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Units of Molarity are mol/L also represented by ‘M’ or Vapour pressure of a liquid/solution is the pressure exerted
‘Molar’. by the vapours in equilibrium with the liquid/solution at a
“Density of a solution is mass of the solution per unit particular temperature.
volume” Vapour pressure v escaping tendency
Mass of sol. 2.2 Vapour pressure of liquid solutions and
Density, d m/V
Vol. of sol. Raoult’s Law :
7. Molality, m
(Raoult’s law for volatile solutes)
“It represents moles of solute present per kg of solvent”
Raoult’s law states that for a solution of volatile liquids,
Moles of solute the partial vapour pressure of each component in the
Molality, m
Mass of solvent in kg solution is directly proportional to its mole fraction.
Consider a solution containing two volatile components
Units of molality are mol/kg which is also represented by
1and 2 with mole fractions x1 and x2 respectively. Suppose
‘m’ or ‘molal’.
SOLUTIONS & COLLIGATIVE PROPERTIES
p1 D x 1
p2 = y2 ptotal
SOLUTIONS & COLLIGATIVE PROPERTIES
Eg. solution of benzene and toluene, Pressure composition curves for solution showing
solution of n-hexane and n-heptane negative deviation
When a solution does not obey Raoult’s law over the entire
range of concentration, then it is called non-ideal solution.
x 'HMIXING > 0
x 'VMIXING > 0
3. SOLUBILITY
The solutions that show large negative deviation from Effect of pressure :
Raoult’s law form maximum boiling azeotrope at a specific Does not have any significant effect as solids and liquids
composition. Nitric acid and water mixture containing 68% are highly incompressible.
nitric acid forms an azeotrope with a boiling point of 393.5
K. 3.2 Henry’s law
Characteristics of KH :
According to Raoult’s Law : The increase in boiling point 'Tb = T b – Tb0 where Tb0 is
p1 x1 p10 the boiling point of pure solvent and Tb is the boiling point
of solution is known as elevation of boiling point.
The reduction in the vapour pressure of solvent ('p1) is
Expression :
given as:
'Tb = Kb m
'p1 p10 p1 p10 p10 x1
Kb is called Boiling Point Elevation Constant or Molal
p10 (1 x1 ) Elevation Constant (Ebullioscopic Constant).
SOLUTIONS & COLLIGATIVE PROPERTIES
M1 = Molar mass of solvent in Kg/mol, Substituting this value of molality in equation we get :
K f u w 2 u 1000
'Tf
M 2 u w1
K f u w 2 u 1000
M2
'Tf u w1
Kf :
Determination of Kf :
The vapour pressure curve for solution lies below the R u M1 u Tf2
Kf
curve for pure water. The diagram shows that ' Tb 1000 u 'fus
denotes the elevation of boiling point of a solvent in
solution. where : R = gas constant (8.314 JK/mol),
Tf = freezing temperature in K,
SOLUTIONS & COLLIGATIVE PROPERTIES
w 2 RT
SV
M2
w 2 RT
or M2
SV
Isotonic solutions :
If a pressure larger than the osmotic pressure is applied to The number of particles will always increase due to
the solution side, the solvent will flow from the solution dissociation and hence i > 1.
into the pure solvent through the semi permeable membrane.
This phenomenon is called reverse osmosis. An o nA
Total no. of moles of particles after association (dissociation) The distribution of molecular kinetic
No. of moles of particles before association (dissociation) energies in a liquid
Claussius-Clapeyron Equation
Association :
In p2/p1 = ('HVAP/R) (1/T1 – 1/T2)
Number of particles will always decrease due to association
therefore i < 1. where 'HVAP represents the enthalpy of vaporisation of
the liquid.
nA o An
6. THERMODYNAMICS OF DISSOLUTION
Let initial particles (ni) = 1
If the interactions grow stronger the process is exothermic
Final number( nf) = 1 – D + D/n and if they go weaker during the formation of solution
the process becomes endothermic. In general 'S is
van’t Hoff factor, i = nf/ni = 1 – D + D/n positive in dissolution process. If the mixing process is
spontaneous/natural then 'G has to be negative.
SOLUTIONS & COLLIGATIVE PROPERTIES
'GVAP = 0
Tb = 'HVAP/'SVAP
The non-volatile solute increases the randomness of the
The lower freezing point of a solution relative to that of a
solution phase and the entropy of the vapours remains
pure solvent is due to a difference in their entropies
the same. Due to this, 'SVAP decreases thus giving rise to
the boiling point. of fusion, 'Sfusion.
IMPORTANT FORMULAE
In the formulae given below A represents solvent and B represents solute, also
MA = Molar mass of solvent MB = Molar mass of solute
WA = Mass of solvent VB = volume of solute
V = Volume of solution d = density of solution.
WB
1. Mass of percentage (w/w) = W W u 100
A B
VB
Volume percentage (v/v) = V V u100
A B
§w· WB u100
Mass by volume percentage ¨ v ¸
© ¹ V (mL)
WB
Parts per million (ppm) = W W u10
6
A B
nA
2. Mole fraction of A, xA = n n
A B
nB
mole fraction of B, xB = n n
A B
xA + xB = 1
Moles of solute nB WB
3. Molarity (M) = Volume of solution in litre V( L) M B u V( L)
p u d u10
Normality
Eq. mass (solute)
8. Dilution formula : If the solution of some substance is diluted by adding solvent from volume V1 to volume V2, then
9. Molarity of a mixture : If V1 mL of a solution of molarity M1 is mixed with another solution of same substance with volume
V2 and molarity M2, then molarity of the resulting mixture of solution (M) can be obtained as :
M1V1 M 2 V2
M
V1 V2
where pA and pB are partial vapour pressures of component ‘A’ and component ‘B’ in the solution. p 0A and p0B are vapour
pressures of pure components ‘A’ and ‘B’ respectively.
pA0 p nB nB WB M A
xB u (For a dilute solution nB << nA)
p0A nA nB nA M B WA
p 0A p A
where xB is mole-fraction of solute and p 0A is relative lowering of vapour pressure.
K b u WB u 1000
MB
'Tb u WA
K f u WB u 1000
MB
'Tf u WA
S).
14. Osmotic pressure (S
S= cRT where ‘c’ is molarity.
15. Van’t Hoff factor.
p0A pA
(a) ix B (b) 'Tb = i Kbm
p0A
i 1
16. D wher D is degree of dissociation, ‘i’ is van’t Hoff factor, ‘n’ is number of ions produced per formula of the compound.
n 1
1 i
17. D
1
1
n
1 1
where D is degree of association, , n is the number of molecules of solute associate to form an associated molecule, 1.
n n
18. If i > 1, solute undergoes dissociation.
i < 1, solute undergoes association.
i = 1, neither association nor dissociation.
1
i , solute is dimer..
2
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