 51 gm
therefore, Molality of H2SO4 sol. = Number of moles of H2SO4 / Mass of solvent in kg.
= 0.5 / (51/1000)
= 0.5 x 1000 / 51 m
= 9.8 m or 9.8 mol kg-1

Vapour pressure of solution


If a pure liquid is covered with a bell-jar, a part of liquid evaporates and fills the available space with the
vapour. The vapours formed will have a tendency to change back to the liquid state by the process of
condensation. At a particular temperature, an equilibrium will be established between liquid and vapour
phases. The pressure exerted by the vapour in such situation at a given temperature is called the
vapour pressure of the liquid or solvent.

If a non-volatile solute is added to a solvent to make a solution, the vapour pressure of the solution will be the
vapour pressure of the solvent because only solvent molecules will be converted in vapour phase. As shown in
fig.b. on the surface of the solution, solvent and solute molecules are there. Only solvent molecules will go in
to vapour phase because solute is non volatile. On the surface of a solution, now small no. of molecules of
solvent are there, less vaporization will take place and so vapour pressure of solution is found to be less than
that of pure solvent.

Vapour pressure of a liquid depends upon.

1. Nature of liquid
2. Temperature, vapour pressure increases with increase of temperature
3. Presence of impurities or solute - the presence of non-volatile impurities lower the vapour pressure and
presence or addition of volatile impurities (solute) raises the vapour pressure of solutions.

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 6

Raoult's law
He stated that
The vapour pressure of a solution containing non volatile is directly proportional to the mole fraction
of solvent
Vapour pressure of solution α mole fraction of solvent
PA α XA
PA = PoA XA PoA is the pressure of pure component A.
In a solution of two miscible volatile liquids A and B having mole fraction XA and XB respectively and if their
partial vapour pressure is PA and PB then
PA α XA
PA = PoA XA, PoA is the vapour pressure of pure component A.
And
PB α XB
= PoB XB , PoB is the vapour pressure of pure component B.

Now total vapour pressure P, exerted by the solution is the sum of partial pressure PA and PB as per the
Dalton's law of partial pressure
We may write P = PA + PB

The relationship between vapour pressure of a component and its mole fraction is called Raoult's law which
states that for a volatile liquid the partial vapour pressure of each component in the solution is directly
proportional to its mole fraction. The law will not be applicable if the mixture of volatile liquids do not form a
solution.
According to Raoult's law for two miscible volatile liquids
PA = PoA XA --------- (I)
PB = PoB XB --------- (ii)
We will take equation (I)
here PA = PoA XA
When XA = 1, then PA = PoA
If we plot a graph between PA and XA we will get a straight line.
The maximum value of XA is one, So maximum value of PA will be equal to PoA (Vapour pressure of pure
solvent)
When XA = 0, then PA = 0
Similarly we can plot a graph between PB and XB and values of PB and XB will change in the same way as
above. We get a graph like this

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 7

Partial and total vapour pressure curves for solutions, which follow Raoult's law.

A graph between PA and XA is shown by I in the above figure and its a straight line.
A graph between PB and XB is shown by II in the above fig. and it's a straight line.
In line III, the total vapour pressure P of solution for any composition is shown. Here, P = PA + PB.
The solutions which obey Raoult's law are called ideal solutions. For such solutions, the vapour pressure of
the solution always lies between the vapour pressure of the pure components.

Relative lowering of vapour pressure


Suppose we are considering a solution which is obtained by addition of non volatile solute to the volatile
solvent. eg. Glucose dissolved in water. In such type of solution, vapour pressure of solution depends upon
the vapour pressure of solvent. Although solute is there but it has no contribution for the vapour pressure.
Solute is present on the surface also, so vaporization of solution will be slow and vapour pressure of solution
will be less than the vapour pressure of pure solvent.
Suppose vapour pressure of solvent is PA
Then, PA α XA
PA = PoXA ----- (I) XA is mole fraction of solvent, PoA is vapour pressure of pure solvent.
Suppose mole fraction of solute is XB
Then, we know that XA + XB = 1
Therefore XA = 1 - XB
Putting the value of XA in (I) we have
PA = PoA (1-XB)
= PoA - PoA x XB
PoA XB = PoA - PA
XB = PoA - PA / PoA
Or
PoA - PA / PoA = XB ------ (ii)
Here, PoA - PA is lowering of vapour pressure and PoA - PA / PoA is called Relative Lowering of Vapour Pressure
Equation (ii) is the alternate statement of Raoult's law for solution of non-volatile solutes.

Raoult's law for solution of non-volatile solutes


The relative lowering of vapour pressure for a solution is equal to the mole fraction of solute when solvent
alone is volatile.
PoA - PA / PoA = XB
If we want to know the behaviour of solutions, Raoult's law is helpful to give the information accordingly.

Colligative properties
The properties of solutions, which depend on the number of solute and solvent particles(molecules or ions) but
not upon their nature of the solute are called colligative properties. Here we will take non-volatile solute. Some
of the colligative properties are

i. Relative lowering of vapour pressure


ii. Elevation of boiling point
iii. Depression of freezing point
iv. Osmotic pressure

Relative lowering of vapour pressure


We have already discussed that when a non-volatile solute is added to a solvent, the vapour pressure of
solution decreases. Let XA is the mole fraction of solvent, XB is the mole fraction of solute and PoA is the
vapour pressure of pure solvent and PA is the vapour pressure of pure solution. Then we have already proved
that

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 8

PoA - PA / PoA = XB
Or relative lowering of vapour pressure of an ideal solution containing non volatile solute is equal to the mole
function of solute and solvent, when solvent alone is volatile.

Elevation of boiling point


We know that when the temperature of liquid is raised, its vapour pressure increases. When the vapour
pressure of liquids equals to the atmospheric pressure then liquid begins to boil.
So boiling point of a liquid may be defined as the temperature at which its vapour pressure becomes equal to
atmospheric pressure.

A variation of vapour pressure of solvent and solution at different temperature is shown in the above fig. The
curve AB gives the vapour pressure of pure solvent at different temperature and curve C D gives the vapour
pressure of solution at different temperature. The curve CD representing the vapour pressure of solution at
different temperature lies below the curve AB which corresponds to the vapour pressure of pure solvent. This
is only due to fact that vapour pressure of solution is less than that of pure solvent.
It is clear from the fig. that the vapour pressure of pure solvent is equal to atmospheric pressure at X and the
vapour pressure of solution becomes equal to atmospheric pressure at Y. At X, temperature is Tob and at y it is
Tb. It is now clear that Tob is the boiling point of solvent and Tb is the boiling point of solution. Since, Tb is
greater than Tob, there is an elevation or increase in boiling point of the solution as compared to that of the
solvent. Suppose elevation in boiling point is Δ Tb
Therefore Δ Tb = Tb - T ob
It is found that the elevation of boiling point is directly proportional to the number of moles of solute in a given
amount of solvent.
Δ Tb α m
or
Δ Tb = Kb m
where m is molality and kb is called boiling point elevation constant or molal elevation constant or ebullioscopic
constant.
Here if m = 1
Δ Tb = kb
Thus molal elevation constant kb is defined as the elevation in boiling point for 1 molal solution i.e a solution
containing 1 gm mole of solute dissolved in one kg of the solvent.
Unit of kb is k kg mol-1

Depression of freezing point


The freezing point is the temperature at which the solid and liquid state of substance have the same vapour
pressure. It has been observed that when a non-volatile solute is added in a solvent, the freezing point of
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 9

solution is lower down than the pure solvent. eg. the freezing point of water is Ooc but when a non volatile
solute is added to it then freezing point may be -1oC or -1.5oC depending upon the amount of solute.
At the freezing point of a solvent, the solid and the liquid are in equilibrium. It means that they must have the
same vapour pressure. In pure solvent we are adding some non-volatile solute and making the solution. We
also know that vapour pressure of solution in lower than the pure solvent. When a solution freezes, the solid
that separates out is the pure solid solvent.
Since the vapour pressure of a solution is lower than the pure liquid solvent, then it is natural that a solution
and the solid solvent can be in equilibrium only if the vapour pressure of solid solvent can become lower. This
will happen if the temperature of freezing of solution is lower than the temperature of freezing of the solvent.
Thus, a solution and the pure solid solvent can only be in equilibrium at a lower temperature compared to the
temperature at which a pure liquid solvent is in equilibrium with the pure solid solvent.

In the figure, curve BC gives the vapour pressure of the pure solvent. DE is the vapour pressure curve for the
solution at different temperature. The curve AB corresponds to the vapour pressure of the solid at different
temperature.
B is the point where solvent freezes and at point D solution freezes. To is the freezing point of solvent and T1 is
the temperature at which solution freezes and Δ Tf is the freezing point depression.
The depression of the freezing point is also a colligative property, because the extent of lowering depends only
on the number of molecules of solute and not on its nature.
It is found that the depression freezing point is directly proportional to the no. of moles of solute in a given
amount of solvent Δ Tf α m
Or
Δ Tf = Kf m
Where m is molality and Kf is called Freezing point depression constant or molal depression constant or molal
cryoscopic constant
Here if m = 1
Then Δ Tf = kf
Thus, molal depression constant kf is defined as the depression in freezing point for 1 molal solution i.e. a
solution containing 1 gm mole of solute dissolved in one kg of the solvent.
Unit of kf is k kg mol-1
Values of kb and kf for some common solvents are given below.

Kf
kb (K kg
Solvent B.P (k) FP1 (k) (K kg
mol-1)
mol-1)
Water (H2O) 373.0 0.52 273.0 1.86
Ethylalchohol 351.5 1.20 155.7 1.99
Benzene 353.3 2.53 278.6 5.12
Chloroform 334.3 3.63 209.6 4.70
Carbon 350.0 5.03 250.5 31.8
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 10

tetrachloride
Carbon disulphide 319.4 2.34 164.2 3.83
Osmotic pressure
When a solution is separated from pure solvent by a semi permeable membrane, then it is
observed that the solvent flows from the region of pure solvent in to solution. A semi permeable membrane
is a membrane which blocks the solute molecule but allows the passage to solvent molecules only. Animal
bladder is an example of natural semi permeable membrane. Parchment paper, cellophone and copper
ferrocynide are some examples of artificial semi permeable membranes.
If two solutions of different concentration are separated by a semi permeable membrane then the solvent
flows from solution of lower concentration to solution of higher concentration.
The passage of solvent from pure solvent or from solution of lower concentration to solution of
higher concentration through a semi permeable membrane is called osmosis.

In the above fig. an inverted thistle funnel having semi permeable membrane and solution of sugar is placed in
it. Semi-permeable membrane may be of animal bladder or parchment paper. The thistle funnel is lowered into
beaker containing water. The membrane will allows only the molecules of the solvent and not the solute to
pass through it. There will be movement of water molecules from pure solvent into the solution. As a result
water passes into the thistle funnel and level of solution in the thistle funnel rises gradually. This process is
called Osmosis.
The passage of solvent through the membrane can be stopped if adequate pressure is applied on the
solution side, this pressure is known as osmotic pressure.

Reverse osmosis
If the pressure applied on the solution is greater than osmotic pressure, then solvent starts passing
from solution into the solvent. This is called reverse osmosis.
This principal is used for the purification of sea water or hard water. Sea water is placed in contact with pure
water through semi permeable membrane. Pressure greater than Osmotic pressure is applied on sea water.
This causes the movement of pure water from sea water side to pure water side.

Isotonic solution
The two solutions having equal osmotic pressure are called Isotonic solutions.
0.9 % NaCl solution is isotonic with human blood. In this solution, the blood cell neither swell or shrink.
Therefore medicine are mixed with saline water before being injected in to veins. If the NaCl solution is less
concentrated, its osmotic pressure will be low and water will move in to the blood cell causing it to swell and
finally burst. On the other hand, if the solution is more concentrated its osmotic pressure will be high and the
water of blood cell will move out of the cell causing the cell to shrink.

Hypertonic and hypotonic solutions


A solution having higher osmotic pressure than some other solution is said to be hypertonic with respect to the
other solution.
A solution having low osmotic pressure relative to some other solution is called Hypotonic.

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 11

Osmotic pressure is colligative property and it depends upon the molar concentration of solute but does not
depend upon its nature. It is related as under:

π V = nRT
π = n/v RT
π = CRT
where n is the number of moles of solute
R = gas constant
T = Temperature
V = Volume of solution
C = Concentration of solution in moles/litre or it is molarity

By measuring osmotic pressure, molecular mass of solute can be determined. The method is widely used to
determine the molecular masses of macromolecules such as protein and polymers.
Other colligative properties such as elevation in boiling point or depression in freezing point are too small to be
measured. On the other hand measurement of osmotic pressure is done at room temperature and it is
measurable for a very dilute solution also.
This is useful for biological molecules, as they are generally not stable at higher temperature.

Non ideal solutions and abnormal molecular masses


.
Ideal solutions
Solutions which obey Raoult's law, are called ideal solutions. This is a very simple definition. According to
Raoult's law the partial vapour pressure of two components. A & B may be given as
PA = PoA XA and PB = PoB XB
And total pressure P is given by
P = PA + PB
= PoA XA + PoB XB
The ideal solutions also have the following characteristics

1. Heat change on mixing is zero or Δ Hmix = 0.


There is no change in magnitude of attractive forces in the two components present as A and B.
2. Volume change on mixing is zero or Δ Vmix = 0
The properties of an ideal solution are the average of the properties of the components present as per
their mole fraction. If an ideal solution having components A and B in equal number of moles, then
solution will have vapour pressure exactly midway between the vapour pressure of A and B.

An ideal solution will be formed only when the components or substances composing them are similar in
structure and polarity.
If two liquids A and B form an ideal solution this means that force of attraction between A and B molecules i.e.
A - B molecular interaction force is similar to the force of attraction between A - A or B - B molecules.

Liquid Hexane (C6H14) and Heptane (C7H16) when mixed in any proportion, form nearly ideal solution. A perfect
ideal solution is rare but many solutions are nearly ideal in behaviour. Here nearly ideal solution means a very
small deviation from Raoult's equation.

Example of ideal solution


i) Hexane and Heptane,
ii) C2H5 Br and C2H5I,
iii) C6H6 and C6H5 - CH3,
iv) C6H5Cl and C6H5 Br.
Generally all the solutions tend to become ideal when they are dilute

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 12

Non - ideal solutions


The solutions which do not obey Raoult's law are called non ideal solutions. For non ideal solution following
conditions are there
i. PA # PoA XA, PB # PoB XB
ii. Enthalpy change on mixing Δ Hmix # 0
iii. Volume change on mixing Δ V # 0

Types of non- ideal solutions


They are of two types
a. Non Ideal solutions showing positive deviations from Raoult's law.
b. Non Ideal solution showing negative deviations from Raoult's Law.

a. Non ideal solutions showing positive deviations from Raoult's law


Suppose we are preparing a solution by two components A and B. If the interaction between A and B (A---B) in
the solutions are weaker than the interaction between A - A and B - B, then the escaping tendency of A and B
types of molecules from the solution becomes more than from pure liquids. As a result of this the partial
vapour pressure of each component will be greater than the expected on the basis of Raoult's law. The total
vapour pressure of solution will be greater than the vapour pressure as per the Raoult's law.

In the above figure, we see that total vapour pressure P is greater than expected. The dotted line is expected
vapour pressure. The above type of behaviour of solution is described as positive deviation from Raoult's law.
Mathematically we may express as
PA > PoA XA
PB > PoB XB
and total vapour pressure P = PA + PB is always greater than
PoA XA + PoB XB
For the solutions which show positive deviations, there is an intermediate composition of components for
which the vapour pressure is maximum and hence, boiling point will be minimum. For such composition the
solution having minimum boiling point and it will distil at a particular temperature without change in
composition.
A solution which distils without change in composition at a particular temperature is called
Azeotropes or Azeotropic mixture.
The azeotropic mixture showing positive deviations is called minimum boiling azeotrope.

Explanation for positive deviations


Suppose we are preparing an solution of ethyl alcohol and cyclohexane. In ethyl alcohol, molecules
are held together by hydrogen bonds as shown below

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 13

When cychlohexane is added to ethyl alcohol, the molecules of cyclohexane tend to occupy the spaces
between ethyl alcohol molecules. So some hydrogen bonds in alcohol molecules break and the attraction
forces in alcohol molecules is weakened. The escaping tendency of alcohol and cyclohexane molecules from
the solution is greater than the vapour pressure as expected by Raoult's law.
Solutions, which are showing positive deviation, they will have

1. H mixing > 0 or positive because energy is required to break A ---- A or B ----- B attractive forces.
Therefore making solution will be endothermic process.
2. As the molecules are loosly held in the solution, there will be increase in volume on mixing.
Δ V mixing > 0 or positive.
b) Non - ideal solution showing negative deviations
In this type of deviation the partial vapour pressure of each component of solution is less than the vapour
pressure as expected according to Raoult's law. In such solutions (component A and B), the A ---- B
interactions are stronger than the A --- A and B-----B interaction. Due to stronger A ----B interaction, the
escaping tendency of A and B types of molecule from the solution becomes less than from pure liquids. Each
component of solution has a partial vapour pressure less than expected on the basis of Raoult's law and total
vapour pressure becomes less than the corresponding vapour pressure expected in case of ideal solution.

Here PA < PoA XA and PB < PoB XB


P = PA + PB is always less than PoA XA + PoB XB
Δ H mixing < 0 or negative
Δ V mixing < 0 or negative.

Explanation for negative deviations


We will take the example of solution prepared by mixing acetone and chloroform. When they are mixed, there
will be a attractive force between the molecules as shown under

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 14

The new type of force which is acting between the molecule is hydrogen bonding. Vapour pressure of solution
will be less than expected for an ideal solution.
Here Δ Vmixing < 0 because energy is released due to increase in attractive forces. Dissolution process is
exothermic and heating the solution will decrease the solubility.
Δ Vmixing < 0 because molecules are held together more strongly and so there will be decrease in volume.
For the solution with negative deviation there is an intermediate composition for which vapour pressure of the
solution is minimum and hence boiling point is maximum. At this composition the solution distil at constant
temperature without the change in composition. So it is an azeotrope. The solutions which show negative
deviations from Raoult's law are also called maximum boiling azeotropes.

Table - non ideal solutions

Solution showing positive Solution showing negative


deviations deviation
1. (CH3)2CO + CS2
2. (CH3)2CO + C2H5OH
1. CH3COOH + C5H5N (Pyridine)
3. C6H6 + (CH3)2 CO
2. CHCl3 + (CH3)2 CO
4. CCl4 + C6H6
3. CHCl3 + C6H6
5. CCl4 +CHCl3
4. CHCl3 + C2H5 - O - C2H5
6. CCl4 + C6H5CH3
5. H2O + HCl
7. H20 + CH3OH
6. H20 + HNO3
8. H20 + C2H5OH
7. (CH3)2CO + C6H5NH2
9. CH3CHO + CS2
10. CHCl3 + C2H5OH

Abnormal molecular masses


Collegative properties are used for the determination of molecular masses of the solute. We are familiar with
the formulas, which has been derived in Relative lowering of vapour pressure, elevation in boiling point,
depression in freezing point and osmotic pressure. Relation between all the above collegative properties and
molecular mass of the solute is based on the following two assumptions.

1. The solution is dilute so that Raoult's law is obeyed.


2. The solute neither undergo dissociation not association in solution.

If the above assumptions are not valid in a solution, we will find discrepancies between the observed and
calculated values of Collegative property.

Reason of discrepancies will be discussed in two heads


1. association of solute molecules
2. dissociation of solute molecules

1) Association of solute molecules


In certain solvents generally non polar, the solute molecules undergo association. Two, three or even more
molecules exist in combine state and form a bigger molecules
n A ---------------------------------> An
n single molecules one molecule
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 15

Therefore, the total number of molecules in solution become less than the number of molecules of the
substances added. So, colligative properties will be lower. Colligative property is directly proportional to the
number of solute particle and inversely proportional to the molar mass of the solute.

i.e. Colligative property α ( 1 / molecular mass of solute )

Here, molecular masses of solute will come greater than theoretical values. Let we take an example of acetic
acid and Benzoic acid dissolved in Benzene. Both acids exist in dimer form
2CH3COOH (CH3COOH)2

2C6H5COOH (C6H5COOH)2
The association of solute molecules in a solution is generally due to hydrogen bonds between these
molecules.

Acetic acid dissolved in Benzene shows a molecular mass 120 (Normal Molecular Mass 60) and Benzoic acid
dissolved in Benzene is found to have molecular mass double of its normal molecular mass. It is only due to
formation of dimer of acetic acid and benzoic acid in Benzene.
Here number of particles (solute) will be half of the number dissolved because of association. As a colligaive
property depends upon the number of particles and not of their nature, Δ T value for benzoic acid dissolved
in benzene will be half of the normal value. The molar mass calculated on the basis of this Δ T will, therefore,
be twice the expected value.

2) Dissociation of solute molecules


A number of electrolytes dissolved in solvent dissociates. If we dissolve KCl. After dissociation of KCl, we get
K+ and Cl- ions. For some other electrolytes we may get more than two ions also. Therefore, the number of
solute particles in solution will be more than expected. Such solutions exhibit higher values of colligatives
properties.
Δ T value of such solution will be twice due to increase of number of particle as it has become double. Since,
colligative property are inversely proportional to the molecular masses, therefore molecular masses of such
substances as calculated from colligative properties will be less than their normal values. For KCl

KCl K + + Cl -

Since each KCl unit is dissociated into two ions, the molar mass of KCl will come half of its Normal Molar
mass.

Van't Hoff factor

In 1886, Van't Hoff introduced a factor (i) called Van't Hoff factor to express the extent of association or
dissociation of solutes in solution. It is ratio of the normal and observed molecular masses of the solute i.e.
i = (Normal molecular mass / Observed molecular mass )
In case of association, observed molecular mass being more than normal, the factor i has value less than one
but in case of dissociation, the Van't Hoff factor is more than one because observed molecular mass has a
lesser value than the normal molecular mass. If there is no association or dissociation, i is one.
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 16

i=1 No association or dissociation of solute


i>1 Dissociation of solute
i<1 Association of solute

Since, colligative properties are inversely proportional to molecular masses, the Van't Hoffs factor may also be
written as

i = ( Observed value of colligative property / Calculated value of colligative property assuming no


association or dissociation )

or

i = ( No. of particles after association or dissociation / No. of particle before association or dissociation
)

Inclusion of the Van't Hoff factor modifies the equation for the colligative properties as follows

iii. (PoA - PA) / (PAo) = i xB


iv. Δ Tb = i kb m
v. Δ Tf = i kf m
vi. π = icRT

Degree of dissociation
It is defined as the function of total molecules which dissociates into simpler molecules or ions.
Suppose a molecule of an electrolyte gives m ions after dissociation. If we are taking 1 mole of electolyte
and α is the degree of dissociation, then at equilibrium.

Number of moles of ions formed = m α


Number of mole of solute left undissolved = 1 - α
Therefore, Total Number of moles of particle at equilibrium =
1- α+m α
Therefore, Vant's Hoff factor i
= ( Total no. of particle after dissociation / No. of particle before dissociation )

i = ((1 - α ) + m α / 1 ) = 1 + (m - 1) α

Therefore, (m - 1) α = i - 1

α = ( i - 1 / m - 1)
For the electrolyte of type AB, such as KCl, NaCl, NaOH etc. the number of particle in solution i.e. m = 2.

Therefore, α = i - 1 = ( i - 1 / 2 - 1 )

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 17

For the electrolyte of type AB2 like CaCL2, Ba (NO3) 2 etc.

The value of m = 3 so
α =i-1/3-1=i-1/2
Degree of association.
It is defined as the fraction of total number of molecules, which associate or combine together resulting in the
formation of a bigger molecules.

Degree of association =
( No. of moles of substance associated / Total no. of moles of substance taken )

In order to calculate the degree of association, suppose that m particles of solute associate to form one
particle and α is the degree of association as given in the following equation

mA -----------> Am

In mA
No. of moles in the beginning = 1 moles
No. of moles after association = (1 - α ) Moles

In mA
No. of moles in the beginning = 0 moles
No. of moles after association = α / m moles

Here α molecular are going to associate, then α / m molecules will be formed due to association.

Therefore,
Total no. of Moles after association = ( 1- α + α / m) Moles.

Therefore,
Van't Hoff factor
= ( No. of particles or moles after association / No. of particle or mole before association )

i=(1- α + α/m)/1=1- α+ α/m

α/m- α=i-1

α (1/m - 1) = i - 1

Therefore, α = i -1 / ( 1/ m - 1 )

Numerical problem
1) Benzene (C6H6) with B.P 353.1 k and toluene (C6H5 - CH3) with BP 383.6 k are two hydrocarbons which
form nearly ideal solution. At 313 k, the vapour pressure of pure benzene and pure toluene are 160 mm of Hg
and 60 mm Hg respectively. Calculate the partial pressures of C6H6 and C6H5 - CH3 and the total pressure
under the following condition
i) A solution made by mixing equal number of moles of 8H6 and C6H5-CH3
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 18

ii) A solution made by mixing 4 moles of toluene and 1 mole of Benzene.


iii) A solution made by mixing equal masses of toluenes and Benzene.

Solutions
i) Suppose a moles of Benzene and a moles of toluene are mixed up.
Therefore, Mole fraction of Benzene = a / a + a = .5 = XA
and mole fraction of toluene = 1-.5 = .5 = XB
We know PA = PoA XA
Where PA is the partial V.P. of Benzene in the solution. And PoA is the V.P of Pure Benzene.
Therefore, PA = 160 x .5 = 80 mm.
And PB = PoB XB
Where PB is partial VP of Pure Toluene
Therefore PB = 60 x .5 = 30 mm
Total vapour pressure (VP) = 80 + 30 = 110 mm Hg.

ii) a mixture of 4 moles of toluene and 1 mole of Benzene


therefore; Mole function of Benzene = ( 1 / 4+1 ) = ( 1 / 5 ) = .2 = XA
and Mole fraction of toluene = 1 -.2 = .8 = XB
We know PA = PoA XA
PA = 160 x .2 = 32 mm
so partial vapour pressure of Benzene is 32 mm.
also PB = P0B XB = 60 x .8 = 48 mm
partial V.P of toluene is 48 mm.
Total V.P = 48 + 32 = 80 mm of Hg

iii) Suppose x gm of Benzene and x gm of toluene are there in the solution


Therefore, No. of moles of Benzene
= ( X / 78 ) molecular wt. of Benzene is 78
and No. of moles of Toluene
= ( X / 92 ) molecular wt. of toluene is 92
Mole fraction of Benzene XA = x/78 / ( X/78 + x/92 )
= 0..541
Mole fraction of Toluene XB = 1 - .541 = 0.459
partial vapour pressure of Benzene PA = PoA XA
= 100 x .541 = 86.56 mm
partial vapour pressure of Toluene PB = PoB XB
= 60 x .459 = 27.54 mm
Total Vapour Pressure = 86.56 + 27.54 = 114.10 mm of Hg.

Q.No.2. The vapour pressure of a dilute aqueous solution of glucose (C6H12O6) is 750 mm of mercury at 373 k.
Calculate (I). Molality, (ii). Mole function of the solute (IIT - 1989)

Soln. 1. Suppose molality of the solution = i x.


It means x moles of glucose is dissolved in 1000 gm water.
here no. of moles of glucose = x
and no. of moles of water = ( 1000 / 18 ) = 55.55
here VP of water at 373 k is 760 mm
we know
( PoA - PA / PoA ) = XB
here mole function of solute = ( x / x + 55.55 )

Therefore ( 760 - 750 / 760 ) = ( x / x + 55.55 )

( 10 / 760 ) = ( x / x + 55.55 )
760x = 10 x + 555.5
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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES 19

750 x = 555.5
x = ( 555.5 / 750 )
= .74 Mol Kg-1

II. Here Mole fraction of solute Glucose = x / X + 55.55

= ( .74 / .74 + 55.55 )

= .74 / 56.29

= .013

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