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(VLE): Introduction
1
The Phase Rule. Duhem’s Theorem
π = # of phase(s)
N = # of chemical species
2
From the given information
π =
N=
3
Consider a P-T diagram
S V
4
Example Determine a dof of a
system of a single species and a
single phase (e.g., either liquid or
vapour)
N=
5
When considering a P-T diagram,
in order to be able to specify the
exact point on the liquid (i.e. LHS of
the dome) or vapour (i.e. RHS of the
dome) zone, we need both P and T;
only P or T does not suffice
6
Example Determine a dof of a “triple
point” of a pure species
7
This implies that, for any pure species
(a single species), when we know the
triple point, we will automatically know
the name of the substance, or vice
versa
We do NOT need to know any other
Thermodynamic properties
S V
Triple point
8
Duhem’s Theorem
Applied to “closed” systems
9
For a 2 species system (i.e. a
binary mixture) with 2 phases (e.g.,
V+L), from the phase rule, we obtain
F = 2 −π + N
= 2−2+2
=2
In addition to T or P, we need to know
a chemical composition of a mixture, in
the from of either mole or mass fraction
Since it is a binary mixture, we need
to know mole or mass fraction of only
one substance; mole or mass fraction of
another substance will automatically be
fixed
Hence, dof = 1+1 = 2
10
For an n species system (i.e. N = n),
from the phase rule, we get
F = 2 −π + N
= 2−2+n
=n
This means that we need to know
either P or T, and mole (or mass)
fraction of n − 1 components
Hence, dof = 1+ ( n − 1) = n
11
VLE: Qualitative Behaviour
A+B
A+B
Liquid phase
Let
mole fraction of A in a liquid
phase = xA
and
mole fraction of A in a gaseous
phase = y A
12
At any given P, we vary T and
measure the values of xA and y A , and
then plot a graph between T and xA or
y A , or a Txy diagram as illustrated below
T Dew-point
Vapour curve
zone
T2 C
B
T1 A
T3
D
Bubble-point
curve
Liquid
zone
xA1 yA1
xA or yA
13
From a Txy diagram,
at any given T (e.g., T1)
Point A = saturated liquid state
of a liquid mixture at which the mole
fraction of species A = xA1
Point B = saturated vapour state
of a gaseous mixture where the mole
fraction of species A = yA1
14
Additionally, at T = T1
• a mixture with a mole fraction
of A lower than xA1 is in the form
of compressed or sub-cooled
liquid
• a mixture with a mole fraction
of A higher than yA1 is in the
form of superheated vapour
15
At a given xA (e.g., xA1)
when T is increased from the
state of compressed liquid (e.g., at T
= T3) to the point where T = T1, the
mixture starts to boil at the point A
If T is kept increasing, the
mixture is in the form of the vapour-
liquid mixture until T = T2 (point C),
where the mixture changes to the
form of a saturated vapour
and if T is still increased, the
mixture is in the form of superheated
vapour
16
On the other hand, if T is
decreased from the vapour zone,
where the mole fraction of species A
= yA1, to the point at which T = T1
(point B), the mixture turns to be
saturated vapour (there is a first drop
of liquid at this point)
If T is kept decreasing, the mixture
is in the form of liquid-vapour mixture
until T = T3 (point D), where the
mixture turns to be liquid completely
(or becomes saturated liquid)
17
When we draw Txy diagrams at
various P, we get
T
CB
P3
CA
P2
CA
P1
xA or yA
18
Note that
CA & CB = critical P of A & B,
respectively
that
P1 < P2 < P3
and that
P1 < Pc of A & B
P2 is in between Pc of A & B
P3 > Pc of A & B
19
At any given T, a Pxy diagram can
be drawn as follows
Bubble-point
P curve
Liquid
zone
L+V
Vapour
zone
Dew-point
curve
xA or yA
20
Pxy diagrams at various T are as
illustrated below
T3 CB
CA
T2
CA
T1
xA or yA
21
Note that
CA & CB = critical T of A & B,
respectively
that
T1 < T2 < T3
and that
T1 < Tc of A & B
T2 is in between Tc of A & B
T3 > Tc of A & B
22
In the case where either a Txy or a
Pxy diagram is as follows
T
Q
xAQ
xA or yA
24
At any mole fraction of A, we can
draw a P-T diagram as follows
P Critical
Bubble-point point
curve
Dew-point
curve
25
When we combine a P-T diagram at
different mole fractions of A, we obtain
P
CA
Critical
locus
CB
26
When we draw a graph of xA and
yA at a given T & P, we get
yA
yA = xA
xA
27
At the point where xA = yA, i.e. the
point where the composition of a
mixture in the gaseous phase is the
same as that in the liquid phase, we
cannot separate the mixture by
distillation
28
Simple Models for VLE Calculations
Raoult’s law
Assumptions for a Raoult’s law
• The VAPOUR PHASE is an IDEAL
GAS
• The LIQUID PHASE is an IDEAL
SOLUTION
29
Hence,
• Raoult’s law is applicable for a
system where P is not too high
(in order that a vapour phase
behaves as an ideal gas)
• The mixture should be in similar
chemical nature and not too
different in size – in order that it
behaves as an ideal solution
30
Raoult’s law
y i P = xi Pi sat (4.1)
where
yi = mole fraction of species i
in a gaseous phase
xi = mole fraction of species i
in a liquid phase
P = total pressure of a system
Pi sat = vapour pressure of
species i
31
Since
y i P = Pi (4.2)
where
Pi = partial pressure of species i
in a gaseous phase
Pi = xi Pi sat (4.3)
32
How can we obtain the value of Pi sat ?
Example
Saturated propane: T-table
Specific Volume
T (oC) P (bar)
vf vg
0 4.743 … ….
.. … … ….
.. … … ….
20 8.362 … ….
.. … … ….
.. … … ….
40 13.69 … ….
33
From Charts (e.g., a Cox chart)
34
Using Empirical Equations
Example
⎛ C2 ⎞
P sat
= exp ⎜ C1 + + C3 ln T + C4 T C5 ⎟
⎝ T ⎠
(4.4)
where
P sat is in the unit of Pa
T is in the unit of K
C1 − C5 are properties of a
substance
Note that C1 – C5 can be obtained
from, e.g., Table 2.6, pp. 2-50 – 2-54 of
Perry’s Chemical Engineers’ Handbook (7th
ed.)
35
Example The values of C1 − C5 of
propane are as follows:
C1 = 59.078 ; C2 = −3492.6 ;
C3 = −6.0669 ; C4 = 1.0919 × 10 −5 ;
C5 = 2
36
Another Empirical Equation
B
log P sat
= A− (4.5)
T +C
where
P sat is in the unit of bar
T is in the unit of oC
A − C are properties of a substance
Note that A – C are available in, e.g.,
Section D of Appendix A, pp. A.48 – A.60 of
The Properties of Gases and Liquids (5th ed.)
37
Example The values of A − C for
propane are as follows:
A = 3.92828
B = 803.9970
C = 247.040
38
Applying a summation for all
species to a Raoult’s law (Eq. 4.1)
y i P = xi Pi sat (4.1)
yields
∑ i
y P = P = ∑ ii
x P sat
(4.6)
39
Combining Eqs. 4.7 & 4.8 gives
P = x1P1sat + (1− x1 ) P2sat
= x1P1sat + P2sat − x1P2sat
40
Note that dashed lines are the
P − x1 lines from a Raoult’s law
41
Since liquid boils when ∑y i = 1, Eq. 4.6
1
P= (4.10)
∑ i i )
( y / P sat
42
Example Draw a Pxy diagram of
propane for a propane + ethane
mixture at T = 75 oC using a Raoult’s
law and an Antoine equation
The values for an Antoine
equation for propane and ethane
are as follows
Propane: Ethane:
A = 3.92828 A = 3.95405
B = 803.9970 B = 663.720
C = 247.040 C = 256.681
43
Employing an Antoine equation to
calculate P sat of propane and ethane
at 75 oC yields
44
Applying Eq. 4.9
P = x1 ( P1sat − P2sat ) + P2sat (4.9)
equation results in
45
Using Eq. 4.11 to calculate the
values of P at various xpropane results in
46
When the values of P at different
xpropane are obtained, the values of y propane
........ xpropane
and y propane =
P
47
From the Table in the previous
page, we can plot a Pxy diagram as
follows
100
80 Bubble-point
P-x curve
60
P [bar]
P-y
40
Dew-point
20
curve
0
0 0.2 0.4 0.6 0.8 1
xpropane or ypropane
48
Example Draw Txy diagram of
propane for a propane + ethane
mixture at P = 10 bar using a Raoult’s
law and an Antoine equation
B
T= sat
−C
A − log P
49
Thus, T sat at a given P can be
calculated from the following
equation
B
T sat = −C (4.12)
A − log P
At P = 10 bar
50
We, then, pick T between -32.0 –
27.5 oC, for example,
-32.0, -22.0, -12.0, -2.0, 8.0, 18.0, 27.5 oC
Calculating Ppropane
sat
and Pethane
sat
at these
51
Rearranging Eq. 4.9 results in
P − P2sat
x1 = sat
P1 − P2sat
Hence,
sat
P − Pethane
xpropane = sat sat
(4.13)
Ppropane − Pethane
52
The value of y propane can then be
53
sat
T Ppropane sat
Pethane
xpropane y propane
[oC] [bar] [bar]
-32.0 1.547 10.00 0 0
-22 2.268 13.42 0.307 0.070
-12 3.218 17.44 0.523 0.168
-2 4.438 22.28 0.688 0.306
8 5.968 27.95 0.817 0.487
18 7.849 34.49 0.919 0.722
27.5 10.000 41.54 1.000 1.000
54
A Txy diagram can then be drawn
as follows
40
20
Dew-point T-y
curve
T [oC]
-20
T-x Bubble-point
curve
-40
0.0 0.2 0.4 0.6 0.8 1.0
xpropane or ypropane
55
Bubble-Point Calculations
When we know mole fraction of a
substance in liquid phase ( xi ) and T, we
can calculate a “bubble-point P”
Vice versa, when we know mole
fraction of a substance in liquid phase
( xi ) and P, we can calculate a “bubble-
point T”
56
At a bubble point, ∑y i =1
xi Pi sat
yi = (4.1a)
P
xi Pi sat
∑ yi = ∑ P
1
1 = ∑ xi Pi sat
P
yields
P = ∑ xi Pi sat (4.6)
57
Given
P = 10 bar
xpropane = 0.3 Î xethane = 0.7
guessed T, as follows
58
Substituting the values of resulting
sat
Ppropane and Pethane
sat
into Eq. 4.14 yields
59
Since the resulting P is higher than
10.0 bar, it indicates that the guessed
value of T (-20 oC) are too high Î we
need a NEW GUESS
∑ i i = 10 bar
x P sat
60
Dew-Point Calculations
When we know mole fraction of a
substance in gaseous phase ( yi ) and
T, we can calculate a “dew-point P”
Vice versa, when we know mole
fraction of a substance in gaseous
phase ( yi ) and P we can calculate a
“dew-point T”
61
Example Calculate a dew-point P of
a propane + ethane mixture at T =
0 oC and y propane = 0.6
At a dew point, ∑x i =1
yi P
∑ xi = ∑ Psat
i
yi
1 = P∑ sat
Pi
62
results in
1
P= (4.10)
⎛ yi ⎞
∑ ⎜ Psat ⎟
⎝ i ⎠
Given
T = 0 oC
y propane = 0.6 Î yethane = 0.4
63
Thus,
64
Precautions for the use of Raoult’s law
• Can be used at not-too-high P
• Can be used at T < Tc
• Can be used with species whose
mole fractions approach 1 (if mole
fractions are too low, e.g., 5% or
0.05, Raoult’s law is NOT suitable)
• Can be used with a mixture whose
components are in chemical similar
nature and shape
65
Henry’s Law
66
For example, a Raoult’s law is NOT
applicable when we want to perform
VLE calculations for the CO2 (Tc =
304.12 K) + water system at 373.15 K,
since, by using a Raoult’s law, we
shall NOT have vapour pressure data
of CO2 at the temperatures above its
critical point
67
Henry’s law can help you
Henry’s law
“The partial pressure of the
species in the vapour phase is
directly proportional to its
liquid-phase mole fraction”
y i P = xi Η i (4.16)
where
Η i = Henry’s constant
For instances,
Η i of CO2 at 10 oC = 900 bar
69
Example Determine why we should
keep pop or soda at a low
temperature, using both Henry’s &
Raoult’s laws. Henry’s constants ( Η i )
70
Since CO2 can scarcely be dissolved
in water, its mole fraction of CO2 in
water is low
Hence, we should use a Henry’s law
for VLE calculations of CO2
71
Hence,
for CO2:
PCO2 = yco2 P = xco2 Η co2
for water:
sat
Pwater = y water P = xwater Pwater
72
Assume that 5% (by mol) of CO2 is
dissolved in water ( xCO 2
= 0.05 Î
xwater = 0.95 )
Thus, at 10 oC
74
Approximately, the amount of CO2
dissolved in water reduces by half
(5% to 2.7%) when T is increased from
10 to 25 oC
75
Assume that we use a compressor
to increase the total pressure of the
system from ~45 bar to 80 bar
Thus, the amount of CO2 dissolved
in the solution, at 25 oC, can be
calculated as follows
76
• Keep T of a solution (soda/pop)
at low temperatures (and a
bottle should also be capped)
• Keep P of the system at high
pressures, using, e.g., a
compressor
77
VLE Calculations by a MODIFIED
Raoult’s Law
79
From Lecture 3, we knew that
giE
ln γ i = (3.135)
RT
where giE = gi − giid , which indicates the
deviation from the ideal solution
80
We can use Eq. 4.17 to calculate a
bubble point and a dew point in the
same way we use Eqs. 4.6 and 4.10,
by keeping in mind that
• at a bubble point: ∑y i =1
• at a dew point: ∑x i =1
81
At a bubble point, ∑y i =1
Thus,
P = ∑ xiγ i Pi sat (4.18)
At a dew point, ∑x i =1
Hence,
1
P= (4.19)
⎛ yi ⎞
∑ ⎜ γ Psat ⎟
⎝ i i ⎠
82
How can we calculate activity
coefficients (γ i )???
83
ln γ 1 = Ax22
ln γ 2 = Ax12
where
A = P + QT
84
Example For a methanol (1) + methyl
acetate (2) binary mixture, activity
coefficients of methanol and methyl
acetate can be calculated using the
following equations: lnγ 1 = Ax22 and
ln γ 2 = Ax12 , where A = 2.771− 0.00523 T ( T in
K)
The values of A, B , & C for Antoine
equation are as follows
A = 5.20277 A = 4.18621
B = 1580.080 B = 1156.430
C = 239.500 C = 219.690
85
Determine
a) bubble-point P at T = 300 K and
x1 = 0.2
and
86
Vapour pressure of each
species can be calculated using an
Antoine equation, as follows
87
Hence, a bubble-point P can
be calculated as follows
89
b) dew point T at P = 1 bar and y1 = 0.3
90
Thus, we need to employ a
TRIAL & ERROR
technique
Thus,
91
Accordingly, the first guess of T
should be between 56.6 and 64.2 oC
(WHY??)
92
At a dew point, ∑x i =1
Thus,
1
P= (4.20)
⎛ yi ⎞
∑ ⎜ γ Psat ⎟
⎝ i i ⎠
94
and
95
Since T is still the same (= 60 oC),
Pi sat is also still the same
96
Substituting new corresponding
values into Eq. 4.20 results in
97
and
98
Trial & Error Procedure
• Calculate γ 1 and γ 2 from x1
and x2
• Guess new T
• Calculate Pi sat at new guessed T
• Calculate P and determine if it
is close to 1 bar (in an
acceptable level), if NOT,
another Trial & Error
99
c) if an azeotropic point exists at T = 300
K. If so, determine the composition of
each species at the azeotropic point
100
Thus,
y1 γ 1P1sat
= (4.21)
x1 P
y2 γ 2 P2sat
and = (4.22)
x2 P
(4.21)/(4.22) yields
y1 γ P sat
1 1
x1
= Psat
y2 γ 2 P2
x2 P
y1 / x1 γ 1P1sat
= α12 = (4.23)
y 2 / x2 γ 2 P2sat
101
From the relationships
ln γ 1 = Ax22
ln γ 2 = Ax12
and ln γ 2 = A Î γ 2 = exp ( A)
102
Hence, in the case where x1 = 0
P1sat exp ( A)
α12 = (4.24)
P2sat
and when x1 = 1
P1sat
α12 = sat (4.25)
P2 exp ( A)
103
Substituting corresponding
values into Eqs. 4.24 & 4.25 yields
104
From the values of α12 (@ x1 = 0 )
105
At the azeotropic point, α12 = 1
Hence,
γ 1P1sat
= α12 = 1
γ 2 P2sat
P1sat γ 2
=
P2sat
γ1
Substituting corresponding
values (from Question a)) gives
P1sat
sat
=
P2
106
ln γ 1 = Ax22 and ln γ 2 = Ax12
Hence,
γ2
ln γ 2 − ln γ 1 = ln = A ( x12 − x22 )
γ1
γ2 1
ln = A ( x1 − x2 )( x1 + x2 )
γ1
= A ( x1 − x2 )
= A ( 2 x1 − 1)
Thus,
107
The composition at the
azeotropic point of species 1 is
………………………………………………
108
VLE from K-value Correlations
109
DePriester, C.L. (1953) constructed
the relationship between yi and xi in the
form of Ki , as follows
yi
Ki = (4.26)
xi
y i = xi Ki (4.28)
110
At a bubble point, ∑y i =1
∑y = ∑x K
i i i =1 (4.29)
At a dew point, ∑x i =1
111
Example Determine a bubble-point T
at 150 psia of a mixture comprising
10 mol% methane, 20% ethane, and
70% propane
At bubble point, ∑y = ∑x K
i i i =1
Given
xCH4 = 0.10
xC2H6 = 0.20
xC3H8 = 0.70
112
Try T = 50 oF as the first guess
Thus,
113
Guess a new T Î T = 0 oF
Hence,
114
The resulting T is bubble-point T at
P = 150 psia
Try doing it yourself
(the answer is -50 oF)
118
Suppose F mol of feed with a
composition of each species of zi is
introduced into a flask tank
Let
V is the number of moles of feed
that evaporates
and
L is the number of moles of liquid
(or the number of moles of feed that
does not evaporate)
119
Material Balance
Overall balance
F=V+L (4.31)
Species balance
z i F = y i V + xi L
(4.32)
fi = vi + li
120
Rearranging gives
zi F
li = Lxi =
⎛ V ⎞
⎜ Ki + 1⎟
⎝ L ⎠
At a dew point, ∑x i =1
Thus,
zi F
∑ li = ∑ Lxi = L∑ xi = L = ∑ ⎛ V ⎞
⎜ Ki + 1⎟
⎝ L ⎠
121
Substituting Eq. 4.26
yi
xi = (4.26)
Ki
Rearranging gives
z i Ki F
vi = y i V =
⎛ L⎞
⎜ Ki + ⎟
⎝ V⎠
122
At a bubble point, ∑y i =1
Hence,
z i Ki F
∑ vi = ∑ yiV =V ∑ yi = V = ∑ ⎛ L ⎞
⎜ Ki + ⎟
⎝ V⎠
123
Example Perform a flash calculation
for the following mixture:
methane 10% mol
ethane 20% mol
propane 70% mol
fed into a tank with P = 200 psia and
T = 50 oF
Thus,
100 = V + L
124
Since there are 2 unknowns (V &
L), but we have only ONE equation,
we need to use a trial & error
technique
125
The resulting value of ∑v i or V is
126
fi z i Ki F
vi =
Component zi Ki L
[kmol] Ki +
V
Methane 10 0.10 9.8 ( 0.10 )( 9.8 )(100 ) = 8.04
71.3
9.8 +
28.7
CLOSE ENOUGH!!
127
The results of the flash calculation
are summarised in the following Table
fi vi li
Component
[kmol] [kmol] [kmol]
Methane 10 8.04 10 – 8.04 = 1.96
Ethane 20 8.35 11.65
Propane 70 12.30 57.70
100 28.69 71.31
128