KESETIMBANGAN

UAP-CAIR
Consider a system with two phases (vapor and
liquid) at given values of pressure and temperature
P
T
V
L
What we want to know is the equilibrium relationship between
the measurable variables P, T, yi, xi in this system
The simplest relationship is Raoults law, which is based on
assumptions of ideal gas for the vapor phase and
ideal liquid solution for the liquid phase:
i
sat
i i
x P Py =
Component Phase Equilibrium Single
If there is only a single component in a mixture,
there is only a single possible temperature (at a
given pressure) for which phase equilibrium is
possible.
For example, water at standard pressure (1 atm)
can only remain in equilibrium at 100
o
C. Below
this temperature, all of the water condenses, and
above it, all of the water vaporizes into steam.
If the atmospheric pressure is higher than the
vapor pressure, the liquid will not boil. Vapor
pressure is strongly temperature-dependent
Multiple-Component Phase
Equilibrium: Phase Diagrams
When a mixture begins to boil, the vapor
does not, in general, have the same
composition as the liquid. Instead, the
substance with the lower boiling
temperature (or higher vapor pressure) will
have a vapor concentration higher than
that with the higher boiling temperature,
though both will be present in the vapor
Raoult's Law: the Simplest Case
The simplest case (by far) to analyze occurs
when an ideal solution is in equilibrium with an
ideal gas
In an ideal liquid, the pressure exerted by a
certain component on the gas is proportional to
the vapor pressure of the pure liquid
the partial pressure of the liquid component on
the gas component is:


where is the vapor pressure of pure
component A.
Recall that the partial pressure of an ideal gas in a mixture
is given by:
P
A
= y
A
* P
Therefore, since the partial pressures must be
equal at equilibrium, we have the Raoult's Law
equation for each component: Raoult's Law for
component A :


Dew & Bubble Point Calculation
Dew Point is the very state at which condensation
is about to occur.
Dew Point Temperature Calculation at a Given Pressure
Dew Point Pressure Calculation at a Given Temperature
Vapor Fraction is 1 at Dew Point

Bubble Point is the very state at which
vaporization is about to occur.
Bubble Point Temperature Calculation at a Given Pressure
Bubble Point Pressure Calculation at a Given Temperature
Vapor Fraction is 0 at Bubble Point
Bubble Point and Dew Point with Raoult's Law
When calculating either a bubble point or a dew
point, one quantity is key, and this is the overall
composition, denoted with the letter z
It is important to remember that the dew and
bubble points of a multi-component mixture are
limits. The bubble point is the point at which a
very small amount of the liquid has evaporated -
so small, in fact, that in essence, the liquid
phase composition remains the same as the
overall composition
Making this assumption, it is possible to
calculate the composition of that single bubble of
vapor that has formed
Similarly, the dew point is the point at which a
very small amount of the vapor has condensed,
so that the gas phase composition remains the
same as the overall composition, and thus it is
possible to calculate the composition of the
single bubble of liquid.

Bubble Point
Recall that the dew point of a solution is the set
of conditions (either a temperature at constant
pressure or a pressure at constant temperature)
at which the first drops of a vapor mixture begin
to condense.
Let us first consider how to calculate the dew point
pressure (at a constant temperature) of a mixture of 2
components A and B,
write Raoult's Law for each component in the mixture.


We can add these two equations together to
yield:


y
A
+ y
B
= 1. In addition, recall that since we are
considering the bubble point, the liquid
composition is essentially equal to the overall
composition. Therefore, x
A
= z
A
and x
B
= z
B
.

Hence we have the following equation
valid at the bubble point for an ideal
equilibrium:
Bubble point equation for two
components under Raoult's Law


Therefore, if the temperature and overall
composition are known, the bubble
pressure can be determined directly.

If the pressure is held constant and the bubble point
temperature is required, it is necessary to calculate the
temperature by an iterative method. The temperature
dependence is contained in the Antoine equation for
vapor pressure of each component. One method to
solve for the temperature is to:

Guess a temperature , T
Use the guess and the Antoine equation to calculate
the vapor pressure of each component in the
mixture.P
O

Calculate an equilibrium pressure using the bubble
point pressure equation.
If the calculated pressure does not equal the known
pressure, it is necessary to change the temperature
and try again.

Bubble point equation for multiple
components under Raoult's Law


(summed over all components i)

Dew Point
The Dew Point calculation is similar,
although the equation that results from the
derivation is somewhat more complex.
The starting point is the same: assume
that Raoult's Law applies to each
component.



Now we want to eliminate the liquid
compositions in a similar manner to how
we eliminated the vapor compositions in
the previous derivation. To do this we
need to divide by the vapor pressures:


Adding the equations and recalling that x
A

+ x
B
= 1, we have:
:




Since this is the dew point, the gas-phase
composition is essentially the overall
composition, and therefore we have the
following dew point equation:
Dew Point Equation for Two
Components under Raoult's Law

Bubble-point pressure problem -- T,x
given -- P,y unknown.
This is a straight-forward calculation. The vapor
pressures are found at the given temperature, which
allows direct calculation of the pressure and vapor mole
fractions


= =
=
Py P P x
y
P x
P
i i
sat
i
i
i
sat
i
Bubble-point temperature problem -- P,x
given -- T,y unknown
A trial and error procedure must be followed, where T is
assumed, the vapor pressures calculated, and then see
if the correct total pressure is obtained (or the vapor
mole fractions sum to unity).
y
P x
P
i
i
sat
i

= = 1
y K x
i i i
= = 1
Dew-point pressure problem -- T,y given --
P,x unknown
No trial and error is needed, as P can be
directly calculated.
( )
x
Py
P
x
P
y P
i
i
i
sat
i
i i
sat
= =
=

1
1
/
Dew-point temperature problem -- P,y
given -- T,x unknown.
Guess a T, find the vapor pressures, and
see if the liquid mole fractions sum to
unity.
x
Py
P
i
i
i
sat

= = 1
x y K
i i i
= = 1 /
K-values, flash calculations, and relative
volatilities

A vapor-liquid equilibrium ratio (K-value) is defined for a
component as the ratio of mole fraction in the vapor to
mole fraction in the liquid for that component.
The criteria for flash calculations can be written if various
forms. A useful one is given below.





T, P, and feed compositions (zis) are know. A trial and
error for V must be done (fraction to vapor stream).





( )
K
y
x
P
P
f P T
z K
V K
i
i
i
i
sat
i i
i
= = =

+
=

( , )
( )
1
1 1
0
According to Raoults law, the relative
volatility (defined below) is just the ratio of
component vapor pressures.
Relative volatility:
o
ij
i i
j j
i
j
i
sat
j
sat
y x
y x
K
K
P
P
= = =
/
/
Isothermal Flash Calculations
Liquid
feed
T,P,F
z
i
T & P
L, x
i
Heater Valve
Flash
Drum
Equilibrium Flash Vaporization
The equilibrium flash separator is the simplest
equilibrium-stage process with which the
designer must deal. Despite the fact that only
one stage is involved, the calculation of the
compositions and the relative amount of the
vapor and liquid phases at any given pressure
and temperature usually involves a tedious trial-
and-error solution.

Buford D. Smith, 1963

Flash Calculation (1 of 4)
MESH Equation

Material Balance
Equilbrium Relations
Summation of Compositions
Enthalpy(H) Balance
Flash Calculation (2 of 4)
Overall Material Balance


Component Material Balance


Equilibrium Relations
L V F + =
i i i
Lx Vy Fz + =
i i i
x K y =
(1)
(2)
(3)
Flash Calculation (3 of 4)
Summation of Compositions


Defining


Combining (1) through (5), we obtain:

=
i
i
x 1
F V = |
( )
( )
( )

=
+

=
i
i
i i
K
K z
F 0
1 1
1
|
|
(4b)
(5)
(6)

=
i
i
y 1
(4a)
where:









































Flash Calculation (4 of 4)
From ideal Raoults law


K-value can be rewritten as:



From Antoine equation
vap
i i i
P x P y =
P
P
x
y
K
vap
i
i
i
i
= =
( )
( ) C C t
B
A kPa P
o
vap
i
+
= log
(7)
(8)
(9)
Antoine Coefficients
Benzene Toluene
A 6.01788 6.08436
B 1203.677 1347.620
C 219.904 219.787
( )
( ) C C t
B
A kPa P
o
vap
i
+
= log
Rachford-Rice Function
|
0.0 0.2 0.4 0.6 0.8 1.0
F
(
|
)
-0.15
-0.10
-0.05
0.00
0.05
0.10
707 . 0 = |
( )
( )
( )

=
+

=
i
i
i i
K
K z
F 0
1 1
1
|
|
Flash Calculation Results (1 of 3)
Vapor Flowrate (K-mole/hr)


Liquid Flowrate (K-mole/hr)


(1)
(2)
( ) 7 . 70 ) 707 . 0 ( 100 = = = | F V
3 . 29 7 . 70 100 = = = V F L
Flash Calculation Results (2 of 3)
Mole Fraction at the liquid phase




Mole Fraction at the vapor phase


(3)
(4)
( ) 1 1 +
=
i
i
i
K
z
x
|
4479 . 0 =
B
x
5521 . 0 =
T
x
(5)
(6)
( ) 1 1 +
= =
i
i i
i i i
K
z K
x K y
|
6631 . 0 =
B
y
3369 . 0 =
T
y
Flash Calculation Results (3 of 3)
Mole Fraction of Benzene
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P
r
e
s
s
u
r
e

(
k
P
a
)
60
80
100
120
140
160
180
200
4329 . 0 =
B
x
6429 . 0 =
B
y

determine the state of humid moist air
The Dry Bulb, Wet Bulb and Dew Point
temperatures are important to determine
the state of humid air

Dry Bulb Temperature - Tdb

The Dry Bulb temperature, usually referred
to as air temperature, is the air property
that is most common used. When people
refer to the temperature of the air, they are
normally referring to its dry bulb
temperature.
The Dry Bulb Temperature refers basically
to the ambient air temperature. It is called
"Dry Bulb" because the air temperature is
indicated by a thermometer not affected by
the moisture of the air.
Wet Bulb Temperature - Twb
The Wet Bulb temperature is the temperature of adiabatic
saturation. This is the temperature indicated by a moistened
thermometer bulb exposed to the air flow.

Wet Bulb temperature can be measured by using a thermometer
with the bulb wrapped in wet muslin. The adiabatic evaporation of
water from the thermometer and the cooling effect is indicated by a
"wet bulb temperature" lower than the "dry bulb temperature" in the
air.

The rate of evaporation from the wet bandage on the bulb, and the
temperature difference between the dry bulb and wet bulb, depends
on the humidity of the air. The evaporation is reduced when the air
contains more water vapor.

The wet bulb temperature is always lower than the dry bulb
temperature but will be identical with 100% relative humidity (the air
is at the saturation line).