Solutions

• Solution is a homogeneous mixture of two or more

substances.
• Concentration of solutions
• Mass%= Mass of solute x100
• Mass of solution
• Example- 10% aq solution by mass of NaCl
• In 100 g Solution, 10 g NaCl(solute) and 90 g water
(solvent)
• Volume % = Volume of solute x100
• Volume of solution
• Example- 5% by volume of ethanol
• In 100 ml solution, 5 ml is ethanol(solute) and 95 ml
water(solvent)
• Mole fraction-
• Number of moles of a component
• Total number of moles in the solution
• Example- 4 g of NaCl dissolved in 72 g of water
• nNaCl = Mass of solute/ Molar mass of solute
• = 4/40= 0.1 moles
• nH2O = 72/18= 4
• Mole fraction
• X NaCl = 0.1/4.1= 0.024
• x H2O = 4/4.1= 0.976
• Molarity- It is the number of moles of solute in 1 litre
solution
• M = Number of moles of solute
• Volume of solution in litres
•
• M= Mass of solute x1000 cm3
• Molar Mass of solute x volume of solution cm3
• M = % mass of solute x10 x Density of solutiong/cm3
• Molar mass of solute
• Molality – It is the number of moles of solute in 1 Kg solvent
• m = Number of moles of solute
• Mass of solvent in Kg
• m = Mass of solute x1000
• Molar mass of solute X mass of solvent in g
• = % mass of solute x1000
• Molar mass of solute x (100-% mass of solute)
• Effect of temperature on concentration of solution-
• In a closed system, increase in temperature will not
affect the mass of solute and solvent. Volume of solution
will decrease on heating the solution.
• There increase in temperature has no effect on molality.
• Increase in temperature decreases the molarity of the
solution.
• Solubility is the amount of solute that can be
dissolved in a given amount of solvent at a
particular temperature.
• Solid in a liquid to give a solution:
• If the dissolution process is endothermic Δ>0
• Solubility increases with the increase in
temperature.
• If the dissolution process is exothermic Δ<0
• The solubility decreases with the increase in
temperature.
• Pressure has no significant effect on the solubility of
solid in liquid.
• Solubility of gas in a liquid- The dissolution process is
exothermic. Therefore solubility decreases with the
increase in temperature.
• Solubility of gas increases with the increase in pressure.
• Henry’s law- At constant temperature, the solubility of a
gas in a liquid is directly proportional to the partial
pressure of the gas above the solution.
• p = K H xg
• The mole fraction of the gas in the solution is directly
proportional to partial pressure of the gas above the
solution. KH Is Henry’s law constant
• At a given pressure, higher the value of KH
lesser is the solubility of the gas in the liquid.
• KH is a function of nature of gas. It increases
with the increase in temperature. Therefore
solubility of the gas decreases with the
increase in temperature. Therefore aquatic
species are more comfortable in cold water
than in warm water.
• p = K H xg = K H n g
• ng+nsolvent
• When ng is very less
• p = KH xg = KH ng / nsolvent
• = KH Mass of gas x Molar mass of solvent
• Molar mass of gas X Mass of solvent
•
 Application of Henry’slaw
• 1. Solubility of carbon dioxide in soda water is increased
by dissolving the gas at a higher pressure.
• 2. Solubility of gases increases as we move deep in sea
water due to increase in pressure. When the divers come
to the surface of water, the pressure decreases
gradually. The dissolved gases get released and it
results in the formation of bubbles of nitrogen gas in the
blood. This blocks capillaries and creates a medical
condition called bends. These bends are painful and
dangerous to life.
• Scuba divers use tanks containing a mixture of 11.7%
He, 56.2% nitrogen and 32.1% oxygen. It reduces the
concentration of nitrogen in the blood
• At higher altitudes, the partial pressure of oxygen is less.
• Therefore the concentration of oxygen in the blood
decreases at a higher altitudes. Low blood concentration
of oxygen in blood causes climbers to become weak
and unable to think clearly, symptoms of conditions
known as anoxia.
 Raoult’s law
• Vapour pressure of a solution containing two volatile
solvents
• Let the partial vapour pressure of solvent A is PA and
vapour pressure of solvent B is pB
• Total pressure= PTotal = PA+PB
• In a solution containing two or more volatile solvents, partial
vapour of each component is directly proportional to its mole
fraction in solution
• Let pA0 be the vapour pressure of pure solvent A and
• pB 0is the vapour pressure of solvent B
• PA = PA 0 xA and PB = pB 0 XB
• Total pressure of solution= pA+pB
• PTotal =PA 0 xA +pB 0 XB
• Mole fraction in vapour phase
• YA = PA0 xA /Ptotal
• yB = PB 0 xB /PTotal
• Consider a pure solvent in a closed system. Solvent
molecule having higher vapor pressure than the average
energy of the molecule moves to the vapor phase.
Molecules in the vapor phase condenses and move back
to liquid phase. The pressure exerted by vapor phase at
equilibrium is called Vapor pressure of the liquid P0
• Add a non-volatile solute to the above solvent to make a
solution. Vapor pressure of a solution(p) containing a
non-volatile solute is lesser than that of pure solvent
• P0-p is lowering of vapor pressure and (P0-p)/ P0 Is called
• Relative lowering of vapor pressure.
• For a solution containing a non-volatile solute and a
volatile solvent, relative lowering of vapor pressure is
equal to mole fraction of solute in the solution.
• Let A be the non volatile solute dissolves in volatile
solvent B to give the solution AB
• PTotal = PA0 xA + PB 0 xB
• Solute is non volatile. Therefore vapour pressure of
solution is equal to the partial vapor pressure of volatile
solvent B in the solution
• PTotal = PB 0 xB = PB 0 (1-xA)
• = P B 0 - P B 0 xA
• PA0 Is the vapor pressure of non volatile solute and PB 0 Is the
vapor pressure
• of volatile solvent
• XA = PB 0 –Ptotal
• PB 0
• XA = PB 0 –Ptotal
• PB 0
• = nsolute
• nsolute+nsolvent
• For a dilute solution nsolute is very less when compared to
nsolvent
• P0-P = Mass of solute x Molar mass of solvent
• P0 Molar mass of solute x mass of solvent
• Pgas = KH xgas
• Raoult’s law
• P A = P A 0 xA
• In both the laws, partial vapor pressure of volatile component
is directly proportional to its mole fraction in solution.
Raoult’s law is a special case of Henry’s law when P0 =KH
•
Ideal solution
• Conditions for a solution to be ideal
• Solution which obeys Raoults law over a wide range of
concentrations are called ideal solution.
• Example-Benzene-Toulene
• No bond is formed or broken. ΔHmixing=0
• No change in volume Δvmixing=0
• A-B interaction is nearly equal to A-A and B-B interaction
• PA is equal to pA0 xA pB is equal to p B0 xB
 Non-ideal solution
• Non ideal solution do not obey Raoult’s law over the
entire range of concentration of the solution.
• In a binary solution of AB, A-B interaction is not the same
as A-A or B-B interaction. New bond is made or broken
• ΔHmixing is not equal to zero and ΔVmixing is not equal to zero
• PA is not equal to pA0 xA pB is not equal to p B0 xB
• Two types of deviation- a) Positive deviation b) Negative
deviation
• Positive deviation- Bond is broken when two solvents are
mixed to form a solution. Example- Ethanol and
n-hexane.
• Ethanol forms intermolecular hydrogen bonding
• n-hexane breaks hydrogen bonding. Therefore
• ΔHmixing >0 and ΔVmixing >0 Solution shows positive deviation
due to weakening of attraction. Temperature decreases.
• P A > p A 0 xA p B > p B 0 xB
• Negative deviation- New bond is formed when two
solvents are mixed to form a solution. Example-
Propanone(Acetone) and Chloroform (CHCl3)
• Hydrogen bond is formed between acetone and chloroform.
Therefore ΔHmixing <0 and Δvmixing <0 Solution shows negative
deviation due to increase in attraction between the solvents.
Temperature decreases.
• P A < p A 0 xA p B < p B 0 xB
• Deviation in a solution made by mixing the solvents phenol and
aniline.
• Both phenol and aniline forms intermolecular hydrogen bonding.
When Phenol is mixed with aniline, the hydrogen bond formed
between the proton of phenol and the lone pair of electron on N in
aniline is stronger than the hydrogen bonding in both phenol and
aniline. Therefore it exhibit negative deviation
•
• Azeotropes are the binary mixtures having the same
composition in liquid and vapour phase. They boil at a
constant temperature with no change in its composition.
• Solution which exhibits positive deviation forms minimum
boiling azeotrope at a particular composition. Example
95% by volume of ethanol and 5 % by volume of water.
• Solution which exhibit negative deviation forms
maximum boiling azeotrope. Example- 68% by mass of
nitric acid and 32% by mass of water.
• Azeotrope boil off with no change in its composition.
Therefore their components can’t be separated by
fractional distillation.
 Elevation of boiling point

• Colligative properties depends on the number of moles

of the solute particles and not on the nature of the
particles.
• Example- elevation of boiling point, depression of
freezing point, Osmotic pressure.
• Boiling point is the temperature at which vapour pressure
of a liquid becomes equal to atmospheric pressure.
• Vapor pressure of a solution containing a non volatile
solute is lesser than that of the pure solvent. Therefore
the boiling point of the solution is higher than that of pure
solvent.
• Elevation of boiling point = Boiling point of solution-
Boiling point of solvent=ΔTb = Kb m
• Kb is molal elevation constant or ebullioscopic constant and
m is the molality of the solution.
• Kb is the boiling point elevation for one molal solution
• m = Mass of the solute x 1000
• Molar mass of solute x Mass of solvent
• = % mass of solute x1000
• Molar mass of solute (100-% mass of
• solute)
• Molar mass of solute determined by this
method is called ebullioscopic method.
 Depression of freezing point

• Freezing point of a substance is the temperature at

which its vapour pressure in the liquid phase becomes
equal to its vapour pressure in its solid phase. Vapour
pressure of a solution containing a non volatile solute is
lesser than that of the pure solvent.
• When a pure solvent freezes, it loses the heat of fusion, and
the molecules come closer to one another to solidify. But, the
presence of solute particles block such coming closer of the
solvent molecules, and so the solvent does not freeze at the
normal freezing point. When the temperature is reduced
further, the solute-solvent interactions become weakened,
and the solvent molecules are able come closer and freezes.
Thus, the presence of a solute causes the depression in
freezing point of a solvent.
• Depression of boiling point= Freezing point of
solvent-Freezing point of solution= ΔTf = Kf m
• Kf is molal depression constant or cryoscopic constant and m is
the
• molality of the solution.
• Kf is the freezing point depression for one molal solution
• m = Mass of the solute x 1000
• Molar mass of solute x Mass of solvent
• = % mass of solute x1000
• Molar mass of solute (100-% mass of solute)
• Molar mass of solute determined by this method is called
cryoscopic method.
• Kf and Kb depends on the nature of the solvent.
• Kb = R T 2 b M 1
• ∆Hvaporisation
•
• Kf = R T 2 f M 1
• ∆Hfusion
• R= 8.314 x10-3 KJ K-1 mol-1 Tb= Boiling point of solvent M1= Molar
mass of solvent
• ∆H= KJ/mol
• R is gas constant M1 is the molar mass of solvent,
• Tf and Tb are the freezing point and boiling point of the solvents
respectively.
• Osmotic pressure-It is the pressure applied on the
solution to prevent the flow of solvent from solvent to
solution or from a solution of lower concentration to the
solution of higher concentration through a semi
permeable membrane. Solvent molecules move from a
region of lower concentration to a region of higher
concentration till an equilibrium is achieved.
•
• πv=nRT π= CRT C is concentration in terms of
molarity. π is osmotic pressure R is gas constant. T is
temperature in kelvin
• π= Mass of solute x R XT
• Molar mass of solute x volume of solution in litres
• Advantage of determining the molar mass of solute by
• Osmotic pressure method
• 1. Molarity of solution is used instead of molality.
• 2. A small change in pressure gives rise to a few cm
level in the solution and hence easier to measure.
• 3. Carried out at room temperature. Therefore suitable to
determine the molar mass of macro molecules like
protein. Protein gets denatured at a higher temperature.
• Isotonic solution- Two solutions having same osmotic
pressure at a particular temperature. When such
solutions are separated by semi permeable membrane,
no osmosis occur.
• Example of isotonic solutions- Fluid inside the blood cell
is isotonic with 0.9%(mass/volume) sodium chloride
solution. It is called normal saline solution and it is used
for intravenous injection.
• When two solutions are taken at a particular
temperature, the solution having higher concentration of
solute is called hypertonic solution and the solution
containing lower concentration of solute is called
hypotonic solution.
• Example – Blood cell kept in a solution having more than
0.9%(mass/volume) –Hypertonic solution. Blood moves
out of the cell and the blood cell will shrink.
• Blood cell kept in a solution having less than
0.9%(mass/volume) sodium chloride.- hypotonic solution.
Water will flow out of saline solution to the blood cell.
Blood cell will swell and burst.
• Application of osmosis.
• 1. intravenous injection given by mixing the medicine
with 0.9%(mass/volume) sodium chloride solution.
• 2. A raw mango kept in concentrated salt solution, loses
water through osmosis and shrivel into pickles.
• 3. A carrot that has become limp by losing water
molecule to the atmosphere is placed in water to make it
firm.
• 4. People taking lot of salt or salty food experiences
retention of water in tissue cells and intercellular spaces
due to osmosis. It results in puffiness or swelling called
edema.
• 5. Meat is preserved by keeping it in salt water and fruit
is kept in sugar solution. Water will flow out of meat and
fruit through osmosis. Bacteria present in meat and fruit
shrivel and die.
• Reverse osmosis- In this process, solvent flows from
solution to solvent through a semi permeable membrane.
It occurs by applying pressure higher than osmotic
pressure on the solution side. It is used in desalination of
sea water. Fresh water and sea water are kept in a tank
and it is separated by semi permeable membrane.
Pressure higher than osmotic pressure is applied on sea
water. Fresh water flows from sea water to fresh water
through the semi permeable membrane.
• Abnormal molar mass- Molar mass of solute obtained by
colligative properties is higher or lower than the actual
molar mass.
• a) Dissociation of solute- Ionic compounds dissociates in
aqueous solution. KCl(aq) K+ (aq)+ Cl-(aq)
• One particle of KCl behaves as two particles. Colligative
properties are directly proportional to the number of particles
and inversely proportional to molar mass.
• Assume 1 molal KCl undergoes 100% dissociation. ΔTb=Kb m
• Expected ΔTb = 1x0.52= 0.52K. 1 molal KCl gives 2 particles.
• ΔTb= 2x0.52= 1.04K. Molar mass of KCl determined is half the
actual molar mass
• Actual molar mass.
• b) Association of solute- Example acetic acid in benzene

• .

• 2 molecules of acetic acid associates through hydrogen

bonding and behaves as a single particle. Assuming
complete association, colligative property measured is
half the expected value and the molar mass calculated is
double the actual molar mass.
• Van’t factor i accounts for the extent of association or dissociation
of solute in a solution.
• i= Normal molar mass/ Experimental molar mass
• = observed colligative property/ calculated colligative property
• Degree of dissociation α = i-1/ n-1
• Example- AlCl3is 90% dissociated
• α= 90/100 = i-1/4-1 Therefore i=3.7
• Degree of association α = i-1/(1/n -1 )
• Example- Benzoic acid exist as a dimer and is 90% associated
• 90/100 = i-1/(1/2-1)
• i=0.55
• Therefore
•
• i>1- Dissociation of solute
• i<1- Association of solute
• i=1 Neither association nor dissociation of solute
• Conditions to exact molar mass of solute
• 1. Solute molecule neither associated nor dissociated
• 2. Dilute solution is taken.