Chemical Process Principles

CHE 113

Instructor:
Dr. Faisal Ahmed
 Single Phase Systems
 Before you carry out a complete material balance, determine various physical
properties to derive additional relations
 Look it up: If you need density, vapor pressure, solubility or heat capacity, try
to find it because there are chances that someone has measured it and
published the results. Some sources are:
 Estimate it: Sometimes you find the data but for conditions other than ones
for which you need them.
A large number of empirical correlations are available to estimate physical
properties when no data are available and to extrapolate available data to
conditions other than the ones at which the data were obtained.

 Measure it: When no information on a particular physical property of a

substance can be found in literature, perform an experiment (which are
usually costly).
Liquid and Solid Densities:
 Find: for example in Perry’s Chemical Engineer’s Handbook provides data for
mixtures and solutions of a number of substances on pp. 2-99 through 2-118.
 Estimate: for example
Volume additivity
avg. of densities

= density of mixture of n liquids, = mass fraction

 Volume additivity works best for mixtures of liquid species with similar
molecular structure (e.g. all straight chain hydrocarbons of nearly equal
molecular weight, such as n-pentane, n-hexane and n-heptane)
alternatively
Ideal Gas equation of state:

or

 Ideal gas equation of state is an approximation

 Works well at temperatures above about 0oC and pressures below about 1
atm, let Xideal=P, T, n or V
Problem
Ideal Gas Mixtures:

and

divide
Problem
Equation of state for nonideal gases:
For example, Virial equation, the van der Waals equation, Soave-Redlich-Kwong (many others)

Critical temperature and critical pressure:

Virial equation:

Note that, if all coefficients are zero, it gives ideal gas equation of state. Should be used for nonpolar
species (one with a dipole moment close to zero and symmetrical molecular structure).
Procedures for estimating the coefficients are not well developed specially for those beyond B.
Problem
Cubic equation of state:
Problem
The Compressibility factor equation of state: (An alternative to nonideal equation
of state:
Problem
The Law of corresponding states:
Compressibility factor (z) for certain temperature and pressure is different for different species.

Massive volume of data

Alternative to avoid massive volume of data

The empirical law of corresponding states holds that the values of a certain physical properties of a
gas such as the compressibility factor depend to great extent on the proximity of the gas to its critical
state

 The reduced temperature and pressure provide a measure of this proximity

The closer Tr and Pr are to the 1, the closer the gas to its critical state.

This observation suggests that a plot of z vs Tr and Pr and Vrideal should be approx. same for all
species.
Generalized
Compressibility
Chart
(low pressures)
Generalized
Compressibility
Chart
(medium pressures)
Generalized
Compressibility
Chart
(high pressures)
Problem
Problem
Problem
Nonideal gas mixtures:

Problem