A general property of exact dierentials :

consider f (x , y )and df = gdx + hdy , where g ≡ g (x , y ) and h ≡ q (x , y )

A general property of exact dierentials :
consider f (x , y )and df = gdx + hdy , where g ≡ g (x , y ) and h ≡ q (x , y ) e.g., for
U (S , V ), dU = TdS − pdV
A general property of exact dierentials :
consider f (x , y )and df = gdx + hdy , where g ≡ g (x , y ) and h ≡ q (x , y ) e.g., for
U (S , V ), dU = TdS − pdV when df is an exact dierential,
∂g ∂2f ∂2f
= ∂∂ xh y
 

∂y = =
x ∂y ∂x ∂x ∂y
| {z }
both x and y, vary
Maxwell relations :
for reversible changes in systems with no non-mechanical work
Maxwell relations :
for reversible changes in systems with no non-mechanical work
dU = TdS − pdV
∂T ∂p

 
∂V S =− ∂S
V
Maxwell relations :
for reversible changes in systems with no non-mechanical work
dU = TdS − pdV
∂T ∂p

 
∂V S =− ∂S
V
dH = TdS + Vdp
∂T ∂V
 

∂p = ∂S p
S
Maxwell relations :
for reversible changes in systems with no non-mechanical work
dU = TdS − pdV
∂T ∂p

 
∂V S =− ∂S
V
dH = TdS + Vdp
∂T ∂V
 

∂p = ∂S p
S
dA = −SdT − pdV
∂p ∂S
 

∂T = ∂V T
V
Maxwell relations :
for reversible changes in systems with no non-mechanical work
dU = TdS − pdV
∂T ∂p

 
∂V S =− ∂S
V
dH = TdS + Vdp
∂T ∂V
 

∂p = ∂S p
S
dA = −SdT − pdV
∂p ∂S
 

∂T = ∂V T
V
dG = Vdp − SdT
∂V ∂S

 
∂T p=− ∂p
T
Another denition of temperature
Another denition of temperature
∂S
dU = TdS − pdV =⇒ T1 =


∂U V
Another denition of temperature
∂S
dU = TdS − pdV =⇒ T1 =


∂UV
dH = TdS + Vdp =⇒ T1 = ∂∂HS p


Thermodynamic equation of state :
dU = TdS − pdV
∂U ∂S ∂S
∂V T = T ∂V T − p or, πT = T T −p




∂V
Thermodynamic equation of state :
dU = TdS − pdV
∂U ∂S
∂ V T = T ∂ V T − p or, = T ∂∂VS T − p




 T
π
∂p
Using Maxwell relation = ∂∂VS T


∂T
V

πT = T ∂∂Tp −p
 
V
Thermodynamic equation of state :
dU = TdS − pdV
∂U ∂S
∂ V T = T ∂ V T − p or, = T ∂∂VS T − p




 T
π
∂p
Using Maxwell relation = ∂∂VS T


∂T
V

πT = T ∂∂Tp −p
 
V

For perfect gas, show that this leads to πT = 0

Thermodynamic equation of state :
dU = TdS − pdV
∂U ∂S
∂ V T = T ∂ V T − p or, = T ∂∂VS T − p




 T
π
∂p
Using Maxwell relation = ∂∂VS T


∂T
V

πT = T ∂∂Tp −p
 
V

For perfect gas, show that this leads to πT = 0

Find for van der Waals gas., πT = a Vn 2
2
Thermodynamic equation of state :
dU = TdS − pdV
∂U ∂S
∂ V T = T ∂ V T − p or, = T ∂∂VS T − p




 T
π
∂p
Using Maxwell relation = ∂∂VS T


∂T
V

πT = T ∂∂Tp −p
 
V

For perfect gas, show that this leads to πT = 0

Find for van der Waals gas., πT = a Vn 2 > 0 =⇒ ∂U
2
T >0


∂V
Gibbs' Free energy and entropy
Gibbs' Free energy and entropy

∂G
p = −S < 0


∂T
Gibbs' Free energy and entropy

∂G
= −S < 0


∂ T p
∂G
∂p =V >0
T
 = −Sm
 
chemical potential and phase equilibrium : ∂µ
∂T
p
sublimation before melting
 ∂G
=V >0
 
∂p
T
Gibbs-Helmholtz equation :
∂G G −H


∂T p= T
G]
 
= − TH2
∂[ T
Use this to show : ∂T
p

∂ [ ∆TG ]
 
= −∆ H
∂T T2
p
 Rpf
Change in G with p : G (pf ) = G (pi ) + Vdp
pi
 Rpf
Change in G with p : G (pf ) = G (pi ) + Vdp
pi
for condensed phases gases
 Rpf
Change in G with p : G (pf ) = G (pi ) + Vdp
pi
for condensed phases gases
 Rpf
Change in G with p : G (pf ) = G (pi ) + Vdp
pi
for condensed phases gases

Rpf dp pf
Gm (pf )=Gm (pi)+Vm (pf − pi) Gm (pf )=Gm (pi)+RT p =Gm (pi)+ RT ln pi
pi
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pp⊖
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p′ p ′
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p ′ p ′

Rp
(Vm − Vperfect, m ) dp = RT ln ff′ − ln pp′
 

p′
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p ′ p ′

Rp
(Vm − Vperfect, m ) dp = RT ln ff′ − ln pp′
 

p′
p
or, ln pf − ln pf ′ = RT
1 R (V − V
perfect, m ) dp
′
m
p′
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p ′ p ′

Rp
(Vm − Vperfect, m ) dp = RT ln ff′ − ln pp′
 

p′
p
or, ln pf − ln pf ′ = RT
1 R (V − V
perfect, m ) dp
′
m
p′
Lt f → p
p →0
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p ′ p ′

Rp
(Vm − Vperfect, m ) dp = RT ln ff′ − ln pp′
 

p′
p
or, ln pf − ln pf ′ = RT
1 R (V − V
perfect, m ) dp
′
m
p′
p
Lt f → p =⇒ ln pf = RT 1 R (V − V
m perfect, m ) dp
p →0 0
molar Gibbs energy vs p : Gm (p ) = Gm⊖ + RT ln pf⊖ ; f (fugacity)= ϕ .p
|{z}
fugacity coe
Rp
Vm dp = Gm (p)− Gm (p ) = Gm + RT ln pf⊖ Gm + RT ln pf⊖
n o n ′
o
′ ⊖ ⊖
−
p′

Rp Rp dp p
Vperfect, m dp = RT p = RT ln p′
p ′ p ′

Rp
(Vm − Vperfect, m ) dp = RT ln ff′ − ln pp′
 

p′
p
or, ln pf − ln pf ′ = RT
1 R (V − V
perfect, m ) dp
′
m
p′
p
Lt f → p =⇒ ln pf = RT 1 R (V − V
m perfect, m ) dp
p →0 0
Rp
or, ln ϕ = Z − p dp
1
0
phase : form of matter that is uniform throughout in chemical composition and
physical state
P =# phases in a system
Phase equilibria - triple point (T3 ) and critical point (TC )

P=1 P=1

.
P=1
Along each curve, P=2
at triple point, P=3

.
phase : form of matter that is uniform throughout in chemical composition and
physical state
P =# phases in a system
Phase equilibria - triple point (T3 ) and critical point (TC )

P=1 P=1

.
P=1
Along each curve, P=2
at triple point, P=3

.
For water : T3 = 273.16 K and 611 Pa (6.11 mbar)
▶ Triple point marks the lowest pressure at which a liquid phase can exist
▶ If the slope of the solidliquid phase boundary is positive
▶ then triple point also marks the lowest temperature at which the liquid
can exist
▶ the critical temperature is the upper limit
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases

single-component, single-phase
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases

single-component, single-phase

F =1−1+2=2
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases

single-component, single-phase

F =1−1+2=2
single-component, two-phases
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases

single-component, single-phase

F =1−1+2=2
single-component, two-phases
F =1−2+2=1
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases

single-component, single-phase

F =1−1+2=2
single-component, two-phases
F =1−2+2=1
phases α and β in equilibr. at given p , T
µα (p , T ) = µβ (p, T )
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component

single-component, single-phase

F =1−1+2=2
single-component, two-phases
F =1−2+2=1
phases α and β in equilibr. at given p , T
µα (p , T ) = µβ (p, T )
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component
three-phases
single-component, single-phase

F =1−1+2=2
single-component, two-phases
F =1−2+2=1
phases α and β in equilibr. at given p , T
µα (p , T ) = µβ (p, T )
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component
three-phases
single-component, single-phase F =1−3+2=0
F =1−1+2=2
single-component, two-phases
F =1−2+2=1
phases α and β in equilibr. at given p , T
µα (p , T ) = µβ (p, T )
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component
three-phases
single-component, single-phase F =1−3+2=0
phases α, β and γ in equilibr. at
F =1−1+2=2 given p , T ,
single-component, two-phases µ (α, p , T )=µ (β, p , T)
F =1−2+2=1 = µ (γ, p , T )
phases α and β in equilibr. at given p , T
µα (p , T ) = µβ (p, T )
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component
three-phases
single-component, single-phase F =1−3+2=0
phases α, β and γ in equilibr. at
F =1−1+2=2 given p , T ,
single-component, two-phases µ (α, p , T )=µ (β, p , T)
F =1−2+2=1 = µ (γ, p , T )
phases α and β in equilibr. at given p , T two eqns. for two unknowns p
µα (p ,T ) = µβ (p, T ) and T
eqn. relates p and T ,
so only one variable is independent
 Phase Rule : F = C − P + 2
F =#degrees of freedom, C =#components, P = #phases
single-component
three-phases
single-component, single-phase F =1−3+2=0
phases α, β and γ in equilibr. at
F =1−1+2=2 given p , T ,
single-component, two-phases µ (α, p , T )=µ (β, p , T)
F =1−2+2=1 = µ (γ, p , T )
phases α and β in equilibr. at given p , T two eqns. for two unknowns p
µα (p ,T ) = µβ (p, T ) and T
eqn. relates p and T , xed soln.
so only one variable is independent so no variation possible
Typical phase diagram
 Experimental phase diagrams
H2 O CO2 He
 Experimental phase diagrams
H2 O CO2 He
 Experimental phase diagrams
H2 O CO2 He
Phase transition : Thermal analysis and Cooling curve
Phase transition : Thermal analysis and Cooling curve

metastable phases : Kinetic barriers

Response of melting to applied pressure
Response of melting to applied pressure
= Vm
 
pressure-dependence of chemical potential : ∂µ
∂p
T
usual liquids :Vm (l ) > Vm (s ) water : Vm (l ) < Vm (s )
for pressure induced change in gas-liq equilibr.
d µ(g) = d µ(l)
for pressure induced change in gas-liq equilibr.
d µ(g) = d µ(l) or,RTdp = V (l )dp
p m
integrating from an initial pvap = p ∗ to p , we have, ln pp∗ = VRT
m ( l ) ∆p
vap

Pressure is applied to condensed phase

for pressure induced change in gas-liq equilibr.
d µ(g) = d µ(l) or,RTdp = V (l )dp
p m
integrating from an initial pvap = p ∗ to p , we have, ln pp∗ = VRT
m ( l ) ∆p
vap

Pressure is applied to condensed phase

either (a) by compressing directly
or (b) by subjecting it to an inert
pressurizing gas
for pressure induced change in gas-liq equilibr.
d µ(g) = d µ(l) or,RTdp = V (l )dp
p m
integrating from an initial pvap = p ∗ to p , we have, ln pp∗ = VRT
m ( l ) ∆p
vap

Pressure is applied to condensed phase

either (a) by compressing directly
or (b) by subjecting it to an inert
pressurizing gas
When pressure is applied, the vapour
pressure of the condensed phase increases
 ∂p ∂S ∆trs S
 
location of phase boundaries :


∂T = ∂V T = ∆trs V
V
 ∂p ∂S ∆trs S
 
location of phase boundaries :


∂T = ∂V T = ∆trs V
V

dp = ∆fus H
solid/liq. : dT T ∆fus V
 ∂p ∂S ∆trs S
 
location of phase boundaries :


∂T = ∂V T = ∆trs V
V

dp = ∆fus H
solid/liq. : dT T ∆fus V
When pressure is applied to a system
with two phases in equilibrium (at a), the
equilibrium is disturbed
It can be restored by changing T , moving
state of system to b
 ∂p ∂S ∆trs S
 
location of phase boundaries :


∂T = ∂V T = ∆trs V
V

dp = ∆fus H
solid/liq. : dT T ∆fus V
When pressure is applied to a system
with two phases in equilibrium (at a), the
equilibrium is disturbed
It can be restored by changing T , moving
state of system to b
relation between dp and dT ensures that
system remains in equilibrium as either
variable is changed