EQUILIBRIUM PHASES OF PURE SUBSTANCE

For a pure substance , the equilibria criterium can be writtenas :

μ αi =μ βi

For infinitesimal changes of temperature (T ) and pressure (P )

∂μ αi =∂μ βi

Writing chemical potential as a function of T and P , we have :

α α α
∂μi =V ∗dP−S ∗dT
∂μ βi =V β∗dP−S β∗dT
β α β α
(V −V )∗dP=(S −S )dT

Convention is to goes from α phase to β phase

β α
(V −V )=Δ V
( Sβ−S α )=Δ S

Rearringing
∂P Δ S
= Clapeyron equation
∂T Δ V

1
 Clapeyron Equation
The Clapeyron equation is very useful for the qualitative and quantitative description of
phases equilibrium of a pure substance. Below is a qualitative description of the Clapeyron
equation for a pure substance:
Transition solid ( α )−liquid( β )
Solid ⇋ liquid
Δ S melting >0 ; it is always positive for all substances .
Δ V melting >0 ; it is positive for most substances and negative for some of them .
For example , the water ( H 2 O) has a Δ V melting <0.
∂P
Then , can take positve or negative values , but water would have a negative slope .
∂T

Transition solid ( α )−vapor ( β )

Solid ⇋ vapor
Δ S sublimation >0 ;it is always positive for all substances .
ΔV sublimation >0 ; it is always positive for all substances ..
∂P
>0 ; it is positive always .
∂T

Transition liquid ( α )−vapor ( β )

Liquid ⇋ vapor
Δ S vaporization >0 ; it is always positive for all substances .
Δ V vaporization >0 ; it is always positive for all substances .
∂P
>0 ; it is positve always .
∂T 2
 Phase Diagrams of Pure Substances

Figure 1. Phase Diagram for CO2 Figure 2. Phase Diagram for H2O

Mahshid Kalani Robiah Yunus. Application of supercritical https://courses.lumenlearning.com/chemi

antisolvent method in drug encapsulation: a review. nter/chapter/phase-diagram-for-water/
International Journal of Nanomedicine · July 2011

Calculations of Clapeyron Equations

Transition solid−liquid ∂P Δ H melting
∂P ΔS =
= ∂T (T Δ V melting )
∂T ΔV ΔH
∂Q P ∂ P= ∂T
∂ S= (T ΔV melting )
T
Δ H melting ln ( T 2 /T 1 )
∂Q P=∂ H P P 2−P1=Δ P=
Δ V melting 3
 Transition solid−vapor or liquid−vapor

∂P Δ H subl /vap
=
∂ T (T ΔV subl / vap )
Δ H subl /vap
∂ P= ∂T
(T Δ V subl /vap )
Generally V vapor ≫V liquid /solid
At low presures the ideal gas can be used PV =RT , replacing Δ V por V gas ideal
∂ P Δ H subl / vap P
=
∂T R T2
Under assumption that Δ H subl / vap no dependent of T
∂ P Δ H subl / vap ∂ T
= Clausius−Clapeyron equation .
P RT
2

P2 T2
∂P Δ H subl /vap ∂T
∫ P ∫ RT 2=
P
1 1 T
−Δ H subl / vap 1 1
ln ( P 2 / P1 )=
R ( −
)
T 2 T1
This last equation is a linear equation( y=mx +b) .
Where :
ln (P 2 / P1 ) dependent variable y
1
independent variable x .
T2
4
Δ H subl =Δ H vap +Δ H melting