MULTIPHASE SYSTEMS

Yeditepe University
Department of Chemical Engineering
• All commercial chemical processes involve operations in which
material is transferred from one phase (gas, liquid, or solid) into
another.
• Multiphase operations:
o Phase-change operations on a single species: freezing, melting, evaporating,
condensation
o Separation
o Purification
Example:
• Brewing a cup of coffee: hot liquid water + solid ground coffee beans soluble
constituents of the beans are transferred from the solid phase to a liquid
solution (coffee) then the residual solids (ground) are filtered from the
solution. (leaching)
• Adsorption, scrubbing, distillation, liquid extractions, adsorption,
crystallization …

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Single Component Phase Equilibrium
Phase Diagrams
• At most temperature and pressure, a single pure substance at
equilibrium exists entirely as a solid, liquid or gas.
• But certain T and P → two or even all three phases can be found
• A phase diagram of a pure substance is 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.
• Most common phase diagrams: temperature vs pressure

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• Phase diagram experiments
• Heat can be added or withdrawn so temperature can be fitted any
desired value.
𝐹+𝑊
• The absolute pressure:
𝐴

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Several familiar terms:
• Vapor pressure / boiling point / boiling point temperature
• Normal boiling point
• Melting point or freezing point
• Sublimation point
• Triple point
• Tc, Pc

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Estimation of Vapor Pressure
• Volatility: The degree to which the species tends to transfer from the
liquid (or solid) state to the vapor state.
• Highly volatile substance: mostly found vapor phase
• Low volatile substance: condensed phase
• For example; distillation process

→The vapor pressure of a species is a measure its volatility.

Find or Estimate?

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Clapeyron equation
𝑑𝑝∗ ∆𝐻෢𝑣
=
𝑑𝑇 𝑇(𝑉෡𝑔 − 𝑉෡𝑙 )
Unless the very high-pressure condition, 𝑉෡𝑔 − 𝑉෡𝑙 ≈ 𝑉෡𝑔
𝑅𝑇
෢
If we assume this, apply ideal gas EoS to the vapor 𝑉𝑔 = ∗
𝑝

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 𝑑(𝑙𝑛𝑝∗ ) ∆𝐻𝑣
=−
𝑑(1/𝑇) 𝑅

→This is the most common experimental method to determine heat of

enthalpy!
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• Suppose now ∆𝐻𝑣 is independent of T:
∗
∆𝐻𝑣
𝑙𝑛𝑝 = − +𝐵
𝑅𝑇
Clausius-Clapeyron equation

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• Cox chart: vapor pressure/temperature plots a straight the mainly for
petroluem hydrocarbons.

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• A relatively simple empirical equation that correlates vapor-pressure-
temperature data extremely well is Antoine equation
𝐵
log10 𝑝∗ =𝐴−
𝑇+𝐶
𝐵
ln 𝑝∗ =𝐴 −
𝑇+𝐶

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Example 1:
Ethyl acetate has a vapor pressure of 118.3 mm Hg at 29.5oC and a
normal boiling point of 77.0oC. Estimate the vapor pressure at 45.0oC
using (a) the Antoine equation and constants from the corresponding
table; (b) the Clausius-Clapeyron equation and the two given data
points. Taking the first estimate to be correct, calculate the percentage
error associated with the second estimation.

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The Gibbs Phase Rule
• When two phases are brought into contact with each other (A+B+C)
• Between gas & liquid phases
• Specify the system temperature & pressure
• The masses of each phase and two mass or mole fractions for each
phase would certainly be sufficient. However, these are not
independent, once some of specified others are fixed by nature and
in some cases, may be calculated from physical properties of the
system components.

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• Variables
o Extensive variables: depend on the size of system such as mass, volume
o Intensive variables: not depend on the size of system such as temperature,
pressure, density, specific volume, mass and mole fractions

• DF anaysis «Gibbs phase rule without reaction»

DF = 2 + c − Π
The number of
The number of phases in a system
chemical species at equilibrium

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Gibbs Phase Rule examples
i. Pure liquid water

ii. A mixture of liquid, solid, and vapor water

iii. A vapor-liquid mixture of acetone and methyl ether ketone

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Gas-Liquid Systems: One Condensable
Component
• Separation systems
• Evaporation, drying and humidification → transfer of liquid into gas
• Condensation, dehumidification → condensable species from the gas to liquid
• Suppose a chamber
• Initially contains dry air at 75oC and 760 mm Hg without water (𝑝𝐻2 𝑂 =0)
• Water molecules consequently begin to evaporate
• 𝑦𝐻2𝑂 increases
• 𝑝𝐻2𝑂 = 𝑦𝐻2𝑂 𝑃
• After a while → no change (saturated)
• DF = 2 + 2 – 2 = 2 (2 out of 3 variables T, P and 𝑦𝐻2𝑂 can be specified

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• A law that describes the behavior of gas-liquid systems over a wide
range of conditions provides the desired relationship
• If a gas at T and P contains a saturated vapor whose mole fraction is y,
(mol vapor/ total mol), and if this vapor is the only species that would
condense if the T were slightly lowered, then the partial pressure of
vapor in the gas equals the pure-component vapor pressure 𝑝𝑖∗ (𝑇)
and system T.
• Raoult’s Law (single condensable species)
𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝𝑖∗ (𝑇)

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Several important points:
1. A gas in equilibrium with a liquid must be saturated with the
volatile components of that liquid.
2. The partial pressure of a vapor at equilibrium in a gas mixture
containing a single condensable component cannot exceed the
vapor pressure of the pure component at the system temperature.
If 𝑝𝑖 = 𝑝𝑖∗ , the vapor is saturated; any attempt to increase 𝑝𝑖 either
by adding more vapor to the gas phase or by increasing the total
pressure at constant temperature.

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3. A vapor present in a gas in less than its saturation amount is referred
to as a superheated vapor
𝑝𝑖 = 𝑦𝑖 𝑃 < 𝑝𝑖∗ (𝑇)
But inequality becomes the equality of Raoult’s law
o Increasing pressure at constant T
o Decreasing pressure at constant T

4. If a gas containing a single superheated vapor is cooled at constant

pressure, the temperature at which the vapor becomes saturated is
referred to as the dew point of the gas
𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝𝑖∗ (𝑇𝑑𝑝 )

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• Degrees of superheat: The difference between the temperature and
the dew point of a gas

• If any two quantities yi, P, Tdp are known, the third can be determined
by using 𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝𝑖∗ (𝑇𝑑𝑝 )

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Humidity
• Gas-vapor combination «air-water system»
• Suppose a system at temperature and P contains a vapor; partial
pressure pi and vapor pressure 𝑝𝑖∗ (𝑇)
𝑝𝑖
• Relative humidity: ℎ𝑟 = × 100%
𝑝𝑖∗ (𝑇)
RH of 40% → partial pressure of water vapor 4/10 of the vapor pressure of water at
the Tsystem
𝑝𝑖 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟
• Molal humidity: ℎ𝑚 = =
𝑝−𝑝𝑖 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟−𝑓𝑟𝑒𝑒 𝑑𝑟𝑦 𝑔𝑎𝑠
𝑝𝑖 𝑀𝑖 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟
• Absolute humidity: ℎ𝑎 = =
(𝑝−𝑝𝑖 )𝑀𝑑𝑟𝑦 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 𝑔𝑎𝑠
ℎ𝑚 𝑝𝑖 Τ(𝑃−𝑝𝑖 )
• Percentage humidity: ℎ𝑃 = × 100% = × 100 %
∗
ℎ𝑚 𝑝𝑖∗ Τ(𝑃−𝑝𝑖∗ )

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Multicomponent Gas-Liquid Systems
• Gas-liquid processes: chemical reactions, distillation and transfer of
one or more species from a gas to a liquid (adsorption, scrubbing)
• When multicomponent gas liquid phases are in equilibrium, a limited
number of intensive system variables may be specified arbitrarily, and
the remaining variables can then be determined using equilibrium
relationships for the distribution of components between the two
phases.

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1. Vapor-Liquid Equilibrium Data
2. Raoult’s Law and Henry’s Law
𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝑝𝐴∗ (𝑇)

𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝐻𝐴 𝑇

A gas-liquid system in which the vapor-liquid equilibrium

relationship for every volatile species is either Raoult’s Law or Henry’s
Law is said to exhibit ideal solution behaviour.

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3. Vapor-Liquid Equilibrium Calculations for Ideal Solutions
• Once you have a single component, heat it and turn to vapor
• What if you have mixture? → The vapor generated will have a
composition different from that of the liquid.
• Important while designing evaporation or condensation process due
to transition from liquid to vapor or vapor to liquid

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• Bubble point: The temperature at which saturation occurs in the
liquid phase. In the case of a liquid solution, the composition of the
vapor in the bubbles that form in the liquid is not the same as that of
the liquid.
• Dew point: The temperature at which saturation occurs in the gas
phase for a given pressure. The degree of superheat refers to the
difference in temperature between the actual temperature and the
dew point.

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Example 2:
The latest weather report includes the following the statement: «The
temperature is 78oF, barometric pressure is 759.5 mm Hg, and the
relative humidity is 87%.» From this information, estimate the mole
fraction of water in the air and the dew point (oC), molal humidity,
absolute humidity, and percentage humidity of the air.

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Solutions of Solids in Liquids
a) Solubility and Saturation
• Solubility: the maximum amount of the substance that can be
dissolved
• Saturated: at equilibrium condition

• If a saturated solution is cooled, the solubility of the solute generally

decreases.

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b) Solid solubilities and hydrated salts
• Gibbs phase rule shows that specifying T and P for a two-component
system at equilibrium containing a solid solute and a liquid solution
fixes the value of all other intensive variables.
• Solubility plots → effect of temperature change
• Hydrated salts: containing water molecules bonded to solute
molecules

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Example 3:
An aqueous solution of potassium hydroxide is fed at a rate of 875 kg/h
to an evaporative crystallizer operating at 10oC, producing crystals of
KOH·2H2O. A 5 g aliquot of the feed solution is titrated to neutrality
with 22.4 mL of 0.85 molar H2SO4. The solubility of KOH at 10oC is 103
kg KOH/100 kg H2O. At what rate must water be evaporated to
crystallize 60% of the KOH in the feed?

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c) Colligative solution properties
• Colligative properties: vapor pressure, boiling point, freezing point
etc.
• It is important like pure water recovery by evaporation or freezing of
seawater processes.

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Equilibrium Between Two Liquid Phases
• Miscibility is important
• Example process → liquid extraction
• If you have a ternary mixture

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Adsorption on Solid Surfaces
• Adsorbent: Solid including zeolites, activated carbons, porous
coordination networks, metal-organic frameworks etc.
• Adsorbate: Component attracted to the adsorbent

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Consider how an adsorption isotherm determined → CCl4/AC
o Place a known mass of activated carbon (AC) in a chamber (T is known)
o CCl4 vapor: AC until desired P is reached.
o Allow to system reach the equilibrium and determine the mass of CCl4
adsorbed by weighting solid.
o Repeat the procedure.

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