Chapter 6 - Multiphase Systems

Phase Diagrams for Pure Substances

See Fig. 6.1-1 on p. 241 for reference. Learn the definitions of the following
terms, and their location on a phase diagram:
critical point
triple point
vapor pressure curve
melting curve
sublimation curve
normal boiling point
normal melting point
saturated liquid
saturated vapor
solid, liquid, and gas regions
supercritical region
Vapor Pressures
Clausius-Clapeyron equation
Relates slope of vapor pressure curve to enthalpy change and volume
change on vaporization.
In approximate, integrated form (Eqn. 6.1-3) predicts that ln p* vs 1/T is a
straight line, which is the basis for interpolation of vapor pressures.
Cox chart
Plot log p* versus log p*ref for any number of substances, then replace the
scale on the x-axis with a temperature scale (using experimental data for
the reference substance).
The result is a Cox chart (Fig. 6.1-4, p. 247), which will turn out to give
nearly straight lines for all substances. Become familiar with this chart and
the species for which vapor pressures are represented on it.
Test yourself. 1. What are the triple point conditions for CO2?
2. Why does dry ice sublime at atmospheric pressure?
3. What is the normal boiling point for mercury?
4. What is the vapor pressure of methanol at 250 oF?
5. What is the vapor pressure of propane at 250 oF?
Antoine equation:

3-parameter fits to data - see Table B.4, p. 640 for constants for some
species.
better than Clausius-Clapeyron equation.
more accurate than reading information off the Cox chart.
stay within the specified ranges for good accuracy
Gibbs Phase Rule
F = degrees of freedom = number of phase equilibrium variables (T, P, mole
fraction compositions in each phase) which can be independently specified
m = number of components
= number of phases
F=m+2-
Example. In a system containing two components (m = 2, e.g., water and carbon
dioxide) and two phases ( = 2, e.g., vapor and liquid phases present), two of the
phase equilibrium variables must be given (F = 2) to fix all the others, for example,
P and T can be fixed, or P and xA, or T and yB, etc.
If r = the number of independent chemical reactions at equilibrium in the system,
then the phase rule must be modified to become
F=m+2--r
Gas-Liquid Systems with One Condensable Component
Two components: 1) a volatile liquid A (e.g., water) 2) a non-condensable gas B
(e.g., air)
m=2
Two phases: 1) liquid 2) vapor
=2
No reactions: r = 0
Degrees of freedom: F = 2 + 2 - 2 = 2
Variables: P, T, yA

(Note: yB = 1 - yA; and xA = 1 exactly)

Thus, fix any two and find the third from the equilibrium relationship (see
below).
General phase-equilibrium relationship:
The fugacity of any component is the same in all phases at equilibrium.
fAV = fAL
Raoults law type simplifications to general phase-equilibrium relationship:
Gas phase is an ideal gas mixture:

fAV = PyA = pA (partial pressure)

Pure liquid not at high pressure:

fAL = pA*

(vapor pressure)

PyA = pA*
Terms that need to be learned:
humidification
drying
saturated vapor
dew point
saturated liquid
bubble point
relative saturation (humidity)
molal saturation
absolute saturation
percentage saturation
Psychrometric charts
There are humidity charts (also called psychrometric charts) for the airwater system at 1 atm pressure on pp. 385-6.
Note: These charts are not highly accurate in Pullman, because the
pressure is not 1 atm. What is the approximate barometric pressure in
Pullman? How would you find the saturation curve and the percent
relative humidity lines for this barometric pressure?
Example problem. The dry bulb temperature is measured as 20 oC and the
wet bulb as 15 oC. If the total pressure is 1 atm, what are the relative
humidity and the absolute humidity? Use the humidity chart.
Relative humidity = 59 %
Absolute humidity = 0.0087 kg water/kg dry air
Multicomponent Gas-Liquid Systems

Use of tabulated vapor-liquid equilibrium data

Example. Ammonia gas is absorbed from an air stream by use of liquid
water as a solvent. Conditions in the absorber are 100. oF and 50. psia.
The liquid solution entering the top of the tower is 10.0 mole % ammonia.
What is the composition of the gas stream leaving the top of the absorber,
if it can be assumed to be in equilibrium with the liquid phase? If the inlet
gas contained 30.0 mole % ammonia, what fraction was removed in the
absorber?
From Perrys Handbook, at these conditions, the equilibrium partial
pressures of the two liquid components over a 10.0 mole %
solution are 1.98 psia for ammonia and 0.45 psia for water. Thus,
the mole fractions are
y(NH3) = 1.98/50. = 0.040
y(H2O) = 0.45/50. = 0.010
y(air) = 1 - 0.040 - 0.010 = 0.950
The fraction ammonia removed can be found by (in - out)/in:
frac removed = (0.300-0.040*0.700/0.950)/0.300
= 0.902
Raoults and Henrys laws
Raoults law ideal liquid solution, ideal gas
PyA = pA*xA
Component A must be below its critical temperature.

Henrys law ideal dilute solution, ideal gas

PyA = HAxA
Component A must be in low concentration (solute).
Component A may be above its critical temperature.
Component B (solvent -- binary mix) must obey Raoults law.
xA = solubility of A in the solvent (B)
HA = Henrys law constant (must be found experimentally)
Important terms:

bubble point

dew point
Pxy diagram (at constant T)
Txy diagram (at constant P)
Question: How do you use Raoults law to calculate dew and bubble
points for mixtures?
Solutions of Solids in Liquids
Phase diagrams
P
T
Saturated
Liquid

Solid Phase

Pressure is not usually important for solid-liquid systems.

Temperature is almost always important.
If both the liquid and solid phases are completely miscible (very unusual),
then the phase diagram will look exactly like a liquid-vapor Txy diagram
(Fig. 6.4-1), but it would be a TxLxS diagram.
If the liquid phase is miscible, but the two solids are completely immiscible,
then a eutectic point results.

T
Liquid + Pure
Solid 2

Liquid (L)
Liquid + Pure
Solid 1

L + S1
C

D E
S 1 + S2
0

1
X1

Pure Solid 1

Pure Solid 2

Lever rule:

DE/CE = fraction of S2 in L + S2 system

CD/CE = fraction of L in L + S2 system

Systems with Immiscible or Partially Miscible Liquids
Phase diagrams for ternary systems in liquid-liquid extraction
Component A is a solute distributed between two immiscible liquids.
Components B and C are the major components of the two liquid phases,
one of which is the solvent.
P
T
L1: A+B
L2: A+C

Distribution coefficient:

KA = xA(2)/xA(1)

Refer to Fig. 6.6-1 for an example of equilibrium data and use of the lever
rule in a partially miscible system.
Question: From looking at the figure, how do you know that the wateracetone-methyl isobutyl ketone system is a partially miscible system?