Separation Processes I

Topic 2: Vapour-Liquid Equilibrium

110

Bubble curve
Dew curve
100
T/°C

90

80
0 0.2 0.4 0.6 0.8 1
x, y

1
 Phase rule
• The thermodynamic properties of a multi-phase system at
equilibrium may be described by specifying the values of a
number of intensive variables
• Intensive variables are constant throughout a given phase (e.g.
density) or possibly throughout the whole system (e.g.
temperature and pressure)*
• The number of such variables that must be given to specify the
state of the system is the number of degrees of freedom, Nf
• The phase rule states that: Nf = Nc + 2 − Np
• where
– Nc is the number of chemical components
– Np is the number of phases
* Conversely, an extensive variable (e.g. volume) scales with the system size such that, if the system
is divided into two parts, the value for the whole system if the sum of the values in the two parts.
2
 Single component system
Phase Diagram of Methane
1000 No. Phases Degree of
Np Freedom Nf
100 1 2
Solid-Liquid (Melting) Curve 2 1
10
Critical Point 3 0
p /MPa

S L
1 Single component: Nc = 1
Hence, with 2 phases we
Vapour-Liquid (Boiling) Curve
0.1 can e.g. choose T (but p is
then fixed) or choose p (but
G
0.01 Triple Point T is then fixed).
Point to note:
Vapour-Solid (Sublimation) Curve
0.001 • Methane was used here
as an example
50 100 150 200 250 300
• Lines separate phases
T /K
• Semi-log scale used
3
 Two-phase binary system
• Consider a binary mixture in two-phase Nf = Nc + 2 − Np
vapour-liquid equilibrium (VLE):
Nc = 2, Np = 2, hence Nf = 2 Binary Mixture

• Usually, in experimental VLE measurements, No. Phases

Np
Degree of
Freedom Nf
one fixes either T or p leaving one remaining 1 3
degree of freedom
2 2
• e.g. Isobaric VLE in a binary system: having 3 1
fixed p, the state of the system can be 4 0
determined by one composition variable; e.g.
T = T(x1) and y1 = y1(x1), both considered as
yi
functions of x1
T, p
• xi = mole fraction of component i in the liquid xi
• yi = mole fraction of component i in the
vapour 4
 Composition in binary mixtures
• Since the two mole fractions add up to unity, we often specify
the mole fraction of one component only
• This is normally the more volatile component (MVC)
• For clarity, the component in question should be specified

Notation is as follows:
• z = mole fraction of the MVC in the feed to a steady-flow
process, or in the whole system for a batch process
• x = mole fraction of the MVC in the liquid phase
• y = mole fraction of the MVC in the vapour phase

5
 Vapour-liquid systems
Expansion of a mixture in a variable volume

A B C D E
Increasing temperature (p fixed) or decreasing pressure (T fixed)

A. This is a sub-cooled liquid state: a single homogeneous liquid phase

B. This is the bubble point: the appearance point of the first bubble of vapour
C. This is a point in the two-phase region: macroscopic amounts of vapour and
liquid coexist
D. This is the dew point: the vanishing point of the last drop of liquid
E. This is a super-heated vapour state: a single homogeneous vapour phase

6
Material balance for vapour-liquid system

Vapour, mole
A B C D E Whole system, fraction y of MVC
mole fraction z Liquid, mole
of MVC fraction x of MVC

• Material balance equation for MVC: z ntotal = x nliquid + y nvapour

where n is amount of substance (moles)

• Hence: z = (1 – β)x + βy
where β is the vapour fraction on a molar basis β = nvapour/ntotal

• Alternatively: z =qx + (1 – q)y

where q = 1 – β is the liquid fraction on a molar basis q = nliquid/ntotal
7
 Isothermal p,x,y diagram
Benzene + Toluene at T = 61°C
55 • Diagram shows the vapour-liquid phase
behaviour of a simple binary mixture
45 (benzene + toluene in this example)
• Fixed temperature (61°C in this
35 example), below the critical
p/kPa

temperatures of both components

25 • Hence, coexistence over the full
Bubble curve
composition range
Dew curve
15 • Blue curve shows the locus of bubble
0 0.2 0.4 0.6 0.8 1 pressures p(x)
x, y • Red curve shows the locus of dew
• A horizontal line connecting a point on the pressures p(y)
bubble curve with the corresponding • The end points are the vapour
point on the dew curve is called a tie line pressures of the pure compounds
• The end points represent co-existing • For this example at T = 61°C
phases and we can read off the pressure p o x = 0 (pure toluene), psat = 19 kPa
and the phase compositions x and y: o x = 1 (pure benzene), psat = 54 kPa
e.g. p = 31 kPa, x = 0.34, y = 0.58
8
 Example: isothermal vapour-liquid system
Benzene + Toluene at T = 61°C
55
• Start with a homogenous
liquid mixture of benzene +
toluene, containing mole
45 fraction 0.4 benzene at 61°C
and ambient pressure
• Benzene is the MVC
• Expand the mixture at
p/kPa

35 constant T until p = 30 kPa

• Determine graphically the
equilibrium compositions of
the co-existing liquid and
25 Bubble curve vapour phases at p = 30 kPa
• Also determine, for the
Dew curve same overall composition,
the dew pressure and the
15 composition of the co-
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 existing liquid at the dew
x, y point

9
 Isobaric T,x,y diagram
Benzene + Toluene at p = 101.3 kPa
110
• Diagram shows the vapour-liquid phase
behaviour of a simple binary mixture
Bubble curve
Dew curve
(benzene + toluene in this example)
100 • Fixed pressure (101.3 kPa in this
example), below the critical pressures
T/°C

of both components
90
• Hence, coexistence over the full
composition range
80
• Blue curve shows the locus of bubble
0 0.2 0.4 0.6 0.8 1 temperatures T(x)
x, y • Red curve shows the locus of dew
• A horizontal line connecting a point on the temperatures T(y)
bubble curve with the corresponding point • The end points are the boiling
on the dew curve is called a tie line temperatures of the pure compounds
• The end points represent co-existing • For this example at p = 101.3 kPa
phases and we can read off the o x = 0 (pure toluene), Tsat = 110.6 °C
temperature T and the phase compositions o x = 1 (pure benzene), Tsat = 80.0 °C
x and y:
e.g. T = 96 °C, x = 0.38, y = 0.60 10
 Isobaric vapour-liquid equilibrium
Benzene + Toluene at p = 101.3 kPa
110 E

Bubble curve
Heating with p constant
D
Dew curve
100 F C G
B
T/°C

90 A

A B C D E
80
0 0.2 0.4 0.6 0.8 1 Increasing temperature
x, y

• Point A is sub-cooled liquid with feed composition z = 0.3 (all liquid, so x = z = 0.3)
• Point B is the bubble point. The horizontal tie line connects B with the incipient vapour.
• Point C: the horizontal tie line connects coexisting vapour at G (mole fraction y = 0.45) with
liquid at F (mole fraction x = 0.26) and the fraction vaporized is (z – x)/(y – x) = 0.22
• Point D is the dew point. The horizontal tie line connects D with the incipient liquid
• Point E is super-heated vapour (all vapour, so y = z = 0.3)
11
 K Factors
• The components of a mixture generally have differing
relative volatility
• Hence, co-existing vapour and liquid phases generally have
different compositions
• For component i in a mixture, we define the vaporization
equilibrium ratio, or K factor, as follows:
Ki = yi/xi
• Thus, for a binary mixture, we have two K factors:
K1 = y/x and K2 = (1 – y) /(1 – x), where x = x1 and y = y1, and
component 1 is the MVC.
• The K factors generally depend upon temperature, pressure
and composition in a complex way.
• We will later consider the simple case of an ideal mixture for
which K depends only on T 12
 Relative volatility
For a binary system of components 1 and 2, we define the relative
volatility α as follows:
K1 ( y1 / x1) y (1 − x ) αx
α= = = ⇒ y=
K 2 ( y 2 / x2 ) x(1 − y ) 1 + x(α − 1)

• α typically declines with 2.6

Relative Volatility of Benzene + Toluene

increasing temperature at p = 101.3 kPa

Relative volatility

constant pressure. 2.5

Geometric mean

• α → 1 at the critical point α

• Hence, separation
processes normally operate 2.4
Geometric mean :
below the critical pressure α = α x =0α x =1

• α often approximated by its 2.3

80 90 100 110
geometric mean value T/°C
13
 Isobaric equilibrium curve
• The equilibrium
Benzene + Toluene at p = 101.3 kPa
1 curve is
constructed on an
Equilibrium phase
x-y diagram
0.8 compositions
• Gives the locus y(x)
of equilibrium
0.6 compositions
• Pressure constant
• Temperature varies
y

0.4 along the curve

Equilibrium line
• For constant
45° line
0.2 relative volatility α:
αx
y=
1 + x(α − 1)
0 or
0 0.2 0.4 0.6 0.8 1 y
x=
x α − y (α − 1)
14
 Feed line (q-line)
Benzene + Toluene at p = 101.3 kPa Consider a two-phase feed
1
mixture with overall mole
Equilibrium phase fraction z of the MVC, amount F
0.8 compositions
of feed and liquid fraction q:
0.6 F = feed quantity
L = qF = liquid quantity
y

0.4 q line V = (1 - q)F = vapour quantity

Equilibrium line

0.2
Overall (feed)
composition
45° line
In a steady-flow process, F, L
and V become molar flow rates
0 z qx
0 0.2 0.4 0.6 0.8 1 y= −
x 1− q 1− q
• MVC material balance equation for the feed: zF = xL + yV or z = qx + (1 – q)y
• Hence y =[z/(1 – q)] –[q /(1 – q)]x is the equation of the q line
• This line passes through the feed point x = y = z and has slope -q/(1 – q)
• All points on the q-line satisfy the material balance equation
• All points on the blue curve satisfy the phase equilibrium criteria at the given pressure
• Hence the intersection point gives the equilibrium x and y for the given z and q. 15
 Properties of the q-line
1
Benzene + Toluene at p = 101.3 kPa Bubble-point phase split:
q = 1, L/V = ∞, q-line is vertical
0.8 (↑ on diagram)
Equilibrium phase
compositions
0.6 Dew-point phase split:
q = 0, L/V = 0, q-line is horizontal
y

q line
0.4
Equilibrium line
(← on diagram)
Overall (feed) 45° line
0.2 composition General two-phase split:
0
0 ≤ q ≤ 1, 0 ≤ L/V ≤ ∞, q-line has
0 0.2 0.4 0.6 0.8 1 negative slope
x (e.g. ↖ on diagram)
• y =[z/(1 – q)] –[q /(1 – q)]x (equation of the q line)
• The slope is -q/(1 – q) = - L/V (the negative of the liquid-to-vapour ratio)
• All points on this line satisfy the material balance criterion
• Passes through the point y = x = z on the 45°line
• The point at which the q-line crosses the equilibrium curve also satisfies the phase
equilibrium criterion and is the equilibrium solution for the given z and q. 16
 Raoult’s law and ideal mixtures (1)
• In an ideal liquid mixture, the partial pressure exerted by each
component is the product of liquid mole fraction xi and
saturated vapour pressure pi .
s

• This expressed in Raoult’s law in which the total pressure is

given by:
p = x1p1s + x2 p2s

• So, for ideal mixtures, the isothermal bubble curve p(x1) is a

linear function of mole fraction at constant temperature.
Deviations from Raoult’s law are therefore easily seen on an
isothermal p, x, y diagram.
• Furthermore, in an ideal gas mixture, and the partial pressure of
each component is the product of mole fraction yi and total
pressure p. cont.
17
 Raoult’s law and ideal mixtures (2)
• Since the total pressure, p = x1p1s + x2 p2s , is the sum of the
partial pressures, it follows that the vapour phase compositions
are given by
y i = xi pis /( x1p1s + x2 p2s )

• Hence the vaporization equilibrium ratios or ‘K factors’ are:

K i = y i / xi = pis /( x1p1s + x2 p2s ) = pis / p
• and the relative volatility is simply
α = p1s / p2s only a function of T

• K factors and relative volatility are widely used in the

description of vapour-liquid equilibrium problems.
18
 Vapour pressures of pure substances
• To apply Raoult’s law we need to know the vapour pressures
of the components as functions of temperature
• Many databases exist (e.g. NIST Chemistry Webbook)
• Empirical correlations are also commonly used, notably
Antoine’s equation:
log10 ( p s ) = A − B /(T + C )
where A, B and C are substance-dependent parameters
• This is better expressed in terms of e.g. ps/kPa and T/°C
log10 ( p s / kPa) = A − B /[(T / °C) + C ]
• Constants have been tabulated for many substances
– be careful with units for both pressure (kPa, bar, MPa, mmHg etc all
commonly used) and temperature (°C, K etc).

19
 Azeotropic systems
• Non-ideal liquid mixtures deviate from Raoult’s law.
• ‘Unfavourable’ interactions between the unlike molecules give
positive deviations from Raoult’s law (total pressure greater
than ideal) and can lead to a minimum-boiling-temperature
azeotrope.
• Strong attractions between the unlike molecules give negative
deviations from Raoult’s law (total pressure less than ideal) and
can lead to a maximum-boiling-temperature azeotrope.
1
100
Example: 2-propanol + 95
Bubble curve 0.8

water at p = 101.3 kPa 90

Dew Curve

0.6

forms a minimum-

y1
T/°C

0.4
85

boiling-temperature 80 0.2
Equilibrium
curve
45° line

azeotrope 75 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1, y1 x1 20
Additional VLE Examples in Binary Systems
2-Methylbutane (1) + Cyclohexane (2): at T = 325 K at p = 1 bar

Nearly ideal system

Nitromethane (1) + Tetrachloromethane (2) at 1 bar Acetone (1) + Trichloromethane (2) at 1 bar

Minimum boiling
azeotrope

Maximum boiling
azeotrope

21
Experimental measurement of VLE
• Recirculation still used to
measure VLE at low pressure
• Usually a glass apparatus
• Condensate returns to boiler
• Phases sampled at steady
state to determine xi and yi at
measured T and p.
Z1 – liquid sampling valve
Z2 – condensate sampling valve
Z3 – filling valve
T – thermometer
P – pressure sensor
q - heater
22
Re-circulating Still

23
 Points to note
• Application of the phase rule to VLE problems, especially
binary systems.
• p, x, y and T, x, y diagrams for binary systems
• Definition and significance of relative volatility
• Construction and use of the equilibrium curve and q line
• Raoult’s law and VLE of ideal binary mixtures
• Non-ideal binary mixtures and azeotropes
• What is measured in a low-pressure VLE experiment

24