Solutions

Solutions
• Normality, molality, molarity, mole fraction, ppm, as measures
of concentration. Definition of the above with examples.
Simple problems based on the above.
Solution
• Solution = Solute + Solvent
• Solvent: Present in excess, physical state same as solution.
• Solute: Present in smaller amount
List of terms they should be familiar
• Mass Percentage = mass of solute/mass of solution
• Volume Percentage= volume of solute/volume of solution
• Normality=no. of eq/vol. of solution
• Molarity= no. of moles/vol. of solution
• Molality= no. of moles/wt. of solution
Mole fraction & PPM
• XA=NA/NA+NB
• X A + XB = 1
• PPM (Take 5 % solution example, then 0.5 %, then 0.005 %, if it
becomes further small the value becomes difficult to handle,
that why we need ppm.
Different concentration terms
Problems based on above concepts
Problems based on above concepts
Vapour Pressure of volatile solute
• The vapour particles of A will be in dynamic
equilibrium with the liquid particles (on the surface).
• The pressure exerted by the vapour particles of A at
any particular temperature is called the vapour
pressure of A at that temperature.
• PA=PºAXA ( Raoult’s Law)
• PA= Vapour pressure of the solution
• PºA=Vapour pressure of A in pure state
• XA= mole fraction of A in the solution
Solution of volatile liquids A and B (Raoult’s law)

• Vapour pressure depends on the liquid type and temperature adding

another liquid, B (solute).
• PA & PBdepends on the concentration of each component in the liquid
phase.
• As mole fraction of a component reduces, its partial pressure also reduces
in the vapour phase.
Relation between mole fraction (of liquid) &
partial pressure (of gas) of each component
Combining both
Roalts Law for non-volatile solutes
• If one of the solute is non- volatile
Ideal Solution
• The solutions which obey Raoult’s Law at every range of
concentration and at all temperatures are called Ideal Solutions.
• Mixing liquid A & B, the resulting solution will experience several
intermolecular forces such as A – A, B – B, and A – B.
• When all interactions are almost equal, then the solution is ideal. It
normally exists when the solute and a solvent has similar molecular
size and structure
• Examples: n-hexane and n-heptane, Bromoethane and
Chloroethane, Benzene and Toluene, CCl4 and SiCl4, Chlorobenzene
and Bromobenzene, Ethyl Bromide and Ethyl Iodide, n-Butyl
Chloride and n-Butyl Bromide are some examples of Ideal Solution.
General Characteristics of Ideal
Solutions
• Ideal Solution obeys Raoult’s Law: PA = PA0 XA and PB = PB0 XB
• Enthalpy of mixing of two components should be zero, that is, Δmix H
=0
• No heat is absorbed or released during the mixing
• Volume of mixing of two components should be zero, that is, Δmix V =
0
• Total volume of solution is equal to the sum of the volume of solute and
solution.
• No occurrence of contraction or expansion of volume while mixing two
components.
• The solvent-solvent and solute-solute interaction are nearly equal to
the solute-solvent interaction.
 Non-Ideal Solutions
• In general, Raoult's law is only applicable to ideal solutions (no interaction
between the molecules of the solvent and those of the solute.)
• Most real solutions are non-ideal, so, Raoult's law typically overestimates or
underestimates the actual vapour pressure
Non-Ideal Solution
• Non-Ideal Solutions don’t obey Raoult’s law
• Solute-solute and solvent-solvent interactions are different
from that of solute-solvent interactions.
• Enthalpy of mixing that is, Δmix H ≠ 0
• which means that heat might have released if enthalpy of mixing is
negative (Δmix H < 0)
• heat might have observed if enthalpy of mixing is positive (Δmix H >
0)
• The volume of mixing, i.e., Δmix V ≠ 0
• expansion or contraction in dissolution of liquids.
Types of Non-Ideal Solution

• Non-ideal solutions showing positive deviation from Raoult’s

Law

• Non-ideal solutions showing negative deviation from Raoult’s

Law
Positive Deviation from Raoult’s Law
• Vapour pressure is greater than that is expected in Raoult’s
Law.
• PA > PA0 XA and PB > P0B XB
• E.g: Acetone – Ethanol mixture, acetone when mixed with ethanol,
breaks the intermolecular H bonding in Ethanol, hence the vapour
pressure of ethanol increases.
• The order of interaction (solute and solvent):
• A - B < A - A or B - B
• Δ Hmix > 0 ,
• heat absorbed to form new molecular interaction is less than the
heat released on breaking of original molecular interaction.
• Δ Vmix > 0, as the volume expands on dissolution of
components A and B.
Negative Deviation from Raoult’s Law
• Vapour pressure is lesser than that is expected
in Raoult’s Law.
• PA < PA0 XA and PB < P0B XB
• The order of interaction (solute and solvents):
• A - B > A - A or B - B
• Δ Hmix < 0 ,
• more heat is released when new molecular
interactions are formed.
• Δ Vmix < 0, as the volume decreases on
dissolution of components A and B.
Positive & Negative Deviation from Roaults Law
Azeotropic mixtures – definition,
• An azeotrope (/əˈziːəˌtroʊp/)[1] or a constant heating point mixture is a mixture
of two or more components in fluidic states whose proportions cannot be altered
or changed by simple distillation.[2] This happens because when an azeotrope is
boiled, the vapour has the same proportions of constituents as the unboiled
mixture. Azeotropic mixture behavior is important for fluid separation processes.
• Fractional distillation is a separation method to separate a mixture of two or
more miscible liquids for which the difference in boiling points is less than 25 K.
• Another condition for fractional distillation is that components of the mixture
must not have equal mole fractions at the liquid phase and vapour phase.
• Fractional distillation is used to separate different gases from the air, different
fractions from petroleum products etc. The apparatus for fractional distillation
has almost the same apparatus as simple distillation but with a fractionating
column installed in between the distillation flask and the condenser.
• Azeotropes do not follow Raoult’s Law. It means these
mixtures are not ideal solutions and show deviation from
Raoult’s Law.
• In azeotropic mixtures, one component has either a higher or
lower boiling point than another component. In these
mixtures, components exhibit the same mole fraction in the
liquid phase and vapour phase. So, they cannot be separated
by fractional distillation.
• Positive azeotrope or minimum boiling azeotrope
• Negative azeotrope or maximum boiling azeotrope
Main points about azeotropic mixtures

• These are binary solutions with one solute and one solvent. For example, in azeotrope
ethyl alcohol, ethyl alcohol is mixed with water.
• Solute and solvent both are in a liquid state in the azeotropic mixture. For example, in
an azeotropic mixture of ethyl alcohol and water, both are taken in the liquid state.
• Solute and solvent are taken in fixed compositions to form azeotropes. For example, in
an azeotropic mixture of ethyl alcohol and water, 96% of ethyl alcohol and 4% of water
are mixed.
• Azeotropic mixture solution boils at a constant temperature. For example, an
azeotropic mixture of ethyl alcohol (96%) and water (4%) boils at 78.10C.
• Separation of constituents of an azeotropic mixture by fractional distillation is not
possible. For example, as the mole fraction of ethyl alcohol is the same at the liquid
phase and vapour phase and mole fraction of water is also the same at the liquid phase
and vapour phase so the azeotropic solution of ethanol and water boils at 78.10C and
cannot be separated by fractional distillation.
• Positive Azeotrope or Minimum Boiling Azeotrope – Those
azeotropic mixtures which show large positive deviation
from Raoult's Law at specific composition are called positive
azeotropes. They show boiling points lower than the boiling
points of their constituents. That’s why they are also called
minimum boiling azeotropes. These types of mixtures
exhibit the highest vapour pressure and lowest boiling point.
For example, an azeotropic mixture of 96% (or 95.6%)
ethanol and 4% water is a positive azeotrope. It shows a
large positive deviation from Raoult’s law. It is represented
by the graph below, where A = water and B = ethanol –

• This azeotropic mixture boils at 78.20C while the water

boils at 1000C and ethanol at 78.50C. It is also represented
by the graph below –
• Negative Azeotrope or Maximum Boiling Azeotrope –
Those azeotropic mixtures which show large
negative deviation from Raoult's Law at specific
composition are called negative azeotropes. They
show boiling points higher than the boiling points of
their constituents. That’s why they are also called
maximum boiling azeotropes. These types of
mixtures exhibit lower vapour pressure and the
highest boiling point. For example, an azeotropic
mixture of hydrogen chloride and water is a
negative azeotrope. It shows a large negative
deviation from Raoult’s law. It is represented by the
graph below –
• This azeotropic mixture boils at 110 ºC while the
water boils at 100 ºC and HCl at -84 ºC. It is also
represented by the graph below –
 Solubility of gases in liquids: Henry’s
Law
• Henry’s Law: “the partial pressure applied
by any gas on a liquid surface is directly
proportional to its mole fraction present in a
liquid solvent.”
•P∝ X
• ( P = partial pressure of gas, X = Mole fraction
of gas in liquid
• P = KH.X
• Where KH is called Henry’s law constant.
Henry’s Law: Numericals
Colligative Properties
 Lowering of Vapour Pressure
• In a pure solvent, the entire surface is
occupied by the molecules of the solvent.
• If a non-volatile solute is added, the surface
now has both solute and solvent molecules;
the volatile solvent doesn’t evaporate much
• The vapour pressure of the solution is found
to be lower than that of the pure solvent.
Derivation based on Raoult’s Law
For Non-Volatile Solutes
Elevation of Boiling Point
Boiling point is the temperature at which the vapour pressure of the liquid
becomes equal to the atmospheric pressure. As we know that the vapour
pressure of solution is always less than that of solvent, the solution has to
be heated more in order to equalize its vapour pressure to the atmospheric
pressure. Therefore, the boiling point of the solution is more than that of
pure solvent. The difference in the boiling point of solution (T;) and the
solvent (To) is called elevation in boiling point.
 Elevation of Boiling Point:
mathematical expression

∆H = Enthalpy or latent heat of vaporization (per mole) of the

solvent
Notice that M1 has been incorporated in Kb as it is constant and pertains to the solvent
Kb Values for Some Common Solvents
Depression of Freezing Point
Freezing point is the temperature at which the vapour pressure
of the solid and the liquid (in equilibrium) are same. On
addition ofnon-volatile solute in the liquid, the vapour pressure
of the solution gets lowered and the solution freezes at lower
temperature than that of pure solvent or liquid. The difference
in the freezing point of the pure solvent and the solution is
known as depression in freezing point.
∆T= To-Ts
 Depression of Freezing Point:
mathematical expression

Notice that M1 has been incorporated in Kf as it is constant and pertains to the

Osmosis, Diffusion & Osmatic Pressure
• Osmosis : The flow of solvent particles from the less concentrated solution
to higher concentrated solution through semipermeable membrane is
called osmosis. It takes place only in solutions and it can be reversed.
• Diffusion: The solvent and the solute molecules move directly in to each
other without semipermeable membrane. It takes place in solutions as
well as gases, it cannot be reversed.
• The minimum excess pressure which is required on the higher
concentrated solution side in order to prevent the flow of solvent particles
towards them through semipermeable membrane is called osmotic
pressure. Actually, it is equal to the hydrostatic pressure due to liquid
column. Osmotic pressure of a solution is determined experimentally by
Berkley and Hartley's method.
Boyle – vant Hoff’s Law
At Constant Temperature
Charles’ – vant Hoff’s Law
At Constant conentration
Vant-Hoffs theory of dilute solutions
Hypertonic and Hypotonic Solutions
• The solution having more osmotic pressure than other solution
is known as hypertonic solution but a solution having less
osmotic pressure than some other solution is called hypotonic
solution. A 0.91% aqueous solution of NaCl(w/v) is isotonic with
RBC.
Explanation of some phenomena on the
basis of Osmosis
• Raw mangoes shrivel (shrink) into pickle when placed in concentrated
common salt solution due to outflow of water through semi-permeable
membranes of mangoes due to osmosis.
• People taking a lot of salt develop swelling of their tissues (called
'edema' disease) due to retention of water in the tissue cells and
intercellular space due to osmosis.
• Wilted flowers revive when placed in fresh water because of flow of
water into them through their semi-permeable membranes due to
osmosis.
• Meat can be preserved by salting because the bacterium, responsible
for spoiling them, loses water in the salted meat due to osmosis. As a
result, it shrivels (shrinks) and dies.
Reverse Osmosis :
• When a pressure higher than the osmotic pressure is applied to
the solution, the solvent from the solution starts flowing
towards the pure solvent. This process is called reverse
osmosis. This process is very useful to get
• pure water from sea water known as desalination of sea water.
Abnormal Molecular Masses
• We have discussed that the colligative properties help us to
calculate the molar masses of solutes. The accurate values of
molar masses can be obtained only if (1) the solutions are
dilute and (2) the solute must not dissociate or associate in
solution.
• Discrepancies in determination of molar mass arise when the
solute dissociate or associate on dissolving in a solvent. As
colligative properties depend only upon the number of the
particles, they are expected to show certain deviations which
in turn influence the molar masses. The discrepancy in molar
mass is called abnormal molar mass.
van't Hoff Factor (i)

i = no. of particles after dissociation or associated

no of particles without dissociation or association
van't Hoff factor and extent of dissociation
or association in an electrolytic solution :