Multicomponent

and Multiphase
Systems
ZAIN ALI 51102
 Single component System

Vapour Pressure: To calculate the vapour pressure the

Clapeyron Equation is used.

p* = vapour pressure of the pure substance

= latent heat of vapourization.

Vg and Vl = specific molar volumes for the gas and liquid

phases.

For Ideal gas (Vg =RT/p*) the equation becomes

 The Gibbs Phase Rule
The Gibbs Phase Rule is useful for understanding how many intensive
variables must be specified to fully fix, for example, the composition of
phases and streams in a process.

Intensive variables: Variables that do not depend on system size. Examples

are temperature, pressure, chemical potential, density, specific volume,
viscosity, thermal conductivity, mass fractions, mole fractions, among
others.

Gibbs Phase Rule: For simplicity the effect of body fields is neglected. If the
chemical phase is uniform and comprises of c chemical species, c+1
intensive variables need to be specified while keeping all other intensive
variables fixed.
 The Gibbs Phase Rule (contd)

If the system contains phases, each with its own composition, in

principle one would need to specify (c+1) intensive variables to
completely determine the intensive state of each phase and hence
the system.
In the case of phase equilibrium where the temperatures and
pressures of each phase is equal then we need to specify (c+1)
(1) (1)=(c1) + 2 intensive variables.
However equilibrium also means that the chemical potential of each
phase must be equal which yields another (1) independent
equations for each component, for a total of c(1) constraints.
DF = (c1) + 2 c(1)
DF = 2 + c
 Multicomponent Systems

Multicomponent systems are the mixtures (the solutions) which

consist of several pure (individual) substances (components).

The initial amount each of the substances in the -component

system may be represented in terms of the component masses
mi(1 i ).

The system composition can also be classified in terms of the

number of moles of a component, Ni= mi/Mi, where Miis the
molecular mass of the component.
 Behavior of Multicomponent
Systems
The thermodynamic behavior of a multicomponent system can be
described using the first and second laws of thermodynamics.
If the system under observation is an open one then both energy and
mass exchange need to be taken into consideration. When no
external force fields are present the first and second laws can be
combined to the equation below:

where U, S and V are the total internal energy, entropy and volume of
the system; iis a chemical potential. For equilibrium or quasistatic
process an equals sign is used whereas for other cases the un
equality sign is valid
If the
set of independent variables are not convenient to use then
the Lejandre transformation can be used to get other
thermodynamic potentials such as enthalpy H(S, p, N 1, . . ., Nv) = U
+ pV, Helmholtz energy A(T, V, N1, . . ., Nv) = U TS and Gibbs
energy G(T,p,N1..., Nv) = H TS.
For enthalpy we take the first equation:
dU=T dS-P dV
The function U(S,V) needs to be changed to H(S,P). A table of
equivalences is constucted:
fU (the original function)
xS(the variable that doesnt need to be changed)
u)y=)V =T (conjugate of unswitched variable)
y=V (varible that needs to be switched)
w)x=)S=-P(conjugate of switched variable)

Using the equation gf-wy we get:
gf-wy=(U)-(-P)(V)=U+PV=H(S,P)
Diffrentiate H to get:
dH=TdS+VdP
Similarly we can obtain the Gibbs Energy function:
dG=VdP-SdT
dG=VdP-SdT+i
For equilibrium conditions in a multicomponent system.
S=-p,N1,,Nv; V=-T,N1,,Nv
i=T,p,Nji
Raoults law for multi component
systems
Given a solution which contains one or more volatile components i,
partial pressure Pi for a gas that is in equilibrium with a liquid the
equation for that system is
P i = y i P = x i pi *
where P is the total pressure, yi is mole fraction of i in the gas
phase, xi is mole fraction of i in the liquid phase, and pi * is the
vapor pressure of pure liquid i.
It is important to note however in this equation the fact that the
approximation has to work well when xi approaches 1. This equation
works best for components with similar molecular weights and
polarity.
 Henrys Law

Henrys Law is similar in form to Raoults Law, except that it applies

to vapor-liquid equilibrium when the volatile species i is dilute in the
liquid solution.
The law states that, given a liquid solution with a volatile
component i, the partial pressure of i in a gas mixture in equilibrium
with the liquid is given by
Pi = y i P = x i H i
Here Hi is called the Henrys Law constant of species i. Like the
vapour pressure, Henrys Law constant is also a function of
temperature.
 Bubble point and Dew point

Bubble point: If a pure liquid is heated to the point where the

vapour pressure of the liquid equals to the external pressure of the
gas above it, the liquid will start to boil and bubbles will start to
form.
Similarly in a solution with multiple chemical species as
temperature is increased, bubbles will start to form at some point.
The temperature at which this happens is known as the bubble
point temperature. (Tbp)
This temperature unlike the boiling temperature which is for pure
liquids changes as the liquids composition changes.
Dew-point temperature: In a solution with multiple chemical
components the temperature at which the first droplets begin to
form is known the dew-point temperature (Tdp)
 Bubble point temperature and
pressure calculations:
The calculation is easier in a regime where Raoult and/or Henrys laws

apply (i.e. the solution behaves ideally).

A solution needs to be considered with q number of volatile species. The
bubble point temperature is to be calculated when the external pressure
of the gas above the solution is P. The sum of the vapour pressures must
add up to P. Assuming the liquid solution follows Raoults law the partial
pressure at bubble point temperature is given as:
Pi= xipi*(Tbp)
Xi is the mole fraction and pi*is the quantity that needs to be evaluated
at Tbp. For bubble point the equation is:

The equation above can be solved if we know the mole fractions and the
vapour pressures as a function of temperature.
Dew point temperature and
pressure calculations:
For dew
point temperature similar assumptions will be made and
Raoults law will be expressed as:
yiP= xipi*
yi is the gas mole fraction and xi is the liquid mole fraction.
Furthermore another physical constraint needs to be satisfied which is

Which can also be expressed as:

If the total pressure is known as well as y i and pi* are known as

functions of temperature then the dew-point temperature can be
found.
Txy and Pxy Diagrams

These diagrams are used to correlate bubble-point temperature and

bubble-point pressure data for binary (two-component) gas-liquid
systems. Examples for the benzene-toluene system are shown
below.
 References

[1] Levicky, "Multiphase systems". [Online]. Available:

http://faculty.poly.edu/~rlevicky/Handout5.pdf. [Accessed: 28-
Sep- 2016].
[2]"Thermopedia - A-Z Index", Thermopedia.com. [Online].
Available: http://www.thermopedia.com/content/969/. [Accessed:
28- Sep- 2016].
[3]C. Mungan, "Legendre Transforms for Dummies", 2014.
[Online]. Available:
https://www.aapt.org/docdirectory/meetingpresentations/SM14/M
ungan-Poster.pdf. [Accessed: 31- Sep- 2016].