Arindam das

Bs-15 253
B.sc chemistry honors
supervised by :-
Dr. s Muni
 Index
s.no contents Page no.

1
Introduction
2 Colligative properties
3 Relative lowering of vapour pressure
4 Boiling and freezing point
5 Boiling point elevation
6 Freezing point depression
7 Osmotic pressure
Introduction

 In chemistry, colligative properties are properties of

solutions that depend on the ratio of the number of
solute particles to the number of solvent molecules
in a solution, and not on the nature of the chemical
species present. The number ratio can be related to
the various units for concentration of solutions. The
assumption that solution properties are
independent of nature of solute particles is only
exact for ideal solutions, and is approximate for
dilute real solutions. In other words, colligative
properties are a set of solution properties that can be
reasonably approximated by assuming that the
solution is ideal.
 Here we consider only properties which result from
the dissolution of nonvolatile solute in a volatile
liquid solvent. They are essentially solvent
properties which are changed by the presence of
the solute. The solute particles displace some
solvent molecules in the liquid phase and
therefore reduce the concentration of solvent, so
that the colligative properties are independent of
the nature of the solute. The word colligative is
derived from the Latin colligatus meaning bound
together.
 Colligative properties
 Colligative properties include:

 Relative lowering of vapor pressure

 Elevation of boiling point
 Depression of freezing point
 Osmotic pressure
 For a given solute-solvent mass ratio, all colligative
properties are inversely proportional to solute molar mass.
 Measurement of colligative properties for a dilute solution
of a non-ionized solute such as urea or glucose in water or
another solvent can lead to determinations of relative
molar masses, both for small molecules and for
 polymers which cannot be studied by other means.
Alternatively, measurements for ionized solutes can
lead to an estimation of the percentage of
dissociation taking place.
 Colligative properties are mostly studied for dilute
solutions, whose behavior may often be approximated
as that of an ideal solution.
 Relative lowering of vapour
pressure
 Experimentally, we know that the vapor pressure of the
solvent above a solution containing a non-volatile solute
(i.e., a solute that does not have a vapor pressure of its own)
is directly proportional to the mole fraction of solvent in
the solution. This behavior is summed up in Raoult's Law:
 Psolvent = XsolventPosolventwhere:
 Psolvent is the vapor pressure of the solvent above the
solution,
Xsolvent is the mole fraction of the solvent in the
solution, and
Posolvent is the vapor pressure of the pure solvent.
 when Xsolvent = 1 (pure solvent), Psolvent = Posolvent, and
 when Xsolvent < 1 (solute(s) present), Psolvent < Posolvent
(i.e., the vapor pressure of the solvent above the solution is
lower than the vapor pressure above the pure solvent).
 Volatile Solutes
 A volatile solute (i.e., a solute that has a vapor pressure of
its own) will contribute to the vapor pressure above a
solution in which it is dissolved. The vapor pressure above
a solution containing a volatile solute (or solutes) is equal
to the sum of the vapor pressures of the solvent and each
of the volatile solutes.
 Psolvent = XsolventPosolvent
 Psolute = XsolutePosolute
 Psolution = Psolvent + Psolute + ... = XsolventPosolvent +
XsolutePosolute + ...
Boiling point and freezing point
 Addition of solute to form a solution stabilizes the solvent in the
liquid phase, and lowers the solvent chemical potential so that
solvent molecules have less tendency to move to the gas or solid
phases. As a result, liquid solutions slightly above the solvent
boiling point at a given pressure become stable, which means that
the boiling point increases. Similarly, liquid solutions slightly
below the solvent freezing point become stable meaning that the
freezing point decreases. Both the boiling point elevation and the
freezing point depression are proportional to the lowering of vapor
pressure in a dilute solution.
 These properties are colligative in systems where the solute is
essentially confined to the liquid phase. Boiling point elevation
(like vapor pressure lowering) is colligative for non-volatile solutes
where the solute presence in the gas phase is negligible. Freezing
point depression is colligative for most solutes since very few
solutes dissolve appreciably in solid solvents.
Boiling point elevation
(ebullioscopy)
 The boiling point of a liquid at a given external pressure is the temperature ( T b {\displaystyle T_{\rm
{b}}} ) at which the vapor pressure of the liquid equals the external pressure. The normal boiling point
is the boiling point at a pressure equal to 1 atm.
 The boiling point of a pure solvent is increased by the addition of a non-volatile solute, and the
elevation can be measured by ebullioscopy. It is found that
 Δ T b = T b ( s o l u t i o n ) − T b ( s o l v e n t ) = i ⋅ K b ⋅ m {\displaystyle \Delta T_{\rm {b}}=T_{\rm
{b}}(solution)-T_{\rm {b}}(solvent)=i\cdot K_{b}\cdot m}
 Here i is the van 't Hoff factor as above, Kb is the ebullioscopic constant of the solvent (equal to
0.512 °C kg/mol for water), and m is the molality of the solution.
 The boiling point is the temperature at which there is equilibrium between liquid and gas phases. At
the boiling point, the number of gas molecules condensing to liquid equals the number of liquid
molecules evaporating to gas. Adding a solute dilutes the concentration of the liquid molecules and
reduces the rate of evaporation. To compensate for this and re-attain equilibrium, the boiling point
occurs at a higher temperature.
 If the solution is assumed to be an ideal solution, Kb can be evaluated from the thermodynamic
condition for liquid-vapor equilibrium. At the boiling point the chemical potential μA of the solvent
in the solution phase equals the chemical potential in the pure vapor phase above the solution.
 μ A ( T b ) = μ A ⋆ ( T b ) + R T ln x A = μ A ⋆ ( g , 1 a t m ) {\displaystyle \mu _{A}(T_{b})=\mu
_{A}^{\star }(T_{b})+RT\ln x_{A}\ =\mu _{A}^{\star }(g,1atm)} ,
 where the asterisks indicate pure phases. This leads to the result K b = R M T b 2 / Δ H v a p
{\displaystyle K_{b}=RMT_{b}^{2}/\Delta H_{\mathrm {vap} }} , where R is the molar gas constant, M
is the solvent molar mass and ΔHvap is the solvent molar enthalpy of vaporization.[4]
Freezing point depression
(cryoscopy)
 The freezing point ( T f {\displaystyle T_{\rm {f}}} ) of a pure solvent is lowered
by the addition of a solute which is insoluble in the solid solvent, and the
measurement of this difference is called cryoscopy. It is found that
 Δ T f = T f ( s o l u t i o n ) − T f ( s o l v e n t ) = − i ⋅ K f ⋅ m {\displaystyle \Delta
T_{\rm {f}}=T_{\rm {f}}(solution)-T_{\rm {f }}(solvent)=-i\cdot K_{f}\cdot m}
 Here Kf is the cryoscopic constant (equal to 1.86 °C kg/mol for the freezing
point of water), i is the van 't Hoff factor, and m the molality.
 In the liquid solution, the solvent is diluted by the addition of a solute, so that
fewer molecules are available to freeze. Re-establishment of equilibrium is
achieved at a lower temperature at which the rate of freezing becomes equal to
the rate of liquefying. At the lower freezing point, the vapor pressure of the
liquid is equal to the vapor pressure of the corresponding solid, and the
chemical potentials of the two phases are equal as well. The equality of
chemical potentials permits the evaluation of the cryoscopic constant as K f = R
M T f 2 / Δ H f u s {\displaystyle K_{f}=RMT_{f}^{2}/\Delta H_{\mathrm {fus}
}} , where ΔHfus is the solvent molar enthalpy of fusion.
Osmotic pressure
 The osmotic pressure of a solution is the difference in pressure between the solution and the pure liquid solvent when
the two are in equilibrium across a semipermeable membrane, which allows the passage of solvent molecules but not
of solute particles. If the two phases are at the same initial pressure, there is a net transfer of solvent across the
membrane into the solution known as osmosis. The process stops and equilibrium is attained when the pressure
difference equals the osmotic pressure.
 Two laws governing the osmotic pressure of a dilute solution were discovered by the German botanist W. F. P. Pfeffer
and the Dutch chemist J. H. van’t Hoff:
 The osmotic pressure of a dilute solution at constant temperature is directly proportional to its concentration.
 The osmotic pressure of a solution is directly proportional to its absolute temperature.
 These are analogous to Boyle's law and Charles's Law for gases. Similarly, the combined ideal gas law, p V = n R T
{\displaystyle pV=nRT} , has as analog for ideal solutions Π V = n R T i {\displaystyle \Pi V=nRTi} , where Π
{\displaystyle \Pi } is osmotic pressure; V is the volume; n is the number of moles of solute; R is the molar gas constant
8.314 J K−1 mol−1; T is absolute temperature; and i is the Van 't Hoff factor.
 The osmotic pressure is then proportional to the molar concentration c = n / V {\displaystyle c=n/V} , since
 Π = n R T i V = c R T i {\displaystyle \Pi ={\frac {nRTi}{V}}=cRTi}
 The osmotic pressure is proportional to the concentration of solute particles ci and is therefore a colligative property.
 As with the other colligative properties, this equation is a consequence of the equality of solvent chemical potentials of
the two phases in equilibrium. In this case the phases are the pure solvent at pressure P and the solution at total
pressure P + π
