Multiphase Systems

Virtually all commercial chemical processes involve operations in which

material is transferred from one phase (gas, liquid, or solid) into another.
These multiphase operations include all phase-change operations on a single
species, such as freezing, melting, evaporation, and con-densation, and most
separation and purification processes, which are designed to separate com-
ponents of mixtures from one another. Most separations are accomplished by
feeding a mixture of species A and B into a two-phase system under
conditions such that most of the A remains in its original phase and most of
the B transfers into a second phase. The two phases then either separate
themselves under the influence of gravity—as when gases and liquids or two
immisci-ble liquids separate—or are separated with the aid of a device such as
a filter or a skimmer.

Here are some examples of multiphase separation processes.

Brewing a cup of coffee. Hot liquid water and solid ground coffee beans are
contacted. Solu-ble constituents of the beans are transferred from the solid
phase to a liquid solution (coffee), and then the residual solids (grounds) are
filtered from the solution. The operation of dis-solving a component of a
solid phase in a liquid solvent is referred to as leaching.
Removal of sulfur dioxide from a gas stream. If a fuel that contains sulfur
is burned, the product gas contains sulfur dioxide. If the gas is released
directly into the atmosphere, the
 SO2 combines with atmospheric oxygen to form sulfur trioxide. The SO 3 in
turn combines with water vapor in the atmosphere to form sulfuric acid (H 2
SO 4), which eventually precip-itates as acid rain. To prevent this
occurrence, the combustion product gas is contacted with a liquid solution
in an absorption or scrubbing process. The SO 2 dissolves in the solvent
and the clean gas that remains is released to the atmosphere.

Recovery of methanol from an aqueous solution. After being used as a

reactant or sol-vent, methanol (methyl alcohol) often leaves a process in an
aqueous mixture (combined

with water). Methanol has a higher vapor pressure than water, meaning that
it has a greater tendency to vaporize when a mixture of the two species is
heated. The separation process distillation exploits this difference by
partially vaporizing a liquid mixture, yielding a vapor relatively rich in
methanol and a residual liquid relatively rich in water. Subsequent partial
condensations and vaporizations can be used to recover almost pure
methanol. The recov-ered methanol can be recycled and reused, resulting in
considerable savings in raw material costs.

Separation of paraffinic and aromatic hydrocarbons. Liquid paraffinic

hydrocarbons (such as pentane, hexane, and heptane) and liquid aromatic
hydrocarbons (such as benzene, toluene, and xylene) have different chemical
characteristics; for example, the paraffinic compounds are almost completely
immiscible with liquid ethylene glycol, while aromatic compounds and
ethylene glycol readily form homogeneous liquid mixtures. Paraffinics and
aromatics may therefore be separated from each other by blending a mixture
of the two with ethylene glycol. When allowed to settle, the aromatic
compounds distribute between a paraffin-rich phase and a glycol phase. This
process is known as liquid extraction. Subsequent processing separates the
aromatics from the glycol, recovering the glycol for recycle and reuse in the
extraction process.

Separation of an isomeric mixture. Para-xylene, a constituent in the

synthesis of polyesters, must be separated from two of its isomers, ortho- and
meta-xylene.

Two alternative commercial operations have been developed to perform the

separation. In one, a mixture of the isomers is contacted with a molecular
sieve that has pores large enough to accommodate para-xylene but not the
meta or ortho isomers. This operation is referred to as adsorption. In another
process, the difference in freezing points of the three isomers ( para-xylene
freezes at 13.3 C, ortho at 25 .2 C, and meta at 47 .9 C) forms the basis of a
crystallization operation. The mixture is cooled to a temperature at which
para crystallizes and can then be separated physically from the remaining
ortho and meta liquid.
When a species transfers from one phase to another, the transfer rate
generally decreases with time until the second phase is saturated with the
species, holding as much as it can hold at the prevailing process conditions.
When the concentrations of all species in each phase no longer change with
time, the phases are said to be in phase equilibrium. The effectiveness of any
of the separation processes described above depends both on how species are
distributed between the phases at equilibrium and on the rate at which the
system approaches equilibrium from its initial state.

TEST YOURSELF
Two alternative commercial operations have been developed to perform the
separation. In one, a mixture of the isomers is contacted with a molecular
sieve that has pores large enough to accommodate para-xylene but not the
meta or ortho isomers. This operation is referred to as adsorption. In another
process, the difference in freezing points of the three isomers ( para-xylene
freezes at 13.3 C, ortho at 25 .2 C, and meta at 47 .9 C) forms the basis of a
crystallization operation. The mixture is cooled to a temperature at which
para crystallizes and can then be separated physically from the remaining
ortho and meta liquid.

When a species transfers from one phase to another, the transfer rate
generally decreases with time until the second phase is saturated with the
species, holding as much as it can hold at the prevailing process conditions.
When the concentrations of all species in each phase no longer change with
time, the phases are said to be in phase equilibrium. The effectiveness of any
of the separation processes described above depends both on how species are
distributed between the phases at equilibrium and on the rate at which the
system approaches equilibrium from its initial state.

Suggest a method that might be suitable to achieve each of the following

separations.
1. Separate crude oil into volatile low molecular weight compounds
(naphthas used to make gasoline and light chemicals), intermediate
molecular weight compounds (used for heat-ing oils), and nonvolatile
high molecular weight compounds (used for lubricating oils).

2. Remove water from an aqueous slurry of bleached wood pulp.

3. Obtain fresh water from seawater.

4. Separate NH3 from a mixture of N 2 , H 2 , and NH3. Ammonia is highly
soluble in water; also, it condenses at 33.4 C.

5. Concentrate O2 for breathing-impaired patients.

CREATIVITY EXERCISE

A gas contains two species, A and B. Suggest as many methods as you can think of, both con-
ventional and unconventional, for separating the two species. Briefly indicate the conditions
required for each method to work. (For example, find a third substance, C, that reacts with A to
form a solid, and introduce C into the mixture. A will react and the product will deposit as a solid,
leaving B in the gas phase.)

6.0 INSTRUCTIONAL OBJECTIVES

After completing this chapter, you should be able to do the following:
Explain in your own words the terms separation process, distillation, absorption, scrubbin
g, liquid extraction, crystallization, adsorption, and leaching. (What are they and how do
they work?)

Sketch a phase diagram ( P versus T ) for a single species and label the regions (solid,
liquid, vapor, gas). Explain the difference between a vapor and a gas. Use the phase
diagram to define (a) the vapor pressure at a specified temperature, (b) the boiling point at
a specified pressure, (c) the normal boiling point, (d) the melting point at a specified
pressure, (e) the sublimation point at a specified pressure, (f) the triple point, and (h) the
critical temperature and pressure. Explain how the melting and boiling point temperatures
of water vary with pressure and how P and T vary (increase, decrease, or remain constant)
as a specified path on the diagram is followed.

Estimate the vapor pressure of a pure substance at a specified temperature or the boil-ing
point at a specified pressure using (a) the Antoine equation, (b) the Cox chart, (c) the
Clausius–Clapeyron equation and known vapor pressures at two specified temperatures, or
(d) Table B.3 for water.

Distinguish between intensive and extensive variables, giving examples of each. Use the
Gibbs phase rule to determine the number of degrees of freedom for a multicomponent
multiphase system at equilibrium, and state the meaning of the value you calculate in
terms of the system’s intensive variables. Specify a feasible set of intensive variables that
will enable the remaining intensive variables to be calculated.

In the context of a system containing a single condensable species and noncondensable

gases, explain in your own words the terms saturated v apor, superheated v apor, dew
point, degrees of superheat, and relative saturation. Explain the following statement from
a weather report in

terms a first-year engineering student could understand: The temperature is 75 F,

barometric pressure is 29.87 inches of mercury and falling , the relative humidity is 50%,
and the dew point
is 54 F.

Given an equilibrated gas–liquid system containing only a single condensable component

A, a correlation for pA(T ), and any two of the variables yA (mole fraction of A in the gas
phase), temperature, and total pressure, calculate the third variable using Raoult’s law.

Given a mixture of a single condensable vapor, A, and one or more noncondensable gases,
a correlation for p A(T ), and any two of the variables yA (mole fraction of A), temperature,
total pressure, dew point, degrees of superheat, and relative, molal, absolute, and
percentage saturation (or humidity if A is water and the noncondensable gas is air), use
Raoult’s law for a single condensable species to calculate the remaining variables.

For a process system that involves a single condensable component, a vapor-liquid phase
change, and specified or requested values of feed or product stream properties (tempera-
ture, pressure, dew point, relative saturation or humidity, degrees of superheat, etc.), draw
and label the flowchart, carry out the degree-of-freedom analysis, and perform the
required calculations.

Explain the meaning of the term ideal solution behavior applied to a liquid mixture of
volatile species. Write and clearly explain the formulas for Raoult’s law and Henry’s law,
state the
conditions for which each relationship is most likely to be accurate, and apply the
appropriate one to determine any of the variables T , P , x A , or yA (temperature, pressure,
and mole fractions of A in the liquid and gas phases) from given values of the other three.

Explain in your own words the terms bubble point, boiling point, and dew point of a
mixture of condensable species, and the difference between v aporization and boiling. Use
Raoult’s law to determine (a) the bubble-point temperature (or pressure) of a liquid
mixture of known composition at a specified pressure (or temperature) and the
composition of the first bubble
that forms; (b) the dew-point temperature (or pressure) of a vapor mixture of known com-
position at a specified pressure (or temperature) and the composition of the first liquid drop
that forms; (c) whether a mixture of known amount (moles) and composition (component
mole fractions) at a given temperature and pressure is a liquid, a gas, or a gas–liquid mix-ture
and, if the latter, the amounts and compositions of each phase; and (d) the boiling point
temperature of liquid mixture of known composition at a specified total pressure.

Use a Txy or Pxy diagram to determine bubble- and dew-point temperatures and pressures,
compositions and relative amounts of each phase in a two-phase mixture, and the effects of
varying temperature and pressure on bubble points, dew points, and phase amounts and
compositions. Outline how the diagrams are constructed for mixtures of components that
obey Raoult’s law.

For a process system that involves liquid and gas streams in equilibrium and vapor–liquid
equilibrium relations for all distributed components, draw and label the flowchart, carry out
the degree-of-freedom analysis, and perform the required calculations.

Explain in your own words the terms solubility of a solid in a liquid, saturated solution, and
hydrated salt. Given solubility data, determine the saturation temperature of a feed solution
of given composition and the quantity of solid crystals that form if the solution is cooled to a
specified temperature below the saturation point.

Given a liquid solution of a nonvolatile solute, estimate the solvent vapor-pressure lower-ing,
the boiling-point elevation, and the freezing-point depression, and list the assumptions
required for your estimate to be accurate.

Explain the term distribution coefficient (or partition ratio) for a solute distributed between
two nearly immiscible liquids. Given feed-stream flow rates and compositions for a liquid ex-
traction process and either solute distribution coefficient data or a triangular phase diagram,
calculate the product stream flow rates and compositions.

Explain the term adsorption isotherm. Given adsorption equilibrium data or an expression for
an adsorption isotherm, calculate the maximum quantity of adsorbate that can be re-moved
from a gas by a specified quantity of adsorbent or, conversely, the minimum quantity of
adsorbent needed to remove a specified quantity of adsorbate.

6.6 EQUILIBRIUM BETWEEN TWO LIQUID PHASES

6.6a Miscibility and Distribution Coefficients

If water and methyl isobutyl ketone (MIBK) are mixed at 25 C, a single phase results if the
mixture contains more than either 98% water or 97.7% MIBK by mass; otherwise, the
mixture separates into two liquid phases, one of which contains 98% H 2O and 2% MIBK and
the other 97.7% MIBK and 2.3% H2O. Water and MIBK are examples of partially miscible
liquids; they would be termed immiscible if one phase contained a negligible amount of
water and the other a negligible amount of MIBK.

If a third substance is added to a two-phase liquid mixture, it distributes itself accord-ing

to its relative solubility in each phase. For example, acetone is soluble in both water and
chloroform—two nearly immiscible liquids—but much more so in chloroform. If a mixture
of acetone and water is contacted with chloroform, a substantial portion of the acetone enters
the chloroform-rich phase. Separation of the acetone and water may then be accomplished
easily by allowing the mixture to settle and separating the two phases. This example
illustrates the separation process of liquid extraction.
Suppose A and S are two nearly immiscible liquids and B is a solute distributed between
the phases of an A–S mixture. The distribution coefficient (also known as partition ratio)
of component B is the ratio of the mass fraction of B in the S phase to that in the A phase.
Perry’s Chemical Engineers’ Handbook (see footnote 1) on pp. 15-10 through 15-14 lists
distribution coefficients for a number of ternary (three-component) liquid systems. Example
6.6-1 illus-trates the use of this physical property in a material balance calculation.

EXAMPLE 6.6-1

Extraction of Acetone from Water

Two hundred cubic centimeters of an acetone–water mixture that contains 10.0 wt% acetone
is mixed with 400.0 cm3 of chloroform at 25 C, and the phases are then allowed to settle.
What per Equipment centage of the acetone is transferred from the water to the chloroform?

Basis: Given Quantities

Since density data for the acetone–water system are not readily available, let us use Equation
5.1-1 to estimate the density of the feed solution:

Let us next assume that chloroform and water are immiscible. (How to deal with partial
miscibil-ity is discussed in Section 6.6b.) In drawing the flowchart for this problem, it is
advisable to label the quantities of each component in each of the two output streams, rather
than the total stream masses and component mass fractions. (Labeling in the latter manner
results in having to solve four simultaneous equations in four unknowns.)

The distribution coefficient for the A-C-W system is given on p. 15-12 of Perry’s Chemical
Engi-neers’ Handbook (see footnote 1) as 1.72. If x denotes mass fraction of acetone,

Test yourself

In practice, extraction is often carried out in several consecutive stages, with the solution
leaving each stage being contacted with additional solvent in the next stage. If enough stages
are used, almost complete transfer of the solute can be achieved. Problem 6.91 at the end of
this chapter illustrates this method of operation.
1.What is a distribution coefficient? What is liquid extraction?
2.The distribution coefficient for the system water–acetic acid–vinyl acetate is
mass fraction of acetic acid in vinyl acetate
0.294 mass fraction of acetic acid in water
Is acetic acid more or less soluble in vinyl acetate than in water? If you use vinyl acetate
to extract a large portion of the acetic acid in an aqueous solution, how would the relative
masses of the two phases compare ( mVA mW , mVA mW , or m VA mA)?