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240 l14 PDF
240 l14 PDF
Chapter 6 of Atkins
Sections 6.1-6.6 (6th, 7th Eds.), Sections 4.1-4.6 (8th Ed.)
Phase Diagrams
Stabilities of Phases
Phase Boundaries
Three Typical Phase Diagrams
Phase Boundaries
separate regions and
show p and T where
two phases exist in
equilibrium
Triple Point Critical Temperature
scientists in a playful manner. The focus is Ice-nine was the last gift Felix Hoenikker
created for mankind before going to his
on the fictional Dr. Hoenikker, the inventor of just reward.
From:McHugh, Mark A.; Krukonis, Val J., Supercritical Fluid Extraction (2nd Edition), © 1994 Elsevier
4
Phase Diagram of Helium ( He)
# At low temperatures, helium behaves
unusually - solid and gas are never in
equilibrium: He atoms are so light that they
vibrate with high amplitude motions which
“shake the solid apart”
# Solid helium can only be obtained at low
temperature and very high pressure - hcp
and bcc denote hexagonal close packing
and body-centred cubic packing
# The 8-line marks a special phase transition
where heat capacity becomes infinite,
marking the fluid-superfluid transition of
liquid Helium
# The He-II liquid phase is a superfluid, as it
flows without any viscosity
# 4He and 3He have different phase diagrams;
in fact, the entropy of 3He (l) is less than that
of 3He(s), so melting is exothermic
Close Packing in Solids
In a solid, atoms pack together in different arrangements
to occupy as much space as possible - close packing
Each atom A is surrounded by six other A
atoms in one layer, atoms are then piled on
top in the B and C “holes”
Atoms that pack in the arrangment ABC.ABC.ABC... are
said to have cubic close packing (ccp) which is also
called face-centred cubic (fcc) packing (e.g., gold)
Packing in the arrangement AB.AB or AC.AC results in
hexagonal close packing (hcp) - there is often
competition between ccp and hcp phases, dependent
upon long range forces of the atoms (e.g., low temp Na)
Liquid
Graphite
Diamond Metallic
The left p-T diagram shows the high-T high“metallic” phase of carbon, where
as the right T-p diagram shows the high-T low p vapour phase. Hatched
regions indicate “metastable” phases, where both phases can co-exist.
Carbon also has a pure allotropic forms known as buckminsterfullerenes or
buckyballs (C60, C70, etc.), which are produced via chemical reactions.
Phase diagrams of some metals
Bismuth and iron have complex one-component phase diagrams
µ1 µ2
so, the slope of chemical potential vs. pressure is equal to molar volume
Increase in pressure raises the liquid liquid
chemical potential of most pure
substances, because Vm must be
greater than zero
m p m
dp p
RT ' Vm(l) dP RT ln ' Vm(l) )P
(
(
p p(
p
rearrange, q.e.d.
Estimating Effect of Pressure
Example: Derive an expression from the equation below that is valid for
small changes in vapour pressure and calculate the fractional increase of
vapour pressure of water for an increase in pressure of 10 bar @ 25oC
V m )P / RT
p ' p (e ex = 1 + x + x2/2! + x3/3! + ..., so if x « 1, ex . 1 + x
dp )trsS
'
dT )trsV
where )trsS = S$,m - S",m and )trsV = V$,m - V",m are entropy and volume of
the transition (exact expression for the slope of a phase boundary -
applies to phase equilibrium of any pure substance)
Solid-Liquid Boundary
Melting (fusion) has an enthalpy change )fusH occurs at T. Molar entropy
at melting at T is )fusH/T, and we write the Clapeyron equation as
dp )fusH
'
dT T )fusV
)fusV is change in molar volume on melting
Enthalpy of melting is positive (except 3He) and
volume change is usually +ve and small, so
dp/dT is steep and positive
Formula for boundary is obtained by integration
assuming that )fusH and )fusV are constant
(very small changes):
p
)fusH T
dT
dp '
(
)fusV T
p T(
Solid-Liquid Boundary, 2
After integration, an approximate equation of the solid-liquid phase
boundary is written as
(
)fusH T
p ' p % ln
)fusV T(
When T is close to T* (the melting temperature when pressure is p*)
T T & T( T & T(
ln ' ln 1 % .
( (
T T T(
dp 85 J K-1 mol-1
' ' 3.4 x 103 Pa K-1
dT 25 x 10-3 m3 mol-1 K
This is 0.034 atm K-1, so dT/dP = 30 K atm-1 (+0.1 atm pressure change
alters the boiling point by approximately +3 K)
Liquid-Vapour Boundary, 2
Since Vm(g) » Vm(l), )vapV . Vm(g). If gas behaves perfectly, Vm(g) = RT/p
dp )vapH d ln p )vapH
' , '
dT T (RT / p) dT RT 2
since dx/x = d ln x. If )vapH is independent of temperature, then
integration of this equation yields
)vapH 1 1
p ' p (
e &P
, P ' &
R T T(