SOLUTION

In normal life we rarely come across pure substances. Most of these are mixture containing
two or more pure substance . for examples brass (mixture of copper and zinc ) ,German
silver (mixture of copper ,zinc and nickel ), bronze (mixture of copper and tin )

1ppm of fluoride ions in water prevent tooth decay .while 1.5ppm causes the tooth to
become mottled . high concentration of fluoride ions can be poison( for example sodium
fluoride is used in rat poison )
Intravenous injection are always dissolved in water containing salt .
Mixture : mixture consists of two or more substance present in any ratio .
For example : Salt solution in water ,air, tea,mixture of salt and sugar , mixture of mud and
sand .

Mixture are classified into two type

1. Homogeneous mixture
2. Heterogeneous mixture

Homogeneous mixture : in a homogenous mixture the component are completely

mixed with each other and its composition is uniform throughout.

For example :sodium chloride in water , glucose in water ,

Heterogeneous mixture : the component are not completely mixed with each other
and its composition is not uniform throughout.

for example : mixture of salt and sugar , mixture of mud and sand are heterogeneous

Solution : Solution are homogeneous mixture of two or more than two component are
uniform throughout the mixture
Solution having two component a) Solvent
b)Solute
Solvent: The component that is present in the largest quantity is known as solvent .
Solvent determine the physical state in which solution exists.
Solute : one or more components present in the solution other than solvent are called
solutes.
For example : salt dissolved in water . water is solvent and salt is solute .
Binary solution :Solution containing two component system is called binary solution
Solution classified into three types

TYPE OF SOLUTION SOLUTE SOLVENT EXAMPLES

Gaseous solution Gas Gas Mixture of oxygen and nitrogen
Liquid Gas Chloroform mixed with nitrogen
Solid Gas Camphor in nitrogen gass

Liquid solution Gas liquid Oxygen dissolved in water

Liquid liquid Ethanol dissolved in water

Solid liquid Glucose dissolved in water

Solid solution Gas solid Solution of hydrogen in palladium

Liquid solid Amalgam of mercury with sodium

Gas solid Copper dissolved in gold

Expressing concentration of solution

Composition of a solution can be described by expressing its concentration
Dilute solution : Relatively very small quantity of solute .
Concentration solution : Relatively very large quantity of solute.

There are several ways by which we can describe the concentration of the solution
quantitatively

1. Molality (m)
2. Molality (m)
3. Mole fraction (x)
4. Mass percentage (w/w)
5. Volume percentage (v/v)
6. Mass by volume percentage (w/v)
7. Parts per million (ppm)

1) Molarity (M): is defined as number of mole of solute dissolved in one liter solution
 mole of solute
Molarity (M) =
Volume of solution∈1liter

For example 0.25mol L-1 (0.25M) solution of NaoH means that 0.25mol of NaoH has been dissolved in
one liter (one cubic decimeter)

2)Molality(m):Molality is defined as the number of mole of the solute per kilogram (kg) of the
solvent a it is expressed as

mole of solute
Molality (m) =
mass of solvent ∈kg

For example :1.00 mol kg-1 (1.00m)solution of KCl means that 1 mol (74.5g) of KCl in 1kg of water

3) Mole fraction (x) : Mole fraction can define as ratio of number of mole of component by total
number of mole of all the component in solution

number of mole of component

Mole fraction of component =
total number of mole of all the component ∈solution

For example : in a binary mixture ,if the number of mole of A and B are nA and nB respectively .
the mole fraction of A will be

nA
XA=
nA+ nB

nB
The mole fraction B will be XB=
nA+ nB

nc
The mole fraction C will be Xc=
nA+ nB

The mole fraction of all component is unity XA+XB+XC=1

4).Mass percentage (w/w) : Mass percentage can be define as mass solute in gram is
dissolved in 100gm of solution

mass of the component ∈the solution

Mass ٪ of component = ×100
Total mass of solution
For example , if a solution is described by 10٪ glucose in water by mass .it means that 10g
of glucose is dissolved in 90g of water resulting in a 100g solution
Use of Mass percentage
In industrial chemical applications for example : commercial bleaching solution contains
3.62g mass percentage of sodium hypochlorite in water .
5)Volume percentage (v/v): The volume percentage is defined as volume solute in cm3 is
dissolved in 100cm3 of solution

volume of thecomponent
Volume ٪ of a component = ×100
Total volume of solution

For example1) : 10 ٪ ethanol solution in water means that 10 ml of ethanol is dissolved in water such
that the volume of the solution is 100ml

2) A 35% (V/V) solution of ethylene glycol .an antifreeze ,is used in car for cooling the engine .At this
concentration the antifreeze lowers the freezing point of water to 255.4k (-17.6° C)

6)Mass by volume percentage (w/v):It is the mass of solute in gm dissolved in 100ml of the
solution .It is used in medicine and pharmacy

6)Part per million (ppm):a solute is present in trace quantities . or The ratio number of part of
the component by total number of part of all component of the solution multiply with 10 6

number of part of the component

Part per million = ×106
total number of part of all component o f the solution

Ppm can also express as mass to mass, volume to volume and mass to volume

For example : A liter of sea water contains about 6×10-3g of dissolved oxygen (O2)

The unit of ppm is expressed µgmL-1

Solubility
Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent at a specified temperature .

It depends on a) Nature of solute

b) solvent
c) Temperature
d) pressure

Solubility of a solid in a liquid

Every solid does not dissolved in a given liquid . for example :Nacl and sugar dissolved
readily in water .but Naphthalene and Anthracene do [Link] hand Naphthalene and
Anthracene dissolved readily in benzene but sodium chloride and sugar do no .

Mean that polar solute dissolved in polar solvent and non polar solute dissolved in a
solvent if the intermolecular interaction are similar in the two or we may say like
dissolves like
Solid solute is added to the solvent ,some solute is dissolves and its concentration increases
in solution . this process is known as dissolution

Some solute particle in solution collide with the solid solute particle and get separated out
of solution .this process is known as crystallization .

Number of solute particle going into solution will be equal to the solute particle separating
out and a state of dynamic equilibrium is reached.

Saturated solution :Solution in which no more solute can be dissolved at same

temperature and pressure .

Unsaturated solution : solution in which more solute can be dissolved at the same
temperature .

Factor depends on solubility of a solid in a liquid :

1. Nature of the the substance

2. Temperature

Pressure unaffected by changes in solid in liquid

Solubility of a Gass in a liquid

Many gases dissolved in water .oxygen dissolved only to small extent in water .it is this
dissolved oxygen which sustains all aquatic life . HCl is highly soluble in water .

Factor depend on solubility of Gass in a liquid

1) Pressure 2)Temperature

Henry law
Henry law gives relation between pressure and solubility of a gass in solvent .

The law say that “The solubility of gas in a liquid is directly proportional to the partial pressure
of the gass present above the surface of liquid or solution”

OR

“Mole fraction of gas in the solution is directly proportional to the partial pressure of the gas
over”

OR
“The partial pressure of the gass in vapour phase (P) isdirectly proportional to the mole
fraction of the gass (x) in the solution”

P=kHX Where kH---------- is the Henry law constant

x--------------mole fraction

p--------------- partial pressure

Different gases have different kH values at the same temperature . this suggests that kH is a
function of nature of gass . the higher the value of kH at given pressure ,the lower solubility
of the gas in the liquid that KH value for both N2 and O2 increases with increases of
temrature that solubility of gasses increases with decrease of temperature . it is due to
reason that aquatic species are more comfortable in cold water rather than warm water .

Application of Henry law

1) To increases the solubility of CO2 in soft drinks and soda water the bottle is sealed high
pressure .

2) scuba diver must cope with high concentration of dissolved gasses while breathing air at
high pressure . Increased pressure increases the solubility of atmospheric gasess in blood .

When the diver come towards surface .the pressure gradually decreases .this releases the
dissolved gases and leads to formation of bubbles nitrogen in the blood .this blocks
capillaries and creates a medical condition known as bends

Avoid bends condition : Air diluted with helium (11.7%) .Nitrogen (56.2%) , and oxygen
(32.1%)

3) At high altitude the partial pressure of oxygen is less than that at the ground level. The
living at high altitude .low blood oxygen causes climbers to become weak and unable to
think clearly this condition known as Anoxia

Effect of temperature
As dissolution is an exothermic process ,the solubility should decrease with increase of
temperature .the solubility increases with decrease of temperature.

Vapour pressure of liquid solution

we shall discuss the solution of liquid and solid in a liquid . such solution may contain one
or more volatile components. Generally the liquid solvent is volatile .the solute may or may
not volatile component . the solution containing two component, the solution 1) liquid in
liquid 2) Solids in liquids.
Let us consider a binary solution of two volatile liquid and taken in a closed vessel ,both the
component would evaporate and equilibrium would eventually an equilibrium would be
established between vapour phase and the liquid phase .let the total vapour pressure at
this stage be pTotal and P1 and P2 partial vapour of the two component 1 and 2 respectively .
these partial pressure are related to the mole fraction x1 and x2 of the two component .

Raoult’s law
Statement “For a solution of volatile liquid s the partial vapour pressure of each
component of the solution is directly proportional to it’ s mole fraction present in
solution “

P1α X1

And P1= P10X1 P 10 ----------------- is the vapour pressure of pure component 1 at the same
temperature

X1 -------------Mole fraction

Similarly .for component 2

P2= P 20X2 P 20------------ The vapour pressure of the pure component 2

According to to Dalton ‘s law of partial pressure

Total pressure (Ptotal) over the solution phase in the container will be the sum of the partial
pressure of the component of the solution

PTotal =P1+P2

Substituting the value of P1 and P2 we get

PTotal = x1P10+x2P20

= (1-x2)P10+ x2P20

=P10+(P20- P10)x2

The following conclusion

1. Total vapour pressure over the solution can be related to the mole fraction of any
one component .
2. Total vapour pressure over the solution varies linearly with the mole fraction of
components .
3. Depending on the vapour pressure of the pure component 1 and 2
 Total vapour pressure over the solution decreases or increases with the increases of
the mole fraction or component.

A Plot of p1 and p2 versus the mole fraction x1 and x2 for a solution gives linear plot as shown fig these
lines (iand ii ) pass through the point for which x1 and x2 equal to unity . similarly the plot (iii) of PTotal
versus x2 is also linear . the minimum value of ptotal is p10 and the minimum value is p20 assuming that
component 1 is less volatile than component 2

Raoult’s law as a special case of Henry ‘s law

if we compare the equation for Raoult’s law and Henry ‘s law .it can be seen that the partial
pressure of the volatile components or gas directly proportional to its mole fraction in
solution only the proportionality constant kH differ from p10 .thus .Raoult’s law became a
special case of Henry’s law in which kH become equal to p10

Vapour pressure of solution of solid in liquids

Solution consist of solid dissolved in liquid for example sodium chloride ,glucose ,urea and
cane sugar in water and iodine and sulphur dissolved in carbon disulphide . physical
properties of those solution are quite different from those of pure solvent .

Vapour pressure liquids at a given temperature vapourise and under equilibrium condition
the pressure exerted by the vapour of the liquid over the liquid phase is called vapour
pressure

Non volatile solute is added to a volatile solvent consequently the number of solvent
molecule escaping from the surface is correspondingly reduced thus the vapour pressure is
also reduced
For example : decreases in the vapour pressure of water by adding 1.0 mol of sucrose to
one kg of water . By adding 1.0 mol of urea to the 1kg of water at same temperature .

The decrease in the vapour pressure of solvent depend on the

1) Quantity of non-volatile solute present in the solution .

2) Nature of solute .

Raoult law :-
Statement “for any solution the partial vapour pressure of each volatile component in
the solution is directly proportional to its mole fraction “

Explaination: in a binary solution ,the solute is non-volatile ,only the solvent molecules
are present in vapour phase and contribute to vapour pressure. the vapour pressure of the
solvent .x1 be its mole fraction P10 be its vapour pressure in the pure state .then according
to Raoult law

P1α X1

P1=X1P10

The proportionality constant is equal to the vapour pressure of pure solvent ,P10 .A plot
between the vapour pressure and the mole fraction of the solvent is linear

liquid –liquid solution can classified into

1)ideal solution

2) non ideal solution

1) Ideal solution : The solution which obey Raoult’s law over the entire range of
concentration are known as ideal solution

1. The enthalpy of mixing of the pure component to form the solution is zero and the
volume of mixing is also zero ∆mixH=0 ∆mix=0
2. The volume of solution would be equal to the sum of volume of the two component
3. In pure component ,the intermolecular attractive interaction will be type A-A and
B-B are nearly equal to those between A-B this leads to the formation of ideal
solution
4. Nearly ideal in behavior .solution of n-hexane and n-heptane ,bromoethane and
chloroethane , benzene and toluene
2) Non ideal solution : The solution does not obey Raoult’s law over the entire range
of concentration .then called non ideal solution

1. The enthalpy of mixing of the pure component to form the solution is not
equal to zero and the volume of mixing is not equal to zero ∆mixH≠O and
∆mix≠0
2. The volume of solution would be not equal to the sum of volume of two
component
3. In the intermolecular attraction A-B interaction are weaker than those
between the A-A and B-B
4. Non ideal behavior solution of mixture of ethanol and acetone ,mixture of
chloroform and acetone .

The vapour pressure of such a solution is either higher or lower than that predicted by
Raoult law . if its higher the solution exhibits positive deviation If its lower the solution
exhibits Negative deviation

Positive deviation : The vapour pressure of such a solution is higher than that
predicted by Raoult law

1. In the case positive deviation A-B interaction are weaker than those between A-A or
B-B , and leads to increases in vapour pressure
or
In the case positive deviation the intermolecular attractive force between the
solute –solvent molecules are weaker than those between the solute-solute and
solvent –solvent molecules , and leads to increases in vapour pressure
Fig

For example : Mixture of ethanol and acetone ,Mixture carbon disulphide and
acetone
Explaination :1) Mixture of ethanol and acetone
In pure ethanol , molecules are hydrogen bond on adding acetone .its molecules get
in between the host molecules and break some of hydrogen bond between
them .due to weakening interaction . the solution shows positive deviation
 2) Mixture of carbon disulphide and acetone
The dipolar interaction between solute-solvent molecules are weaker than the
respective interaction among the solute –solute and solvent-solvent molecules .this
solution also shows positive deviation

2)Negative deviation : The vapour pressure of such a solution is less than that
predicted by Raoult law

1) in case of negative deviation the intermolecular attractive force between A-A and B-B
are weaker than those between A-B and leads to decrease in vapour pressure .

OR

In the case positive deviation the intermolecular attractive force between the solute
–solvent molecules are weaker than those between the solute-solute and solvent –solvent
molecules and leads to decrease in vapour pressure

Fig

For example :Mixture of phenol and Aniline , Mixture of chloroform and acetone

Explaination :1) Mixture phenol and Aniline

In case the intermolecular hydrogen bonding between phenolic proton and lone pair on
nitrogen atom of aniline is stronger that the respective intermolecular hyderogen bonding
between similar molecular

2) Mixture of chloroform and acetone

In this case chloroform mix with acetone to form a solution with negative deviation . This is
becase chloroform molecule is able to form hyderogen bond with acetone molecules .
 This is because chloroform molecules is able to form hyderogen bond with acetone
molecules for each component and consequently the vapour pressure decreases resulting in
negative deviation.

Azeotropes :
Binary mixture having the same composition in liquid and vapour phase and boil at a
constant temperature .it is not possible to separate the components by fractional distillation
.
Azeotropes classified into two types 1) Minimum azeotropes

2) Maximum azeotropes

1) Minimum azeotrope :The solution which show a large positive deviation from
Raoult’s law from minimum boiling point azeotrope at a specific composition

For example : Ethanol –water mixture( Ethanol-95% ,water -5%)

2) Maximum azeotrope: The solution that show large negative deviation from
Raoult’s law from maximum boiling point azeotrope at a specific composition

For example :Nitric acid and water (Nitric acid 68% , water-32%)

Colligative properties and determination of molar mass

The vapour pressure of solution decreases when a non-volatile solute is added to a

volatile solvent . many properties of solution which are connected with this decrease of
vapour pressure .

1. Relative lowering of vapour pressure of solvent

2. Depression of freezing point of the solvent(cryoscopy)
3. Elevation of boiling point of the solvent (Ebullioscopy)
4. Osmotic pressure of solution

Colligative properties :All these properties depends on the number of solute particle
irrespective of their nature relative to the total number of particle present in the
solution .such properties are called colligative properties
1) Relative lowering of vapour pressure of solvent
The vapour pressure of a solvent in solution is less than that of the pure solvent .
lowering of vapour pressure depends on The concentration of the solute particle
independent of their identity .
Relation between vapour pressure of the solution ,the mole fraction and vapour pressure
of the solvent
P1=x1p10

In a solution containing several non-volatile solute , the lowering of the vapour pressure
depends on the sum of the mole fraction of different solute .

∆ P 1 P 1−P 1
= =X2
P1 P1

The reduction in the vapour pressure of solvent (∆P1) is given as

∆P1= P10⎼ P1= P10⎼ P10x1

= P10(1-X1)

Knowing that x2=1-x1 equation reduce to

∆P1= X2P10
In a solution containing several non volatile solution ,the lowering of the vapour pressure
depend on the sum of the mole fraction of different solute

∆ P 1 P 1−P 1 n2
= =x2 x2=
P1 P1 n 1+ n 2
 P 1−P 1 n 2
=
P1 n1

P 1−P 1 w 2× M 1
=
P1 M 2 ×W 1

Here w1 -------------mass of solvent M1-----------Molar mass of solvent

W2-------------mass of solute M2------------Molar mass of solute

2)Elevation of boiling point :(Ebullioscopic )

Vapour pressure of a liquid ncreases with increase in temperature . the variation of vapour
pressure of a pure solvent and that of the solution of a non-volatile solute dissolved in it .

The vapour pressure of a solution of a non-volatile solute in a volatile solvent is always lower
than of the pure solvent . further a liquid boils at a temperature when its vapour pressure
becomes equal to atmospheric pressure . therefore ,the boiling point of the solution is always
higher than that of the pure solvent .

Let Tb0 be the boiling point of the pure solvent and Tb that of the solution . the increases in
boiling point ∆Tb=Tb-Tb0 is known as the elevation of boiling point

The elevation of boiling point .∆Tb is directly proportional to the molal concentration of the
solution ∆Tb α m

∆Tb=kb×m

M is the molality of the solution Kb s known as the boiling point elevation constant or molal
elevation constant (or ebullioscopic constant)

Kb = ∆Tb if m=1

Thus , molal elevation constant of a solvent is define as the elevation of boiling point caused
by dissolving one mole of a non-votatile solute in 1000g of the solvent.M

The unit of Kb is k molal-1 or k( mol kg-1)-1 or k kg mol-1

If wb g of a solute of molar mass