Chapter 6.

Multiphase Systems
6.1 Single-Component Phase Equilibrium

• Phase diagram of pure substance: a plot of one system variable against another that shows the
conditions at which the substance exists as a solid, a liquid, and a gas, or any combination of the three.

• Vapor-liquid equilibrium curve: (terminates at critical point)

P is vapor pressure (p*) at temperature T, T is boiling point temperature (Tb) at pressure P.
• Solid-liquid equilibrium curve:
T is melting point or freezing point (Tm) at pressure P.
• Solid-vapor equilibrium curve:
P is vapor pressure of solid at temperature T, T is sublimation point (Ts) at pressure P.
• Point at which solid, liquid, and vapor phases coexist: triple point.
It is much easier to make supercritical fluid from CO2 than H2O.
6.1 Single-Component Phase Equilibrium

• Volatility: tendency of species to transfer from the liquid (or solid) state to the vapor state.
• Vapor pressure reflects volatility.
• Clapeyron equation: 𝑑𝑑𝑝𝑝∗ ∆𝐻𝐻 �𝑉𝑉 �𝑉𝑉
𝑑𝑑(ln 𝑝𝑝∗ ) ∆𝐻𝐻
= 𝑅𝑅𝑅𝑅 =−
𝑑𝑑𝑑𝑑 𝑇𝑇(𝑉𝑉�𝑔𝑔 − 𝑉𝑉�𝑙𝑙 ) � � �
𝑉𝑉𝑔𝑔 − 𝑉𝑉𝑙𝑙 ≈ 𝑉𝑉𝑔𝑔 ≈ ∗ 𝑑𝑑(1/𝑇𝑇) 𝑅𝑅
𝑝𝑝

A relationship between p*, the vapor pressure of a pure substance, and T, the absolute temperature

• Clausius-Clapeyron equation: From Gibbs-Duhem relation;

�𝑉𝑉
∆𝐻𝐻
∗
ln 𝑝𝑝 = − + 𝐵𝐵
�𝑉𝑉 is constant
If ∆𝐻𝐻 𝑅𝑅𝑅𝑅

• Antoine equation (empirical): 𝐵𝐵

l𝑜𝑜𝑜𝑜10 𝑝𝑝∗ = 𝐴𝐴 −
𝑇𝑇 + 𝐶𝐶

Example 6.1-1:

T1 = 7.6 ˚C, p1* = 40 mmHg �𝑉𝑉 can be estimated

The latent heat of vaporization ∆𝐻𝐻
T2 = 15.4 ˚C, p2* = 60 mmHg
 - Extensive variables; depend on the size of the system, mass, V
- Intensive variables; does not depend on the size of the system, P, T, density, fraction

6.2 Gibbs Phase Rule

• Degrees of freedom (DF): the number of intensive variables (no dependence on system size) that
can be specified independently for a system at equilibrium.
• Gibbs phase rule: DF = 2 + c – Π – r
No. of independent chemical species No. of phases
No. of independent equilibrated chemical reactions among the species

• Example: pure water liquid (DF = 2+1-1-0 = 2), a mixture of liquid, solid, and vapor water (DF = 2
+1-3-0 = 0), a vapor-liquid mixture of acetone and methyl ethyl ketone (DF = 2 + 2 – 2 – 0 = 2)
6.3 Gas-Liquid Systems: One Condensable Component

• Water and air in gas-liquid phase (water is only condensable): DF = 2 + c – Π – r = 2

• Only two of T, P, yH2O can be specified: some relationship must exist!
• Partial pressure of the vapor in the gas equals the pure-component vapor pressure at the system
temperature (pi*):

pi = yiP = pi*(T) (Raoult’s law for single condensable species)

pA = yAP = xApA*(T)

• At equilibrium, pi = pi*
• Superheated vapor: a vapor with pi < pi*(T); only saturated vapor can condense
• Dew point: the temperature at which the vapor becomes saturated; pi = pi*(Tdp)
• Degrees of superheat: T – Tdp
• Example: a stream of air at 100˚C and 5260 mmHg contains 10.0% water by volume

1) Calculate the dew point and degrees of superheat of the air.

pi = yH2OP = 526 mm Hg. Tdp = 90˚C from a table for pi* = pi, Degree of superheat: 10˚C

2) Calculate the percentage of the vapor that condenses and the final composition of the gas phase if the
air is cooled to 80 ˚C at constant pressure.
Cooling to 80˚C at const. P: three unknown (n1, n2, y) – 2 components – 1 relation (Raoult’s law) = 0

Raoult’s law: y = pH2O*/P = 355/5260 = 0.0675

Air balance: 90 mol = n2(1 – y)  n2 = 96.5 mol
Total balance: 100 mol = n1 + n2  n1 = 3.5 mol
 35% condensation

BDA: bond-dry air (water free component of an air-water vapor mixture)

3) Calculate the percentage condensation and the final gas-phase composition if, instead of being cooled,
the air is compressed isothermally to 8500 mmHg.
Raoult’s law: y = pH2O*(100oC)/P = 760/8500 = 0.0894
Air balance: 90 mol = n2(1 – y)  n2 = 98.8 mol
Total balance: 100 mol = n1 + n2  n1 = 1.2 mol
 12% condensation
6.3 Gas-Liquid Systems: One Condensable Component
𝑝𝑝𝑖𝑖
• Relative Saturation (Relative humidity): 𝑠𝑠𝑟𝑟 𝑜𝑜𝑜𝑜 ℎ𝑟𝑟 = × 100%
𝑝𝑝𝑖𝑖∗ (𝑇𝑇)
𝑝𝑝𝑖𝑖 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
• Molal Saturation (Molal humidity): 𝑠𝑠𝑚𝑚 𝑜𝑜𝑜𝑜 ℎ𝑚𝑚 = =
𝑃𝑃−𝑝𝑝𝑖𝑖 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 ′𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣−𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓′ (𝑑𝑑𝑑𝑑𝑑𝑑) 𝑔𝑔𝑔𝑔𝑔𝑔

𝑝𝑝 𝑀𝑀 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣

• Absolute Saturation (Absolute humidity): 𝑠𝑠𝑎𝑎 𝑜𝑜𝑜𝑜 ℎ𝑎𝑎 = (𝑃𝑃−𝑝𝑝𝑖𝑖 )𝑀𝑀𝑖𝑖 =
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑑𝑑𝑑𝑑𝑑𝑑 𝑔𝑔𝑔𝑔𝑔𝑔
𝑖𝑖 𝑑𝑑𝑑𝑑𝑑𝑑

• Percentage Saturation (Percentage humidity): 𝑠𝑠 𝑜𝑜𝑜𝑜 ℎ = 𝑠𝑠𝑚𝑚 × 100% = 𝑝𝑝𝑖𝑖 /(𝑃𝑃−𝑝𝑝𝑖𝑖 )

× 100%
𝑝𝑝 𝑝𝑝 ∗ 𝑠𝑠𝑚𝑚 𝑝𝑝𝑖𝑖∗ /(𝑃𝑃−𝑝𝑝𝑖𝑖∗ )

• Example: humid air at 75˚C, 1.1 bar (825 mm Hg), and 30% relative humidity is fed into a process
unit at a rate of 1000 m3/h.
1) Molar flow rates:
pH2O*(75˚C) = 289 mm Hg  pH2O = 0.3×289 mm Hg = 86.7 mm Hg  y = 86.7/825= 0.105
𝑃𝑃𝑉𝑉̇ (1.1 𝑏𝑏𝑏𝑏𝑏𝑏)(1000 𝑚𝑚3 /ℎ)
𝑛𝑛̇ = = = 38.0 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘/ℎ
𝑅𝑅𝑅𝑅 (0.0831 𝑚𝑚3 � 𝑏𝑏𝑏𝑏𝑏𝑏/𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 � 𝐾𝐾)(348 𝐾𝐾)
 ṅH2O = 38.0 kmol/h × 0.105 = 3.99 kmol/h, ṅBDA = 38.0 kmol/h × 0.895 = 34.0 kmol/h
 ṅO2 = 34.0 kmol/h × 0.21 = 7.14 kmol/h
2) Molal humidity, absolute humidity, and percentage humidity:
𝑝𝑝𝑖𝑖 86.7 ∗ 𝑝𝑝𝑖𝑖∗ 289
ℎ𝑚𝑚 = = = 0.117 mol H2O/mol BDA ℎ𝑚𝑚 = = = 0.539
𝑃𝑃−𝑝𝑝𝑖𝑖 825 −86.7 𝑃𝑃−𝑝𝑝𝑖𝑖∗ 825−289

𝑀𝑀𝑖𝑖 18.0 ℎ𝑚𝑚

ℎ𝑎𝑎 = ℎ𝑚𝑚 = 0.117 × = 0.0726 kg H2O/kg BDA  ℎ𝑝𝑝 = ∗ × 100% = 21.7%
𝑀𝑀𝑑𝑑𝑑𝑑𝑑𝑑 29.0 ℎ𝑚𝑚
6.4 Multicomponent Gas-Liquid Systems

• Raoult’s law: pA = yAP = xApA*(T) (generally valid for xA ~ 1)

• Henry’s law: pA = yAP = xAHA(T) (generally valid for xA ~ 0: dilute solution)
• Ideal solution: a gas-liquid system which follows equilibrium relationship of either Raoult’s law
or Henry’s law.

• Example 1: A gas containing 1.00 mole% ethane is in contact with water at 25.0˚C and 20.0 atm.
Henry’s law (low concentration)
xC2H6= yC2H6P/HC2H6 (25.0˚C)= 0.0100×20.0 atm/(2.67×104 atm/mole fraction) = 7.49×10-6

From Perry’s Handbook

Hydrocarbons normally are relatively insoluble
in water, so that the solution of ethane is
probably extremely dilute. Then Henry’s law
can be applied. From handbook, HA for ethane
can be found.
 • Example 2: An equimolar liquid mixture of benzene (B) and toluene (T) is in
equilibrium with its vapor at 30.0˚C. Then gas composition??
Raoult’s law (two structurally similar compounds)

pB = xBpB* = 0.500 ×119 mm Hg = 59.5 mm Hg

pT = xTpT* = 0.500 ×36.7 mm Hg = 18.35 mm Hg

P = pB + pT = 77.9 mm Hg, yB = pB/P = 0.764, yT = pT/P = 0.236

These relations can be found in the Table B.4.

• Bubble-point temperature: temperature at which first vapor bubble forms during

slow heating of liquid at constant pressure, P.
pi = xipi*(Tbp), where i = A, B, C, …  P = xApA*(Tbp) + xBpB*(Tbp) + …
 Get Tbp for known xi and P using a solver  Get yi = pi/P
• Bubble-point pressure: pressure at which first vapor bubble forms during slow decompression of
liquid at constant temperature, T. For known xi and T,
Pbp = xApA*(T) + xBpB*(T) + …  Get yi = pi/Pbp= xipi*(T)/Pbp

• Dew-point temperature: temperature at which first droplet forms during slow cooling of gas at
constant pressure, P.
𝑦𝑦𝑖𝑖 𝑃𝑃 𝑦𝑦𝐴𝐴 𝑃𝑃 𝑦𝑦𝐵𝐵 𝑃𝑃
𝑥𝑥𝑖𝑖 = ∗  𝑥𝑥𝐴𝐴 + 𝑥𝑥𝐵𝐵 + ⋯ = ∗ + ∗ +⋯=1
𝑝𝑝𝑖𝑖 (𝑇𝑇𝑑𝑑𝑑𝑑 ) 𝑝𝑝𝐴𝐴 𝑇𝑇𝑑𝑑𝑑𝑑 𝑝𝑝𝐵𝐵 𝑇𝑇𝑑𝑑𝑑𝑑
𝑦𝑦𝑖𝑖 𝑃𝑃
 Get Tdp for known yi and P using a solver  Get 𝑥𝑥𝑖𝑖 = ∗
𝑝𝑝𝑖𝑖 (𝑇𝑇𝑑𝑑𝑑𝑑 )

• Dew-point pressure: pressure at which first droplet forms during slow compression of gas at
constant temperature, T. For known yi and T,
1 𝑦𝑦𝑖𝑖 𝑃𝑃𝑑𝑑𝑑𝑑
𝑃𝑃𝑑𝑑𝑑𝑑 = 𝑦𝑦𝐴𝐴 𝑦𝑦𝐵𝐵  Get 𝑥𝑥𝑖𝑖 =
∗ + ∗ +⋯ 𝑝𝑝𝑖𝑖∗ (𝑇𝑇)
𝑝𝑝𝐴𝐴 (𝑇𝑇) 𝑝𝑝𝐵𝐵 (𝑇𝑇)
Graphical Representations of Vapor-Liquid Equilibrium

• Txy diagram: a plot of the equilibrium temperature versus the mole fraction of A (more volatile
component) for both liquid and vapor phases
• Pxy diagram: a plot of the equilibrium pressure For benzene-toluene system

• Example: estimate Tbp and equilibrium vapor composition associated with a 40 mole% benzene-60
mole% toluene liquid mixture at 1 atm. If the mixture is steadily vaporized until the remaining
liquid contains 25% benzene, what is the final temperature?
 Tbp ~ 95˚C, yB ~ 0.62. For xB = 0.25, Tbp ~ 100˚C
6.5 Solutions of Solids in Liquids

• Solubility: the maximum amount of substrate that can be dissolved in a specific amount of the
liquid at equilibrium. Highly depends on T
• A solution in equilibrium with solid solute must be saturated.
• Supersaturated: concentration of solute is higher than the equilibrium value

• Example: crystallization and filtration

One hundred fifty kilograms of a saturated aqueous solution of AgNO3 at 100˚C is cooed to 20˚C,
thereby forming AgNO3 crystals, which are filtered from the remaining solution. The wet filter
cake, which contains 80.0% solid crystals and 20.0% saturated solution by mass, is sent to a dryer
in which the remaining water is vaporized. Calculate the fraction of the AgNO3 in the feed stream
eventually recovered as dry crystals and the amount of water that must be removed in the drying
stage.

Solubilities:
925 g AgNO3/100 g H2O at 100˚C
222 g AgNO3/100 g H2O at 20˚C
Degree-of-freedom analysis on subsystem:
Three unknown (m1, m2, m3) – 2 balances (AgNO3, H2O) – 1 relation (80.0% solids) = 0 degrees
Composition of filter cake: m2 = 0.800 (m2 + m3)  m2 = 4m3 m1 = 20 kg
Water balance: 0.095 ×150 kg = 0.311(m1 + m3)  m2 = 104 kg
Total mass balance: 150 kg = m1 + m2 + m3 m3 = 26 kg

Overall AgNO3 balance: 0.905 ×150 kg = 0.689m1 + m5  m5 = 122 kg (Recovery: 89.9%)

Overall mass balance: 150 kg = m1 + m4 + m5  m4 = 8 kg
 Solid Solubility
Example: An aqueous potassium nitrate solution containing 60.0 wt% KNO3 at 80 ˚C is fed to a cooling
crystallizer in which the temperature is reduced to 40 ˚C. Determine the temperature at which the
solution reaches saturation and the percentage of the potassium nitrate in the feed that forms crystals.

Conversion of concentration to solubility:

60.0 g KNO3/40.0 g H2O = 150 g KNO3/100 g H2O  saturation temperature: 74˚C

Degree-of-freedom analysis:
Three unknown (m1, x, m2) – 2 balances (KNO3, H2O) – 1 relation (solubility) = 0 degrees

At 40˚C, solubility = 63 g KNO3/100 g H2O  x = 63/(63 + 100) = 0.386

Water balance: 0.400 ×100 kg = (1 – 0.386)m1  m1 = 65.1 kg
Total mass balance: 100 kg = m1 + m2  m2 = 34.9 kg (Recovery: 58.2%)
Colligative Solution Properties

• Colligative solution properties: properties (vapor pressure, boiling point, freezing point, osmotic
pressure) depend only on the concentration of solute in the solution, and not on what the solute and
solvent are.
• Consider a solution with nonvolatile, nonreactive, and nondissociative solute (mole fraction, x)
• Partial pressure of solvent: ps(T) = (1 – x) ps*(T) = (ps*)e ; effective solvent vapor pressure
• Vapor pressure lowering: Δps* = ps* – (ps*)e = xps* (regardless of T, P, and what the solute and
solvent are)
• Solution boils at a higher T and freezes at lower T than
pure solvent at the same pressure

2
𝑅𝑅𝑇𝑇𝑏𝑏0
∆𝑇𝑇𝑏𝑏 = 𝑇𝑇𝑏𝑏𝑏𝑏 − 𝑇𝑇𝑏𝑏0 = 𝑥𝑥 From ΔTb and mass
∆𝐻𝐻�𝑉𝑉
fraction,
2
𝑅𝑅𝑇𝑇𝑚𝑚0 get x and molecular
∆𝑇𝑇𝑚𝑚 = 𝑇𝑇𝑚𝑚0 − 𝑇𝑇𝑚𝑚 = 𝑥𝑥 weight of solute
∆𝐻𝐻�𝑚𝑚
6.6 Equilibrium between Two Liquid Phases

• Suppose A and S are two nearly immiscible liquids and B is a solute.

• Distribution coefficient (partition ratio) of component B: the ratio of the mass fraction of B in
the S phase to that in the A phase.
• Example (liquid extraction): 200.0 cm3 acetone (A)-water (W) mixture with 10.0 wt% acetone is
mixed with 400.0 cm3 of chloroform (C) at 25˚C (W and C are immiscible).

Densities 𝑛𝑛
1 𝑥𝑥𝑖𝑖 0.100 0.900
A: 0.792 g/cm3 =� = 3
+ 3
= 1.026 𝑐𝑐𝑐𝑐3 /𝑔𝑔  𝜌𝜌̅ = 0.974 g/cm3
C: 1.489 g/cm3 𝜌𝜌̅ 𝜌𝜌𝑖𝑖 0.792 𝑔𝑔/𝑐𝑐𝑐𝑐 1.000 𝑔𝑔/𝑐𝑐𝑐𝑐
𝑖𝑖=1
W: 1.000 g/cm3
Mass of solution fed : 200.0 cm3 × 0.974 g/cm3 = 195 g
Mass of chloroform: 400.0 cm3 × 1.489 g/cm3 = 596 g

• C balance: 596 g = m4
𝑥𝑥𝐶𝐶 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚3 /(𝑚𝑚3 + 𝑚𝑚4 ) • W balance: 0.900 × 195 g = m2  m2 = 175.5 g
𝐾𝐾𝐴𝐴 = = 1.72 =
𝑥𝑥𝑊𝑊 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚1 /(𝑚𝑚1 + 𝑚𝑚2 ) • A balance: 0.100 × 195 g = m1 + m3
•  m1 = 2.7 g, m3 = 16.8 g

• 16.8/19.5 × 100% = 86.1% A transferred

 6.6 Equilibrium between Two Liquid Phases

• Triangular phase diagram for partially miscible ternary systems

20.0 wt% MIBK, 65% acetone, 15.0% water

Singe phase Singe phase

Two phases
Two phases
4% W
20% A
85% W 76% MIBK
12% A
3% MIBK
55% W
15% A
Equilateral triangle 30% MIBK Right triangle
Tie line:
Connect compositions of two liquid phases in equilibrium
(Ex. Overall composition of M results in compositions of L and N)
Gibbs phase rule for two phases: DF = 2 + c – Π – r = 3 (if T and P is fixed, one degree!)
(specifying the mole fraction of one component in one phase is sufficient to determine the composition of
both phases)
6.7 Adsorption on Solid Surfaces

• Example: charcoal to remove unacceptable odors, a bed of calcium chloride to remove water vapor
• Adsorbent: the solid that adsorbs specific compounds
• Adsorbate: the component attracted to the adsorbent
• Adsorption isotherm: adsorbate equilibrium data on a specific adsorbent at a specific temperature

• Langmuir isotherm
𝑎𝑎𝐾𝐾𝐿𝐿 𝑝𝑝𝑖𝑖 𝑎𝑎𝐾𝐾𝐿𝐿′ 𝑐𝑐𝑖𝑖
𝑋𝑋𝑖𝑖∗ = or 𝑋𝑋𝑖𝑖∗ =
1 + 𝐾𝐾𝐿𝐿 𝑝𝑝𝑖𝑖 1 + 𝐾𝐾𝐿𝐿′ 𝑐𝑐𝑖𝑖
6.7 Adsorption on Solid Surfaces

• Example (balances on an adsorption process)

A 50.0 liter tank contains an air-carbon tetrachloride mixture at 1 atm absolute, 34˚C, and 30% relative
saturation. Activated carbon is placed in the tank to adsorb CCl4. The temperature of the tank contents
is maintained at 34 ˚C, and clean air is continuously supplied to the tank throughout the process to
maintain the total pressure at 1.00 atm.

Calculate the minimum amount of activated carbon needed to reduce the CCl4 mole fraction in the gas
to 0.001. Neglect the volume of the activated carbon and the adsorbed CCl4. Why would the actual
amount placed in the tank be larger than the calculated value?

pCCl4* at 34˚C = 169 mm Hg

∗ 𝑎𝑎𝐾𝐾𝐿𝐿 𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝐶𝐶
𝑋𝑋𝐶𝐶𝐶𝐶𝐶𝐶𝐶 (g CCl4 ads/g C) =
1 + 𝐾𝐾𝐿𝐿 𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝐶𝐶
30% relative saturation
(a = 0.794 g CCl4/g C, KL = 0.096 (mm Hg)-1)
n = PV/RT = (1.00 atm)(50.0 L)/(0.08206 L•atm/mol•K)(307 K) = 1.98 mol

pCCl4* at 34˚C = 169 mm Hg  y0P/pCCl4* = 0.300 (relative saturation)  y0 = 0.0667

Mass of CCl4 adsorbed: (0.0667 × 1.98 mol – 0.001 × 1.98 mol ) × 154 g/mol = 20.0 g
MW of CCl4

pCCl4 = yP = 0.001 × 760 mm Hg = 0.760 mm Hg (a = 0.794 g CCl4/g C, KL = 0.096 (mm Hg)-1)

𝑎𝑎𝐾𝐾𝐿𝐿 𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝐶4
Langmuir isotherm: ∗
𝑋𝑋𝐶𝐶𝐶𝐶𝐶𝐶4 = = 0.0540
1 + 𝐾𝐾𝐿𝐿 𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝐶4

Mass of activated carbon required: 20.0 g CCl4 ads / (0.0540 g CCl4 ads/g C) = 370 g C

More activated carbon is needed because;

(1) The rate of adsorption is ~0 at saturation; infinite time required
(2) Langmuir isotherm itself contains some error
(3) Other than CCl4 can be adsorbed on the carbon