Solid-Liquid Equilibrium

Engr. Paul Gabriel E. Lerona

Topic 18
Adamson University
[email protected]

June 19, 2022

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Overview I

1 Phase Equilibrium

2 Cases

3 Solid-Solid-Liquid Equilibrium

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 Phase Equilibrium

Phase Equilibrium

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 Phase Equilibrium

Phase Equilibrium: Criterion I

For a liquid and solid phase:

fˆi l = fˆi s (i = 1, 2, . . . N)

xi γil fi l = zi γis fi s

Define the ratio:

fi S
ψi ≡
fi l

§i γil = zi γIs ψi

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 4 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion II

fi S
Evaluating the ratio: ψi ≡ fi l

fi S (T , P) fi S (T , P) fi S (Tmi , P) fi l (Tmi , P)
= · · l
fi l (T , P) fi S (Tmi , P) fi l (Tmi , P) fi (T , P)

fi S (T , P) fi S (T , P) fi l (Tmi , P)
= · = ψi
fi l (T , P) fi S (Tmi , P) fi l (T , P)

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 5 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion III

Evaluating fi at a particular phase:
fi GR
ln φi = ln = i
P RT

GiR
ln fi = + ln P
RT

"
#
∂ GiR /RT HiR
 
∂ ln fi
= =−
∂T P ∂T RT 2
P

Evaluating the ratio:

T
HiR
Z
fi (T , P)
= exp − dT
fi (Tmi , P) Tmi RT 2

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 6 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion IV

For a liquid and solid:

fi l (T , P) T
HiR,l
Z
= exp − dT
fi l (Tmi , P) Tmi RT 2

fi S (T , P) T
HiR,S
Z
= exp − dT
fi S (Tmi , P) Tmi RT 2
fi s
ψi ≡
fi l
T
Hil − HiS
Z
ψi = exp dT
Tmi RT 2

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 7 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion V

RT Hil −HiS
Evaluating the ratio:ψi = exp Tmi RT 2
dT

Z T
Hi (T ) = Hi (Tmi ) + Cpi dT
Tmi

Z T  
∂Cpi
Cpi (T ) = Cpi (Tmi ) + dT
Tmi ∂T P

Z T Z T  
∂Cpi
Hi (T ) = Hi (Tmi ) + Cpi (Tmi ) (T − Tmi ) + dTdT
Tmi Tmi ∂T P

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 8 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion VI

Evaluating the integral:

T
Hil − His ∆Hlsl T − Tmi ∆Cpsli
    
T − Tmi
Z
T
dT = + ln −
Tmi RT 2 RTmi T R Tmi T
Z T Z T " #
∂ Cpl i − Cpsi
Z T

1
+ 2
dTdTdT
Tmi RT Tmi Tmi ∂T
P

Neglecting the last two terms:

∆Hisl
 
T − Tmi
ψi = exp
RTmi T

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 9 / 28

 Phase Equilibrium

Phase Equilibrium: Criterion VII

For a liquid and solid phase:

fˆi l = fˆi s (i = 1, 2, . . . N)

fi S
xi γil fi l = zi γiS fi S ψi ≡
fi l

xi γil = zi γiS ψi

∆Hisl
 
T − Tmi
ψi = exp
RTmi T

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 10 / 28

 Cases

Cases

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 Cases

Cases I

1 Solubility of a solid in a liquid

∆Hisl
 
T − Tmi
xi γil = zi γiS ψi ψi = exp
RTmi T

Solid(1) is pure solute:

x1 γ1l = ψ1
If the solution is at the melting point solid:

x1 = 1/γ1l

If the solution is at the T < Tmelting of the solid:

x1 = ψ1 /γ1l

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 12 / 28

 Cases

Cases II

2 Ideal liquid and solid solution

∆Hisl
 
T − Tmi
xi γil = zi γis ψi ψi = exp
RTmi T

xi = zi ψi

ideal liquid solution: γil = 1

ideal solid solution: γis = 1
x1 = z1 ψ1 x2 = z2 ψ2
ψ1 (1 − ψ2 ) 1 − ψ2
x1 = z1 =
ψ1 − ψ2 ψ1 − ψ2

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 Cases

Cases III

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 Cases

Cases IV

3 Ideal liquid solution and immiscible solids

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 Cases

Cases V

Depending on the temperature and overall composition, the phases at

equilibrium could be:
Binary liquid phase and pure solid 1 (Region 1)
Binary liquid phase and pure solid 2 (Region 2)
Binary liquid phase, solid 1 and solid 2 (SSLE Line)

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 16 / 28

 Cases

Cases VI

∆Hisl
 
T − Tmi
xi = ψi ψi = exp
RTmi T

SSLE Line (at the eutectic state): both equations apply simultaneously

T = Te

x1 = ψ 1 = 1 − x2 = 1 − ψ 2

∆H1sl ∆H2sl
   
T − Tm1 T − Tm2
exp = 1 − exp
RTm1 T RTm2 T

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 17 / 28

 Cases

Cases VII

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 Cases

Cases VIII

∆Hisl
 
T − Tmi
xi = ψi ψi = exp
RTmi T

Region 1: only for species 1 applies

∆H1sl
 
T − Tm1
X1 = ψ1 x1 = exp
RTm1 T

Region 2: only for species 2 applies

∆H2sl
 
T − Tm2
χ2 = ψ2 x2 = exp
RTm2 T

∆H2sl
 
T − Tm2
x1 = 1 − exp
RTm2 T

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 19 / 28

 Cases

Cases IX

4 Freezing point depression

Consider the equilibrium between a solid and a liquid mixture that is
concentrated in the same species as the solid.
Tf : temperature at which pure solvent begins to separate out as solid
When the solid freezes out:
Solid is pure in the same species as the solvent
Composition of liquid phase not significantly changed by appearance of
small amount of solid phase

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 20 / 28

 Cases

Cases X

For the solvent(1)/solute(2) system:

∆H1sl
 
Tf − Tm1
x1 γ1l = exp
RTm1 Tf

Simplifications:
Tm and Tf usually sufficiently close; Tm1 Tf = Tm1 2

∆H1sl
x1 γ1l ∼
= exp (Tf − Tm1 )
RTm2 1

For very dilute solutes, γ1 → 1; ln x1 = ln (1 − x2 ) → x2

2
RTm1
∆T = (Tm1 − Tf ) ∼
= x2
∆H1sl

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 21 / 28

 Cases

Cases XI

5 Partitioning of a solid between two liquid phases

Consider the system composed of solute(1) and two liquid solvents,
solvent 1(2) and solvent 2(3). Two liquid phases and undissolved
solute are present at equilibrium.
Phases and Components
Solid phase: (1)
Liquid α phase: (1), (2), (3)
Liquid β phase: (1), (2), (3)

Engr. Paul Gabriel E. Lerona SLE June 19, 2022 22 / 28

 Cases

Cases XII

Writing all the expressions needed to define the system at this state
of equilibrium:
Species 1: SLLE
x1α γ1lα = ψ1 x1β γ1lβ = ψ1
Species 2 and 3: LLE

x2α γ2lα = x2β γ2lβ x3α γ3lα = x3β γ3lβ

Material balances:

x1α + x2α + x3α = 1 x1β + x2β + x3β = 1

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 Cases

Cases XIII

6 Solid solutions
Binary solution of a and b
A compound a2 b forms

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 Solid-Solid-Liquid Equilibrium

Solid-Solid-Liquid Equilibrium

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 Solid-Solid-Liquid Equilibrium

Solid-Solid-Liquid Equilibrium I

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 Solid-Solid-Liquid Equilibrium

Solid-Solid-Liquid Equilibrium II

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 Solid-Solid-Liquid Equilibrium

The End

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