CHAPTER 7

One-component Phase Equilibrium and Surfaces

ONE-COMPONENT PHASE EQUILIBRIUM

Closed system in mechanical and thermal equilibrium, P-V work only

phase

P =P T =T

The system reaches material equilibrium. How do you test it?

phase

phase equilibrium =
Mechanical, thermal, material equilibrium: chemical potential of each component is everywhere the same (phase equilibrium, closed system, P-V work only)

if more than one component: i

= i
2

ONE-COMPONENT PHASE EQUILIBRIUM

phase Closed system in mechanical and thermal equilibrium, P-V work only, not yet at material equilibrium

phase

matter is still flowing around from one phase to another

dG < 0 S dT + V dP +
i

dG =

i dni

i dni < 0
i

)dn < 0

matter flows from higher to lower chemical potential

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ONE-COMPONENT PHASE EQUILIBRIUM

phase How many independent intensive variables are needed to define the equilibrium state of a multi-component system?

phase

independent variables = degrees of freedom of the system (f)

1 phase 1 component P, T N components P, T, x1, x2, ..., xN

ONE-COMPONENT PHASE EQUILIBRIUM

Now more than one phase

phase

P , T , x1 , x2 , . . . , xc P , T , x1 , x2 , . . . , xc

phase

f = 2(c + 2)

mechanical & thermal equilibrium

P =P =P

f = 2c + 2

still too many variables!

T =T =T

ONE-COMPONENT PHASE EQUILIBRIUM

Consider (for now) (1) No chemical reactions (2) All phases have all components

p phases (, , , ...) c chemical species

pc mole fractions

f = pc + 2

x1 + x2 + + xc = 1 1 = = = ... . . . . . . . . . c = c = c = ...
1 1

f = pc + 2 - p

p - 1 relations c times f = pc + 2 - p - c ( p - 1 ) phase rule (no reactions) f=c-p+2

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ONE-COMPONENT PHASE EQUILIBRIUM

phase rule (no reactions) f=c-p+2

how many chemical species? c = 1 (H2O) how many phases? p = 2 (liquid and solid)

f=1

ONE-COMPONENT PHASE EQUILIBRIUM

Consider (for now) (1) No chemical reactions (2) All phases have all components aqueous solution of sucrose in equilibrium with solid sucrose : sucrose & water : sucrose

xsucrose xsucrose sucrose = water =

xwater xwater
sucrose

one less intensive variable but also one less chemical potential relation

water
f=c-p+2

ONE-COMPONENT PHASE EQUILIBRIUM

Consider (for now) (1) No chemical reactions (2) All phases have all components

for each reaction

i i

=0

i can be used to eliminate another intensive variable

r reactions

f=c-p+2-r

ONE-COMPONENT PHASE EQUILIBRIUM

Consider (for now) (1) No chemical reactions (2) All phases have all components Additional stoichiometric or electronegativity conditions may further connect mole fractions a relations f=c-p+2-r

f = c - p + 2 - r - a = cind - p + 2 independent components cind = c - r - a

dG =

SdT + V dP +

i dni

i can take this sum over all the components or over only the independent components
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ONE-COMPONENT PHASE EQUILIBRIUM

f = c - p + 2 - r - a = cind - p + 2

What are f and cind in an aqueous solution of HCN and KCN?

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ONE-COMPONENT PHASE EQUILIBRIUM

For now: one component, e.g., H2O f = c - p + 2 - r - a = cind - p + 2

H2 O

H + OH
+
c=3

H2 O = H + + OH
i i i

=0

cind = 1

f=?

r=1

xH + = xOH
a=1
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ONE-COMPONENT PHASE EQUILIBRIUM

For now: one component, e.g., H2O f = c - p + 2 - r - a = cind - p + 2

cind = 1 f=3-p

Pure liquid Pure solid Pure gas

p=1 p=1 p=1

f = 2 (P,T) f = 2 (P,T) f = 2 (P,T)

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ONE-COMPONENT PHASE EQUILIBRIUM

For now: one component, e.g., H2O f = c - p + 2 - r - a = cind - p + 2

cind = 1 f=3-p

solid - liquid solid - vapor liquid - vapor

p=2 p=2 p=2

f = 1 P or T f = 1 P or T f = 1 P or T

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ONE-COMPONENT PHASE EQUILIBRIUM

For now: one component, e.g., H2O f = c - p + 2 - r - a = cind - p + 2

cind = 1 f=3-p

triple point

p=3

f=0

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ONE-COMPONENT PHASE EQUILIBRIUM

generic phase diagram

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ONE-COMPONENT PHASE EQUILIBRIUM

The Clapeyron equation to study two-phase equilibrium as a function of T and P

= Gm,1 = Gm,2 = Gm,1 + dGm =

Gm,1 Gm,2 Gm,1

dGm

dGm =

Sm dT + Vm dP
Sm dT + Vm dP
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Sm dT + Vm dP =

ONE-COMPONENT PHASE EQUILIBRIUM

The Clapeyron equation to study two-phase equilibrium as a function of T and P

= Gm,1 = Gm,2 = Gm,1 + dGm =

Gm,1 Gm,2 Gm,1

dGm

Sm dT + Vm dP = dP Sm = dT Vm
Sm Vm

Sm dT + Vm dP

Hm Sm = Vm T Vm
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ONE-COMPONENT PHASE EQUILIBRIUM

phase rule f = c - p + 2 - r - a = cind - p + 2 f = degrees of freedom = number of independent intensive variables needed to specify the intensive state of a system

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ONE-COMPONENT PHASE EQUILIBRIUM

dGm =
P fixed = P1

Sm dT + Vm dP Gm T Gm P

=
P

Sm

solid liquid gas

= Vm
T

Tf

Tb

T
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ONE-COMPONENT PHASE EQUILIBRIUM

dGm =
P2 P1

Sm dT + Vm dP Gm T Gm P

=
P

Sm

solid liquid gas

= Vm
T

Tf

Tb

T
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ONE-COMPONENT PHASE EQUILIBRIUM

dGm =
P2 P1

Sm dT + Vm dP Gm T Gm P

=
P

Sm

solid liquid gas

= Vm
T

Tf

Tb

T
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ONE-COMPONENT PHASE EQUILIBRIUM

The Clapeyron equation to study two-phase equilibrium as a function of T and P

= Gm,1 = Gm,2 = Gm,1 + dGm =

Gm,1 Gm,2 Gm,1

dGm

dGm =

Sm dT + Vm dP
Sm dT + Vm dP
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Sm dT + Vm dP =

ONE-COMPONENT PHASE EQUILIBRIUM

The Clapeyron equation to study two-phase equilibrium as a function of T and P

= Gm,1 = Gm,2 = Gm,1 + dGm =

Gm,1 Gm,2 Gm,1

dGm

Sm dT + Vm dP = dP Sm = dT Vm
Sm Vm

Sm dT + Vm dP

Hm Sm = Vm T Vm
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SOLID-SOLID TRANSITIONS
Water phase diagram

15 known phases of ice

Characterizing and understanding the properties of water is a challenging task!

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HIGHER-ORDER TRANSITIONS
First-order transitions

T, P = constant qP = 0 H=0
CP

CP =

H T

=?
P

T
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HIGHER-ORDER TRANSITIONS
Second-order transitions

qP =

H=T S=

V =0

Transitions between different phases of 3He

CP

T
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HIGHER-ORDER TRANSITIONS
Lambda transitions

qP =

H=T S=

V =0
superfluidity

Transitions between 4HeI and 4HeII

CP

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SURFACES

Molecules at the surface are in different environments than those in the interior of the phase

Fewer attractions less tightly bound

Fraction of atoms/molecules at the surface increases as the systems becomes smaller

Most physical and chemical properties of nanosystems vary with size (e.g., macroscopic gold is not a good catalyst but gold nanoparticles are)

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SURFACES
Ions distribution at aqueous surfaces

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SURFACES
Ions distribution at aqueous surfaces

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SURFACES
It requires work to increase the area of the interface vapor A = area of the interface interface liquid

winterf ace =

dA
surface tension 15-50 mN/m: organic and inorganic liquids 73 mN/m: water 490 mN/m: Hg

surface tension

Total work also includes the change in volume

dwrev =

P dV +

dA

Things change when the surface is not flat (see 7.9)

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