Phase Rule

Sulphur System
Upma Shrivastava
Asstt. Prof.
Govt. V.Y.T.PG.Auto.College
Durg
Chhattisgarh
 B.Sc Part II, Paper III, Unit IV Phase rule – Sulphur System

Sulphur system

It is one component system because only one chemical symbol used to

express composition of all phases present in this system (S) .

Four phases are present in this system:-

(1) Sulphur Rhombic (Solid) – SR

(2) Sulphur monoclinic (Solid) – SM
(3) Sulphur liquid – SL
(4) Sulphur vapour (gas) – SV
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 Phase Rule applied for this system :-

F= C-P+2 or F+P= C+2

F= Degree of freedom
C= No of components
P= No of phases

Here no. of component (C) = 1

So, F+P = 1+2 = 3
minimum no of phases in any system = 1
and minimum no of degree of freedom = 0

so if F=0 then P=3

F=1 then P=2
F=2 then P=1
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Maximum no of degree of freedom = 2 which is temperature and pressure

Here concentration is constant for one component system.

So we draw P-T graph for this system. Before draw a phase diagram we have
some information about this system.

(1) At room temp (25°C) SR is stable.

(2) below 50°C SV not exist.
(3) transition temp of SR and SM is 95.6°C at 1 atm.
(4) m.p of SM = 120°C at 1 atm.
(5) b.p of SL = 444°C at 1 atm.
(6) metastable m.p of SR = 115°C at 1 atm.
(7) density of SR = 2.07 g/cm3, SM = 1.96 g/cm3
(8) When we increase pressure m.p. of SM , transition temp of SM and
SR ,metastable m.p. of SR also increases (151°C at 1288 atm)
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 Phase Diagram

E
151°C, 1288 atm

SR SL

M
/S

L
SM /S
R
S

L
S /S
R
SM
H
1 atm A C
B D
SR/SV SM/SV SL/SV

SV
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50°C 95.6°C 115°C 120°C 444°C
First of all we explain, curves, triple points then areas.

Curves:-
1. AB curve (sublimation curve of SR )
Two phase SR and SV present in equilibrium
SR ⇌ SV P=2
Phase rule,
F= C-P+2
F= 1-2+2
F= 1

only one variable (temperature or pressure) required to explain any point of

this curve
Below 50°C SV not exist so, minimum value of ‘A’ point is 50°C and ‘B’
point is 95.6°C which is transition temp of SR and SM
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2. BC curve (Sublimation curve of SM )

Two phases SM and SV present in equilibrium

SM ⇌ SV
P = 2 and F = 1
‘C’ is m.p. of SM = 120°C at 1 atm. pressure

3. CD curve (Vapour pressure curve of SL )

Two phases SL and SV present in equilibrium

SL ⇌ SV
P= 2 and F= 1
here D is b.p. of SL = 444°C at 1 atm. pressure.
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4. BE curve (transition curve of SR and SM )
SR and SM present in equilibrium
SR ⇌ SM
P= 2, F= 1

Slope of BE curve is away from pressure axis which shows that transition
temp. increases with pressure.
Transition temp. at 1atm. = 96.5°C
and at 1288 atm. = 151°C
Reason:- Density of SR = 2.07 g/cm3
and SM = 1.96g/ cm3
According to Le Chatelier’s principle when we increase pressure, equilibrium
shifted to that direction where volume is less,
Volume of SR is less than SM Hence when we increase pressure, transition
temp. also increases.
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5. CE curve (Melting curve of SM )

SM and SL present in equilibrium

SM ⇌ SL
P= 2, F= 1

slope of CE curve is away from pressure axis which shows that m.p. pf S M
increases with pressure

m.p. at 1 atm. = 120°C

at 1288 atm. = 151°C

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Metastable curves :-
1. BH - metastable sublimation curve of S R

SR ⇌ SV
P= 2, F=1
point H = 115°C, m.p. of SR at 1 atm.
2. CH - metastable vapour pressure curve of S L
SL ⇌ SV
P= 2 , F = 1
3. HE – metastable melting curve of SR
S R ⇌ SL
P=2, F=1
This curve shows that m.p. of SR increases with pressure
at 1 atm. = 115°C
and at 1288 atm. = 151°C
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EG curve
Regular melting curve of SR

Triple points
Point Phases F Temp. & Pressure
B -Transition Temp. of SR , SM SR , SV , SM = 3 0 96.5°C at 1 atm.
C – Melting Point of SM SM , SV , SL = 3 0 120°C at 1 atm.
E SR , SM , SL = 3 0 151°C at 1288 atm.
H – Metastable m.p. of SR SR , SL , SV = 3 0 115°C at 1 atm.

Triple Points are Invariant System

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 Areas
1. ABEG – Phase – SR
P=1, F=2, bivariant System

2. DCEG – Phase – SL
P=1, F=2, bivariant System

3. ABCD – Phase SV
P=1, F=2, bivariant System

4. BCE – Phase SM
P=1, F=2, bivariant System
To Explain any point in area we required both variable pressure and temp.

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Thank You
Upma Shrivastava
Asstt. Prof.
Govt. V.Y.T.PG.Auto.College
Durg
Chhattisgarh

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