CE2106 Week 5

Solutions and Phase equilibrium of solutions

 Ideal solutions
 Non-ideal solution and partial molar properties
 Activity and activity coefficient
 Criteria for phase equilibrium of non-ideal solution
 Vapour-liquid equilibrium of non-ideal solution
 Equilibrium phase diagrams
Partial molar properties
We mix alcohol (A) and water (B):

Alcohol Va before Vb before Vtotal before Vtotal after ∆V, ml

wt% mixing, mixing, mixing, mixing,
ml ml ml ml
10 12.67 90.36 103.03 101.84 1.19

50 63.35 50.20 113.55 109.43 4.12

90 114.03 10.04 124.07 122.25 1.82

~ ~
Vtotal ≠ naVm,A + nbVm,B Vtotal = n a Va + n b Vb
~
Vi = Partial molar volume of i
Partial molar properties
 The partial molar volume is broadly understood as the contribution
that a component of a mixture makes to the overall volume of the
solution.
 When one mole of water is added to a large volume of water at
25 °C, the volume increases by 18 cm3. The molar volume of pure
water would thus be reported as 18 cm3 mol−1.
 However, addition of one mole of water to a large volume of pure
ethanol results in an increase in volume of only 14 cm3.
 The value 14 cm3 is said to be the partial molar volume of water
in ethanol.
 The reason that the increase is different is that the volume occupied
by a given number of water molecules depends upon the identity of
the surrounding molecules.
Partial molar properties
Partial molar properties
 The partial molar volume, Vi, of any substance i at a general
composition, is defined as:
𝜕𝜕𝑉𝑉
𝑉𝑉�𝑖𝑖 =
𝜕𝜕𝑛𝑛𝑖𝑖 𝑃𝑃, T, nj
where the subscript nj indicates that the amount of all the other
substances is held constant.
 The most common method of measuring partial
molar volumes is to measure the dependence
of the volume of a solution upon its composition.
The observed volume can then be fitted to a
function of the composition, and the slope of this
function can be determined at any composition
of interest by differentiation.
 Once the partial molar volumes of the two components of a mixture at
the composition and temperature of interest are known, the total
volume of the mixture can be calculated from, e.g. for a binary system:
~ ~
Vtotal = n a Va + n b Vb
Partial molar properties
We can define all the partial molar properties of V, H, S, G as:

𝜕𝜕𝑋𝑋
𝑋𝑋�𝑖𝑖 =
𝜕𝜕𝑛𝑛𝑖𝑖 𝑃𝑃, T, nj

where X – represents V, H, S, G

Every extensive property of a mixture has a corresponding partial molar

property For example, for Gibbs free energy

𝜕𝜕𝐺𝐺
𝐺𝐺�𝑖𝑖 =
𝜕𝜕𝑛𝑛𝑖𝑖 𝑃𝑃, T, nj
Partial molar properties
~ ~
Partial molar properties Hi Gi

can be manipulated in the same way as total-energy

properties :
~ ~ ~
H i = U i + PV i
~ ~ ~
Gi = H i − T S i
Ideal solutions
 The concept of an ideal solution is fundamental to chemical
thermodynamics and its applications, such as the use of colligative
properties.

 An ideal solution or ideal mixture is a solution in which the enthalpy

of solution (ΔHsolution=0) and volume variation (ΔVsolution=0) in mixing
are zero.

 With the closer to zero the enthalpy of solution, the more "ideal" the
behavior of the solution becomes.

 Since the enthalpy of mixing (solution) is zero, the change in Gibbs

energy on mixing is determined solely by the entropy of mixing
(ΔSsolution).
Ideal solutions
Raoult's law

 It states that the vapour pressure of a solvent above a solution (𝑃𝑃� i) is

equal to the vapour pressure of the pure solvent at the same
temperature (Pi0) scaled by the mole fraction of the solvent present
(xi).
~
0
Pi = xi Pi
 At any given temperature for a particular solid, there is a pressure at
which the vapour formed above the substance is in dynamic
equilibrium with its liquid form.
 At equilibrium, the rate at which the liquid evaporates is equal to the
rate that the gas is condensing.
 Combining with Dalton’ law
~
Pi = xi Pi0 = yi Pt
Ideal solutions
Henry's
 It states at a constant temperature, the amount of a given gas that
dissolves in a given type and volume of liquid is directly proportional
to the partial pressure of that gas in equilibrium with that liquid.
~
P i = K i xi
 An equivalent way of stating the law is that the solubility of a gas in a
liquid is directly proportional to the partial pressure of the gas above
the liquid.
𝑥𝑥𝑖𝑖 = 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
 In the solution, the sum of molar fractions of all the components
equals to 1.
∑ 𝑥𝑥𝑖𝑖 = 1
 In the gas phase, the sum of molar fractions of all the vapour
components equals to 1.
𝑃𝑃
∑ 𝑦𝑦𝑖𝑖 = 1, 𝑦𝑦𝑖𝑖 = 𝑖𝑖
𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
Non-ideal solutions
 Non-ideal solutions
 For non-ideal solutions, activity and activity coefficient have been
introduced to correct their performance deviation from ideal solutions.
 Activity is defined as the ratio of the fugacity of a compound at a state
divided by its fugacity at a reference state
~
fi
ai ≡ 0
fi
 An activity coefficient is used to account for deviations from ideal
behaviour in a solution. ~
ai fi
ai = γ i x i γi = =
x i x i fi0
Non-ideal solutions
Standard states

Arbitrary state chosen for advantages gained in use for calculations.

Each component has a standard state which is always defined with

respect to the system temperature.

Unfortunately the pressure of the standard state may vary according to

the systems under study.
Non-ideal solutions
Standard states --- Gases

(1) The pure gas as an ideal gas at 1 atm total pressure.

(2) The pure gas at the pressure of the system. If the total pressure is
higher than the saturation pressure of gas, theoretically the gas
should condense and the state is only imaginary.
Non-ideal solutions
Standard states --- Liquids
(1) Pure liquid at 1 atm pressure. If a liquid at the system temperature has
a vapour pressure greater than 1 atm this value becomes imaginary.

(2) Pure liquid at the system's pressure. If a liquid is above its

saturation or critical temperature, this state is imaginary.

(3) Pure liquid at its vapour pressure.

Non-ideal solutions
Standard states --- Solids

The solid standard state is normally taken as the pure solid at 1 atm
total pressure.

NOTE:

Standard conditions for temperature and pressure

T= 273.15 K; P= 1 Bar
Non-ideal solutions
Activity and activity coefficients and their estimation are important
concepts for equilibrium calculations.

The variation of the Gibbs free energy of a component i of a solution at

constant temperature is linked to its activity by

∆Gi,T = RT ln ai,T
 Criteria for phase equilibrium
At equilibrium the chemical potential and fugacity of each
component is the same in each phase present in the system

Example: for vapour-liquid system at equilibrium

µ =µl
i
v
i

~ ~
fi,v = f i,l
 Criteria for phase equilibrium
Liquid fugacities
Similar to the gas case, the chemical potential of a pure liquid/solid can
be expressed as
fi
µi (T ,P ) = µ i (T ,P * )+ RT ln
fi *

µi(T,P)- chemical potential of pure liquid i at temperature T and pressure P

µi(T,P*)- chemical potential of vapour i at temperature T and Pressure P*=1 atm

fi*- fugacity of pure vapour i at temperature T and pressure P*. fi*=P* if the vapour
is ideal gas.

fi- fugacity of pure liquid i

Criteria for phase equilibrium
~
Since: fi = ai fi 0 and ai = γ i x i

~ ~
For a vapour-liquid equilibrium fi,v = f i,l
we get

γ y i fi
v
i
0 ,v
= γ x i fi
i
l 0,l

0,v
fi – fugacity of pure vapour i at a reference state

0,l
fi – fugacity of pure liquid i at a reference state
 Criteria for phase equilibrium
For the gas the reference state is often chosen as being the fugacity of the
pure gas under the same temperature and pressure of the system.
0,v v
fi = fi

For the liquid the reference state is often chosen as being the fugacity of
the pure liquid under the same temperature and pressure of the system.

It is approximated as being the fugacity of the pure liquid at its saturated

vapour pressure at T
0,l s
fi = fi
Vapour-liquid Equilibrium
For an ideal vapour-liquid system

γ =1
v
i γ =1
i
l

and fi = Pt
v
fi l = Pi 0

Pt– total pressure of the gas phase

Pi0– pressure of saturated vapour i at T of the system

xi Pi 0
yi =
Pt
 Vapour-liquid equilibrium
For a non-ideal vapour-liquid system
~ ~ ~ ~
For the vapour phase: f = φ P = φ yi Pt
i
V V
i i
V
i

~
Therefore we get: φ y i Pt = γ il x i 𝑓𝑓i s
i
V

At low enough pressure, the fugacity coefficient of the species i is equal

to the fugacity coefficient of the pure substance at the system pressure
and temperature.
~
φ = φi
i
V

Therefore we get:

φi yi Pt = γ il xi f i s
Exercises
• From past paper
 Equilibrium phase diagrams
Ideal systems
The total pressure P is

PA PB
The composition of the vapour is given by: yA = and y B =
PA + PB PA + PB

𝑥𝑥𝐴𝐴 𝑃𝑃𝐴𝐴0
which rearranges to 𝑦𝑦𝐴𝐴 = 0 0 and yB = 1- y A
(𝑃𝑃𝐴𝐴 −𝑃𝑃𝐵𝐵 )𝑥𝑥𝐴𝐴 +𝑃𝑃𝐵𝐵0
 Mole fraction of A(g)
yA
P/PA0
1 1
10
PA0
=1
0.8 0.8 PB0

4 2
0.6 0.6
2 4
0.4
0.4 PA0 10
=1
0.2 PB0
0.2

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1

Mole fraction of A(l), xA Mole fraction of A(g), yA

 Pressure-Composition Phase Diagram (T fixed)

PA*
Pressure
Liquid only
1 phase α
L+V
Equil. L-V 2 phases
βL β
P = f(xA)
βV
P = f(yA)
γ Vapour only
P*
B 1 phase
zA
0 xA yA 1
Mole fraction of A(global), zA or A(l), xA or A(g), yA
 PA

Pressure
Liquid only *
1 phase α
L+V
Equil. L-V
βL β 2 phases
P = f(xA)
βV
P = f(yA)
γ
Vapour only
P*
B 1 phase
zA
0 xA yA 1
Mole fraction of A(global), zA or A(l), xA or A(g), yA

We consider 3 points (α, β, γ) of the same global composition zA,

but different P.

At α, it is not possible to find a combination of liquid and vapour

phases at the equilibrium at this P that gives this global
concentration (both are richer in A, xA >zA and yA >zA )

⇒ only one phase exists, which is liquid

 PA

Pressure
Liquid only *
1 phase α
L+V
Equil. L-V
βL β 2 phases
P = f(xA)
βV
P = f(yA)
γ
Vapour only
PB 1 phase
*
zA
0 xA yA 1
Mole fraction of A(global), zA or A(l), xA or A(g), yA

At γ, it is not possible to find a combination of liquid and vapour

phases at the equilibrium at this P that gives this global
concentration (both are poorer in A, xA <zA and yA<zA )

⇒ only one phase exists, which is vapour

 PA*

Pressure
Liquid only
1 phase α
L+V
Equil. L-V
βL β 2 phases
P = f(xA)
βV
P = f(yA)
γ
Vapour only
P*B 1 phase
zA
0 xA yA 1
Mole fraction of A(global), zA or A(l), xA or A(g), yA

At β, it is possible to find a combination of liquid and vapour

phases at the equilibrium at this P that gives this global
concentration (A, xA <zA and yA>zA )

⇒ the L(xA) and V(yA) co-exist

To determine the molar proportion of the liquid (nl) and vapour
(nv), we draw the tie line and use the reverse lever rule:

Liquid
L+V
Vapour
βL lL β lV
βV

lV
nL lL = nv lv n L l L = (1- n L )lV and n L =
lv + l L

lv lL
nL = and n v =
lv + l L lv + l L
 Exercises
The vapour-liquid equilibrium compositions for a mixture of
Component A and B are to be determined at 56°C. At this
temperature, the vapour pressure of pure A is 0.8142 bar and of B
is 0.5548 bar.
(a) calculate the activity coefficients using van Laar equation below.
The van Laar coefficients for the mixtures are A = 0.6184, B =
0.5795.
𝐵𝐵𝑥𝑥𝐵𝐵 𝐴𝐴𝑥𝑥𝐴𝐴
𝑙𝑙𝑙𝑙𝛾𝛾𝐴𝐴 = 𝐴𝐴 × ( )2 𝑙𝑙𝑙𝑙𝛾𝛾𝐵𝐵 = 𝐵𝐵 × ( )2
𝐴𝐴𝑥𝑥𝐴𝐴 +𝐵𝐵𝑥𝑥𝐵𝐵 𝐴𝐴𝑥𝑥𝐴𝐴 +𝐵𝐵𝑥𝑥𝐵𝐵
(b) Determine the vapour-liquid equilibrium compositions of the
acetone/methanol system at the temperature given in the text.
State any assumptions used.
© Plot the results in a pressure-composition diagram.
 Vapour-liquid equilibrium
For a non-ideal vapour-liquid system
~ ~ ~ ~
For the vapour phase: f = φ P = φ yi Pt
i
V V
i i
V
i

~
Therefore we get: φ y i Pt = γ il x i 𝑓𝑓i s
i
V

At low enough pressure, the fugacity coefficient of the species i is equal

to the fugacity coefficient of the pure substance at the system pressure
and temperature.
~
φ = φi
i
V

Therefore we get:

φi yi Pt = γ il xi f i s
(a) Calculation of Activity coefficient
𝐵𝐵𝑥𝑥𝐵𝐵 𝐴𝐴𝑥𝑥𝐴𝐴
𝑙𝑙𝑙𝑙𝛾𝛾𝐴𝐴 = 𝐴𝐴 × ( )2 𝑙𝑙𝑙𝑙𝛾𝛾𝐵𝐵 = 𝐵𝐵 × ( )2
𝐴𝐴𝑥𝑥𝐴𝐴 +𝐵𝐵𝑥𝑥𝐵𝐵 𝐴𝐴𝑥𝑥𝐴𝐴 +𝐵𝐵𝑥𝑥𝐵𝐵

A = 0.6184, B = 0.5795

XA XB LNrA LNrB rA rB
1 0 0.0000 0.5797 1.0000 1.7855
0.9 0.1 0.0055 0.4755 1.0055 1.6088
0.8 0.2 0.0223 0.3805 1.0225 1.4630
0.7 0.3 0.0508 0.2950 1.0521 1.3432
0.6 0.4 0.0915 0.2195 1.0958 1.2455
0.5 0.5 0.1448 0.1544 1.1558 1.1670
0.4 0.6 0.2113 0.1001 1.2353 1.1053
0.3 0.7 0.2914 0.0571 1.3383 1.0587
0.2 0.8 0.3856 0.0257 1.4705 1.0260
0.1 0.9 0.4946 0.0065 1.6398 1.0065
0.05 0.95 0.5548 0.0016 1.7415 1.0016
0 1 0.6188 0.0000 1.8567 1.0000
(a) Calculation of vapour phase composition
Assumption: vapor phase is ideal gas over a non-ideal solution

φi yi Pt = γ il xi f i s
∅𝑖𝑖 = 1 𝑃𝑃𝐴𝐴0 = 0.8142 𝑏𝑏𝑏𝑏𝑏𝑏 𝑃𝑃𝐵𝐵0 = 0.5548 𝑏𝑏𝑏𝑏𝑏𝑏

XA XB rA rB PA PB PT YA YB
1 0 1.0000 1.7855 0.8142 0.0000 0.8142 1.0000 0.0000
0.9 0.1 1.0055 1.6088 0.9168 0.1143 1.0311 0.8891 0.1109
0.8 0.2 1.0225 1.4630 0.8288 0.2079 1.0367 0.7994 0.2006
0.7 0.3 1.0521 1.3432 0.7461 0.2863 1.0325 0.7227 0.2773
0.6 0.4 1.0958 1.2455 0.6661 0.3540 1.0201 0.6530 0.3470
0.5 0.5 1.1558 1.1670 0.5855 0.4146 1.0001 0.5854 0.4146
0.4 0.6 1.2353 1.1053 0.5006 0.4713 0.9718 0.5151 0.4849
0.3 0.7 1.3383 1.0587 0.4067 0.5266 0.9334 0.4358 0.5642
0.2 0.8 1.4705 1.0260 0.2980 0.5833 0.8812 0.3381 0.6619
0.1 0.9 1.6398 1.0065 0.1661 0.6437 0.8098 0.2051 0.7949
0.05 0.95 1.7415 1.0016 0.0882 0.6762 0.7644 0.1154 0.8846
0 1 1.8567 1.0000 0.0000 0.7106 0.7106 0.0000 1.0000
©P-composition diagram

T=50°C

XA/YA
Exercice

The pressure-composition diagram of a nearly ideal

hexane+heptane mixture at 70ºC is given.

Consider a system of global

composition 50% hexane and 50%
heptane (Zheptane = 0.5).

Describe the system (number and

nature (L or V) of phase(s),
composition in heptane of
individual phases if more than one,
and proportions of the phases if
more than one) at the following
pressures: 700, 550 and 300 torr.
 L
At 700 torrs,

We have a single
liquid phase.

V
 L
Liquid and gas exist:

Gas: y=0.3 heptane

Liquid: x=0.56 heptane lv
lL

lv lL
nL = and n v =
lv + l L lv + l L
V

nL= 0.77
nV= 0.23
y x
 L
At 300 torrs,

We have a single
vapour phase.

V
 Temperature-Composition Diagram (P fixed).
Fractional distillation

Similarly, Temperature-Composition diagrams can be obtained at P fixed.

BPB* Vapour only

Temperature

a’2 Vapour
composition
a2
L+V Boiling
point of
liquid
a1 BPA*
a3 a’3
Liquid only

0 1
Mole fraction of A, zA
 BPB* Vapour only

Temperature
a’2 Vapour
composition
a2
L+V Boiling
point of
liquid
a1 BPA*
Liquid only a3 a’ 3

0 1
Mole fraction of A, zA

In a1, a single liquid phase is present, of composition a1.

When the temperature is raised up to the point a2, the liquid
starts boiling and the vapour has a different composition a2’.

If this vapour is removed and condensed at a lower temperature,

the liquid obtained is richer in A than it was in a1. If we boil this
liquid, its vapour will have a composition a3’, again much richer in
A, etc…
⇒ A can be obtained in high purity in only a few successive
distillations
 Equilibrium phase diagrams

Non Ideal systems

Non Ideal
Ideal
Example: Water-Ethanol Mixture
 Example: Water-Ethanol Mixture

For the water-ethanol mixture, the azeotrope concentration corresponds to

~95% of ethanol in the mixture. This is the limit that can be reached by
distillation of a less-alcohol-rich mixture.
Exercise 5.1:

The temperature-composition diagram of a nearly ideal hexane+

heptane mixture at 760torr is given.

Consider a system of global

composition 50% hexane and 50%
heptane (Zheptane = 0.5).
Describe the system (number and
nature (L or V) of phase(s),
composition in heptane of individual
phases if more than one, and
proportions of the phases if more
than one) at the following
temperatures: 90, 80 and 70 ºC
 V
At 90ºC, there is a
single vapour phase

L
At 80ºC, liquid and gas exist:

Gas: y=0.3 heptane V

Liquid: x=0.56 heptane

lv lL
nL = and n v =
lv + l L lv + l L

nL= 0.77 L
nV= 0.23
 V
At 70ºC, there is a
single liquid phase