Phases

and
Solution
Learning outcomes
Able to determine the degree of freedom of
a system
Able to distinguish the types of phases and
components in a system
Able to perform calculations involved in
phase transformations and equilibria.
Contents
3.1 Phases
3.2 Vapour pressure
3.3 Ideal solutions
3.4 Equilibrium between phases
3.5 Partial molar quantities
3.6 Clausius-Clapeyron equation
3.7 Interphase region
Phase
- a form of matter that is uniform (homogeneous
portion) throughout, not only in chemical
composition but also in physical state (system)
3.1 Phases
Number of phases is denoted by P :
P = 1 for gas, gaseous mixture, crystal, two
miscible liquids, ice
P = 2 for slurry of ice and water, immiscible
metal alloys
A phase can consist of several disconnected
pieces (i.e. AgBr crystals in equilibrium with
an aqueous solution)
Note that the defination of a phase does not
mention solids, liquids or gases.
A system can be entirely liquid (or entirely
solid) and still have more than one phase.
A system composed of two or more phases is
heterogeneous.
Phase recognition
System Phase
Water (H
2
O) One water phase
Ice + water Ice and water phases
Ice + water + oil Ice, water and oil
phases
Water + CCl
4
Two liquid phases of
water and CCl
4
Solid diamond and
graphite
Two solid phases of
diamond and graphite
Chemical species, is denoted by c :
chemicals that present in a system. For example, a mixture
of water and ethanol has 2 chemical species, c =2.
Independent Components, is denoted by c
ind
:
chemically independent component of the system. The
number of components in a system, C
ind
, is the minimum
number of independent species needed to define the
composition of all of the phases present in the system
Phase Rule
J.W. Gibbs, deduce the phase rule, which is
general relation between degree of freedom, f,
the number of chemical species, c , and the
number of phases at equilibrium, p, for a system
of any composition:
f = c - p + 2(phase rule)
the no. of phases at
equilibrium
no. of independent intensive
variables needed to specify the
intensive state of the system.
the no. of chemical
species
(a) No reaction
f = c - p + 2
f = degree of freedom = no. of independent
intensive variables needed to specify the
intensive state of the system.
p = number of phase present
c = number of chemical species
Described by
specifying P, T, x
i
in each phase.
(b) With reaction
f = c - p + 2 - r - a
r = number of independent
chemical reaction.
a = additional restrictions
c
ind
= c - r - a number of
independent component
f = c
ind
- p + 2
Arising from
stoichiometric and
electroneutrality
conditions
example
Pure H
2
O, no reaction
c = 1,
r = 0,
p = 1
c
ind
= c - r - a = 1
f = c
ind
- p + 2 = 1 - 1 + 2 = 2
example
Pure H
2
O, dissociation of H
2
O
H
2
O H
+
+ OH
-
r = 1, c = 3
x (H
+
) = x (OH
-
)
electroneutrality condition, a = 1
So,
c
ind
= 3 - 1 - 1 = 1
f = 1 -1 + 2 = 2
Pure H
2
O only has 1 independent component and 2
degree of freedom (T, P).
Evaporation is the process of vaporisation in which liquids are
converted into gas (vapour).
In an open system, evaporation continues until all liquid is
gone
In a closed system, evaporation and condensation occur
simultaneously until the system achieved equilibrium.
3.2 Vapour Pressure
Vapour
Liquid
Equilibrium is achieved
when the evaporation rate
equals condensation rate
Vapour Pressure
is the pressure of vapour in equilibrium with the
condensed phase
The vapour can be assumed to obey the ideal gas law.
For a given liquid, the value of its vapour pressure depends
on the strength of its intermolecular forces. (the higher the
intermolecular forces, the lower the vapour pressure).
The vapour pressure is independent of the volume of the
container but depends on the temperature ( n/V is constant
at T).
The vapour pressure of a liquid always increases as
temperature rises.
A solution is a homogeneous mixture of a
solute dissolved in a solvent.
A solution may be solid, liquid or gas
(physical state).
It can be consisting of one phase or two or
more phases
The components of a solution can be any
number.
3.3 Ideal Solutions
Phase rule (Degrees of
Freedom, f)
The Degrees of Freedom, f, is the number of intensive
variables in a system that can be changed independently
without disturbing the number of phases in equilibrium.
f = c - p + 2(w reaction)
f = c
ind
- p + 2(wo reaction)
Where, c
ind
= c-r-a
In a single-component, single-phase system (C=1, P=1)
the pressure and temperature may be changed
independently without disturbing the number of phases in
equilibrium:
Raoults Law
Ideal solutions obey Raoults law
For an ideal solution formed between
two volatile liquids A and B, the
partial vapour pressure of component A
is proportional to the mole fraction of A
in the solution:
o
A A A
P x P =
o
B B B
P x P =
x
A
= mole fraction of component A in the solution
x
B
= mole fraction of component B in the solution
x
A
+ x
B
=1
P
A
=partial vapour pressure of component A
P
B
=partial vapour pressure of component B
P
o
A
, P
o
B
=vapour pressure of pure A and B
P
A
+ P
B
= P
Tot
Total Pressure
o
A A A
P x P =
o
B B B
P x P =
0
1
x
B
=1
o
B
P
o
A
P
Mole fraction, x
A
Vapour pressure of a mixture of two
volatile liquids A and B (fixed T)
A is more volatile
than B
The vapour
pressure of
component B is
lowered by the
presence of
component A
(and vice versa)
As x
A
increases,
the total pressure
of the solution
increases.
x
A
=1
P
Tot
Daltons Law
For an ideal solution of a two component
system, the composition of the vapour in
equilibrium with the solution is not the same
as that of the solution.
The vapour phase is richer in the more
volatile component.
T
A A
P y P =
T
B B
P y P =
T
A A
P y P =
T
B B
P y P =
y
A
= mole fraction of component A in the vapour
y
B
= mole fraction of component B in the vapour
y
A
+ y
B
=1
P
A
=partial vapour pressure of component A
P
B
=partial vapour pressure of component B
P
T
= P
A
+ P
B
= Total pressure of the system
Henrys Law
In an ideally dilute solution, the solvent obeys Raoults
law and the solute obeys Henrys law.
Henrys law states that the vapour pressure of solute i
above an ideally dilute solution is proportional to the
mole fraction of i in the solution.
i i i
x K P =
x
i
= mole fraction of i in the solution
P
i
= partial pressure of i in the vapour in equilibrium with an
ideally dilute solution
K
i
= Henrys law constant (unit in pressure)
exercise
At 20
o
C, P
o
benzene
=74.7 torr and P
o
toluene
=22.3 torr
A certain solution of benzene and toluene at 20
o
C
has a vapour pressure 46.0 torr. Find the benzene
mole fraction in this solution and in the vapour
above this solution.
ans
Let, benzene = b and toluene =t
Total pressure P
Tot
=P
b
+ P
t
From Raoults law,
P
b
= x
b
P
o
b
P
t
= x
t
P
o
t
P
Tot
=P
b
+ P
t
=x
b
P
o
b
+ x
t
P
o
t
=x
b
P
o
b
+ (1-x
b
)P
o
t
,where(x
A
+ x
B
=1)
Cont,
P
Tot
= x
b
P
o
b
+ (1-x
b
)P
o
t
,where(x
A
+ x
B
=1)
46.0torr= x
b
(74.7torr) + (1-x
b
)(22.3torr)
x
b
=0.452 (mole fraction of benzene in the sol.)
partial vapour pressure of benzene in solution, P
b
P
b
= x
b
P
o
b
=(0.452)(74.7torr)
=33.8torr
Mole fraction of benzene in vapour
phase is
Daltons Law
P
b
=y
b
P
Tot
Y
b
= P
b
/P
Tot
= 33.8torr/46.0torr
=0.735
Phase Diagram
-Shows regions of pressure and temperature
where phases are thermodynamically stable.
3.4 Equilibrium between phases
Phase diagrams are extremely useful for systems
with multiple components, and serve to describe
physical and chemical equilibria over a range of
different compositions, as well as points where
substances are mutually miscible, or even when a
system has to be brought to a specific set of
conditions for equilbrium to exist (e.g., pressure,
temperature and composition)
Phase Diagrams
All phase diagrams are developed around one
relationship, the phase rule, which was
derived by J.W. Gibbs - it can be applied to a
wide variety of systems
Phase diagrams: pictorial way of
understanding the properties of a system
Phase diagram
for CO2, Fire
Extinguishers &
Coffee
example
Phase diagrams
Phase diagrams are very important in the
development of:
# alloys # ceramic materials
# steels # semiconductors
# plastics # superconductors
# cosmetics # petroleum product
separations
# food products # glasses
Equilibrium between phases
One-component system
solid
gas
liquid
0
D
A
C
(f = 2)
(f = 0)
(f = 2)
(f = 2)
218
atm
4.6
Torr
P
T (C)
0.01
374
A: triple point (3 phase
in eqm)
C: critical point (surface
between two phases
disappears)
0 A : Sublimation curve
A D : Melting point line
A C : Boiling point curve
f = 1
One-phase regions, p =1, f = 2 both
P and T must be specified to
described the intensive state.
Along the lines except point A, 2
phases are present in equib. Thus, f
=1. E.g. Can vary T anywhere along
AC, but once T is fixed, then P is also
fixed.
Line AC gives b.p of water as a
function of P.
Line AD gives m.p. of ice as a function
of P.
At any temperature above T
c
, liquid
and vapour phases cannot coexist in
equilibrium.
solid
gas
liquid
0
D
A
C
(f = 2)
(f = 0)
(f = 2)
(f = 2)
218
atm
4.6
Tor
r
P
T (C)
0.01
374
critical point
-point at which a liquid surface
disappears and above which a liquid
does not exist at whatever the
pressure. Critical pressure is vapour
pressure at critical temp.
triple point
-three phase
boundaries meet
and all three phases
are in mutual
equilibrium
Definition
Critical Points
The container need to be strong. T
c
of water is
374
o
C and vapour pressure is 218atm
Boiling Points
In an open vessel, at the temperature where the
vapour pressure is equal to the external pressure,
free vapourization occurs throughout the liquid, and
vapour can expand freely into the surroundings.
Free vapourization is known as boiling
The normal boiling point, T
b
, is the temperature
of free vapourization at a pressure of 1.0 atm
The standard boiling point is the temperature of
free vapourization at a pressure of 1.0 bar (0.987
atm) (e.g., water: 99.6
o
C for T
b
= 100oC)
Melting Temperature
The temperature at a specified pressure
where the liquid and solid phases coexist in
equilbrium
The normal freezing point, T
f
, is the
temperature of freezing at a pressure of 1.0
atm (for water, T
f
= 0
o
C)
The standard freezing point is the
temperature of freezing at a pressure of 1.0
bar (0.987 atm) (negligibly different from T
f
)
Two-component system
A two-component system is called a binary
system
The phase rule, f = c - p + 2 (without
reaction) becomes f = 4 - p
For a one-phase, two-component system, f
= 3 (P, T, mole fraction).
Multicomponent systems have important
applications in chemistry, geology and
material science.
Metal, semiconductor, polymers, ceramics and
composites e.g SiC, Si
3
N
4
, Al
2
O
3
etc
T B
*
B B B
P y P x P = =
T C
*
C C C
P y P x P = =
C B T
P P P + =
B
*
C
*
B
*
C T
x P P P P + =
*
B
T B
B
P
P y
x =
Eqn 1 - bubble point line
*
B
*
B
*
C B
*
C
*
B
T
*
B
T B
*
C
*
B
*
C T
P P P y
P P
P
P
P y
P P P P
+
=
+ =
Eqn 2 dew point line
where
(a)Two-component liquid-vapour equilibrium
Two liquids B and C form an ideal solution.
(i) Ideal solution at fixed temperature
( )
B
*
C
*
B
*
C T
x P P P P + =
Points on the dew
point line and
bubble point line at
the same pressure,
P represent the
compositions of
vapour and liquid
phases in
equilibrium and
they are connected
by a horizontal line
called tie line.
Bubble point line
above this line, the
system is in liquid state
Dew point line below
this line, the system is in
vapour state
P
C
*
P
B
*
0 mole fraction B 1
P
liquid
vapour
( )
*
B
*
B
*
C B
*
C
*
B
T
P P P y
P P
P
+
=
(ii) Ideal solution at fixed pressure
The upper curve
gives the T as a
function x
B
while
the lower curve
gives the T as a
function of y
B
.
The tie line
gives the
composition of
the vapour and
liquid phases in
equilibrium at T
At fixed pressure, the phase diagram is a boiling point diagram.
T
B
*
and T
C
*
are normal boiling point of pure B and C if the
fixed pressure is 1 atm.
Bubble point line
below this line, the
system is in liquid
state
Dew point line
above this line, the
system is in vapour
state
T
C
*
T
B
*
0 mole fraction B 1
T
liquid
vapour
T vs. y
B
T vs. x
B
(b) Two-component liquid-liquid equilibrium
When ethanol and water are shaken and mixed together at room
temperature, a single phase is always obtained - complete miscibility
When 1-butanol and water are shaken together at room temperature,
two liquid phases are obtained: one phase is water containing some
dissolved 1-butanol and the other 1-butanol containing small amount of
dissolve water partial miscibility
Two phases
One phase
T
C
T
0 x
B
1
As the temperature is raised,
the region of liquid-liquid
immiscibility decreases, until at
T
C
(critical solution
temperature) it shrinks to zero.
Above T
c
, the liquids are
completely miscible.
The two-phase region is called
miscibility gap.
(c) Two-component liquid-solid equilibrium
The effect of pressure on solids and liquids is small.
Normally, pressure is fixed at 1 atm and the T-x
B
solid-liquid
phase diagram is examined.
(i) Solid solutions
A pair of solids are miscible in all proportions in the
solid/liquid form.
(ii) Liquid phase miscibility and solid-phase
immiscibility
Substances B and C are miscible in all proportions in the
liquid phase and completely immiscible in the solid phase.
Cooling a liquid solution of B and C will cause either pure B
or pure C to freeze out of the solution.
(ii)
T
C
*
and T
B
*
are freezing
points of pure C and pure
B.
E is the eutectic point.
AE is the freezing point
depression curve of C due
to solute B
DE is the freezing point
depression curve of B due
to solute C
l.s.+solid C
l.s.+
solid B
Liquid solution (l.s.) of B + C
Solid B + solid C
T
B
*
T
C
*
x
B
0 1
A
E
D
|
|
.
|

\
|
~
T T
H x ln R
*
B
B , fus , m B
1 1
A
|
|
.
|

\
|
~
T T
H x ln R
*
C
C , fus , m C
1 1
A
(iii) Liquid-phase miscibility and solid-phase miscibility
l.s. + s.s.
Liquid solution (l.s.)
solid solution (s.s.)
0 x
Ni
1
Cu Ni
Pair of substance that
completely miscible in
the solid state. E.g. Cu-
Ni, Sb-Bi, Pd-Ni etc.
With complete
miscibility in both the
liquid and the solid
phases, the T-X
B
binary
phase diagram may
look like for Cu-Ni
phase diagram.
1000
o
C
1200
o
C
1400
o
C
T
3.5 PARTIAL MOLAR QUANTITIES
The solvents partial molar properties are the same as
for an ideal solution-component.
For the solute partial molar properties:
i
V
is the change in V when 1 mol of i is
added to an infinitely large amount of solution
at constant T, P
= infinite dilution
O
= standard state
o
A , m
A
V V =
o
A , m
A
H H =
A
o
A , m
A
x ln R S S =

= =
i
o
i i
V V V
is the molar volume of the pure solvent A
o
A , m
V

= =
i
o
i i
H H H
i
o
i i
x ln R S S =
Relation between solution volume
and partial molar volume
V=En
i
V
i
i
3.6 CLAUSIUS-CLAPEYRON EQUATION
A phase change at constant T and P is accompanied
by an enthalpy change, AH - latent heat of transition
(heat of fusion: solidliquid, heat of sublimation:
solidvapour, heat of vaporisation: liquidvapour,
heat of transition: solid
1
solid
2
).
The Clausius-Clapeyron equation is used to calculate
the T or P or AH for vaporisation, sublimation
and melting processes.
Derivation of Clapeyron Equation
Consider two infinitesimally close points 1 and 2 on
such a line:
o + |
Phase o
Phase |
2
1
T
P
dP
dT
One component
2 phase equilibrium
2
For equilibrium phase change:
Clapeyron equation
3.6.1 Liquid/vapour and solid/vapour equilibria.
If ideal gas:
since
V T
H
V T
H
dT
dP
m
m
A
A
=
A
A
=
gas , m liq m gas , m m
V , V V V ~ = A
P
RT
V
gas , m
=
2
RT
H P
P
RT
T
H
dT
dP
m m
A
~
|
.
|

\
|
A
=
P ln d
P
dP
=
or
Clausius-Clapeyron
equation.
since
lnP
1/T
2
RT
H
dT
P ln d
m
A
~
dT
T
T
d
|
.
|

\
|
=
|
.
|

\
|
2
1 1
R
H
T
d
P ln d
m
A
~
|
.
|

\
|

1
R
H
slope
m
A
=
If AH is constant:
gives vapour pressure vs T for solid &
liquid.
} }
~
2
T
dT
R
H
P ln d
m
A
|
|
.
|

\
|
~
1 2 1
2
1 1
T T R
H
P
P
ln
m
A
If AH
fus
, AV
fus
are constant:
Determine melting point at different pressure.
Normal melting point of a solid is the melting
point at 1 atm pressure.
3.6.2 Solid-liquid equilibrium
For melting:
fus
fus
V T
H
dT
dP
A
A
= dT
V T
H
dP
fus
fus
} }
A
A
=
|
|
.
|

\
|
|
|
.
|

\
|
A
A
~
1
2
1 2
T
T
ln
V
H
P P
fus
fus
3.7 INTERPHASE REGION
3.7.1 Planar interface
BULK
PHASE o
BULK
PHASE |
A
C D
B
INTERFACIAL LAYER, SURFACE
LAYER OR INTERPHASE
REGION
Transition region between bulk
phases o and |.
Properties vary from those of o
and |.
Because of differences in
intermolecular interactions,
molecules in the interphase
region have different average
interaction energy.
C
B D
A
Liquid
Vapour
|
o
z
C
i
Boundaries of
interfacial layer
Intermolecular interactions in a liquid lower the
internal energy.
Molecules at the surface have fewer attractions
from other liquid-phase molecules have a higher
average energy.
The stronger the intermolecular attractions in a
liquid, the greater the work needed to bring
molecules from the bulk to the surface.
vapour
liquid
It requires work to increase the area of the
interface.
The work done on the closed system of phases o
and | is:
dw
rev
= -PdV +
o|
dA (plane interface)
where
o|
= surface tension (N/m)
dA = the increase in interfacial area
P = pressure in each bulk phase
dV = the change in volume
At the critical temperature (T
c
), the liquid-vapour
interface disappears, only one phase is present.
At T
c
,
o|
= 0
3.7.2 Curved Interface
Surface tension causes equilibrium pressure in
phases o and | to differ
If lower piston is pushed, more phase o goes into
the conical region, area of interface increases. P
o
>
P
|
The relation between P
o
and P
|
was derived using
the modified setup (Fig b)
P
|
(Fig a) (Fig b)
o
|
o
|
R
P
o
P
|
For spherical interface
P
|
_ = surface tension
o
|
R
Is the basis for the capillary-rise
method of measuring surface tension
for liquid-vapour and liquid-liquid
interfaces.
As R -->, pressure difference -->0
For H
2
O, if R= 1 cm, P
o
- P
|
= 0.1 Torr
if R = 0.01 cm, P
o
- P
|
= 10 Torr
R
P P

| o
2
=
3.7.3 Capillary Rise
r = R cos q
where r = radius of capillary tube
q = contact angle

|
and
o
= densities of phases o and |, respectively
g = gravitational acceleration = 981 cm/s
2
,
= surface tension or interfacial tension
h = capillary rise
( )ghR
o |
=
2
1
u
u
Capillary rise
Contact angles
between a liquid and
and a glass tube
(a) 0
o
C s q < 90
o
C (b) 90
o
C < q s 180
o
C
( )
u

o |
cos
ghr
2

=
The surface tension _ has unit of work (or energy)
divided by area.
cgs unit for _ : ergs cm
-2
SI unit for _ : J m
-2
= N m
-1
1 erg = 1 dyn cm
1 erg cm
-2
= 1 dyn cm
-1
= 10
-3
J m
-2
= 10
-3
N m
-1
material _ (dyn cm
-1
) at 20
o
C
organic/inorganic liq 15 - 50
water 73
mercury 490
_ decreases as T increases
At 20
o
C, the interfacial tension for n-hexane and
water is 52.2 ergs cm
-2
. The densities of n-hexane
and water at 20
o
C are 0.6599 and 0.9982 g cm
3,
respectively. Assuming a zero contact angle,
calculate the capillary rise at 20
o
C in a 0.350 mm
inside diameter tube inserted into a two-phase n-
hexane-water system.
_ = 52.2 ergs cm
-2
u
o
= 0.6599 u
|
= 0.9982
g = 980.7 cm/s
2
r = 0.0175 cm