Phase equilibria

Phase changes are transformations between the states of matter, i.e. phase changes are changes
of state.

Every phase change is accompanied by a change in the energy of a system e.g. when a solid
melts, the melting process is called fusion. The heat of fusion or enthalpy of fusion is denoted
Hfus. The heat of fusion of ice for example is 6.01 kJ mol-1.
As the temperature of a liquid phase increases, the concentration of gas-phase molecules over the
liquid increases. These gas molecules exert a pressure called the vapour pressure. Vapour
pressure increases with increasing temperature until it equals the external pressure over the
liquid, which is usually atmospheric pressure. At this point, the liquid boils. The energy required
to cause this transition is called the heat or enthalpy of vaporisation, denoted Hvap. For water,
the heat of vaporisation is 40.7 kJ mol-1.
Hvap values tend to be larger than Hfus because when changing from liquid to vapour, all
intermolecular forces of attraction between the liquid particles must be broken. When changing
from solid to liquid, some intermolecular forces remain between the particles. The enthalpy
change from solid to gas is called heat of sublimation, denoted Hsub.
Hsub = Hfus + Hvap. e.g. Hsub for water is 47 kJ mol-1.

Heating curves
A heating curve is a graph of temperature of a system vs. the amount of heat added.

e.g. Consider the heating curve for water:

Calculating the enthalpy change for the entire system:
For a process where the temperature is changing, the enthalpy change is:
H = mcT where m = mass (or number of moles)
c = specific or molar heat capacity
T = change in temperature (in Kelvin)

Where the temperature is constant but the phase is changing:

H = no. of mols. x Hfus Or: H = no. of mols. x Hvap

e.g. Calculate the energy change upon converting 1.00 mol of ice at -25oC to water vapour
(steam) at 125oC under a constant pressure of 1 atm. The specific heat capacities of ice,
water and steam are 2.03, 4.18 and 1.84 J g-1 K-1 resp. For water: Hfus = 6.01 kJ mol-1;
Hvap = 40.67 kJ mol-1
[Refer to heating curve diagram above]

Several different regions/ sections of the heating curve must be taken into account:

Region AB: Heating ice at -25oC to ice at 0oC:

H = mcT
m = 1.00 mol. x 18 g mol-1 = 18 g
cice = 2.03 J g-1 K-1
T = 25 K (After deducting the two temperatures, put the unit for T as K not oC)
H = (18 g)(2.03 J g-1 K-1)(25 K) = 914 J

Region BC: Melting ice at 0oC to water at 0oC:

H = n x Hfus = 1.00 mol. x 6010 J mol-1 = 6010 J [Recall: fusion means solid liquid]
Region CD: Heating water at 0oC to water at 100oC:
H = mcT
= (18 g)(4.18 J g-1 K-1)(100 K) = 7524 J

Region DE: Boiling water at 100oC to steam at 100oC:

H = n x Hvap = 1.00 mol. x 40 670 J mol-1 = 40 670 J [Recall: vap. means liquid gas]

Region EF: Boiling water at 100oC to steam at 125oC:

H = mcT
= (18 g)(1.84 J g-1 K-1)(25 K) = 828 J

All the above changes are endothermic (energy is being supplied to break intermolecular forces).

For the overall process:

H = all individual H values
= 914 J + 6010 J + 7524 J + 40 670 J + 828 J
= 55 946 J = 56 kJ

Cooling curve the opposite of a heating curve; vapour state liquid state solid state.
 Vapour pressure

At any given temperature, molecules of a liquid can acquire sufficient energy to escape from the
surface of the liquid and enter the gas phase above the surface of the liquid via evaporation. As a
result, the pressure exerted by the vapour in the space above the liquid will increase.
After a short time, the pressure of the vapour will attain a constant value, which is called the
vapour pressure of the substance. When the gas-phase molecules strike the surface, they can be
recaptured by the liquid. That is, the gas molecules above the surface of the liquid will eventually
lose energy and therefore re-enter the liquid phase.
Eventually the rate at which the molecules return to the liquid equals the rate at which they
escape.
i.e. Rate of entry of molecules into the vapour phase = Rate of re-entry of gaseous
molecules into the liquid phase.

Vapour pressure becomes constant and equilibrium is reached. The vapour pressure of a liquid
is the pressure exerted by its vapour when the liquid and vapour phases are in equilibrium.
Substances with a high vapour pressure evaporate more quickly than substances with a low
vapour pressure. Liquids that evaporate easily are said to be volatile. A volatile liquid is one
which has a measurable vapour pressure while a non-volatile liquid does not.
For any liquid, an increase in temperature will increase the vapour pressure since the
molecules in the liquid phase will be provided with greater kinetic energy to be able to escape
from the liquid phase.
A liquid boils when its vapour pressure equals the external pressure acting on the surface
of the liquid.
The boiling point at 1 atm. is called normal boiling point (Tb).
Solids tend not to have any significant vapour pressure.

The Clausius-Clapeyron Equation

Vapour pressure increases with increasing temperature. The relationship between vapour
pressure and temperature is given by an equation called the Clausius-Clapeyron equation:
ln P = Hvap + C where P = vapour pressure
RT T = absolute temperature (K)
R = molar gas constant (8.314 J mol-1 K-1)
Hvap = molar enthalpy of vaporisation
C = a constant/ the y-intercept

The equation shows that a graph of ln P vs. 1/ T would give a straight line.

The slope of the line gives Hvap / R.

Therefore, we can use this plot to determine the enthalpy of vaporisation of a substance.
However, if instead of being given experimental data and told to plot the graph, we are only
given 2 points: (T1, P1) & (T2, P2)
Then for (T1, P1) the Clausius-Clapeyron equation becomes:
ln P1 = Hvap + C (i)
RT1
Likewise for (T2, P2):
ln P2 = Hvap + C (ii)
RT2
Equ. (ii) (i): ln P2 ln P1 = Hvap + C Hvap + C
RT2 RT1
ln P2 = Hvap + Hvap
P1 RT2 RT1

ln P2 = Hvap 1 1 (The Modified Clausius-Clapeyron

P1 R T2 T1 Equation)

e.g. Given (373.6 K, 1.018 atm.) & (372.6 K, 0.982 atm.) calculate Hvap.
ln P2 = Hvap 1 1
P1 R T2 T1
ln 0.982 atm. = Hvap 1 1
1.018 atm. 8.314 J mol-1 K-1 372.6 K 373.6 K
Hvap = 41.7 kJ mol-1

[N.B.: Troutons Rule: Hvap / Tb = 88 J mol-1 K-1; this relationship is used in certain
calculations to estimate the Hvap before the Clausius-Clapeyron equation is used.)

Phase Diagrams
The equilibrium between a liquid and its vapour is not the only equilibrium that can exist
between states of matter. Under appropriate conditions of temperature and pressure, a solid can
be in equilibrium with its liquid state or even with its vapour state. A phase diagram is a graph
showing the conditions under which equilibria exist between the different states of matter.
This graph also allows us to predict the phase of a substance that is stable/ exists at any given
temperature and pressure.
x-axis of the graph temperature
y-axis of the graph pressure

There are 3 important curves, each of which represents the conditions of temperature and
pressure at which the various phases can coexist at equilibrium. That is, the phase diagram is
separated into its different components/ regions (solid, liquid & gas) by lines/ curves called
phase boundaries. The phase boundaries are where 2 phases are in equilibrium with each other.

The 3 curves/ phase boundaries are:

The solid/ liquid phase boundary
The liquid/ gas phase boundary
The solid/ gas phase boundary
The graph may be described as follows:

The curve from T to C is the vapour-pressure curve of the liquid (i.e. the liquid/ gas phase
boundary). It represents the equilibrium between the liquid and its gas phases. The point on
this curve where the vapour pressure is 1 atm. is the normal boiling point of the substance. The
vapour pressure curve ends at the critical point (C), which is at the critical temperature and
the critical pressure of the substance. Beyond the critical point, the liquid and gas phases
become indistinguishable from each other, and the state of a substance is a critical fluid.

The curve that separates the solid phase from the gas phase (i.e the solid/ gas phase boundary)
represents the change in the vapour pressure of the solid as its sublimes at different temperatures,
i.e. it is the equilibrium between the solid and gas phases.

The line that separates the solid phase from the liquid phase (i.e. the solid/ liquid phase
boundary) corresponds to the change in melting point of the solid with increasing pressure.
The line usually slopes slightly to the right as pressure increases, because for most substances,
the solid form is denser than the liquid form. An increase in pressure usually favours the more
compact solid phase, therefore higher temperatures are required to melt the solid at higher
pressures. The melting point of a solid is identical to its freezing point. The two differ only in
the direction in which the phase change is approached. The melting point at 1 atm. is the normal
melting point (Tm). The melting/ freezing point of a substance is the temperature at which
the solid and liquid phases are in equilibrium at an atmospheric pressure of 1 atm. [similar
to boiling point which is the temperature at the equilibrium between liquid & vapour phases at 1
atm.].

Point T, where the 3 curves intersect is known as the triple point. All three phases are in
equilibrium at this temperature and pressure, i.e. all 3 phases intersect/ are in existence.
Any other point on the curves represents the equilibrium between 2 phases. Any point on the
graph that does not fall on the line correspond to conditions under which only 1 phase is present.
The gas phase for example, is stable at low pressures and high temperatures, while the solid
phase is stable at low temperatures and high pressures. Liquids are stable in the region between
the 2.

Critical temperature the highest temperature at which a distinct liquid phase can form, i.e. the
highest temperature at which the liquid phase can exist
Critical pressure the pressure required to bring about liquefaction at this critical temperature.
Interpreting a Phase Diagram
e.g.

At point 1 H2O exists totally as a gas (water vapour)

At point 2 both ice and water vapour exist (i.e. a solid-gas equilibrium is established)
At point 3 as pressure increases, all H2O is converted to ice
At point 4 some ice melts so both ice and water exist at equilibrium
At point 5 pressure increases further so only water exists
At point 6 only ice exists
At point 7 as temperature increases the ice has been converted entirely to water
At point 8 at even higher temperatures, both water and water vapour exist at equilibrium
At point 9 further heating converts water entirely to water vapour
 The phase diagrams of water (H2O) and carbon dioxide (CO2)

The solid-liquid phase boundary follows the typical behaviour, slanting to the right meaning
that melting point increases as pressure increases i.e. solid CO2 is more dense than liquid CO2.
In contrast, the solid-liquid phase boundary is atypical in H2O, slanting instead to the left
meaning that ice is less dense than water.
The triple point of CO2 is much higher than that of H2O. This means that CO2 does not have a
normal melting point (i.e. a melting point at 1 atm.) instead it has a normal sublimation point
(it sublimes at 1 atm. instead of melting/ freezing like H2O): point Y in the above diagram.

Reduction of vapour pressure

Dissolving a non-volatile solute (which can either be a solid, liquid or gas) in some pure solvent
will result in a reduction in the vapour pressure exerted by the solvent in that resulting solution.
What is the origin of this lowering of vapour pressure?
When a solute is dissolved in solvent to form a homogenous/ uniform solution, it is now
unavoidable that some solute particles will now occupy space near the surface of the solution
which was previously occupied by the solvent particles. Consequently, since the solute does not
exert a vapour pressure (since it is not volatile), less solvent particles will be presented with the
opportunity to enter into the gaseous phase and hence, the vapour pressure exerted by that
solution will inevitably be lower than that of the pure solvent.
The extent to which a non-volatile solute lowers the vapour pressure is proportional to its
concentration.

Pure solvent Solution (solvent + solute); vapour pressure is reduced

Raoults Law
This quantifies the extent to which the reduction in vapour pressure occurs.
This relationship is expressed by Raoults Law which states that the partial vapour pressure
exerted by a solvent in its solution is equal to the product of the mole fraction of that
solvent (in the solution) and the vapour pressure of the pure liquid solvent, i.e.
PA = XAPAo where PA = vapour pressure of the solvent in the solution
PAo = vapour pressure of the pure liquid solvent A
XA = mole fraction of solvent A in the solution
Since XA < 1
PA will always be < PAo

Calculating mole fraction (XA):

XA = nA = no. of mols. of solvent A
nA + nB no. of mols. of solvent A + no. of mols. of solute B
e.g. The vapour pressure of water is 17.5 atm. at 20oC. If glucose is added to the water such that
Xwater = 0.8 and Xglucose = 0.2, then the vapour pressure of the water in the glucose solution
will be:
Pwater = XwaterPwatero
= 0.8(17.5 atm.) = 14 atm.
i.e. the vapour pressure of water was reduced from 17.5 atm. to 14 atm. by adding glucose

Raoults Law predicts that when we increase the mole fraction of the non-volatile solute particles
in a solution, the vapour pressure of the solution will be reduced. In fact, the reduction in vapour
pressure depends on the concentration of the solute particles present in the solution.

Certain conditions are necessary for Raoults Law to be fully obeyed:

the solute concentration must be very low
the solute and solvent particles must have a similar molecular size
the solute and solvent must have similar intermolecular forces of attraction

An ideal solution obeys Raoults Law. An ideal solution has the 3 characteristics stated above.
Many solutions however, do not obey Raoults Law exactly: they are not ideal solutions.
If the intermolecular forces of attraction between solvent and solute are weaker than those
between solvent and solvent and between solute and solute, then vapour pressure tends to be
greater than that predicted by Raoults Law. (Positive Deviation)
If the solvent-solute forces are stronger than the solvent-solvent and solute-solute forces, then
vapour pressure tends to be lower than that predicted by Raoults Law. (Negative Deviation)
These two scenarios are departures/ deviations from ideal behaviour/ Raoults Law.

Ideal solutions with two or more volatile components

Solutions sometimes have 2 or more volatile components. To understand such mixtures,
consider an ideal solution containing 2 components, A and B. The partial pressures of A and B in
the solution of A and B are given by Raoults Law:
PA = XAPAo and PB = XBPBo
The total vapour pressure above the solution is therefore the sum of the partial pressures of each
of the volatile components, i.e. A and B:
Ptotal = PA + PB = XAPAo + XBPBo

e.g. Consider a mixture of benzene and toluene containing 1.0 mol of benzene and 2.0 mol of
toluene. At 20oC the vapour pressures of the pure substances are:
Pbenzeneo = 75 atm.
Ptolueneo = 22 atm.

First, calculate the mole fraction of each component in the mixture:

Xbenzene = 1.0/ (1.0 + 2.0) = 0.33
Xtoluene = 2.0/ (1.0 + 2.0) = 0.67

Then, calculate the partial vapour pressure of each component in the mixture:
Pbenzene = XbenzenePbenzeneo = 0.33(75 atm.) = 25 atm.
Ptoluene = XtoluenePtolueneo = 0.67(22 atm.) = 15 atm.

Therefore, the total vapour pressure of the mixture is:

Ptotal = Pbenzene + Ptoluene = 25 atm. + 15 atm. = 40 atm.

The composition of the vapour above the mixture is then:

Pbenzene : Ptoluene
25/ 40 : 15/ 40
0.625 : 0.375 or 62.5% benzene

It can be seen that the vapour of the mixture is richer in benzene, the more volatile component,
because: Pbenzene > Ptoluene i.e. benzene contributes more to the total vapour pressure.

(N.B. Several different units exist for pressure: atm., kPa, Nm-2, mmHg & torr. You should
utilize the units given to you in the question and give your answers in terms of those units.)
Common unit conversions :- 1 atm. = 101 kPa = 760 mmHg
Non-ideal solutions Departure from ideal behaviour/ Raoults Law

Positive deviations
In this case, the vapour pressure of the mixture is much greater i.e. more positive than that
predicted by Raoults Law. For a mixture of A and B, the A B forces of attraction in the
mixture are weaker than the A A or B B forces present in each of the pure liquids, A and B:
A B forces < A A or B B forces
This positive deviation is so great that there is a mixture of a particular composition that has a
vapour pressure higher than any other mixture composition. This is point C in the diagram. This
same mixture composition has the lowest boiling point, point D. Such a mixture is called an
azeotropic mixture or simply an azeotrope. This particular azeotrope is called a minimum
boiling point azeotrope. e.g. ethanol and water can form this type of azeotrope

Negative deviations
In this case, the vapour pressure of the mixture is much lower i.e. more negative than that
predicted by Raoults Law. For a mixture of A and B, the A B forces of attraction in the
mixture are stronger than the A A or B B forces present in each of the pure liquids, A and B:
A B forces > A A or B B forces
This negative deviation is so great that there is a mixture of a particular composition that has a
vapour pressure lower than any other mixture composition. This is point C in the diagram. This
same mixture composition has the highest boiling point, point D. This particular azeotrope is
called a maximum boiling point azeotrope. e.g. ethyl ethanoate and trichloromethane
An important characteristic of azeotropes is that they cannot be separated into its components
by fractional distillation. An azeotropic mixture boils at a constant temperature without
separation.

Ideal solution Positive deviation Negative deviation

Any other composition/ mixture of F and G in the above diagram can be separated into pure F
and pure G, except for the azeotropic mixture of F and G.

Distillation
Four main types of distillation can be used to purify liquid mixtures:
(1) Simple distillation:
Simple distillation is commonly used to purify mixtures containing a volatile liquid and a non-
volatile solute, e.g. saltwater. It can also be used to separate mixtures of liquids which have a
large difference in boiling points (usually a difference of > 25oC). e.g. methanol and water.
 Apparatus used for
simple distillation

Application:
Purifying
organic
solvents in
the lab.

(2) Fractional distillation:

Apparatus used for

fractional distillation

Some applications:
Distillation of
crude oil
Distillation of
alcoholic
beverages

Boiling point composition curves:

A liquid mixture in which the mole fraction of A is 0.5 gives a vapour in which the mole fraction
of A is 0.6. Hence, the vapour is richer in the more volatile component, A.

The dotted lines show how a liquid in which the mole fraction of A is 0.5 gives a vapour richer
in A, the component with the lower boiling point. If this vapour was allowed to condense and
was then re-distilled, a liquid even richer in A would be obtained. This is the principle of
fractional distillation in which the process of vaporisation/ condensation continuously takes
place in a fractionating column.

Vapour pressure composition curve Boiling point composition curve

e.g. Consider the fractional distillation of a mixture of water and methanol. The boiling point of
water is 100oC. The boiling point of methanol is 64.7oC (methanol therefore is the more
volatile component). An equimolar mixture of the two liquids (point a on the graph below)
has a boiling point of 77.5oC (b) and gives a vapour of mole fraction 0.7 (c) methanol. On
condensation, the 0.7 methanol mixture (d) boils at 71oC and gives a vapour of mole fraction
0.85 methanol (e). Therefore, the vapour becomes richer in methanol with each vaporisation
and condensation process until a vapour containing pure methanol is achieved at the top.
The water remains in the round-bottomed flask. Thus the two liquids are separated.

Summary: The liquid mixture, a boils at temperature, b with vapour c richer in the more volatile
component. This condenses to liquid d in the column which vaporises to give vapour e which is
even richer in the more volatile component. (Raoults Law can be used to calculate the
composition of the distillate/ vapour.)

Each horizontal line/ step represents a theoretical plate. The number of steps which can be
drawn on the boiling point/ composition diagram is called the number of theoretical plates.
Increasing the number of theoretical plates ultimately leads to better separation.
Important points:
Fractional distillation is used when the boiling points of the liquids are very close
(< 25oC) or if the liquids are quite miscible and difficult to separate. e.g. mixtures of
alcohols such as methanol (B. pt. 64.7oC) and ethanol (B. pt. 78oC).
Fractional distillation has to be done slowly to achieve good separation.
The packing material in the column is usually glass (e.g. glass beads).
The most efficient fractionating columns are long and densely packed.
Fractional distillation is a much better, more efficient method of separation than simple
distillation.

(3) Steam distillation:

Steam distillation is commonly used to extract an oil, which is immiscible (does not mix) with
water, from a mixture by using steam as a carrier liquid. It is used to purify heat-sensitive
compounds or liquids that have high boiling points.

Steam distillation relies on the principle that immiscible liquids each exert their own vapour
pressure independently of each other. Thus, for two such liquids, A (in this case, water) and B
(the oil), with vapour pressures, PA and PB, boiling the mixture gives a mixed vapour for which:
PA + PB = 1 atm.
The presence of the steam allows the oil to vaporize at a lower temperature than it normally
would. Remember, boiling occurs when (internal) vapour pressure equals 1 atm. In other words,
the oil boils and vaporizes at 1 atm., before its actual boiling point has been reached.
Both the vapour of the oil as well as the steam condense forming an oil-water mixture which is
collected and undergoes further purification to obtain the pure oil from the mixture.
Steam distillation is used to obtain the essential oils from plant materials e.g. leaves, seeds, etc.
Essential oils are oils produced by plants which have a pleasant aromatic scent e.g. rose oil and
lavender oil are used in perfumes and other commercial products as well as in aromatherapy.
Other essential oils e.g. those from citrus plants can be used as flavourings in foods and
beverages.

(4) Reduced Pressure/ Vacuum Distillation:

This type of distillation occurs when a vacuum is applied in order to reduce the pressure of the
system. In this way, liquids having very high boiling points e.g. dimethylsulfoxide (B. pt. 189oC)
can be purified at much lower temperatures i.e. without heating the liquid to its boiling point.
These liquids are unable to be distilled at normal atmospheric pressure.
By reducing the vapour pressure above the liquid, more liquid molecules must enter the gas
phase in order to re-establish the vapour pressure, until eventually the liquid begins to boil.

Heat-sensitive
compounds can also be
purified using vacuum
distillation.