SOLUTION

5. Mole fraction: It is defined as:

 Solutions are homogeneous mixtures
Mole fraction of a component =
of two or more than two components.
Homogenous mixture means that its Number of moles of the component
composition and properties are uniform Total number of moles of all the components
throughout the mixture.
For example, in a binary mixture, if the
 The component that is present in the number of moles of A and B are nA and
largest quantity is known as solvent. nB respectively, the mole fraction of A
Solvent determines the physical state will be
in which solution exists.
nA
 One or more components present in the xA = n  n
solution other than solvent are called A B

solutes. For a solution containing i number of

 Binary solutions: Solution consisting components.
of two components. Components of a
n1 ni
binary solution are solute and solvent. xA = n  n  ......  n =  n
1 2 i i
a. When the solvent is in solid state,
solution is called solid solution. It can be shown that in a given solution
b. When the solvent is in liquid state, sum of all the mole fractions is unity,
solution is called liquid solution. i.e.
c. When the solvent is in gaseous state, x1 + x 2 + .................. + xi = 1
solution is called gaseous solution. 6. Molarity: Molarity (M) is defined as
Expressing Concentration of Solution number of moles of solute dissolved in
one litre (or one cubic decimetre) of
There are several ways by which we
solution.
can describe the concentration of the
solution quantitatively. Moles of solute
1. Mass percentage: Molarity Volume of solution in litre
Mass % of a component 7. Molality. Molality (in) is defined a s
Mass of the component in the soluton the number of moles of the solute per
 100
= Total mass of the solution kilogram (Kg) of the solvent and is
expressed as:
2. Volume percentage:
Volume % of a component Moles of solute
Molality (m) = Mass of solvent in Kg
Volume of the component
= Total volume of solution  100 SOLUBILITY
Solubility of a Solid in a Liquid
3. Mass by volume percentage: It is the
mass of solute dissolved in 100 mL of  It is observed that polar solutes dissolve
the solution. in polar solvents and non-polar solutes
in non-polar solvents. In general, a
4. Parts per million: When a solute is
solute dissolves in a solvent if the
pr e s e nt i n t r ace q u an t i t i e s , i t i s
intermolecular interactions are similar
convenient to express concentration in
in the two (like dissolves like)
parts per million (ppm) and is defined
as:  When a solid solute is added to the
solvent some solute dissolves and its
Parts per million=
concentration incieases in solution.
Number of parts of the component
×100 This process is known as dissolution.
Total number of parts of all components of the solution
 Some solute particles in solution collide
with the solid solute particles and get
separated out of solution. This process
 2
is known as crystallization. phase (p) is proportional to the mole
 A solution in which no more solute can fraction of the gas (x) in the solution”
be dissolved at the same temperature and is expressed as:
and pressure is called a saturated p = K Hx
so lut ion . Un de r su ch c ondi ti ons,
 Here KH is the Henry’s law constant and
number of solute particles going into
it is a function of the nature of the gas.
solution will be equal to the solute
particles separating out and a state of  It is observed that KH values for both N2
dynamic equilibrium is reached. and O2 inc re ase wi th i ncre ase o f
t e mpe ra t u r e i n d i c a t i n g t h a t t h e
Solute + Solvent  Solution
solub il ity of gase s i ncre as e s wi th
Effect of temperature: The solubility decrease of temperature. It is due to this
of a solid in a liquid is significantly reason that aquatic species are more
af fe c t e d b y t e mp e r at u re ch ang e s comfortable in cold waters rather than
according to Le Chateliers Principle. In in warm waters.
ge n e r al , i f i n a n e ar l y s at u r at e d Applications of Henry’s law
solution, the dissolution process is
 To increase the solubility of CO2 in soft
endothermic  sol H  0  , the solubility drinks and soda water, the bottle is
sh o u l d i n c re ase w i th ri se i n sealed under high pressure.
temperature and if it is exothermic  Scuba divers must cope with high
 sol H  0  the solubility should decrease concentrations of dissolved gases while
with increase in temperature. b r e at h i n g a i r at h i g h p re s s u r e
u n d e r w at e r. In c r e as e d p re s s u r e
Effect of pressure: Pressure does not
increases the solubility of atmospheric
have any significant effect on solubility
gases in blood. When the divers come
of solids in liquids. It is so because
towards surface, the pressure gradually
so l i d s an d l i q ui d s are h i gh l y
decreases. This releases the dissolved
incompressible and practically remain
gases and leads to the formation of
unaffected by changes in pressure.
bubbles of nitrogen in the blood. This
Solubility of a Gas in a Liquid blocks capillaries and creates a medical
 Solubility of gases in liquids is greatly condition known as bends, which are
affected by pressure and temperature. painful and dangerous to life. To avoid
 The solubility of gases increase with bends, as well as, the toxic effects of
increase of pressure. Increasing the high concentrations of nitrogen in the
pressure over the solution phase is done blood, the tanks used by scuba divers
by compressing the gas to smaller are filled with air diluted with helium.
volume. This will increase the number  At high altitudes the partial pressure
of gaseous particles per unit volume of oxygen is less than that at the ground
over the solution and also the rate at level. This leads to low concentrations
which the gaseous particles are striking of oxygen in the blood and tissues of
the surface of solution to enter it. p eop le l ivi ng at h i g h a l ti t u de s o r
Henry’s law climbers. Low blood oxygen causes
 The law states that at a constant climbers to become weak and unable to
temperature, the solubility of a gas in a think clearly, symptoms of a condition
liquid is directly proportional to the known as anoxia.
pressure of the gas”. If we use the mole Effect of Temperature
fraction of a gas in the solution as a  Solubility of gases in liquids decreases
measure of its solubility, then it can be w i t h ri s e i n t e m pe r at u re . Th e
said that the mole fraction of gas in the dissolution process involves dynamic
solution is proportional to the partial equilibrium and thus must follow Le
pressure of the gas over the solution. Chatelier's Principle. As dissolution is
 So Henry’s law also states that “the an exothermic process, the solubility
partial pressure of the gas in vapour s h ou l d de c re a s e w i t h i n c re as e o f
 3
temperature and vice versa. = 1  x 2  p10  x 2p02
Vapour Pre ssure of Liqu id- Li quid
Solutions
0 0

= p1  p2  p1 x 2
0

Let us consider a binary solution of A plot of p 1 or p 2 versus the mole
two volatile liquids 1 and 2. Let the total fractions x1 and x2 for a solution gives a
vapour pressure of the system be ptotal and linear plot as shown below.
p1 and p2 be the partial vapour pressures
of the two components 1 and 2 respectively.
These partial pressures are related to the
mol e fraction s 1 an d 2 of the two
components 1 and 2 respectively. The
partial pressures of any component in the
solution in a solution of volatile liquids are
given by Raoult’s law.
Raoults law in its general form can
be stated as "for any solution the partial
vapour pressure of each volatile component
in the solulion is directly proportional to its Vapour Pressure of Solutions of Solids
mole fraction " ie for a solution of volatile in Liquids
liquids, the partial vapour pressure of each (solutions of non-volatile solute in volatile
component in the solution is directly solvents)
proportional to its mole fraction. When a non volatile solute is added
Thus, for component 1 to a pure volatile liquid, it is observed that
p1  x1 the vapour pressure of the solution is less
than that of pure solvent. In the case of a
P1  k x1 pure liquid the entire surface is occupied
If x1 =1 (pure liquids), then K become by the mo l e cu l e s o f t h e l i q u i d . I f a
equal to the vapour pressure of pure nonvolatile solute is added to the solvent
then, a portion of the solvent molecules has
solvent. It is denoted as p10 . ie,
been replaced by molecules of the solute.
p1  p10 x1 Consequently, the number of solvent
molecules escaping from the surface is
( p10 is the vapour pressure of pure correspondingly reduced, thus, the vapour
component 1 at the same temperature) pressure is also reduced.
Similarly, for component 2 Raoult's law for solution of non-
volatile solute in volatile solvents: “The
p2 = p1  p10 x 2 vapour pressure of a solution containing a
( p02 represents the vapour pressure of no n vo l at i l e s o l u t e at a p ar ti c ul a r
temperature is directly proportional to the
the pure component 2). mole fraction of the solvent in the liquid
According to Dalton’s law of partial phase.”
pressures, the total pressure (Ptotal) over In a binary solution, let us denote the
the solution phase in the container will solvent by 1 and solute by 2. When the
be the sum of the partial pressures of solute is nonvolatile, only the solvent
the comnonents of the solution and is molecules are present in vapour phase and
siven as: contribute to vapour pressure. Let P1 be
ptotal = p1+ p2 the vapour pressure of the solvent, 1 be
Substituting the values of p1 and p2. we
get its mole fraction, P10 , be its vapour pressure
in the pure solvent. Then according to
ptotal = x1p10  x 2p02 Raoult’s law,
p1  x1
 4

p1  x1p10 Ideal solutions Non- ideal solutions

The so lu tions that o be y When a solution does not
A plot between the vapour pressure and Raoult’s Law over the entire obey Raoult's Law over the
range of concentrations are entire range of concen
the mole fraction of the solvent is linear. tration, then it is called non-
Known as ideal solutions.
ideal solution.
 mix H  0
 mix H  0
and  mix V  0
and  mix V  0
The i n t e rm o l e c u l a r The intermolecular attra
attractive forces between ctive forces between solute
s o l u te m o l e c u l e s a n d molecules and solve nt
solvent molecules are molecules are not equal to
n e a r l y e q u a l t o th o s e t h o s e p re s e n t b e t w e e n
present between solute and
Ideal Solutions solvent molecules i.e. A-A
s o l u te and solvent
molecules i.e. A-A and B-B
The solutions which obey Raoult’s law and B-B interactions are interactions are not equal to
n e a r l y e q u a l t o th o s e those between A-B
over the entire range of concentration are between A-B
known as ideal solutions. For an ideal
solution of two volatile liquids 1 and 2, then Non-ideal Solutions

A solution does not obey Raoult’s law

p1 = p x 0 over the entire range of concentration, then
1 1
it is called non-ideal solution. Non ideal
p2  p02 x 2 solutions are of two types

ptotal = x 1 p10 + x 2 p02 1. Non ideal solutions with positive

The ideal solutions have two other deviation from Raoult’s law
important properties. In case of positive deviation from
1) No heat is absorbed or evolved when the Raoult’s law, A-B interactions are weaker
than those between A-A or B-B, i.e.. in this
components are mixed, ie Hmix  0
case the intermolecular attractive forces
2) The volume of solution would be equal between the solute-solvent molecules are
to the sum of volumes of the two weaker than those between the solute-
components. Vmix  0 solute and solvent-solvent molecules. This
means that in such solutions, molecules
 At molecular level, ideal behaviour of
of A (or B) will find it easier to escape than
the solutions can be explained by
in pure state. This will increase the vapour
considering two components A and B.
pressure and result in positive deviation.
In pure components, the intermolecular
So in this system,
attractive interactions will be of types
A-A and B-B, whereas in the binary  mix H  0 and  mix V  0
solutions in addition to these two Mixture of ethanol and acetone behave
interactions A-B type of interactions will in this manner.
also be present. If the intermolecular
In pu re e t h an o l , m o l e c u l e s a re
attractive forces between the A-A and
hydrogen bonded. On adding acetone, its
B-B are nearly equal to those between
mo l e c u l e s ge t i n b e t w e e n t h e h o s t
A-B, this leads to the formation of ideal
molecules and break some of the hydrogen
solution.
bonds between them. Due to weakening of
 Examples- Solution of n-hexane and interactions, the solution shows positive
n-heptane. bromoethane and chloro deviation
ethane, benzene and toluene etc.
 A solution formed by adding carbon
d is u l phi de t o ace t on e al s o s h o w s
positive deviation.
 Mixiture of cyclohexane and alcohol.
 5
Azeotropes
 The solutions (liquid mixtures) which
boil at constant temperature and distil
ov e r co mp l e t e l y a t t h e s a m e
temperature without any change in
composition are called constant boiling
mixtures or azeotropes. In such cases,
i t i s not po ss i bl e t o s e pa rate th e
components by fractional distillation.
 The solutions whi ch show a large
positive deviation from Raoult’s law
form minimum boiling azeotrope at a
2. Non ideal solutions with negative specific composition. For example,
deviation from Raoult’s law. ethanol-water mixture (obtained by
Here the intermolecular attractive fermentation of sugars) on fractional
fo rce s be t w e e n s o l ut e - so l v e n t ( A - B ) distillation gives a solution containing
molecules are stronger than those between ap pro xi m a t e l y 9 5 % b y v ol u me o f
solute-solute(B-B) and solvent solvent (A- ethanol. Once this composition, known
A) molecules. as azeotrope composition has been
achieved, then the liquid and vapour
So in this system,  mix H  0 and  mix V  0
have the same composition, and no
 An example of this type is a mixture of further separation occurs.
phenol and aniline. In this case the  The solutions that show large negative
i n t e r mo l e c u l a r h y d r o g e n b o nd i ng d e vi ati on fr o m Ra ou l t ’s l a w f o rm
between phenolic proton and lone pair maximum boiling azeotrope at a specific
on nitrogen atom of aniline is stronger composition. Nitric acid and water is an
than the respective inter-molecular example of this class of azeotrope. This
hydrogen bonding between similar az e ot r op e h as th e a p pr ox i ma t e
molecules. composition, 68% nitric acid and 32%
 A mixture of chloroform and acetone water by mass, with a boiling point of
forms a solution with negative deviation 393.5 K.
from Raoult’s law. This is because Colligative Properties and Determina
chloroform molecule is able to form tion of Molar Mass
hydrogen bond with acetone molecule.
The properties of a solution which
This decreases the escaping tendency
depend only on the number of solute
of molecules for each component and
particles but not on the nature of the solute
consequently the vapour pre ssure
are called colligative properties.
de cre as e s re s ul t i n g i n n e g at i ve
deviation from Raoult’s law. 1. Relative Lowering of Vapour Pressure
 Eamples- Chloroform + Ether, Benzene+ When a non volatile solute is added
Chloroform etc. to a pure volatile liquid, it is observed that
the vapour pressure of the solution is less
than that of pure solvent. In a binary
solution, let us denote the solvent by 1 and
sol u t e b y 2. Let P1 be the vapour pressure
of the solvent, 1 be its mole fraction. p10 ,
be its vapour pressure in the pure solvent.
Then according to Raoult’s law,
p1  x1

p1  x1p10
The reduction in the vapour pressure
of  p1  is given as :
 6

p1  p10  p1  p10  p10 x1 and the constant of proportionality, Kb is

called Boiling Point Elevation Constant
= p10 1  x1  or M ol al E l e va t i o n Constant
Knowing that x 2 = 1-X1 (Ebullioscopic Constant).The unit of Kb is
The above equation reduce to Kkg mol–1.
If w2 gram of solute of molar mass M2
p1 p10  p1 is dissolved in w1 gram of solvent, then
  x2
p1 p10 molality, m of the solution is given by the
The expression on the left hand side expression:
of t h e equ at i on i s cal l ed relative lowering 1000  w 2
of vapour pressure and is equal to the m( molality) = M2  w1
mole fraction of the solute. The above
equation can be written as: K b  1000  w 2
Tb 
p10  p1 n2  n2  M2  w1
  sin ce x 2  
p10
n1  n2  n1  n2  1000  w 2  K b
M2 = Tb  w1
Here n 1 and n 2 are the number of
moles of solvent and solute respectively
present in the solution. For dilute solutions
n 2 << n 1 , he n ce n e g l e ct i ng n 2 i n t h e
denominator we have
p10  p1 n2 p10  p1 w 2  M1
 or 
p10 n1 p10
M2  w1
Here w1 and w2 are the masses and
M1 and M 2 are the molar masses of the
solvent and solute respectively. From the
ab o ve e qu a t i o n , kn ow i ng al l o th e r
quantities, the molar mass of solute (M2) 3. Depression of Freezing Point
can be calculated.
2. Elevation of Boiling Point The freezing point of a substance may
A liquidboils at the temperature at be defined as the temperature at which the
which its vapour pressure is equal to the vapour pressure of the substance in its
atmospheric pressure. We know that liquid phase is equal to its vapour pressure
vapour pressure of the solvent decreases in the solid phase.
in the presence of non-volatile solute. Thus It is observed that when a non-volatile
for such a solution the solution has to be solid is added to the solvent its vapour
heated to a higher temperature so as to pressure decreases and so the freezing
e q ual i z e i t s va po u r p re s su re w i t h point of the solution is always lower than
atmospheric pressure. the freezing point of the pure solvent. Let
Thus, the boiling point of a solution Tf0 be the freezing point of pure solvent
is always higher than that of the boiling
and Tf be that of solution, then
point of the pure solvent. Let Tb0 be the
Tf  T0f  Tf is known as depression
boiling point of pure solvent and Tb be the
boiling point of solution. The increase in in freezing point.
the boiling point  T b = Tb - Tb0 is known as Similar to elevation of boiling point,
elevation of boiling point. depression of freezing point (  Tf  for a
Experiments have shown that for dilute solution is directly proportional to
dilute solutions the elevation of boiling molality. Thus
point (  T b ) is directly proportional to the
Tf  m
molal concentration of the solute in a
solution. Tf  K f m
Tb  m or Tb  K b m The proportionality constant, Kf,
which depends on the nature of the solvent
Here (molality) is the number of
is known as Freezing Point Depression
moles of solute dissolved in 1 kg of solvent
 7
 = (n2/V) R T
Constant or Molal Depression Constant Where V is volume of a solution in
or Cryoscopic Constant. The unit of Kf is litres containing n2 moles of solute.
K kg mol –1. If w 2 g ra m s of s o l u t e , o f mo l ar
1000  w 2 mass, M2 is present in the solution, then
m (molality) = M2  w1 n2=w2/M2 and we can write,
w 2RT w2 R T
K  w 2 /M2 V = or M2  V
Tf  f M2
w1 /1000
The osmotic pressure method has the
K  w 2  1000 advantage over other methods as pressure
Tf  f me asu re m e n t i s a rou n d th e ro o m
M2  w1
temperature and the mol arity of the
K f  w 2  1000 solution is used instead of molality. As
M2 = Tf  w1 compared to other colligative properties, its
magnitude is large even for very dilute
sol u ti ons . The t e c h n iqu e of osm o ti c
pressure for determination of molar mass
of s o l u t e s i s pa r t i c u l a rl y u s e fu l f o r
biomolecules as they are generally not
st ab l e at h i g h e r t e m p e r at u r e s a n d
polymers have poor solubility.
 Two solutions having same osmotic
pressure at a given temperature are
called isotonic solution. For example,
the osmotic pressure associated with the
fluid inside the blood cell is equivalent
4. Osmosis and Osmotic Pressure
to that of 0.9% (mass/volume) sodium
O sm o s i s : Th e p h e n o m e no n of
chloride solution, called normal saline
spontaneous flow of solvent molecules
so l u t i o n a n d i t i s s a f e t o i n j e c t
through a semipermeable membrane from
intravenously.
pure solvent to solution or from a dilute
 If a solution has more osmotic pressure
solution to a concentrated solution is called
t h an ot h e r s ol u t i on i t i s c a l l e d
osmosis. A membarane in which allows the
hypertonic solution. For example, if we
flow of only small solvent molecules and
place the cells in a solution containing
not the passage of bigger solute molecules
more than 0.9% (mass/volume) sodium
is known as semipermeable membranes
chloride, water will flow out of the cells
(SPM).
and they would shrink.
 If a solution has less osmotic pressure
than other solution it is called hypotonic
solution.
For example, if we place the cells in a
solution containing less than 0.9%
O s m o ti c p r e s su r e : T h e e x ce ss (mass/volume) sodium chloride, water
pressure that must be applied to solution will flow into the cells and they would
to prevent the passage of solvent into swell.
so l ut i o n t h r o u g h a se m i p e rme ab l e
membrane is called osmotic pressure.
Osmotic pressure is a colligative
property as it depends on the number of
solute particles and not on their identity.
For a dilute solution, osmotic pressure (  ) Phenomena based on osmosis.
is directly proportional to the molarity (C)  A raw mango placed in concentrated salt
of the solution
solution loses water via osmosis and
i.e.  = CRT
shrivel into pickle.
where T is the temperature and R is
Wilted flowers revive when placed in
the universal gas constant.
fresh water
 8
 A carrot that has become limp because mass of solute therefore, higher values
of water loss into the atmosphere can be are obtained for molecular masses.
placed into the water making it firm once (ii) Dissociation of solute molecules:
again. Water will move into them through A number of electrolytes dissociate in
osmosis. solution to give two or more particles
 People taking a lot of salt or salty food (ions).
experience water retention in tissue cells This leads to an increase in the number
and intercellular spaces because of of molecular particles in the solutions
osmosis. The resulting condition is called which results in an increase in the values
edema. of colligative properties.
 Water movement from soil into plant Since colligative properties are inversely
roots and subseque ntly into upper proportional to molecular masses, the
portion of the plant is partly due to molecular masses of such substances
osmosis. will be less than their normal values.
 The preservation of meat by salting and
of fruits by adding sugar protects against
bacterial action. Through the process of
osmosis, a bacterium on salted meat or
candid fruit loses water, shrivels and
dies.
R e ve r s e os m os i s: Th e p r o c e s s o f Van't Hoffs factor (i) :
movement of solvent through a semi In 1886, Van't Hoff introduced a factor
permeable membrane from the solution ‘i’ called Van't Hoffs factor, to express the
to the pure solvent by applying excess extent of association or dissociation of
pressure on the solution side is called solutes in solution.
reverse osmosis. Normal molar mass
Reverse osmosis is used in desalination i = Abnormal molar mass
of sea water. When pressure more than
osmotic pressure is applied, pure water Observed colligative property
is squeezed out of the sea water through = Calculated colligative property
the mem bra ne. A wo rkabl e p oro us
membrane is a film of cellulose acetate =
Total number of moles of particles after association/dissociation
Total number of moles particles before association/dissociation
placed over a suitable support.
Inclusion of van’t Hoff factor modifies the
equations for colligative properties as
follows:
p10  p1 n
 i. 2
p10 n1

K b  1000  w 2
Tb  i.
M2  w1
Abnormal Molar Masses K f  1000  w 2 n RT
Molar mass that is either lower or higher Tf  i. =   i. 2
M2  w1 V
than expected or normal molar mass is
called as abnormal molar mass. These  It is found that ‘i’ is less than one for
abnormalities are primarily due to solute which undergoes association and
(i) Association of solute molecules. greater than one for solute s which
(ii) Dissociation of solute molecules. undergoes dissociation.
(i) Association of solute molecules:  If association (dimerisation) is complete
Certain solutes in solution are found to 'i' will be ½ .
associate. This leads to a decrease in the  If dissociation is complete ‘i’ will be equal
number of molecular particles in the to the number of ions formed by the
solutions. Thus, it results in a decrease dissociation of one molecule.
in the values of colligative properties. For example, forNaCl, i =2
Colligative property  1/ molecular for BaCl2, i=3
for Al 2(SO4)3 i = 5