Physical Transformations of Pure Substances

Chapter 4

Definitions
A phase is a state of matter that is uniform throughout, not only in composition but also in physical state. !! A pure gas !! A gaseous mixture !! Two totally miscible liquids !! A crystal
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Definitions
A solution of sodium chloride !! Ice !! A slurry of ice and water
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Definitions
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An alloy of two metals?

Definitions
An alloy of two metals is a two phase system if the metals are immiscible, but a single phase system if they are miscible. !! Dispersion can be uniform on a macroscopic level, but not on a microscopic scale. !! Dispersions are important in many advanced materials.
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Definitions
Heat treatment cycles are used to achieve the precipitation of a fine dispersion of particles of one phase within a matrix formed by a saturated solid solution phase. !! The ability to control this microstructure resulting from phase equilibria makes it possible to tailor the mechanical properties of the materials.
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Stabilities of Phase
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A phase of a substance is a form of matter that is uniform throughout in chemical composition and physical state. A phase transition is the spontaneous conversion of one phase into another. Phase transitions occur at a characteristic temperature and pressure.

Stabilities of Phase
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At 1 atm, < 0 C, ice is the stable phase of H2O, but > 0 C, liquid water is the stable phase. The transition temperature, Ttrs, is the temperature at which two phases are in equilibrium. So what happens to Gibbs energy?

Stabilities of Phase
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At 1 atm, < 0 C, ice is the stable phase of H2O, but > 0 C, liquid water is the stable phase. The transition temperature, Ttrs, is the temperature at which two phases are in equilibrium. So what happens to Gibbs energy? < 0 C Gibbs energy decreases as liquid " solid. > 0 C Gibbs energy decreases as solid " liquid.

Stabilities of Phase

Phase Diagrams

Vapor Pressure

Boiling Point

Critical Point

Critical Point

Melting and Freezing

Triple Point

Triple Point

Carbon Dioxide

Water

Helium

Definitions
A constituent of a system is a chemical species (an ion or a molecule) that is present. !! A mixture of water and ethanol has two constituents. !! A solution of sodium chloride has three constituents: Na+, Cl-, H2O.
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Definitions
A component is a chemically independent constituent of a system. !! The number of components in a system is the minimum number of independent species necessary to define the composition of all the phases present in the system.
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Definitions
When no reaction takes place and there are no other constraints, the number of components is the equal to the number of constituents. !! Pure water is a one component system !! A mixture of ethanol and water is two component system.
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Definitions
An aqueous solution of sodium chloride is a two component system, because by charge balance, the number of Na+ ions must be the same as the number of Cl- ions. !! A system that consists of hydrogen, oxygen and water at room temperature has three components.
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Definitions
The number of phases, P. !! The number of components, C. !! The variance of the system, F is the number of intensive variables (e.g. p and T) that can be changed independently without disturbing the number of phases in equilibrium.
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Phase Rule
F=CP+2 !! This is not an empirical rule based upon observations, it can be derived from chemical thermodynamics. !! For a one component system F = 3 P !! When only one phase is present, F = 2 and both p and T can be varied without changing the number of phases.
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Phase Rule
When two phases are present, F = 1 which implies that pressure is not freely variable if the temperature is set. !! When three phases are present, F = 0. This special case occurs only at a definite temperature and pressure that is characteristic of the substance.
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Experimental Procedures
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Thermal analysis a sample is allowed to cool and it temperature is monitored. When a phase transition occurs, cooling may stop until the phase transition is complete and is easily observed on a thermogram.

Experimental Procedures
Modern work on phase transitions often deal with systems at very high pressures and more sophisticated detection properties must be adopted. !! A diamond anvil cell is capable of producing extremely high pressures.
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Experimental Procedures
A sample is placed in a cavity between to gemquality diamonds and then pressure is exerted by turning a screw. Pressures up to ~2 Mbar can be achieved. !! One application is the study the transition of covalent solids to metallic solids.
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Experimental Procedures
Iodine, I2, becomes metallic at ~ 200 kbar and makes a transition to a monatomic metallic solid at around 210 kbar. !! Relevant to the structure of material deep inside the Earth and in the interiors of giant planets, where even hydrogen may be metallic.
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Thermodynamics of Phase Transitions

Thermodynamics of Phase Transitions

Thermodynamics of Phase Transitions

Temperature Dependence of Phase Transitions

# "G m & # " & % ( = )Sm % ( = )Sm $ "T ' p $ "T ' p

Melting and Applied Pressure

# "G m & # " & % ( = Vm % ( = Vm $ "p 'T $ "p 'T

Melting and Applied Pressure

# "G m & # " & % ( = Vm % ( = Vm $ "p 'T $ "p 'T

Vapor Pressure and Applied Pressure

p = p*e Vm ( l )"P

RT

p = vapor pressure p* = vapor pressure of condensed phase in the absence of an additional pressure "P = pressure applied

Vapor Pressure and Applied Pressure

Location of Phase Boundaries

" ( p, T ) = # ( p, T )

Location of Phase Boundaries

dG = Vdp " SdT d = Vm dp " Sm dT V# ,m dp " S# ,m dT = V$ ,m dp " S$ ,m dT ( S$ ,m " S# ,m ) dT = (V$ ,m " V# ,m ) dp % trsS dp = % trsV dT " Clapeyron equation

Location of Phase Boundaries

Solid-liquid boundary
" trsS dp = # Clapeyron equation " trsV dT " trsH " trsS = T dp " fusH = dT T" fusV

Solid-liquid boundary

Solid-liquid boundary
dp " fusH = dT T" fusV " fusH dT dp = " fusV T " fusH dT # p* dp = #T * " V T fus
p T

" fusH T dT # p* dp $ " V #T * T trs " fusH % T ( * p$ p + ln' * * " fusV & T )
p

Solid-liquid boundary
# fusH $ T ' p" p + ln& * ) # fusV % T (
*

When T and T* do not differ much # fusH * p" p + * (T * T * ) T # fusV

Liquid-vapor boundary
" trsS dp = # Clapeyron equation " trsV dT " trsH " trsS = T dp " vap H = dT T" vapV

Liquid-vapor boundary
dp dT dT dp " "small" " "large"

Liquid-vapor boundary
dp " vap H = dT T" vapV " vap H dp = dT T ( RT p) d ln p " vap H = dT RT 2 - Clausius - Clapeyron equation

" vapV # Vm (g)

d ln p " vap H = dT RT 2 " vap H d ln p = dT 2 RT ln p T " vap H # ln p* d ln p = #T * RT 2 dT " vap H T dT " vap H % 1 1 ( ln p d ln p = = $ ' $ ** # ln p* # * 2 T R T R &T T ) " vap H % 1 1 ( * ln( p p ) = $ ' $ * R & T T* ) " vap H % 1 1 ( p $+ =e += ' $ ** * p R &T T ) p = p*e$ +

Liquid-vapor boundary

d ln p " vap H = dT RT 2 " vap H d ln p = dT 2 RT ln p T " vap H # ln p* d ln p = #T * RT 2 dT " vap H T dT " vap H % 1 1 ( ln p d ln p = = $ ' $ ** # ln p* # * 2 T R T R &T T ) " vap H % 1 1 ( * ln( p p ) = $ ' $ * R & T T* ) " vap H % 1 1 ( p $+ =e += ' $ ** * p R &T T ) p = p*e$ +

Liquid-vapor boundary

Solid-gas boundary
p= p e
* "#

$ sub H % 1 1 ( #= ' " ** R &T T )