ENTROPY AND EQUILIBRIUM 189

of state for both phases (for example, the SRK equation), and the VLE-condition

g,i
=
l,i
gives

V
i
y
i
=
L
i
x
i
(7.44)
where the fugacity coecients
V
i
and
L
i
are determined from the equation of state.
The K value is then K
i
=
L
i
/
V
i
. Note that (7.44) can also be used for supercritical
components.
7.5 Flash calculations
p, T
F
V
L
z
x
y
i
i
i
Figure 7.4: Flash tank
Flash calculations are used for processes with vapor/liquid-equilibrium (VLE). A
typical process that requires ash calculations, is when a feed stream (F) is separated
into a vapor (V ) and liquid (L) product; see Figure 7.4.
In principle, ash calculations are straightforward and involve combining the VLE-
equations with the component mass balances, and in some cases the energy balance.
Some ash calculations are (with a comment on their typical numerical solution or
usage):
1. Bubble point at given T (easy)
2. Bubble point at given p (need to iterate on T)
3. Dew point at given T (easy)
4. Dew point at given p (need to iterate on T)
5. Flash at given p and T (relatively easy)
6. Flash at given p and H (standard ash, e.g., for a ash tank after a valve)
7. Flash at given p and S (e.g., for condensing turbine)
8. Flash at given U and V (e.g., for dynamic simulation of an adiabatic ash drum)
The last three ashes are a bit more complicated as they require the use of the energy
balance and relationships for computing H, S, etc. The use of ash calculations is best
illustrated by some examples. Here, we assume that the VLE is given on K-value form,
that is,
y
i
= K
i
x
i
190 CHEMICAL AND ENERGY PROCESS ENGINEERING
Table 7.2: Data for ash examples and exercises: Antoine parameters for p
sat
(T), normal
boiling temperature (T
b
) and heat of vaporization vapH(T
b
) for selected components. Data:
Poling, Prausnitz and OConnell, The properties of gases and liquids, 5
th
Ed., McGraw-Hill (2001).
% log10(psat[bar])=A-B/(T[K]+C) Tb[K] dvapHb [J/mol]
A1=3.97786; B1=1064.840; C1=-41.136; Tb1=309.22; dvapHb1=25790; % pentane C5H12
A2=4.00139; B2=1170.875; C2=-48.833; Tb2=341.88; dvapHb2=28850; % hexane C6H14
A3=3.93002; B3=1182.774; C3=-52.532; Tb3=353.93; dvapHb3=29970; % cyclohex C6H12
A4=5.20277; B4=1580.080; C4=-33.650; Tb4=337.69; dvapHb4=35210; % methanol CH3OH
A5=5.11564; B5=1687.537; C5=-42.98; Tb5=373.15; dvapHb5=40660; % water H2O
A6=4.48540; B6= 926.132; C6=-32.98; Tb6=239.82; dvapHb6=23350; % ammonia NH3
A7=3.92828; B7= 803.997; C7=-26.11; Tb7=231.02; dvapHb7=19040; % propane C3H8
A8=4.05075; B8=1356.360; C8=-63.515; Tb8=398.82; dvapHb8=34410; % octane C8H18
A9=4.12285; B9=1639.270; C9=-91.310; Tb9=489.48; dvapHb9=43400; % dodecane C12H26
A10=3.98523; B10=1184.24; C10=-55.578; Tb10=353.24; dvapHb11=30720; % benzene C6H6
A11=4.05043; B11=1327.62; C11=-55.525; Tb11=383.79; dvapHb11=33180; % toluene C7H8
where y
i
is the vapor phase mole fraction and x
i
the liquid phase mole fraction for
component i. In general, the K-value K
i
depends on temperature T, pressure p and
composition (both x
i
and y
i
). We mostly assume ideal mixtures, and use Raoults law.
In this case K
i
depends on T and p only:
Raoult

s law : K
i
= p
sat
i
(T)/p
In the examples, we compute the vapor pressure p
sat
(T) using the Antoine parameters
given in Table 7.2.
7.5.1 Bubble point calculations
Let us rst consider bubble point calculations, In this case the liquid-phase
composition x
i
is given (it corresponds to the case where V is very small (V 0)
and x
i
= z
i
in Figure 7.4). The bubble point of a liquid is the point where the liquid
just starts to evaporate (boil), that is, when the rst vapor bubble is formed. If the
temperature is given, then we must lower the pressure until the rst bubble is formed.
If the pressure is given, then we must increase the temperature until the rst bubble
is formed. In both cases, this corresponds to adjusting T or p until the computed sum
of vapor fractions is just 1, y
i
= 1 or

i
K
i
x
i
= 1 (7.45)
where x
i
is given. For the ideal case where Raoults law holds this gives

i
x
i
p
sat
i
(T)

pi
= p (7.46)
Example 7.17 Bubble point at given temperature T. A liquid mixture contains 50%
pentane (1), 30% hexane (2) and 20% cyclohexane (3) (all in mol-%), i.e.,
x1 = 0.5; x2 = 0.3; x3 = 0.2
ENTROPY AND EQUILIBRIUM 191
At T = 400 K, the pressure is gradually decreased. What is the bubble pressure and
composition of the rst vapor that is formed? Assume ideal liquid mixture and ideal gas
(Raoults law).
Solution. The task is to nd a p that satises (7.46). Since T is given, this is trivial; we
can simply calculate p from (7.46). We start by computing the vapor pressures for the three
components at T = 400K. Using the Antoine data in Table 7.2, we get:
p
sat
1
(400K) = 10.248 bar
p
sat
2
(400K) = 4.647 bar
p
sat
3
(400K) = 3.358 bar
At the bubble point, the liquid phase composition is given, so the partial pressure of each
component is
p1 = x1p
sat
1
= 5.124 bar
p2 = x2p
sat
2
= 1.394 bar
p3 = x3p
sat
3
= 0.672 bar
Thus, from (7.46) the bubble pressure is
p = p1 +p2 +p3 = 7.189 bar
Finally, the vapor composition (composition of the rst vapor bubble) is
y1 =
p1
p
= 0.713; y2 =
p2
p
= 0.194; y3 =
p3
p
= 0.093
For calculation details see the MATLAB code:
T=400; x1=0.5; x2=0.3; x3=0.2
psat1=10^(A1-B1/(T+C1)), psat2=10^(A2-B2/(T+C2)), psat3=10^(A3-B3/(T+C3))
p1=x1*psat1, p2=x2*psat2, p3=x3*psat3, p=p1+p2+p3
y1=p1/p, y2=p2/p, y3=p3/p
Example 7.18 Bubble point at given pressure p. Consider the same liquid mixture
with 50% pentane (1), 30% hexane (2) and 20% cyclohexane (3) (all in mol-%). A p = 5
bar, the temperature is gradually increased. What is the bubble temperature and composition
of the rst vapor that is formed?
Solution. In this case, p and xi are given, and (7.46) provides an implicit equation for T
which needs to be solved numerically, for example, by iteration. A straightforward approach
is to use the method from the previous example, and iterate on T until the bubble pressure is
5 bar (for example, using the MATLAB code below). We nd T = 382.64 K, and
y1 =
p1
p
= 0.724; y2 =
p2
p
= 0.187; y3 =
p3
p
= 0.089
% MATLAB:
x1=0.5; x2=0.3; x3=0.2; p=5;
T=fzero(@(T) p-x1*10^(A1-B1/(T+C1))-x2*10^(A2-B2/(T+C2))-x3*10^(A3-B3/(T+C3)) , 400)
7.5.2 Dew point calculations
Let us next consider dew point calculations. In this case the vapor-phase composition
y
i
is given (it corresponds to the case where L is very small (L 0) and y
i
= z
i
in
Figure 7.4). The dew point of a vapor (gas) is the point where the vapor just begins
192 CHEMICAL AND ENERGY PROCESS ENGINEERING
to condense, that is, when the rst liquid drop is formed. If the temperature is given,
then we must increase the pressure until the rst liquid is formed. If the pressure is
given, then we must decrease the temperature until the rst liquid is formed. In both
cases, this corresponds to adjusting T or p until x
i
= 1 or

i
y
i
/K
i
= 1 (7.47)
where y
i
is given. For an ideal mixture where Raoults law holds this gives

i
y
i
p
sat
i
(T)
=
1
p
(7.48)
Example 7.19 Dew point at given temperature T. A vapor mixture contains 50%
pentane (1), 30% hexane (2) and 20% cyclohexane (3) (all in mol-%), i.e.,
y1 = 0.5; y2 = 0.3; y3 = 0.2
At T = 400 K, the pressure is gradually increased. What is the dew point pressure and
the composition of the rst liquid that is formed? Assume ideal liquid mixture and ideal gas
(Raoults law).
Solution. The task is to nd the value of p that satises (7.48). Since T is given, this is
trivial; we can simply calculate 1/p from (7.48). With the data from Example 7.17 we get:
1
p
=
0.5
10.248
+
0.3
4.647
=
0.2
3.358
= 0.1729bar
1
and we nd p = 5.78 bar. The liquid phase composition is xi = yip/p
sat
i
(T) and we nd
x1 =
0.5 5.78
10.248
= 0.282, x2 =
0.3 5.78
4.647
= 0.373, x3 =
0.2 5.78
3.749
= 0.345
% MATLAB:
T=400; y1=0.5; y2=0.3; y3=0.2
psat1=10^(A1-B1/(T+C1)), psat2=10^(A2-B2/(T+C2)), psat3=10^(A3-B3/(T+C3))
p=1/(y1/psat1 + y2/psat2 + y3/psat3)
x1=y1*p/psat1, x2=y2*p/psat2, x3=y3*p/psat3
Example 7.20 Dew point at given pressure p. Consider the same vapor mixture with
50% pentane (1), 30% hexane (2) and 20% cyclohexane (3). At p = 5 bar, the temperature is
gradually decreased. What is the dew point temperature and the composition of the rst liquid
that is formed?
Solution. In this case, p and yi are given, and (7.48) provides an implicit equation for
T which needs to be solved numerically (e.g., using the MATLAB code below). We nd
T = 393.30 K, and from xi = yip/p
sat
i
(T) we nd
x1 = 0.278; x2 = 0.375; x3 = 0.347
% MATLAB:
y1=0.5; y2=0.3; y3=0.2; p=5;
T=fzero(@(T) 1/p-y1/10^(A1-B1/(T+C1))-y2/10^(A2-B2/(T+C2))-y3/10^(A3-B3/(T+C3)) , 400)
Example 7.21 Dew point with non-condensable components. Calculate the
temperature and composition of a liquid in equilibrium with a gas mixture containing 10%
pentane (1), 10% hexane and 80% nitrogen (3) at 3 bar. Nitrogen is far above its critical
point and may be considered non-condensable.
ENTROPY AND EQUILIBRIUM 193
Solution. To nd the dew-point we use ixi = 1. However, nitrogen is assumed non-
condensable so x3 = 0. Thus, this component should not be included in (7.48), which becomes
y1
p
sat
1
(T)
+
y2
p
sat
2
(T)
=
1
p
Solving this implicit equation in T numerically (e.g., using the MATLAB code below) gives
T = 314.82K and from xi = yip/p
sat
i
(T) the liquid composition is
x1 = 0.245; x2 = 0.755; x3 = 0
7.5.3 Flash with liquid and vapor products
Next, consider a ash where a feed F (with composition z
i
) is split into a vapor
product V (with composition y
i
) and a liquid product (with composition x
i
); see
Figure 7.4 on page 189. For each of the N
c
components, we can write a material
balance
Fz
i
= Lx
i
+V y
i
(7.49)
In addition, the vapor and liquid is assumed to be in equilibrium,
y
i
= K
i
x
i
The K-values K
i
= K
i
(T, P, x
i
, y
i
) are computed from the VLE model. In addition,
we have the two relationships
i
x
i
= 1 and
i
y
i
= 1. With a given feed (F, z
i
), we
then have 3N
c
+2 equations in 3N
c
+4 unknowns (x
i
, y
i
, K
i
, L, V, T, p). Thus, we need
two additional specications, and with these the equation set should be solvable.
pT-ash
The simplest ash is usually to specify p and T (pT-ash), because K
i
depends
mainly on p and T. Let us show one common approach for solving the resulting
equations, which has good numerical properties. Substituting y
i
= K
i
x
i
into the
mass balance (7.49) gives Fz
i
= Lx
i
+ V K
i
x
i
, and solving with respect to x
i
gives
x
i
= (Fz
i
/(L + V K
i
). Here, introduce L = F L (total mass balance) to derive
x
i
=
z
i
1 +
V
F
(K
i
1)
Here, we cannot directly calculate x
i
because the vapor split V/F is not known. To
nd V/F we may use the relationship
i
x
i
= 1 or alternatively
i
y
i
=
i
K
i
x
i
= 1.
However, it has been found that the combination
i
(y
i
x
i
) = 0 results in an equation
with good numerical properties; this is the so-called Rachford-Rice ash equation
5

i
z
i
(K
i
1)
1 +
V
F
(K
i
1)
= 0 (7.50)
which is a monotonic function in V/F and is thus easy to solve numerically. A physical
solution must satisfy 0 V/F 1. If we assume that Raoults holds, then K
i
depends
5
Rachford, H.H. and Rice, J.D.: Procedure for Use of Electrical Digital Computers in Calculating
Flash Vaporization Hydrocarbon Equilibrium, Journal of Petroleum Technology, Sec. 1, p. 19,
Oct. 1952.
194 CHEMICAL AND ENERGY PROCESS ENGINEERING
on p and T only: K
i
= p
sat
i
(T)/p. Then, with T and p specied, we know K
i
and the
Rachford-Rice equation (7.50) can be solved for V/F. For non-ideal cases, K
i
depends
also on x
i
and y
i
, so one approach is add an outer iteration loop on K
i
.
Example 7.22 pT-ash. A feed F is split into a vapor product V and a liquid product L
in a ash tank (see Figure 7.4 on page 189). The feed is 50% pentane, 30% hexane and 20%
cyclohexane (all in mol-%). In the tank, T = 390K and p = 5 bar. For example, we may have
a heat exchanger that keeps constant temperature and a valve on the vapor product stream
that keeps constant pressure. We want to nd the product split and product compositions.
Assume ideal liquid mixture and ideal gas (Raoults law).
Comment. This is a quite close-boiling mixture and we have already found that at 5 bar the
bubble point temperature is 382.64 K (Example 7.18) and the dew point temperature is 393.30
K (Example 7.20). The temperature in the ash tank must be between these temperatures for
a two-phase solution to exist (which it does in our case since T = 390 K).
Solution. The feed mixture of pentane (1), hexane (2) and cyclohexane (3) is
z1 = 0.5; z2 = 0.3; z3 = 0.2
We have Ki = p
sat
i
(T)/p and at T = 390K and p= 5 bar, we nd with the Antoine parameters
in Table 7.2:
K1 = 1.685, K2 = 0.742, K3 = 0.532
Now, zi and Ki are known, and the Rachford-Rice equation (7.50) is solved numerically to
nd the vapor split V/F = 0.6915. The resulting liquid and vapor compositions are (for details
see the MATLAB code below):
x1 = 0.3393, x2 = 0.3651, x3 = 0.2956
y1 = 0.5717, y2 = 0.2709, y3 = 0.1574
% MATLAB:
z1=0.5; z2=0.3; z3=0.2; p=5; T=390;
psat1=10^(A1-B1/(T+C1)); psat2=10^(A2-B2/(T+C2)); psat3=10^(A3-B3/(T+C3));
K1=psat1/p; K2=psat2/p; K3=psat3/p; k1=1/(K1-1); k2=1/(K2-1); k3=1/(K3-1);
% Solve Rachford-Rice equation numerically to find a=V/F:
a=fzero(@(a) z1/(k1+a) + z2/(k2+a) + z3/(k3+a) , 0.5)
x1=z1/(1+a*(K1-1)), x2=z2/(1+a*(K2-1)), x3=z3/(1+a*(K3-1))
y1=K1*x1, y2=K2*x2, y3=K3*x3
Example 7.23 Condenser and ash drum for ammonia synthesis. The exit gas from
an ammonia reactor is at 250 bar and contains 61.5% H2, 20.5% N2 and 18% NH3. The gas
is cooled to 25
o
C (partly condensed), and is then separated in a ash drum into a recycled
vapor stream V and a liquid product L containing most of the ammonia. We want to calculate
the product compositions (L and V ) from the ash drum.
Data. In spite of the high pressure, we assume for simplicity ideal gas. Use vapor pressure
data for ammonia from Table 7.2 and Henrys law coecients for N2 and H2 from page 187.
For ammonia, we assume ideal liquid mixture, i.e., NH3 = 1 (which is reasonable since the
liquid phase is almost pure ammonia).
Solution. The feed mixture of H2 (1), N2 (2) and NH3 (3) is
z1 = 0.615, z2 = 0.205, z3 = 0.18
For ammonia, we have at T = 298.15 K and p = 250 bar (Raoults law):
K3 =
p
sat
3
(T)
p
=
9.83 bar
250 bar
= 0.0393
ENTROPY AND EQUILIBRIUM 195
For H2 and N2, we have from the given data for Henrys coecient at 25
o
C (298.15 K):
K1 =
H1(T)
p
=
15200 bar
250 bar
= 60.8
K2 =
H2(T)
p
=
8900 bar
250 bar
= 35.6
Now, zi and Ki are known, and the Rachford-Rice equation (7.50) is solved numerically to
nd the vapor split V/F = 0.8500. The resulting liquid and vapor compositions of the products
are
x1 = 0.0119, x2 = 0.0067, x3 = 0.9814
y1 = 0.7214, y2 = 0.2400, y3 = 0.0386
This agrees well with ow sheet data from a commercial ammonia plant.
Other ashes
For other ashes, like the pH-ash (which is relevant for an adiabatic ash tank), one
must include also the energy balance. For example, for an adiabatic ash tank, the
steady-state energy balance gives that the enthalpy H is constant. That is, H
in
= H
out
,
and we get
Fh
F

H
= V h
V
+Lh
L
(7.51)
where h
V
and h
L
[kJ/mol; kJ/kg] depend primarily on T, but in general also on x
i
, y
i
and p. One solution approach is to use the pT-ash described above, and iterate on T
in an outer loop until the requirement on H is satised. Another approach is to solve
the equations simultaneously, as shown for the dynamic adiabatic ash of methanol
and ethanol in Example 11.18 (page 317).
7.5.4 Flash exercises
Exercise 7.8

Bubble and dew point at given temperature. A hydrocarbon mixture

contains 10% propane, 80% hexane and 10% dodecane. (a) Find the bubble point pressure at
300 K. (b) Find the dew point pressure at 300 K.
Exercise 7.9

Bubble and dew point at given pressure. A hydrocarbon mixture

contains 10 mol-% propane, 80% hexane and 10% dodecane. (a) Find the bubble point
temperature at 1 bar. (b) Find the dew point temperature at 1 bar.
Exercise 7.10 Bubble point at given pressure. A liquid mixture contains 4 mol-%
hexane and the rest is octane. What is the composition of the rst vapor formed if the total
pressure is 1 atm?
Exercise 7.11

Flash at given p and T. A feed to a ash tank is 100 mol/s and contains
10% propane, 80% hexane and 10% dodecane. Find the amount of vapor product and the
compositions when T = 350K and p = 2bar.
Exercise 7.12 Flash calculation for binary mixture. Calculate the amount of liquid
that will remain at equilibrium when a mixture of 7 kg hexane and 3 kg toluene is vaporized
at 95
o
C and 1.5 bar.
Data: Molecular weights are 86.17 and 92.13.
196 CHEMICAL AND ENERGY PROCESS ENGINEERING
Exercise 7.13

Bubble and dew point calculations. (a) A gas mixture of 15 mol-%

benzene, 5 mol-% toluene and the rest nitrogen is compressed isothermally at 100
o
C until
condensation occurs. What will be the composition of the initial condensate?
(b) Calculate the temperature and composition of a vapor in equilibrium with a liquid that
is 25 mol-% benzene and 75 mol-% toluene at 1 atm. Is this a bubble point or a dew point?
(c) Calculate the temperature and composition of a liquid in equilibrium with a gas
mixture containing 15 mol-% benzene, 25 mol-% toluene and the rest nitrogen (which may be
considered non-condensable) at 1 atm. Is this a bubble point or a dew point?
Exercise 7.14 Condenser for exhaust gas. The exhaust gas from a natural gas power
plant is at 1 bar and contains 76% N2 (1), 12% O2 (2), 4% CO2 (3) and 8% H2O (4). The
gas is cooled to 25
o
C (partly condensed), and is then separated in a ash drum into a gas
product V and a liquid product L containing most of the water. Find the compositions of the
product streams. Are we able to remove any signicant amount of CO2 in the water?
Data: Use pure component vapor pressure data for water and Henrys law coecients for
the gas components (see page 187).