1

CHM431
PHYSICAL CHEMISTRY

CHAPTER 5
PHASE EQUILIBRIUM
 Learning objectives
2

At the end of this chapter, you should be able to

1. Explain how molecular attractive forces affect
macroscopic properties.
2. Explain the concept of vapor pressure and how it
reveals the relative strength of intermolecular attractions
3. Differentiate the concept of boiling points and normal
boiling point.
4. Understand and effectively use of phase diagrams
 PHASE CHANGES
3
 DEFINITIONS
4

 Boiling point – liquid boils at the temperature where the

vapor pressure of the liquid equals to the external pressure
 Normal boiling point – the boiling point of the liquid at 1
atm , that is the temperature at which the vapor pressure of
the liquid is equal to an external pressure of 1 atm.
 Melting point – the temperature at which the solid and
liquid phases of a substance are in equilibrium at a
specified pressure
 Normal melting point or freezing point – the temperature
at which the solid and liquid phases of a substance are in
equilibrium at standard atmospheric pressure of1 atm
 Vapor Pressure
5

Explaining Vapor Pressure on the Molecular Level

 Some of the molecules on the surface of a liquid have enough energy to
escape the attraction of the bulk liquid.
 These molecules move into the gas phase.
 As the number of molecules in the gas phase increases, some of the gas
phase molecules strike the surface and return to the liquid.
 After some time the pressure of the gas will be constant at the vapor
pressure.
 VAPOR PRESSURE
6

Explaining Vapor Pressure on the

Molecular Level
 Dynamic Equilibrium: the point when
as many molecules escape the
surface as strike the surface.
 Vapor pressure is the pressure
exerted when the liquid and vapor
are in dynamic equilibrium.
 VAPOR PRESSURE
7

Volatility, Vapor Pressure, and

Temperature
 If equilibrium is never established

then the liquid evaporates.

 Volatile substances evaporate
rapidly.
 The higher the temperature, the
higher the average kinetic energy,
the faster the liquid evaporates.
 PHASE RULE
8

 Phase rule sates that for every heterogeneous system in equilibrium, the
degree of freedom is equal to the number of components plus 2, minus the
number of phases.

F=C+2–P
Where
 F is the number of degrees of freedom in the system

 C is the minimum number of chemical components required to constitute all

the phases in the system
 The integer in the Gibbs Phase Rule is related to the number of intensive
parameters
 P is the number of phases in the system

 ~the more components in a system, the more degree of freedom

 ~the more phases involved, the less degree of freedom
 DEGREE OF FREEDOM (F)
9

 Also referred as the variance of the system

 Generally refers to the number of variables (e.g. pressure and
temperature) that can be independently changed without altering the state
of the system (i.e. the number of phases and their compositions are
constant).
 Three common types of equilibria are possible:
1) Invariant equilibria, in which neither P or T can be changed; on a phase
diagram, this is represented as a singular invariant point. F = 0.
2) Univariant equilibria, in which either P or T can be changed
independently, but to maintain the state of the system, there must be a
corresponding change in the other variable; on a phase diagram this is
referred to as a univariant curve. F = 1
3) Divariant equilibria, in which both P and T are free to change
independently without changing the state of the system (but bounded by
the conditions defined by the univariant equilibria) . F = 2.
 PHASE DIAGRAM
10

❑ Phase diagram: plot of pressure vs. temperature summarizing all equilibria

between phases.
❑ Given a temperature and pressure, phase diagrams tell us which phase will
exist.
❑ Features of a phase diagram:
❑ Triple point: temperature and pressure at which all three phases are in
equilibrium.
❑ Vapor-pressure curve (liquid - vapor curve): generally as pressure
increases, temperature increases.
❑ Critical point: critical temperature and pressure for the gas.

❑ Melting point curve: as pressure increases, the solid phase is favored if

the solid is more dense than the liquid.
❑ Normal melting point: melting point at 1 atm.
 PHASE DIAGRAM
11

AB: Vapor-pressure curve (vaporization curve)

AD: Melting point curve (fusion curve)

AC: Sublimation curve

 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
12

• The phases present

represent three states of
matter: liquid (water),
solid (ice), and vapor
(steam).
• All have distinct physical
properties (e.g. density)
and chemical properties
(e.g. ΔGformation, molar
volume etc.) so they must
be considered distinct
• The system is entirely composed of
phases.
H2O, so there is only one component
present.
 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
13

• there is only one point on this

diagram where all three phases
coexist in equilibrium -- this "triple
point" is also referred to as an
invariant point; because P and T
are uniquely specified, there are
zero degrees of freedom.

• Each of the curves represents a chemical reaction that describes a phase

transformation: solid to liquid (fusion curve), liquid to vapor (vapor
pressure curve), solid to vapor (sublimation curve).
• There are three univariant curves around the invariant point; it is always
the case that for a C-component system, there will always be C+2
univariant curves radiating around an invariant point.
 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
14

• There are three distinct areas where

only ice, liquid, or vapor exist. These
are divariant fields. T and P are both
free to change within these fields and
you will still have only one phase(a bit
hotter or colder, or compressed or
expanded, but nonetheless the same
phase).

• The end of the "boiling curve", separating the liquid to vapor transition,
is called the "critical point".
• beyond this region the physico-chemical properties of water and steam
converge to the point where they are identical. Thus, beyond the critical
point, we refer to this single phase as a "supercritical fluid".
 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
15
 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
16

 Vapor pressure curve (BD) – the boiling

point of water increases as the external
pressure increases
 As the pressure decreases with increase
elevations above sea level, the boiling
point decreases.

 Fusion curve (BC) – negative slope ;

melting point of water decreases as
the external pressure increases.
 Normal freezing point is 0 ºC at 1
atm
 PHASE DIAGRAM
ONE-COMPONENT SYSTEM (H20 SYSTEM)
17

 The critical temperature (Tc) -- the

temperature above which the vapor
cannot be condensed no matter what
pressure is applied. It is at 374 ºC for
water. At this temperature , the density
of the vapor is equal to that of the
remaining liquid and the liquid that has
completely changed to vapor.
 The critical pressure (Pc) – the pressure
required to produce liquefaction at the
critical temperature. It is at 218 atm for
water.
 SPECIAL FEATURES
PHASE DIAGRAM OF WATER
18

 The fusion curve of water has a negative slope which means that
the melting point of is decreases as the external pressure
increases. This is different from all other substances as the
melting points of other substances as the melting points of most
solids increase with increasing pressure. This behavior is due to
the fact that density of ice is less than that of water because
volume of water increases as it freezes.
 The triple point is below 1 atm (1.013 bar). When ice is heated,
it will not sublime but melt at the normal melting point of 273.15
K. This is different from CO2 which sublimes at atmospheric
pressure.
 TO INTERPRET THE PHASE DIAGRAM
19

 To interpret the phase diagram of water,

consider a series of heating experiments at
several pressure.
1. Heating at 1 atm from -20 ºC to 360 ºC
▪ Ice the only component at temp = -20 ºC and
pressure = 1 atm
▪ As the heating continues until temperature
reaches 0 ºC, ice(solid) begins to melt and ice
in equilibrium with water`(liquid).
▪ Temperature remains constant until all the ice
melted.
▪ Liquid water the only component at vapor
pressure < 1 atm is heated until it reaches 100
ºC, and it begins to boil. Again temperature
remains constant until all the water vaporizes.
▪ After all the water has changed to steam, the
temperature rises as the heating continues to
360 ºC .
 TO INTERPRET THE PHASE DIAGRAM
20

2. Heating at 0.003 atm from -20 ºC to 360 ºC

▪ Ice the only component at vapor pressure at
-20 ºC with a vapor pressure of 0.003 atm.
▪ As the heating proceeds, the temperature
rises to –10 ºC where the ice start sublimes
and the vapor pressure of ice equal to
0.003 atm.
▪ Ice in equlibrium with water vapour and the
temperature remains constant until all the ice
sublimes.
▪ When all the ice sublimes, the temperature
of water rises as heating continues to 360
ºC.
 TO INTERPRET THE PHASE DIAGRAM
21

3. Heating at 0.006 atm from -20 ºC to 360 ºC

▪ Ice the only component at -20 ºC with a
vapor pressure of 0.006 atm.
▪ As the heating proceeds, no new phase
appears until temperature reaches 0.01 ºC ,
the triple point temperature.
▪ At triple point, ice, water and water vapor
have the same vapor pressure of 0.006 atm
and all the three states coexist in equilibrium.
▪ The temperature remains constant until all the
ice and water vaporized, then the
temperature of the vapor rises as heating
continues
 TO INTERPRET THE PHASE DIAGRAM
22

4. The pressure on H20 is gradually raised from

0.001 atm to 218 atm at 0 ºC.
▪ Water vapor is the only component at 0 ºC
with a vapor pressure of 0.001 atm.
▪ As the pressure increases, no new phase
appears until the pressure reaches 0.005
atm , where the water vapor start to freeze
until all the vapor is completely transformed
into solid phase.
▪ As the pressure keep increasing, the ice start
to melt at pressure of 1 atm and becomes
liquid water.
 PHASE DIAGRAM – CO2 SYSTEM
23

▪ Solid-liquid boundary
▪ Fusion curve
▪ Positive slope: melting
point of dry ice of CO2
increases as vapor
pressure increases.

▪ Liquid-gas boundary
▪ Vapor pressure curve
▪ The boiling point of a
▪ Solid-vapor boundary CO2 increases as
▪ Sublimation curve the external pressure
▪ Normal sublimation increases
temperature= -78.3 ºC
 PHASE DIAGRAM – CO2 SYSTEM
24

 Critical point;
Tc = 31.1 ºC & Pc= 73 atm.
 Triple point;
Tt = -56.4 ºC & Pt = 5.11 atm
 Normal sublimation point is -78.5C. (At
1 atm CO2 sublimes it does not melt.)

Special Features
 The fusion curve has positive slope – melting point of dry ice (solid CO2)
increases as the external pressure increases. It is because the dry ice is
more dense than liquid CO2.
 The triple point lies above usual atmospheric pressure of 1 atm which
means liquid CO2 can exist only at pressure > 5.11 atm. So, this implies
that liquid CO2 will not have a normal boiling point and the solid has no
normal melting point.
 Colligative Properties
25

Dissolving solute in pure liquid will change all physical properties of

liquid such as density, vapor pressure, boiling point, freezing point
and osmotic pressure.

Colligative properties are properties of a liquid that change when

a solute is added. The degree of change depend more on the
concentrations of the solute rather than their chemical identities,
 Vapor Pressure Lowering
26

 The nonvolatile solute have no tendency to escape from solution into vapor phase
 It reduces the number of solvent molecules per unit volume at the surface , thus
lowers the escaping tendency of the solvent molecules to the space above the
liquid
 The presence of a non-volatile solute means that fewer solvent particles are at the
solution’s surface, so less solvent evaporates!
 Vapor Pressure Lowering for a Solution
27

 The diagram shows how a

phase diagram is affected
by dissolving a solute in a
solvent.
 The black curve represents
the pure liquid and the blue
curve represents the solution.
 Notice the changes in the
freezing & boiling points.
 Vapor Pressure Lowering for a Solution
28

 The freezing point depression and

the boiling point elevation (∆T)
depend on molality of solution
 Therefore, the higher the
concentration of the nonvolatile
solute, the greater is the value of
∆T.
 When a solution boils or freezes,
only the solvent vaporizes or
freezes while the solute remains in
solution.
 Therefore, the boiling point and
freezing point of a solution are not
constant as they are for pure
solvent.
 Raoult’s Law
29

 Describes vapor pressure lowering mathematically.

 The lowering of the vapour pressure when a non-volatile solute is
dissolved in a volatile solvent (A) can be described by Raoult’s
Law.
 Raoult’s Law: The vapor pressure of the solvent above solution (PA)
or the partial pressure of A is the product of vapor pressure of
pure solvent (P°A) and the fraction of the solvent in the solution (cA)

PA = cAP°A

PA = vapor pressure of solvent A above the solution

cA = mole fraction of the solvent A in the solution
P°A = vapor pressure of pure solvent A
 Raoult’s Law
30

What is the vapor pressure of water above a sucrose (MW=342.3 g/mol) solution
prepared by dissolving 158.0 g of sucrose in 641.6 g of water at 25 ºC? The
vapor pressure of pure water at 25 ºC is 23.76 mmHg.

mol sucrose = (158.0 g)/(342.3 g/mol) = 0.462 mol

mol water = (641.6 g)/(18 g/mol) = 35.6 mol

mol water 35.6

X water = = = 0.987
(mol water) + (mol sucrose) 35.6 + 0.462

Pwater = Xwater Pwater = (0.987)(23.76 mm Hg)

= 23.5 mm Hg
 QUESTIONS
31

Q1: Calculate the lowering of the vapor pressure of water at 20 0C by the addition of 54.1 g
of mannitol (MW=182.2 g/mol) per 1000g of water . The vapor pressure of water at this
temperature is 17.54 torr. The experimental value is 0.0922 torr.
Pw = Xw x Pow = 0.99 x 17.54 = 17.36
Mole water = 1000/18 = 55.56 mole
Mole mannitol = 54.1/182.2 = 0.30
Xw = 55.56/(55.56+0.30) = 0.99
17.54 -17.36 = 0.18 torr

Q2: The vapor pressure of a solution containing 13 g of a non volatile solute in 100 g of water
at 28 0C is 27.371 torr. Calculate the molecular weight of solute assuming that solution is
ideal. The vapor pressure of water at this temperature is 28.065 torr.

Q3: A solution was prepared by adding 20 g of urea to 125 g of water at 25 0C , a

temperature at which pure water has a vapor pressure of 23.76 torr. The observed vapor
pressure of the solution was found to be 22.67 torr. Calculate the molar mass of urea.
 Boiling Point Elevation
32

 Boiling occurs when the vapor pressure of the liquid becomes equal to the
pressure of the environment or external pressure.
 When a nonvolatile solute is added to a volatile solvent
1. The vapor pressure of the solvent is lowered. Thus the solution must be
heated to a higher temperature than the boiling point of the pure
solvent to reach the external vapor pressure of 1 atm in order for
boiling to occur.
2. This means that the presence of nonvolatile solute elevates the boiling
point of the solvent.
 Boiling Point Elevation
33

 Molal boiling-point-elevation constant, Kb , expresses how much ∆T changes with

molality, m:
∆T = Kb x msolution
 Kb = The ebulloscopic constant or the molal boiling point elevation constant of the
solvent. Unit = 0C kg mol-1 or 0C m-1.
 msolution = molality = mole of normal boiling
solute/mass of solvent (kg). Unit mol solvent Kb, oC m-1
point, oC
kg-1 water 100.0 0.512
 The advantage of molality over acetic acid 118.1 3.07
molarity is that molality is benzene 80.1 2.53
independent of temperature
chloroform 61.3 3.63
whereas molarity varies with
nitrobenzene 210.9 5.24
temperature because the volume of
solution change with temperature.
 QUESTIONS
34

Q1 : What is the mole fraction of glycine in an aqueous solution of

molality 0.140 mol kg-1 ?

Q2 : A solution was prepared by dissolving 18 g of glucose in 150 g of

water. The resulting solution was found to be have a boiling point of
100.34 0C. Calculate the molar mass of glucose given the molal boiling
point constant for water is 0.51 0C kg mol-1.

∆T = Kb x msolution
100.34-100 = 0.34 = ΔT
Kb = 0.51
msolution= mole of glucose/mass of water in kg
= (18 g/MW glucose)/0.15kg
 Freezing Point Depression
35

 Normal Freezing Point: FP of Substance at 1atm

 When solute is added, FP < Normal FP
 FP is depressed when solute inhibits solvent from crystallizing.

When solution freezes the solid form is almost

always pure.

Solute particles does not fit into the crystal

lattice of the solvent because of the differences
in size. The solute essentially remains in solution
and blocks other solvent from fitting into the
crystal lattice during the freezing process.
 Freezing Point Depression
36

∆T = - Kf x msolution
 Kf = The cryoscopic constant or the molal freezing point
depression constant of the solvent. Unit 0C kg mol-1 or 0C m-1.
 msolution = molality = mole of solute/mass of solvent(kg). Unit mol
kg-1

solvent normal Kf oC m-1

freezing
point , oC
water 0.0 1.86
acetic acid 16.6 3.9
benzene 5.5 5.12
chloroform -63.5 4.68
nitrobenzene 5.67 8.1
 Osmotic Pressure
37

o Figure below shows a simple osmotic cell. Both compartments

contain water, but the one on the right also contains a solute
whose molecules (represented by green circles) are too large
to pass through the membrane.
o Osmotic flow is simply diffusion of a solvent through a
membrane impermeable to solute molecules.
 Osmotic Pressure
38

o The osmotic pressure ( П ) of a solution

containing nn moles of solute particles in a solution of
volume (V) is given by the van 't Hoff equation:
𝑛𝑅𝑇
П =
𝑉
o R is the constant (0.08216 L atm mol-1 K-1
o T is the absolute temperature

o Since n/V is also equal to molarity, the above

equation can be also rewrite as
П = 𝑀𝑅𝑇
 QUESTIONS
39

Q1 : What mass of ethylene glycol, C2H6O2, the main component of

antifreeze must be added to 10 dm3 of water to produce a solution for
use in car radiator that freezes at -23.3 0C. Assume density of water is 1
gm-3. The molal freezing point of water is 1.86 0C kg mol-1.

Q2 : If 68.4 g of sucrose (MW = 342 g/mole) is dissolved in 1000 g of

water:
a) What is the vapor pressure at 20 0C.
b) What is the freezing point?
The vapor pressure of water at 20 0C is 17.363 torr. The molal boiling
freezing point of water is 1.86 0C kg mol-1.
 TWO COMPONENT SYSTEMS
40
SOLID-LIQUID PHASE DIAGRAM
 Eutectic mixture - A mixture of two or more substances
which melts at the lowest freezing point of any mixture of
the components. This temperature is the eutectic point. The
liquid melt has the same composition as the solid.
 https://www.youtube.com/watch?v=mLl5qt0c-rM
 E.g.: antimony-bismuth, antimony lead, gold-thallium,
benzene-naphthalene, silver chloride-potassium and
benzene-bromomethane.
 TWO COMPONENT SYSTEMS
41
SOLID-LIQUID PHASE DIAGRAM
 Phase diagram for two component systems may be
represented by temperature-composition (constant pressure) or
pressure-composition (constant temperature).

384 torr 384 torr

P (Total)
P (Benzene)
133 torr 133 torr

P (Toluene)

0 X Benzene 1
1 X Toluene 0
 TWO COMPONENT SYSTEMS
42
SOLID-LIQUID PHASE DIAGRAM

▪ The components are A and B, and the

possible phases are pure crystals of A, pure
crystals of B, and liquid with compositions
ranging between pure A and pure B.
▪ The curves separating the fields of A+Liquid
from Liquid and B+Liquid from Liquid are
termed liquidus curves.
▪ The horizontal line separating the fields of
A+Liquid and B+Liquid from A+B all solid, is
termed the solidus curves.
▪ The point, E, where the liquidus curves and
solidus intersect, is termed the eutectic point. At
the eutectic point in this two component system,
all three phases, that is Liquid, crystals of A
and crystals of B, all exist in equilibrium.
 The freezing point
of pure A
The freezing point
of pure A

Curved line shows the

lowering melting points Curved line shows the
of A as the mol fraction lowering melting points
of B increases. Any of B as the mol fraction
point on this curved of A increases. Any
shows the temperature point on this curved
at which the liquid shows the temperature
mixture of definite at which the 43 liquid
composition is at mixture of definite
equilibrium with the composition is at
pure solid A . equilibrium with the
pure solid B .
 TWO COMPONENT SYSTEMS
SOLID-LIQUID PHASE DIAGRAM
44

 Since we looking at a system at constant pressure, the phase rule in this

case is F = C +1 - P. The eutectic point is therefore an invariant point.
 If we change the composition of the liquid or the temperature, the number
of phases will be reduced to 2.
 If the system contains only pure A, then the system is a one component
system and phase A melts at only one temperature, the melting
temperature of pure A, TmA. If the system contains only pure B, then it is a
one component system and B melts only at the melting temperature of pure
B, TmB.
 For all compositions between pure A and pure B, the melting temperature is
drastically reduced, and melting begins at the eutectic temperature TE.
Note that for all compositions between A and B the melting also occurs over
a range of temperatures between the solidus and the liquidus.
 This is true for all compositions except one, that of the eutectic. The eutectic
composition melts at only one temperature, TE.
 COOLING CURVES
45

Case 1 : Consider the crystallization of a

liquid with composition 80% A and 20%
B
 Composition X will be all liquid above
the temperature T1.
 If the temperature is lowered to T1, at T1
crystals of A begin to form. Further
lowering of the temperature causes more
crystals of A to form.
 As a result, the liquid composition must
become more enriched in B as more
crystals of A form out of the liquid.
 COOLING CURVES
46

Cont.
 At the eutectic temperature, TE, crystals
of B will begin to form, and three phases
will coexist; crystals of A, crystals of B,
and liquid. The temperature must remain
at TE until one of the phases disappears.
 When the liquid crystallizes completely,
only pure solid A and pure solid B will
remain and mixture of these two solid
phases will be in the proportions of the
original mixture, that is 80% A and 20%
B.
 COOLING CURVES
47

Case 2 : Consider the cooling of a liquid

with eutectic composition
 If the liquid has the eutectic composition
initially, then the liquid is cools steadily
down to the eutectic temperature without
deposition of A and B solids.
 There is a long eutectic halt (const. temp.)
at eutectic temperature as the eutectic
sample solidifies.
 After all samples solidified, pure solid
solid A and B is obtained and
temperature continues to go down.
 The eutectic temperature is the lowest
temperature of any mixture.
 COOLING CURVES
48

Liquid
Temperature
(0C)

T1
Crystals of
A begin to TE
form TE TE

Eutectic mixture
Cooling curve Cooling curve of
starts to freeze
case 1 eutectic mixture

Time (min)
 TWO COMPLETELY MISCIBLE LIQUIDS
49

Ideal or perfect solutions

 An ideal or perfect solution obey Roult’s law very well over a wide
concentrations. Solutions in which the components are structurally similar
(shape) and being held together in liquid by similar intermolecular forces (type
& strength) are ideal solutions.
 Examples : n-hexane and n-heptane, bromoethane-iodoethane, benzene-
toluene and benzene-dichloroethane.
 VAPOR PRESURE OF IDEAL SOLUTION
50
OF TWO LIQUIDS
 The vapor pressure above a solution varies with temperature and composition
of the solution.
 The change with composition, for ideal solution is controlled by Roult’s law.
 This is solution in which both component A and B are volatile and contribute to
the vapor pressure of the solution.

PA = XAPOA

 XA = Mole fraction of A = nA /(nA + nB)

 POA = the vapor pressure of pure A
 PA = The vapor pressure of A in solution

PB = XBPOB

 Ptotal = Psolution = PA + PB
= XAPOA + XBPOB
51

Q : Vapour pressure of liquids A and B at a particular

temperature are 120 mm and 180 mm of Hg. If 2 moles of A
and 3 moles of B are mixed to form an ideal solution, what
would be the vapour pressure of the solution?
Solution :

pA o = 120 mmHg pBo = 180 mmHg Ptotal = XAPOA + XBPOB

nA = 2 mol nB = 3mol. 2 3
= 120  + 180 
5 5
2 3
xA = xB = = 48 + 108 = 156 mmHg
5 5
 VAPOR PRESURE OF IDEAL SOLUTION
52
OF TWO LIQUIDS
 Since the more volatile liquid has a higher vapor pressure
than the less volatile liquid, the vapor in equilibrium with an
ideal solution of 2 volatile components has higher mole
fraction of the more volatile component.
 To calculate the composition of the vapor in equilibrium with
the solution, use the equation

PB = XB x Ptotal

 XB = mole fraction of B in vapor

 XB = PB_
Ptotal
 NON IDEAL SOLUTIONS :
53
DEVIATION FROM ROULT’S LAW
 The straight line relationship between vapor pressure and composition
for an ideal solution of two liquids become curve when the liquids
deviate from ideal behavior.

 2 types of deviation
1) Positive deviation
2) Negative deviation

 Deviation are small

1) If the concentration of the solute in the mixture is small, that is the
solution is very dilute
2) If the partial pressure of the solvent in the mixture is close to the pure
liquid.
 NON IDEAL SOLUTIONS :
DEVIATION FROM ROULT’S LAW

❖ For solution showing positive ❖ For solution showing negative

deviation from Raoult's law. deviation from Raoult's law.
❖ Ptotal > Pideal ❖ Ptotal < Pideal
 POSITIVE DEVIATION FROM ROULT’S LAW
55

 The total vapor pressure above the liquid is greater than would be
expected for ideal solutions.
 The molecules in the solution having a greater tendency to escape from
the solution than from the pure liquid. This indicates that the molecules
repel each other and so enter the vapor phase more readily than they
do so for the pure liquids.
 The reluctance for the two liquid molecules to mix completely cause the
volume of solution to increase and an absorption of heat on mixing.
 The examples of slight positive deviation are heptane-
tetrachloromethane mixture and pentane-ethanol mixture.
 The deviation maybe large enough for the total pressure to exhibit
maximum such as liquid mixtures ethanol-water and ethylethanoate-
water.
 NEGATIVE DEVIATION FROM ROULT’S
56
LAW
 The total vapor pressure above the liquids is less than it would be if the
liquids were ideal.
 Less tendency for molecules to escape into the vapor phase from the
solution than from the pure liquids indicate stronger attractive forces
between solute and solvent molecules in solution than between those in
the pure liquids.
 Association of one or both of the component in solution or some degree
of compound formation between the components of the solution.
 The solution is formed with evolution of heat and a contraction in
volume.
 Examples of slight negative deviation is pyridine-ethanoic acid mixture.
 The deviation may be large for hydrochloric-water and nitric acid-water
mixtures.
 BOILING POINT-COMPOSITION
57
DIAGRAMS
To obtain the boiling point-composition diagram at fixed pressure from the
corresponding vapor pressure-composition diagram at fixed temperature
 A high pressure corresponds to low boiling point and vice versa.
 A maximum vapor pressure will result in minimum boiling while minimum vapor
pressure will result in a maximum boiling point at that composition.
 Apply fractional distillation to separate the components of mixture.
58
 Fractional Distillation Apparatus
59
 Temperature/ oC
FRACTIONAL DISTILLATION 100 vapor
A B
T1
liquid C
T2
1. A liquid at composition a1 is 66
heated, it boils at T1 . Then the
liquid has composition a1 and the
vapor has composition a2 (at B).
The vapor is richer in the more a1 a2 a3
volatile methanol (composition a2) 0 Mole fraction CH3OH 1
. 1 0
Mole fraction H2O

2. On condensing this vapor will form a liquid with the same composition a2. If
this liquid is again boiled, it will now boil at temperature T2, giving a vapor
of composition a3 (at C) and this vapor (higher composition of methanol)
will condensed into liquid whose composition is a3.

3. By repeating condensing-boiling process called fractional distillation

process, pure methanol could be obtained eventually.
60
FRACTIONAL DISTILLATION: AZEOTROPIC SYSTEM a4
vapor vapor
BOILING POINT – Temperature/ oC
b2’ b2
COMPOSITION DIAGRAM 100 a3 a3 ’
WITH A MAXIMUM a2 a2 ’
liquid
1. Consider a liquid of composition a1 on the
right of the maximum. It boils at a liquid 66
temperature corresponding to a2 and its
vapor (of composition a2’) is richer in the b1 b3
more volatile component, HNO3. a1
0 Mole fraction HNO3 1
2. If that vapor is removed, the remaining
liquid will move toward the composition and 1 Mole fraction H2O 0
boiling point represented by point a3.

3. The vapor in equilibrium with this boiling liquid has composition a3’. The two
compositions are more similar than the original pair. If that vapor is removed, the
boiling mixture has an identical composition to the liquid.

4. As evaporation proceeds, the composition of the remaining liquids shifts towards

H2O as HNO3 is drawn off. The boiling point of the liquid rises and the liquid
becomes richer in H2O. 61
 a4
CONT. oC
vapor vapor
Temperature/ b2’ b2
100 a3 a3 ’
a2 a2 ’
liquid
5. When so much HNO3 has been evaporated,
the liquid has reached a4, the liquid mixture
will boil at constant temperature because liquid 66
liquid and the vapor in equilibrium with it
have the same composition. A solution having b1
its composition corresponding to the a1 b 3
maximum or minimum on the boiling point
0 Mole fraction HNO3 1
curve is called azeotropic . No further
distillation can separate the two liquid 1 Mole fraction H2O 0
because the condensate retains the
composition of the liquid. a3

6. On distilling a mixture of nitric acid and water with composition on the left of the
maximum, the distillate will consist of pure water and mixture the flask will become
concentrated in HNO3 until it reaches the composition a4 which is azeotropic
mixture which boils at a constant temperature.
62
FRACTIONAL DISTILLATION: AZEOTROPIC SYSTEM
BOILING POINT –
COMPOSITION DIAGRAM vapor
WITH A MINIMUM
Temperature/ oC vapor
T1 B A

D
1. A mixture of composition a1 is heated and T2 C
the mixture boils at T1 (at A) to give a E
vapor (at B) of composition a2. this vapor liquid liquid
condenses in the column to a liquid of the a4 a3 a2 a1
same composition a2. This liquid then boils 0 Mole fraction CS2 1
T2 (point C) and reaches equilibrium with 1 Mole fraction (CH3)2CO 0
its vapor at D with composition of a3, with
condenses higher up column to give a
liquid of the same composition.

2. The fractionation therefore shifts the vapor towards the azeotropic composition, at
a4 (point E) but composition cannot move beyond a4 because then the vapor and the
liquid have the same composition. Consequently, the azeotropic vapor emerges from
the top of the column. 63
TUTORIAL QUESTIONS

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