Vapour

• Vapour is the gas phase of substance that is

normally liquid at room temperature

• Some evaporation occurs at all temperature

• substance evaporates easily if IMF ( inter

molecular forces) is weak.
 Vapour Pressure
• Characteristic property of all solids & liquids
• For solids vapour pre is very low at normal conditions

Open system closed system

Evaporation continues until all liquid is gone
Fig b:
Rate of evaporation = rate of condensation
System appears static due to equilibrium
Contd…

Open System
• Evaporation continues until all liquid is gone.
Closed System
• Rate of evaporation = rate of condensation
• System appears static due to equilibrium
 Vapour Pressure

• Pressure exerted by vapour over its liquid

• Depend the temperature.
• When temp increases VP increases
• Does not depend on how much liquid is
present
• Depend on inter molecular forces (IMF)
all liquids: as T ↑ the VP ↑

Boiling
Point
 Boiling Point
• Temperature at which:
VP liquid = external atmospheric Pressure

• Normal Boiling Point:

temp at which VP liquid = 1 atm

• Substances with high boiling points have strong IMF

 Boiling vs. Evaporation
BOILING EVAPORATION
• occurs throughout • occurs at surface of
liquid liquid (or solid)
• occurs at definite T • occurs at all T
• occurs at constant T • liquid cools off as
evaporates
• only spontaneous • spontaneous all the time
when VP = external
pressure
 Boiling and Pressure
• If external pressure is greater than 1atm, boiling
point of water is greater than 100oC

• If external pressure is less than 1atm , the boiling

point of water is less than 100oC
 Inter Molecular Forces in Liquids
WEAK FORCES STRONG FORCES

• High VP • Low VP
• High rate evaporation • Low rate evaporation
• Low bp • High bp
 Clausius-Clapeyron Equation
• Predicts the dependence of vapour pre on temperature

In which:
 P1 and P2 are the vapor pressures at T1 and T2
respectively
 T is temp given in units Kelvin

 R is the gas constant (8.314 J/K mol)

 ∆Hvap is the molar heat of vaporization
 Derivation of the Equation

This diagram represents a generalized

phase diagram.
 The line acts as a phase line, or a
coexistent curve, separating phases
α and β.
 At all points on the line, phases α
and β are in equilibrium.
 Since the phases are in equilibrium
along the line,∆G=0
 ∆G=∆H-T∆S
 Since ∆G=0, ∆S=∆H/T
 The slope of the curve in the case
of the phase diagram is dp/dT.
 To represent the derivative along the
coexistent curve, we write:
Derivation Contd….

• We use the cyclic rule, a rule

of calculus, to find:

We have ∆G=∆H-T∆S.
We can also represent this as ∆G=P∆V-T∆S
(thermodynamic relation).
Taking the derivative of both sides, we find that
d∆G=∆VdP-∆SdT
We have two variables in this differential
equation: T and P. To solve this, we treat this in
two cases. First, we consider P as a constant.
Then, we consider T a constant.
 Contd Derivation

• Substituting in the equation we found

through the cyclic rule, we find:

As ∆S=∆H/T, this can be written as:

This equation is known as Clapeyron
equation.
Contd Derivation….
The Clapeyron equation is can be modified to get Clausius
Clapeyron equation for vapour-liquid equilibrium by using the
following assumptions
• The latent heat of vapourization is constant and independent
of temperature.
• The molar volume of liquid is negligible compared to that of
vapour
• The vapour behaves as an ideal gas
• Then ΔV = VG- VL = VG = RT/P

• Substitute for ΔV in Clapeyron equation

() =
 Contd Derivation…..

• Rearranging and integrating above equation

between the limits
at T = T1, P = P1 and
T = T2, P = P2, we get
ln = ( - )
• The above equation is Clausius Clapeyron equation
and is valid only for moderate temp ranges.
• At high vapour pre , the vapour deviate from ideality
• Constant latent heat of vapourization is only at
moderate temp
 Common Applications
• Calculation of the vapor pressure of a liquid at any
temperature (with known vapor pressure at a given
temperature and known heat of vaporization)
• Calculation of the heat of a phase change
• Calculation the boiling point of a liquid at a non standard
pressure
• Reconstruct a phase diagram
• Determine if a phase change will occur under certain
circumstances
 Antoine equation
• Experimentally measured vapour pressures at different
temperatures used to fit the Antoine Equation:

where T = temperature (Kelvin) , po is Vapour pressure and

A & B are Antoine constants (pressure in atmospheres).
Plotting ln p vs 1/T, with slope = B and
o

intercept = A.
 Vapour Pressure plots
Equal temp reference
substance plots
• The log of vp of a substance
is plotted against log of vp
of reference substance,
both at same temp.
• Water is usually chosen as
reference substance.
• Eg. Cox chart
Equal pre reference substance plots
• The temp of the substance
at given vp is plotted against
temp of reference
substance at same vp
• Eg. Duhring lines
Duhring lines