BEH.360/10.

449 SUPPLEMENTARY HANDOUT #2

FALL 2000

PHASE EQUILIBRIA & MASS TRANSFER: HOW TO SET UP

BOUNDARY CONDITIONS

1. Phase Equilibria
Introduction
A collection of molecules is in equilibrium with its surroundings if there is no net
transfer of energy or matter across the boundaries to the environment. Individual molecules may
constantly be zinging across the boundaries, or bumping into neighbors and transferring heat,
due to thermal motion. But if we average over millions of molecules, the number of molecules
leaving the volume of interest ("control volume") gets cancelled out by an equal number
returning to the control volume, so the net motion across the boundary is zero. This situation is
analogous to chemical reaction equilibrium -- when equilibrium is reached, the rate of the
forward reaction is equal to the rate of the reverse reaction, and there is no net measurable
change in the concentration of reactants or products with time. In each case, the equilibrium is
dynamic, meaning that forward and reverse reactions are constantly occuring. However, the
overall measurable properties of the system do not change with time, and we consider the system
at equilibrium1.
Definitions and Measuring Equilibria
(1) Consider first the situation where Phase I and Phase II are pure components A and B (phases
are liquid, solid, or gas). Imagine that you put A & B together in a closed vial, shook the
vial vigorously, then waited an "infinitely" long time, keeping the vial at constant
temperature. At infinity, you should observe 2 separate phases (e.g., a layer of salt crystals at
the bottom of a layer of water; oil layered on top of water, or liquid/gas). [Note -- if you do
not observe 2 phases at infinite time, then you did not add enough of the component in the
missing phase…i.e., you did not reach its solubility limit. Go back and add more until you
see two phases at infinity…] You then carefully withdraw a small sample of Phase II and
determine the concentration of A in it. This concentration is defined as the "solubility" of A
in B -- it is the most A that will ever dissolve in B at that temperature. You also withdraw a

1
[Note -- we reserve the term "equilibrium" for a system where no net transfer of stuff is occurring. We use "steady
state" to refer to a system where there may be net transfer of mass or energy to designate that the rate of transfer
does not change with time. Steady state of course also implies that concentration profiles or temperature profiles do
not change with time. An equilibrium system is at steady state, but a steady state system is not always at
equilibrium]

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 small amount of Phase I and measure the concentration of B in it. This gives you the
solubility of "B" in "A" at that temperature. How do you know you are at equilibrium? It is
not always easy to tell! Systems come to equilibrium over anywhere from a few minutes to a
few days. equilibrium is determined by careful sampling, always keeping the vial at a
constant temperature. When the concentrations no longer change with time (may require
many many points to determine you have a flat line within statistical significance), you are at
equilibrium.

If "A" (Phase I) is a liquid and "B" (Phase II) is a gas, the equilibrium concentration of A in
B is usually reported as a vapor pressure of A, and is often designated as a "saturation" vapor
pressure. Antoine's equation is a common correlation of the vapor pressures of various
compounds as a function of temperature. Gasses (such as oxygen and nitrogen) are typically
only sparingly soluble in liquids and their solubilities are typically reported as Henry's Law
coefficients. Liquid/liquid solubilities are often reported as volume percents (vol%). [For
example, when water and oil are mixed, a small amount of water dissolves in the oil, as in the
homework problem]. The solubilities of solids in liquids are often reported as weight
percents (wt%). There is no set, standard reporting structure, so just look at units carefully.

(2) Now consider that Phase I and Phase II are pure components A & B and a small amount of
component "C" is added. Component C distributes throughout the two phases according to
its relative solubility in each phase. Visualize a container filled with an oil/water mix
(A&B), to which a brilliant blue hydrophilic dye ("C") is added. The water phase will appear
deep blue, but the oil phase will appear only faintly blue. Hydrophilic means "water-loving,"
and the dye partitions into the aqueous phase. [Note that such dyed, oil/water-filled devices
were a commercial fad not too long ago as "instant ocean" (usually, the "oceans" contained
a tiny air bubble to allow for thermal expansion/contraction).] A key factor in
understanding phase equilibria is to realize that there are two possible routes to
determining the concentrations of the dye (aka, component "C") in each of the two
phases. Both methods give you a parameter known as the partition coefficient -- the
relative solubility in one phase compared to the other, or
c eqm
K = partition coefficient = Ieqm , where c eqm
I denotes the concentration of C in phase I
c II
when the system is at equilibrium, and c eqm II denotes the concentration of C in phase II
when the system is at equilibrium.

METHOD ONE: Conduct experiments such as those in part (a) where you determine the
solubility of C in A and B respectively. In other words, you add C to A so that you have two
phases, and measure the concentration of C in A to get its solubility, and do the same thing
for C mixed with B. An alternative that saves on vials is to mix A, B, & C to get 3 phases
(imagine adding enough dye to the "ocean" that it precipitates out) and measure the
concentration of C in the A & B phases. The partition coefficient is then the ratio of the
solubilities of C in Phase I and Phase II respectively, or K = c so
I
lub ility l i mit
/ c so
II
lub ility lim it
. A
subtle assumption we make with this approach is that the solubilities of A&B in each other
do not affect the solubility of C in either phase. This approach is generally used if you have
tabulated solubilities of C in A and C in B, but no tabulated partition coefficient. So, if you

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 are told for example that the solubility of the dye in water (phase I) is 100 mM and in the oil
it is 0.1mM, the partition coefficient is 100/0.1 = 1000.

METHOD TWO: Simply measure the concentration of C in each phase after the system is
at equilibrium, even if C is well below its solubility limit in the two phases. The chemical
potential of C has to be the same in each phase, and thus the ratio of concentrations in the
two phases is always the partition coefficient. For example, you add a small amount of the
dye to the oil/water mix -- say, just enough to get a visible blue color in the water -- and find
that the concentration in the water (phase I) is 20 mM. You then measure the concentration
in the oil phase and find that it is 0.02 mM. Then K = 20/0.02 = 1000. You then decide to
add more dye to get a deeper blue, and find that the concentration in the water phase (after
the system came to equilibrium) is now 45 mM. You measure the concentration in the oil
phase and find that it is 0.045mM. The partition coefficient is 45/0.045 = 1000. You could
take a similar approach to determine the Henry's law coefficient for oxygen in water -- add
water and a nitrogen/oxygen mix to the vial, and measure the final equilibrium
concentrations in each phase as the nitrogen-oxygen ratio is varied.

2. Mass Transfer Across Interfaces

Mass transfer is inherently a non-equilibrium process, characterized by the net motion of
molecules down a concentration gradient. We study mass transfer at the continuum scale (i.e.,
anything we do is averaged over zillions of molecules), and the concentration profile of the
diffusing solute is continuous within a single phase. Often, mass transfer occurs across the
interface between two phases -- liquid/liquid (e.g., oil/water), liquid/gas (e.g., air/water),
liquid/solid (e.g., water/polymer film), or gas/solid (e.g., air/polymer film). In this class, we will
consider only diffusion of dilute solutes and "slow" mass transfer rates. The nature of the
interface is not disrupted due to convective flow of material across the interface under these
conditions.
At the interface between two phases, the chemical potential of the diffusing solute in
phase I must equal that in phase II. We imagine that the interface between the two phases is an
infinitely thin plane and that the phases are in equilibrium in this plane. There is typically a
discontinuity in concentration at the interface. Here at the interface, the concentration of the
diffusing solute A in Phase I is related to that in Phase II via a partition coefficient, Henry's law
coefficient, vapor pressure, etc. Note that the concentration of A at the interface is often well
below its solubility limit, but that partition coefficients, etc., are simply the relative
concentrations in each phase at equilibrium.

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