BITS Pilani

Pilani Campus

CHEM F211 : Physical Chemistry 1

Lecture - 12, 27 September 2022, Tuesday

Instructor: Dr. Satyajit Patra

 Topics covered in the last lecture

o One component phase equilibria

o Phase diagram for H2O

o Application of Clapeyron equation in phase transition

o Phase transition in the phase diagram of H2O

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Objectives of Today’s Lecture

o Phase transition in the phase diagram of water

o Equilibrium phase transitions of sulphur

• Solid-Solid phase transition
o Trouton’s Rule

o Order of phase transition

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 Phase transition in water phase diagram

At triple point O:

H2O (s) H2O (l) H2O (v)

• Vapor pressure of solid H2O becomes

equal to the vapor pressure of liquid
H2O.
• At triple point, O, the system in
nonvariant because variance, F = 0.
• At triple point, T = 0.00750C and P = 4.6
mm Hg.

o At triple point if the system is heated at constant volume, its

temperature and vapor pressure will not change until the entire solid
melted to liquid.
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 Phase transition in water phase diagram

• Vaporization Curve OA
P

Liquid water at 00C

kept in a bath

OA  Vaporization curve Liquid Vapor

o At a given temperature, the liquid and vapor will co-exist in equilibrium at
a specific pressure.
o Isothermal expansion: Increasing volume at constant T will decrease the
P, but at a given T, P is fixed (F =1). Some amount of liquid will vaporize to
keep the P constant.
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 Phase transition in water phase diagram

o If the isothermal expansion continued,

whole of the liquid will vaporize and the
system contains only the water vapor (1-
phase).
o Isothermal compression: Vapor
condenses to form liquid to keep the
vapor pressure constant.
o Eventually all the vapor condenses to
form liquid (1-phase).
o The piston will be in direct contact with
the liquid at this stage

The region above OA  Liquid phase

The region below OA  Vapor phase
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 Phase transition in water phase diagram

• Metastable Equilibrium
Rapid cooling of water along AO:

o At A’ metastable equilibrium between

liquid and vapor exist.
(Liquid Vapor)metastable
o At A’ liquid water is supercooled.

o The vapor pressure of metastable equilibrium along OA’ line is greater

than the vapor pressure of stable equilibrium (i.e OB line) at the same
temperature.

Metastable Stable transition is spontaneous

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Phase transition in water phase diagram

Metastable (ms) Stable (s) transition is spontaneous

∆𝜇 = 𝜇𝑠 − 𝜇𝑚𝑠 = −𝑣𝑒

s and ms are the chemical potential of the stable and metastable phases, respectively.

o In both stable and metastable phase, the substance is in equilibrium

with the vapor phase. So, we can write

𝜇𝑠 = 𝜇𝑣0 + 𝑅𝑇 ln 𝑃𝑠 (1)

𝜇𝑚𝑠 = 𝜇𝑣0 + 𝑅𝑇 ln 𝑃𝑚𝑠 (2)

𝜇𝑣0  Chemical potential of the vapor at standard state i.e when P = 1 atm
𝑃𝑠  Vapor pressure in the stable phase
𝑃𝑚𝑠 Vapor pressure in the metastable phase
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Phase transition in water phase diagram

𝜇𝑠 = 𝜇𝑣0 + 𝑅𝑇 ln 𝑃𝑠 (1)

𝜇𝑚𝑠 = 𝜇𝑣0 + 𝑅𝑇 ln 𝑃𝑚𝑠 (2)

𝑃𝑚𝑠 > 𝑃𝑠 , So, 𝜇𝑚𝑠 > 𝜇𝑠

Therefore, ∆𝜇 = 𝜇𝑠 − 𝜇𝑚𝑠 = −𝑣𝑒

Metastable (ms) Stable (s) transition is spontaneous

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 Equilibrium phase transitions of sulphur

Solid-Solid transition
Polymorphism
o Sometimes a substance can
exist in more than one
crystalline forms.
o Each form has its own
characteristic form

Example:
o Sulphur exist in two different
solid forms.

Rhombic sulphur and monoclinic sulphur

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 Equilibrium phase transitions of sulphur

o Sulphur exists in four different phases

i. Rhombic Sulphur (S)
ii. Monoclinic Sulphur (S)
iii. Liquid Sulphur (Sl)
iv. Sulphur vapor (Sv)

o Rhombic and monoclinic are the two

different solid form of sulphur.

• AB  Sublimation curve for S Sv

• BC  Sublimation curve for S Sv
• CD  Vaporization curve for Sl Sv
• BE  Transition curve for S S
• CE  Melting curve for S Sl
• EF  Melting curve for S Sl
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 Trouton‘s Rule

Standard entopries of vaporization of liquids

• A wide range of liquids give approximately same standard entopy of

vaporization (about 85 Jmol-1K-1).

• This empirical observation is called Trouton‘s rule.

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 Trouton‘s Rule

Derivation of Trouton‘s Rule from Clapeyron equation

Clapeyron equation for vaporization is

𝑑𝑃 𝐿𝑉
= (3)
𝑑𝑇 𝑇 𝑉𝑚,𝑔 − 𝑉𝑚,𝑙

Approximation: 𝑉𝑚,𝑔 − 𝑉𝑚,𝑙 ≈ 𝑉𝑚,𝑔

𝑑𝑃 𝐿𝑉 . 𝑃
Hence, = (4)
𝑑𝑇 𝑅𝑇 2
𝑑𝑃 𝐿𝑉 𝑑𝑇
⟹ = (5)
𝑃 𝑅 𝑇2

𝐿𝑉 ⇒ Latent heat of vaporization

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 Trouton‘s Rule

Derivation of Trouton‘s Rule from Clapeyron equation

𝑑𝑃 𝐿𝑉 𝑑𝑇
⟹ = (5)
𝑃 𝑅 𝑇2

Integrating equation 5 we obtained

𝐿𝑉 1
ln 𝑃 = − +𝐶 (6)
𝑅 𝑇

When P = 1 atm, T = Tb (normal boiling point)

𝐿𝑉
Hence, from equation 6 we can write = 𝑅𝐶 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (7)
𝑇𝑏
⇒ ∆𝑆𝑣0 = 𝑅𝐶 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (8)
∆𝑆𝑣0 ⇒ Standard entropy of vaporization
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Molecular Interpretation of Trouton’s rule

𝑉𝑓
∆𝑆 = 𝑛𝑅 ln (9)
𝑉𝑖
𝑉𝑖  Initial state 𝑉𝑓  Final state

o Most of the liquids undergo same change in volume upon vaporization

and that is why they have same entropy of vaporization.

Deviation from Trouton’s Rule

o Trouton’s rule do not take into account the intermolecular interactions.
o For liquids which have strong intermolecular interaction shows deviation
from Trouton’s rule. As for example H2O.
o H bonding in liquid water tend to organize the molecules. Upon
vaporization these H bonds breaks and entropy enhances due to greater
dispersal of energy and matter.
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Order of phase transition

Ehrenfest classification of phase transition

Let us consider a phase transition 𝛼 → 𝛽

𝜕𝜇𝛽 𝜕𝜇𝛼
− = 𝑉𝑚,𝛽 − 𝑉𝑚,𝛼 = ∆𝑉𝑡𝑟𝑠 (9)
𝜕𝑃 𝑇
𝜕𝑃 𝑇

𝜕𝜇𝛽 𝜕𝜇𝛼 ∆𝐻𝑡𝑟𝑠

− = −𝑆𝑚,𝛽 + 𝑆𝑚,𝛼 = ∆𝑆𝑡𝑟𝑠 = (10)
𝜕𝑇 𝑃
𝜕𝑇 𝑃
𝑇

o ∆𝑉𝑡𝑟𝑠 and ∆𝐻𝑡𝑟𝑠 are non-zero quantity.

o Slope of the plot of  against P or T would be different on either side of
transition
o First order transition: First order derivative of  with respect to P or T
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Order of phase transition

Ehrenfest classification of phase transition

o First order transition: First order derivative of  with respect to P or T
would be discontinuous.
o Second order transition: Second order derivative of  with respect to P
or T would be discontinuous but first order derivative of  is continuous.

1st order transition

2nd order transition

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Order of phase transition

Example of a second order transition:

Change in symmetry of crystal lattice from Tetragonal to Cubic Symmetry

No change in interaction energy between the atoms and hence no change

in enthalpy for this transition.
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