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Phase Equilibrium: Pure Substance

A substance will spontaneously change into the phase with the lowest Gibbs free energy. At a given temperature and pressure, a system will evolve to the state with minimum Gibbs energy. The phase with minimum molar Gibbs energy is the stable phase. Phase diagrams map the stable phases of a pure substance over ranges of temperature and pressure, showing phase boundaries and triple points. The Clausius-Clapeyron equation relates the slope of phase boundaries to entropy and volume changes during phase transitions.

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41 views

Phase Equilibrium: Pure Substance

A substance will spontaneously change into the phase with the lowest Gibbs free energy. At a given temperature and pressure, a system will evolve to the state with minimum Gibbs energy. The phase with minimum molar Gibbs energy is the stable phase. Phase diagrams map the stable phases of a pure substance over ranges of temperature and pressure, showing phase boundaries and triple points. The Clausius-Clapeyron equation relates the slope of phase boundaries to entropy and volume changes during phase transitions.

Uploaded by

vishals1991
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Phase Equilibrium : Pure Substance

A substance has a spontaneous tendency to change


into the phase with the lowest molar Gibbs energy.
Thermodynamics of Phase
Equilibrium
At given T and p, a system evolves spontaneously to
the state of minimum Gibbs energy. Stable phase is
that of minimum molar Gibbs energy Gm. At 1 atm,
ice is the stable phase of water below 0ºC, while
above 0ºC but below 100ºC, liquid water is the
stable phase, and above 100ºC, steam is the stable
phase. At this pressure, ice and liquid water have
the same value of Gm at 0ºC, and coexist in
equilibrium, while at 100ºC, liquid water and
steam have the same Gm, and coexist in
Variation of G with T and p
For each phase or ‘state of aggregation’ of a
substance, there is a surface representing Gm as a
function of T and p.

dG = dU + d(pV)  d(TS)
and with dU = TdS  pdV one has
dG =  SdT + Vdp
It follows that
(Gm/p)T = Vm
and
(Gm/T)p =  Sm
Variation of G with p at Constant T

(Gm/p)T = Vm
Vapour stable at
low pressures,
liquid at
intermediate
pressures, and
solid at high
pressures.
Transition when molar Gibbs energies are equal .
Gibbs Energy of a Perfect Gas
(Gm/p)T = Vm = RT/p . Integrating at constant
temperature from standard pressure p° to desired
pressure p, Gm = Gm°(T) + RT ln(p/p°)
Variation of G with T at Constant p

(Gm/T)p =  Sm
Solid stable at low
temperatures, liquid
at intermediate
temperatures and
vapour at high
temperatures.

Transition when molar Gibbs energies are equal


Variation of G with T at Constant p

At this pressure, the


liquid is not stable at
any temperatures.
Only a sublimation
transition is observed.
As always, it must be kept in mind that
thermodynamics refers to spontaneity as a
tendency, but makes no reference to the rate at
which the transformation may occur.
Also, phase equilibrium is ‘dynamic’ in the sense
that the forward and reverse transformations are
taking place at the same rates.
Phase Diagram
Map showing ranges of
T and p over which
various phases are
stable.
Phase Boundaries.
Melting, Vaporization •E • D •B
and Boiling Curves.
Triple Point.
Critical Point
Vapour Pressure
Thermal Analysis: Cooling Curves
When two phases  and  of a substance coexist,
the temperature and pressure cannot both be
varied independently if the equilibrium is to
remain. This fact is used in the determination of
phase boundaries using thermal analysis.
Clapeyron Equation
The slopes of the lines of two phase equilibrium in
the p-T phase diagrams are related to the entropy
change and volume change.
Gm(T,p) = Gm(T,p)
For equilibrium of phases  and  at T and p.
Suppose p is changed to p + dp, and T to T + dT,
and the equilibrium is to be maintained, then
dGm(T,p) = dGm(T,p)
Sm dT + Vm dp = Sm dT+ Vm dp
Rearranging, dp/dT = (Sm Sm) /(Vm Vm)
Or dp/dT = transS/transV
(CLAPEYRON EQUATION)
Using transS = transH/T, can rewrite as
dp/dT = transH/T(transV)
Clausius Clapeyron Equation

For solid-gas equilibrium or liquid-gas equilibrium


away from the critical point, (consider the latter
for concreteness),
Vmg Vml  Vmg  RT/p
dp/dT  vapH/TVmg  vapHp/RT2
or d(ln p)/dT = vapH/RT2 which is the Clausius-
Clapeyron equation.
Over small ranges of temperature, this may be
integrated assuming constant vapH yielding
ln (p2/p1) =  (vapH/R)(1/T2 1/T1)
Or
log p = A  B/T
Vapour pressure*

Substance A B/K Temperature range/°C


Benzene, C6H6(l) 7.0871 1785 0 to 42
6.7795 1687 42 to 100
Hexane, C6H14(l) 6.849 1655 10 to 90
Methanol, CH3OH(l) 7.927 2002 10 to 80
Methylbenzene, C6H5CH3(l) 7.455 2047 92 to 15
Phosphorus, P4(s, white) 8.776 3297 20 to 44
Sulfur trioxide, SO3(l) 9.147 2269 24 to 48
Tetrachloromethane, CCl4(l) 7.129 1771 19 to 20
* A and B are the constants in the expression log(p/kPa)  A  B/T.
Vapour Pressure and Temperature
Characteristic Points

Normal Boiling Point


Normal Freezing/Melting
Point
Sublimation Temperature
Triple Point
Critical Point
Critical Temperature

Isotherms of CO2
Slopes of Phase Boundaries
Liquid is not stable at any
temperature below the
triple point pressure.
Gibbs Phase Rule
Suppose three phases ,, and , of a pure
substance are in equilibrium. Then require
Gm(T,p) = Gm(T,p) = Gm(T,p).
The two equations uniquely determine the T and p
at which three phases can coexist. There are no
‘degrees of freedom’ left.
It follows that the maximum number of phases of a
pure substance that can coexist in equilibrium is
three.
Gibbs Phase Rule
F=CP+2
‘P’ is the number of phases
‘C’ is the number of components, the minimum
number of independent species necessary to define
the composition of all phases in system. When there
are no reactions, it is just the number of species.
‘F’ is the number of degrees of freedom or
variance, is the number of intensive variables
which can be freely chosen, and which must be
specified before the system is in a determinate
state.
Gibbs Phase Rule

‘F’ is the number of degrees of freedom or


variance, is the number of intensive variables
which can be freely chosen, and which must be
specified before the system is in a determinate
state. Alternatively stated, it is the number of
intensive variable that can be changed
independently without disturbing the number of
phases in equilibrium.
For a pure substance, C = 1, and so
F = 3 
For P =1, F = 2 (T and p), For P = 2, F = 1 (T or p)
For P = 3, F = 0.
Phase Diagram of CO2
Phase Diagram of H2O
Variation of Vapour Pressure of Water with
Temperature

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