PHYSICAL EQUILIBRIUM

Introduction

This involves the study of behavior of substances as they change phase.

The change of a substance from one phase to another phase is called a physical process.
e.g. evaporation of water, melting of ice.
The equilibrium attained during a physical process is called physical equilibrium.
Physical equilibrium: is the equilibrium established between molecules of a substance
in one physical state or phase and molecules of the same substance in another physical
state or phase, when the rates of conversion from one physical state or phase to another
is exactly balanced by the rate of conversion of molecules to the other.
Examples of physical equilibrium:
Melting
Solid-liquid equilibrium e.g H2O(s) H2O (l)
Freezing
Evaporation
Liquid-vapour equilibrium e.g H2O (l) Condensation H2O (g)

Solid-gas(vapour) equilibrium e.g H2O(s) Sublimation H2O(g)

Deposition

The concept of physical equilibrium

Consider solid-liquid equilibrium e.g H2O(s) H2O(l)
When a pure solid is heated it starts transforming into a liquid at a certain temperature
(melting point of the solid). At this temperature both the solid and the liquid state of the
substance coexist under the given condition of pressure. At this temperature, the solid
state of the substance is in equilibrium with the liquid state of the substance.
If this mixture is taken in a well-insulated container, the interconversion between the
solid state and the liquid state takes place continuously ( it does not stop).The number
of molecules of the solid getting converted into a liquid state is equal to the number of
molecules of liquid state getting converted into solid. Thus the mass of the solid and
mass of the liquid in the system remains constant, this state of equilibrium is called
dynamic equilibrium between a solid and a liquid

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At this stage the rate of melting = the rate of freezing
This can be written as; melting freezing.
Characteristics of physical equilibrium

 The equilibrium is attained in a closed system at given temperature

 At equilibrium state, the measurable properties of the system remains constant
 At equilibrium there is a dynamic balance between the two opposite process

System, Phase and Component:

System:
A System is defined as a specified part of the universe or specified portion of matter
which is under experimental investigation and the rest of universe,i.e,all other matter
which can interact with the system, is surroundings.
A system may be homogeneous or heterogeneous. A homogeneous system shows
uniform composition or structure for example salt solution where as a heterogeneous
system is one with a mixture of state such as liquid-solid or liquid-solid-gas
There are three types of system:
Open system: this type of system can exchange matter as well as energy with
surroundings. The boundary is not sealed and not insulated. For example, hot water or
liquid in an open beaker is an example of open system as water vapour escapes and
heat transferred to the surroundings.
Closed system: this type of system can exchange energy in the form of heat, work or
radiations but not matter with its surroundings. The boundary between system and the
surroundings is sealed but not insulated .For example, liquid in contact with vapour in
sealed tube forms a closed system. Heat can be transferred through the walls of the tube
to the surroundings but total amount of matter remains the same as vapours cannot
escape.
Isolated system: This type of system has no interaction with its surroundings. The
boundary is sealed and insulated. Neither matter nor energy can be exchanged with
surroundings. A substance contained in an ideal thermos flask is an example of an
isolated system.
Phase:
A gas, liquid and solid are known as the three states of matter but solid and liquid
states, each may exist in one or more distinct forms. Each distinct form is described as a
phase.( gases behave alike as do mixtures of gases. Thus a gas is considered as a phase)

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A Phase is a homogeneous part of system which is physically distinct from other parts
of system and can be separated from other parts by a definite boundary surface.

Component:
This is the number of independent chemical species (elements or compound) in terms of
which the composition of a system is specified.
the system can be one component system, for example water system, sulphur system,
two components for example solution of sodium hydroxide ,mixture of ethanol and
water or three component system for example iodine in two immiscible liquids in
contact.
Phase equilibria:

Phase equilibria; Involves the study of the conditions (temperature, pressure and
concentration) under which different phases are in equilibrium.
Phase diagram; is a graphical representation of physical states of a substance under
different conditions of temperature and pressure.
In a phase diagram a phase is represented by a region that is separated from other
regions by lines or curves.
The lines or curves represent the conditions under which two phases can exist in
equilibrium and a triple point describes the conditions under which three phases can
coexist.

Phase diagram of one component system

Example of one component system include; water, carbon dioxide and sulphur

Water system

Water can exist in three possible forms; ice (solid), water (liquid) and water vapour
(gaseous). These three forms can exist in two phase equilibria i.e solid-liquid, solid-
vapour and liquid-vapour or in three phase equilibria as solid-liquid-vapour
The various equilibria which can exist when water is held at various pressures and
temperatures are summarized in the pressure-temperature diagram below.

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 C

B 218atm
Pressure (atm)

LIQUID 1 atm
X Y

O
ICE WATER
VAPOUR
A
0 100 374
Temperature (0C)

Point O is called the triple point of water i.e. the temperature and pressure at which all
the three phases solid, liquid and vapour can co-exist in equilibrium with each other.

Point B is called the critical point of water; it corresponds to the critical temperature.
Critical temperature is the temperature beyond which the vapour cannot be liquefied
no matter the applied pressure, the vapour and liquid become indistinguishable

Curve AO is the sublimation curve for ice. Shows the combination of temperature and
pressure at which ice and its vapour are in equilibrium.

Curve OB is the vapour pressure curve of liquid water or the vaporization curve of
liquid water shows the combination of temperature and pressure at which liquid water
and its vapour can exist in equilibrium the curves show effect of pressure on the boiling
point of water. An increase in pressure causes an increase in boiling point. At any
temperature along this curve, boiling occurs and any particular temperature along this
curve gives the boiling point of liquid water at that pressure.

Boiling point is the constant temperature and pressure at which the liquid turns into a
vapour. Point Y on OB is the boiling point of water at 1 atmosphere

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Curve OC is the melting point curve of ice or the freezing point curve of liquid water.
Shows the combination of temperature and pressure at which a solid and its liquid can
exist at equilibrium the line shows the effect of pressure on the melting point of ice or
the freezing point of liquid water. The curve slopes towards the pressure axis (towards
the left) indicating that the melting point of ice is lowered by an increase in pressure.

ii) The Carbon dioxide system

An example of a substance which melt with increases in volume

B C
Pressure (mmHg)

SOLID CO2 Liquid CO2

Gaseous CO2
A

Temperature (k)

This diagram is similar to that of water though it has two important differences

(i)The line OB slopes away from the vapour pressure axis indicating that the melting
point of solid carbon dioxide is increased with increase in pressure because molecules
of carbon dioxide in the solid phase are parked more closely than in the liquid phase
unlike in water.

(ii) The triple point of carbon dioxide occurs at a higher vapour pressure than that of
water.

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(iii)The sulphur system

Sulphur exists in two allotropic forms i.e the α-sulphur which has rhombic crystalline
form and β-sulphur which has monoclinic crystalline form which are stable over
different temperature.

The temperature at which the two forms are in equilibrium is called transition
temperature and it is 960C monoclinic sulphur is stable above 960C until a temperature
of 1190C when it melt while rhombic sulphur is stable below 960C

SOLID RHOMBIC LIQUID SULPHUR

SULPHUR
PRESSURE

SOLID
MONOCLINIC
SULPHUR C
B
VAPOUR SULPHUR

96 119
TEMPERATURE ((0C)

Curve AB; is called sublimation curve of rhombic sulphur, it shows the variation of
vapour pressure of rhombic sulphur in equilibrium with its vapour with temperature.
Curve BC; is called the sublimation curve of mono clinic sulphur, it shows the
variation of vapour pressure of monoclinic sulphur in equilibrium with its vapour with
temperature.
Curve CD; it is called vaporization curve of liquid sulphur and stable up to point
D,it shows the variation of vapour pressure of liquid sulphur with temperature

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Curve BE; it is called a transition curve Shows the effect of pressure on the transition
point between rhombic sulphur and monoclinic sulphur along this line monoclinic
sulphur is in equilibrium with rhombic sulphur.
Curve CE; is called the fusion curve of monoclinic sulphur, it shows the effect of
pressure on the melting point of monoclinic sulphur
Curve EF; is called the fusion curve of rhombic sulphur, it shows the effect of pressure
on the melting point of rhombic sulphur.
Point B is called the triple point for rhombic sulphur, monoclinic sulphur and sulphur
vapour.
Point C is called the triple point for monoclinic sulphur, liquid sulphur and sulphur
vapour.
Point E is called the triple point for rhombic sulphur, monoclinic sulphur and liquid
sulphur.
Point D is called a critical point of sulphur.
Effect of change of temperature or pressure or both on the system
When temperature or pressure is varied a change of phase normally occurs
Consider the water system

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(i)Suppose ice at point N was heated at constant pressure up to point M

When temperature of ice at point N is raised slowly at constant pressure, the system
moves along the line NM without change in phase. When it reaches curve OC the ice
begins to melt and the temperature remains constant till fusion is complete. During
fusion the ice and liquid water will be in equilibrium with each other. When the whole
of ice is melted, further rise in temperature will make the system move along the line
NM in the liquid region without change in phase. Between curve OC and curve OB the
only change is an increase in the temperature of the liquid. As soon as the curve OB is
reached vaporization sets in and temperature will remain constant till vaporization is
complete. During vaporization, liquid water and vapour will be in equilibrium with
each other. When the liquid has been completely changed to vapour, then the system
will move along NM in vapour region without change in phase. Addition of heat will
merely increase the temperature of the vapour until the point M is reached.

(ii)Suppose water vapour at point T is subjected to an increase in pressure at constant

temperature up to point S

When the pressure at point T is increased at constant temperature, the vapour is

compressed causing a decrease in its volume but it remains a vapour. i.e. No change in
phase occurs until the pressure on curve OB is reached at which pressure the vapour
starts to change into a liquid (condensation) and the two (liquid and vapour remain
in equilibrium at this pressure) further increase in pressure beyond curve OB compress
the remaining vapour causing a further decrease in volume until all is a liquid at
phase S.

(iii)Suppose ice at point N is subjected to decrease in pressure and increase

temperature up to point R

When pressure is slightly decreased and temperature is increased on ice at point N the
solid ice expand causing an increase in its volume without a change in phase. However,
further decrease in pressure and heating of the solid makes it liquefy at its melting point

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which occurs along curve OC. At this point the solid remains in equilibrium with
liquid. The temperature and pressure remains constant at the melting point and a liquid
solid equilibrium is established at the melting point. Further increase in temperature
and decrease in pressure between curve OC and curve OB , the system remains as a
liquid . As soon as the curve OB is reached vaporization sets in and temperature will
remain constant till vaporization is complete. During vaporization liquid water and
vapour will be in equilibrium with each other. When the liquid has been completely
changed to vapour, then the system will move along NR in vapour region. Addition of
heat will merely increase the temperature of the vapour until the point R is reached.

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STUDENT’S ACTIVITY

1. The vapour pressure diagram below shows pressure-temperature curves for water.

(a) State what the following point represents

(i) B – critical point

(ii) O –triple point

(b) (i)state what would happen if ice at point X was heated at constant pressure

It would sublime

(ii) State the differences between water vapour at points P and Q

Water vapour at point P Water vapour at point Q

Water vapour can be liquefied by mere increase in Cannot be liquefied by mere increase in pressure
pressure
Water vapour Permanent gaseous water vapour
c) What is the significance of point O?
all the three phases co-exist
d) Comment on the slope of the line OA.
Line OA slopes towards the pressure axis, this because the melting point of ice decreases with increase in
pressure, ice melts with decrease in volume hence its melting is favoured by high pressure

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e) What will happen if ice at point X is gently compressed, keeping the temperature
constant
it would melt

f) How would you expect the curve OA to change if the above was a phase diagram
of carbon dioxide? Explain your answer.

Curve OA would slope away from the pressure axis. This is because carbon dioxide melts with an increase
in volume. so its melting is favoured at low pressure, hence sloping of OA away from pressure axis to
show increase in melting point with increase in pressure

Qn 2. The phase diagram for a substance E is shown below.

X Triple point
Pressure (mmHg) Solid-1 Critical temperature
liquid
Solid
2-2
Triple point
Triple point
B
gaseous

Temperature (0C)

(a)Label the following on the diagram

(i)The axes.(ii)The phases present.(iii)The critical temperature.(iv)The triple point.

(b)Define the terms;

(i)Critical point; is the point which corresponds to critical temperature, the temperature beyond which
the vapour cannot be liquefied by increasing pressure alone

(ii)Triple point; is the temperature and pressure at which all the three phases solid,liquid and vapour
can co-exist in equilibrium with each other

(c )Explain what would happen when substance E at point X changes to point B.

………………………………………………………………………………………………………
……………………………………………………………………………………………………

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(b)Define the terms;
(i)Critical point
………………………………………………………………………………………………………
………………………………………………………………………………................................
(ii)Triple point.
………………………………………………………………………………………………………
………………………………………………………………………………………………….......
(c )Explain what would happen when the substance at point X changes to point B.
………………………………………………………………………………………………………

………………………………………………………………………………………………………

………………………………………………………………………………………………………

………………………………………………………………………………………………………

………………………………………………………………………………………………………

………………………………………………………………………………………………………

………………………………………………………………………………………………………

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Phase diagram of two component system
TWO-COMPONENT SYSTEMS (mixtures)

A two component system is a system in which two chemically independent components

are involved. For example, a mixture of ethanol and water , Benzene and water.
Mixtures can exist in three possible phases, solid, liquid or gas. These three forms can
exist in two phase equilibria i.e solid-liquid equilibria and liquid-vapour equilibria.

Classification of two component solid-liquid equilibria

Two components solid–liquid equilibria can be classified into three categories
depending on the miscibility of the liquid phase i.e completely miscible, partially
miscible and completely immiscible. These categories are further subdivided depending
on the nature of the solid phase crystallizing from solution i.e solidifying to form
eutectic mixture, solidifying to form a compound with congruent melting point and
solidifying to form a compound with incongruent melting point.
In this chapter we shall consider only, two components which are completely miscible
with one another in liquid state and on solidification, an eutectic mixture is obtained
Eutectic mixture
By cooling a liquid mixture of known composition and recording the temperature at
which solidification begins the conditions under which Solid-liquid equilibrium exist
can be obtained experimentally.
When a liquid form of a pure substance is cooled, a certain temperature is reached
when the liquid is converted to its solid form at constant temperature and pressure.
The constant temperature is the freezing point of the liquid and takes a very narrow
range of values.

The freezing point is the constant temperature at which solid and liquid can exist in
equilibrium with each other. Below the freezing point, the liquid will change completely
into solid. Above the freezing point the solid will change completely into liquid.

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Comparing the cooling curve of a pure substance and that of the mixture

(a)Cooling curve of pure substance

The diagram below shows the cooling curve of molten pure lead.

Temperature Molten lead cooling

(0C)

Crystals of lead being made

Super cooling
328 Solid lead cooling

Room temperature

Time (minutes)
 At first the temperature decreases steadily, then it remains constant, before
finally decreases again,
 Pure molten lead freezes at 3280C
 Super cooling is the cooling below the freezing point without formation of crystal

(b)Cooling curves for mixtures

The cooling curves for the mixtures depend on the proportion of the mixture and are
obtained by varying the amount of each component in the mixture to be cooled.
The freezing point of a liquid is depressed if it contains another substance dissolved in
it. The decrease in freezing point is approximately proportional to the relative amount
of solute added.
The table below shows the freezing points of various mixtures of Tin-lead system

Percentage by mass of lead 100 75 50 36 20 0

Percentage by mass of tin 0 25 50 64 80 100
freezing point (0C) 328 270 210 183 200 232

The composition of the solid formed, from each of the liquid mixtures above is 36%lead
and64%tin and this occurs at temperature of 1830C

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Consider the cooling curves of Liquid Tin-lead mixture
When a liquid mixture containing 25%tin and 75% lead by mass is cooled at constant
pressure, a temperature (2700C) is reached when solid lead separates out of the mixture.
This temperature will be lower than the actual freezing point of molten lead (3280C).As
cooling is continued, the crystallization of lead continues making the mixture less rich
in lead, until a certain composition 36% lead, at which the mixture solidifies completely
at constant temperature of 1830C.

AB – liquid mixture cooling

Temperature(0C)

B B-pure lead begin solidifying out of

270
solution
BC – Lead solidifying
183 C D CD – Both tin and Lead solidifies
DE – solid mixture cooling
E

Time (min)

Cooling curve for a mixture of 25% tin and 75% lead

by mass
Similarly When a liquid mixture containing 80%tin and 20% lead by mass is cooled at
constant pressure, a temperature (2000C) is reached when solid tin separates out of the
mixture. This temperature will be lower than the actual freezing point of molten tin
(2320C). As cooling is continued, the crystallization of tin continues making the mixture
less rich in tin, until a certain composition 64%tin , at which the mixture solidifies
completely at constant temperature of 1830C.

AB – liquid mixture cooling

Temperature(0C)

B
…..
B-pure tin begins solidifying
BC – Tin solidifying
183 C D
CD – both Tin and Lead solidifies
DE – solid mixture cooling
E

Time (min)
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All other compositions will give a similar curve apart from the composition of 64%tin
and 36% lead.
When a liquid mixture of composition 64%tin ( 36% lead) is cooled at constant
pressure, a temperature is reached when the liquid mixture solidifies completely to a
solid mixture of the same composition as that of the liquid mixture (64% lead) at
1830C.

Liquid mixture of tin and lead

cooling
Temperature (0C)

Solid mixture solidifying

Solid mixture cooling

Time (min)

Cooling curve for a mixture of 64% tin and 36% lead

by mass

This cooling curve looks like exactly that of a pure compound rather than a mixture.
This particular mixture which crystallises to form a solid which have the same
composition as that of the liquid mixture is called eutectic mixture.
Eutectic mixture is defined as a liquid mixture which at constant pressure solidifies at
constant temperature to form a heterogeneous solid of the same composition as the
liquid. or
Eutectic mixture is a heterogeneous solid mixture which when heated at constant
pressure will melt at a constant temperature giving a liquid of the same composition as
the solid.
The constant temperature at which the liquid solidifies is called eutectic temperature
Eutectic temperature is defined as the constant temperature at which a liquid mixture
solidifies at constant pressure to give heterogeneous solid of the same composition.

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Pairs of substances that can form eutectic mixture include

 Cadmium and zinc

 Tin and silver
 Bismuth and lead
 Naphthalene and benzene
 Naphthalene and biphenyl
 Sodium nitrate and water or solution of sodium nitrate
 Sodium chloride and water or solution of sodium chloride

Conditions for the formation of eutectic mixtures

 Pure crystals of the components should separate from mixtures on cooling

 The two components must be completely miscible with one another in the liquid
state
 on solidification, only an intimate mixture of the pure components is obtained
Similarities between eutectic mixture and compound

 Both have constant composition at constant pressure

 Both have a constant melting point at constant pressure
 Both have similar cooling curve
Reasons why eutectic mixtures are not compounds

 Their compositions varies with pressure

 Can be separated by physical means
 x-ray analysis shows that eutectic mixtures are not compounds
 Microscopic analysis shows that eutectic mixtures are heterogeneous, made of
crystals of separate substances.
 Composition of eutectic mixture does not correspond to any known compound
 Chemical properties of eutectic mixtures are those of individual components
making up the mixture for example when solder is reacted with dilute
hydrochloric acid, tin reacts whereas lead does not.

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Constructing a Solid-liquid phase diagrams:
Sample question UNEB 2019

Solution:
(a)Eutectic mixture is a heterogeneous solid mixture which when heated at constant
pressure will melt at a constant temperature giving a liquid of the same composition as
the solid.
(b)Mixtures of various compositions of solid naphthalene and biphenyl are prepared.

Each mixture is heated separately until it melts.

Each mixture is allowed to cool while stirring and the constant temperature at
which it freezes is recorded.

The melting point of pure naphthalene and pure biphenyl are determined in the
same way.

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 A graph of melting points against composition is plotted a phase diagram is
drawn.

90
Q
80 Melting point of pure naphthalene
Melting point of pure biphenyl
70 Liquid solution or mixture
Melting point (C)

60
P
50 Solid naphthalene +liquid solution

Solid biphenyl + liquid solution

40 M
A B
30
Solid naphthalene +solid biphenyl
Composition of eutectic mixture
20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of naphthalene

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From 850C,the mixture cools to 540C(point P) without change in phase
(or composition)
At point P biphenyl begins to solidify as the mole fraction (or composition) of naphthalene
increases in the liquid mixture. The composition of naphthalene increases causing a further
decrease in freezing point along PM on the curve up to the eutectic point as further cooling is
done.
At the eutectic point the temperature and composition remains constant while the whole system
solidifies and then solid mixture cools with no change in phase (or composition) up to 300C
e) The melting point of naphthalene reduces up to the eutectic point.
at the eutectic point the melting point is constant and further addition of biphenyl increases the
melting point towards that of biphenyl

(b) Salt -water system.

Constructing phase diagram of salt -water systems.
Consider Sodium nitrate- water system.
 Pure water is allowed to cool while stirring and the constant temperature at
which it freezes is recorded.
 solutions of various compositions of solid sodium nitrate and water are prepared
 Each solution is allowed to cool while stirring and the constant temperature at
which they freeze is recorded.
 A graph of freezing point against composition is plotted and phase diagram
drawn

Phase diagram of sodium nitrate-water system

B
Solution of sodium nitrate in water

A
TEMPERATURE (oC)

Saturated solution +
Ice + solid sodium nitrate

solution

-17.5
E
Solid sodium nitrate and ice

% BY MASS OF NaNO3

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Description

Point A, is the freezing point of water.

Line AE, represent the lowering of freezing point of water as more and more sodium
nitrate is added to it.. Along this line equilibrium is established between the liquid
mixture and ice.
Point E,(a temperature of -17.50C and a composition of 37%sodium nitrate by mass)is
the eutectic point. it corresponds to the lowest temperature which must be reached
before the whole system solidifies, It is also the only point at which the three phase’s
ice, solid sodium nitrate and saturated solution of sodium nitrate in water are in
equilibrium.
Line EB, represent the increase in solubility of sodium nitrate with temperature
(the sharp steepness of the line, shows that there is slight increase in solubility of
sodium nitrate with temperature.)
Application of eutectic mixtures

 Formation of alloys e.g solder , brass

 Industries where it is desirable to lower the melting point of a substance e.g in

extraction of aluminium from bauxite; cryolite is added to bauxite to lower its
melting point.

 Safety appliances as plugs

 Solders for joining metals at relative low temperatures

 determining of identity of organic compounds

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Worked examples

Example one

The table below shows the melting points of various mixtures of tin-lead system

Percentage by mass of lead 0 20 38 67 80 100

Melting point (0C) 232 200 183 250 275 327

a) Draw a fully labeled diagram of tin-lead system

b) Use the phase diagram to determine the:

(i) Eutectic temperature

(ii) Composition of the eutectic mixture
c) Describe the changes that would take place if a liquid mixture of the above
system containing,10%,38% and 80% lead was cooled from 3300C to 1600C
d) Determining the mass of lead that will crystallize if 200g of liquid mixture
contains 80% lead is cooled from 3300C to 2100C
Solution

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 350

330 A
Q R S

310

290
W
Molten tin and lead mixture
270
temperature(0C)

250

C
230 Solid lead +molten
liquid mixture
U
210
T
V
Solid tin+
molten liquid
190 mixture
B
E D
\
170
Solid tin+ solid lead

150
0 10 20 30 40 50 60 70 80 90 100
%of lead in the mixture

Points:
A - Freezing or melting point of pure lead.
B –Eutectic point
C –Freezing or melting point of pure tin.
E-Eutectic temperature

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Curves:
AB-Variation of freezing point of lead as percentage of tin increases
or lowering of freezing Point of lead as percentage of tin increases
BA - Variation of freezing point of lead as concentration of tin is reduced
or increase of melting Point of lead as percentage of tin decreases
CB-Variation of freezing point of tin as lead is added
or lowering of freezing point of tin as percentage of lead increases
BC - Variation of freezing point of tin as concentration of lead in the mixture is
Reduced or increase of melting point of tin as percentage of lead decreases
Regions: Above ABC the system is entirely liquid
BCD- solid tin is in equilibrium with molten mixture.

ABE-solid lead is in equilibrium with molten mixture

Below the line DBE the system is entirely solid

(b)(i) Eutectic temperature is 1830C

(ii) Eutectic mixture is 38% by mass lead

Description of phase changes exhibited on cooling mixtures of different composition

Describe the changes that would take place if a liquid mixture of the above system
containing,10%,38% and 80% lead was cooled from 3300C to 1600C
(i) Cooling a liquid mixture10% lead at point Q
The mixture cools up to218 0C(point U) without visible change in phase. At point
218 0C (point U), on the curve solid tin begins to crystallize out of solution.
The composition of lead increases causing a further decrease in freezing point along UB
on the curve. lead also begins to crystallize out at point B. The freezing temperature and
composition remains constant until all the liquid mixture freezes. Thereafter, the solid
mixture cools further without change in composition and phase to room temperature.
(ii)Cooling a liquid mixture 38%Lead at point R
The mixture cools at constant composition along RB. At 1830C (point B), The freezing
temperature and composition remains constant until all the liquid mixture freezes to

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form a solid of the same composition as R. Thereafter, the solid mixture cools further
without change in composition and phase to room temperature.
(iii) Cooling a liquid mixture 80%lead at point S
The mixture cools up to 2820C(point W) without visible change in phase. At 2820C
(point W) solid lead begins to crystallize. The composition of tin increases causing a
further decrease in freezing point along WM on the curve AM. Tin also begins to
crystallize out at point B. The freezing temperature and composition remains constant
until all the liquid mixture freezes. Thereafter, the solid mixture cools further without
change in composition and phase to room temperature.

Determining the mass of a component that has crystallized/solidified

d)If 200g of liquid mixture of composition 80% lead is cooled from 3300C to 2100C, the
mass of lead remaining can be calculated as follows.

80
Mass of lead in liquid mixture before freezing 100 x 200 =160g
20
Mass of tin in liquid mixture before freezing 100 x 200 =40g

Mass of tin in liquid mixture after cooling to 210 0C is still 40g

Let the mass of lead remaining in the liquid mixture be Mg
Draw a vertical line from 3300 C to 2100C at 80% lead and a horizontal tie line (VT)
through 2100C and then look at the ends of it. at the right hand end you have
100%leadthat represents the solid lead that has frozen from the mixture. At the left
hand end you have the composition of the liquid mixture at 2100C
From the graph the percentage composition of lead in liquid mixture is 50%
Percentage of lead in the liquid mixture at 2100C is
𝑀
x 100 = 50
𝑀+40

M = 40
Mass of lead which has crystallized =160−40=120g

Holistic approach to physical chemistry by Jb Page 25

Example two

The sketch below shows the phase-diagram of mixtures of metals X and Y

a) State how the above curve was obtained.

By cooling the liquid mixtures of various compositions and then plot their cooling
curves. From which the temperature at which crystallization starts is determined.
Temperature at which crystallization begins is then plotted against composition of the
mixture.

b) Identify the regions P, Q, R and S.

i) P Liquid mixture of X and Y

ii) Q Solid Y and liquid mixture (of X and Y)

iii) R Solid X and solid Y

iv) S Solid X and liquid mixture (of X and Y)

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c) State what the following points represent
A -Melting point of pure X
B- It represents the eutectic point.
C- Melting point of pure Y
d) Describe what would happen if a mixture containing 50% by mass of X and Y is
cooled from 410oC to 270oC
The mixture would remain in liquid state during the cooling, until point V on the curve
AB where compound Y begins to solidify out. Composition of X in the mixture
increases causing a further decrease in freezing point along VB
At point B, the eutectic point solid Y also begins to crystallize out together with solid X
Then freezing temperature remains constant until all the mixture freezes.Thereafter,the
mixture cools to 2700C.

e) Draw a cooling curve to represent the above changes in part ( d)

C D
E

Time (minutes)

AB represents cooling of the hot liquid mixture

BC represents cooling of the liquid mixture as Y crystallize out

CD shows the constant temperature when both components solidifies

DE shows the cooling curve of the eutectic mixture

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Example three

Two components A and B form eutectic mixture of composition 55%A. The melting
points of pure A, B and eutectic are 320, 260 and 140oC respectively. Using the above
information sketch a fully labeled phase diagram for the mixture A and B.

(c )Explain what happens if a liquid mixture of 40% B at 400oC cooled to room

temperature.
If the mixture at 400oC is cooled, no visible change along XC, at point C freezing of B
starts and solid B remains in equilibrium with the liquid mixture. Further cooling along
CE more solid B is formed leaving the mixture richer in A, At point E, solid B and A
solidify out together as an eutectic and they do so at a constant temperature until
when all is converted into a solid which is left to cool to room temperature.

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Student activity

1.(a) Define the following terms

(i)Eutectic point

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(ii) Eutectic mixture.

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(b)The table below shows the melting points and compositions of various mixtures of
bismuth and cadmium.

Percentage of 20 35 50 65 80 95
cadmium (%)
Melting point (oC) 226 190 156 184 242 300

Draw a well labeled phase diagram for cadmium –bismuth system.

( c ) Use your graph to

(i)Determine the melting points of pure cadmium and pure bismuth.

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(ii)Determine the composition and melting point of the eutectic mixture.

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(iii)Describe what happens when a mixture liquid containing 10% of cadmium at

350oC is gradually cooled.

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(iv)Determine the mass of bismuth that crystallized when 200g of the mixture

Containing 25% cadmium was cooled from 300oC to 168oC.

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(c) State two similarities and two differences between a eutectic mixture and a pure
compound.

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(2)The table below shows the melting points of various mixtures of ethanoic acid and
water
% of ethanoic acid 0 20 40 60 80 100
Melting point (0C) 0 -10 -20 -19 -1 18

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(i)Draw a well labeled melting point-composition phase diagram for ethanoic acid-water
system.
ii) Determine the eutectic temperature and composition of the eutectic mixture.
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(iii)Explain the phase changes which would take place if a liquid mixture containing 20%
ethanoic acid at 150C was cooled to -300C.
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(iv)135g of the liquid mixture of composition 16% ethanoic acid at 5 0C was cooled to
-220C.Calculate the mass of ice that will crystallize out.
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