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Chapter 6.

Multiphase System

Normal point: the boiling temperature at 1atm


Triple point: Solid, liquid and vapor phase coexist
Critical temperature (Tc) and pressure (Pc):
the liquid and vapor phase is identical above or
on the right of this point.
Sublimation point: The temperature T that
equilibriums the vapor pressure against solid
phase

Estimate vapor pressure


Evaporation is a method that is specially used to separate high and low vapor
pressure materials
Clapeyron equation

Example 6.1-1

Antoine Equation

Gibbs Phase Rule

The minimum number of degrees of freedom for any system is zero. When F = 0,
the system invariant.
This value of is the maximum number of phases witch can coexist at equilibrium
for a system containing C chemical species.

Example
How many degrees of freedom have each of the following systems?
(a) Liquid water in equilibrium with its vapor.
(b) Liquid water in equilibrium with a mixture of water vapor and nitrogen.
(c) A liquid solution of alcohol in water in equilibrium with its vapor.

Solution
(a) The system contains a single chemical species existing as two phases (one
liquid and one vapor). Thus,
(b) In this case two chemical species are present. Again there are two phases.
Thus,

(c) Here C = 2, and = 2, and

For gas-liquid system (Note: it is a phase equilibrium system)

pi is the partial pressure of chemical i in the vapor phase, and pi* is the vapor pressure
of pure chemical i at the same temperature.

If a vapor is less than its saturation amount (Note: it is not a phase


equilibrium), it is referred to as a superheated vapor.

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 dew
point. The difference between the temperature and the dew point is called the
degrees of superheated of the gas.

Example 6.3-1

Problem 6.29

Example 6.3-2

Example 6.3-3

Multicomponent gas-liquid system


Example 6.4-1

Raoults Law
pA: the partial pressure of A in the gas phase; yA: the mole fraction of A
in the gas phase; xA: the mole fraction of A in the liquid phase; pA*: the
vapor pressure of pure liquid A at temperature T.
Roaults law is an approximation that is generally valid when xA is close
to 1.
Henrys law
Where HA(T) is the Henrys law constant for A in a specific solvent.
Henrys law is generally valid for solutions in which xA is close to 0 (dilute
solutions)

Example 6.4-2

Vapor-Liquid Equilibrium Calculations for Ideal Solutions


If the liquid is a mixture of more than one components, evaporation of one liquid
will change the ratio of chemicals in liquid, so both T and P will change during the
evaporation.
Bubble-point temperature: the temperature at which the first vapor bubble forms
Dew-point temperature: the temperature that the first liquid drop forms
Calculating bubble-point temperature or Dew-point temperature is complex for an
mixture, but it can be done for ideal solution (following either Roaults or Henrys
law) and ideal vapor (following ideal gas law).

Problem 6.52

Problem 6.56

Graphs of Vapor-liquid equilibrium

The diagraphs show the different contents of A and B in vapor and liquid phases.
If one component is evaporated, the fraction of liquid phase changed, so the boiling
temperature also moved along the curves.

The boiling point of mixture solution can be determined approximately from

Solutions of solid in liquids


Solubility: the maximum amount of a solid can be dissolved in a special amount of liquid
at equilibrium.
Supersaturated: the concentration of solute is higher than its solubility in that condition,
but no solid (crystallization) happens.

Example 6.5.1

Solid Solubilities and hydrate salts

Solubility of solids is not sensitive to the pressure

Problem 6.78

Colligative property:
lowering vapor pressure, depressing freezing point, increasing boiling point, and increasing
osmotic pressure by dissolving (or dispersing) substance in solvent

Adsorption on solid surface


Adsorption Isotherms: Adsorption
equilibrium data at specific temperature

Example 6.7-1