Process Variables: Composition

Most material streams in process units are mixtures of compounds. We describe the composition of the stream in various
ways.

Composition Fractions
Composition fractions can be based on mass or on moles.

You convert from "fraction" to "percent" by multiplying by 100.

The units of mass measurement used don't make a difference, as long as the top and bottom of the ratio use the same units:

EXAMPLE: A stream contains 20 g of oxygen gas, 70 g of nitrogen, 5 g of helium, and 5 g of hydrogen. Find the mass and
mole fractions, mass and mole percent compositions.

First, you need to find the mass of each component (given), the total mass (add them up). You'll also need to calculate the
moles of each component (divide mass by molecular weight) and the total moles.

Now you have everything you need to calculate the composition fractions.

The fraction results can be checked by adding them up -- they must equal 1.0.

Multiply the fractions by 100 to get the percent composition.

A concentration unit often seen in environmental usage is parts per million or ppm. It is the grams of solute in 1 million
grams of solution. PPM (or ppb) is a special kind of mass fraction.

Often, you will be given a composition in percent or fraction form, but to solve the problem you will need to know the
masses of the individual components (if only to convert to molar composition). Take care of this by assuming a basis of 1 kg,
100 mol, etc. and work from there. After all, if a mixture is 21 mole percent oxygen, it doesn't make a difference if you've got
5 g or 30 lb or 200 mol -- the percentage or fractional composition is the same.
EXAMPLE: Air is about 78 mole percent nitrogen, 21 mole percent oxygen, and 1 percent argon. What is its composition by
mass?

You don't know how much (total moles or total mass) air you have -- but it doesn't make a difference. So choose a basis
amount that will make the calculation easy. When compositions are given in percentages, a basis of 100 is always nice since
it requires no multiplication or division. I think I'll work this in lbmoles.

BASIS: 100 moles air WRITE IT DOWN!

The Average Molecular Weight of a mixture is computed from the molar composition and the molecular weight. It is a
weighted average -- the molecular weights are averaged using the mole fractions as weights.

EXAMPLE: Calculate the average molecular weight of air.

Assume air is 79 mole % nitrogen, 21 mole % oxygen.

BASIS: 1 gmol air

So the answer is 29 g/mol after we allow for significant digits.

You should NOT try to calculate average densities or average specific gravities using a weighted arithmetic mean. If you look
at what this does, the units don't work out. You have to use a weighted harmonic mean.

Concentration
A lot of times, the terms "composition" and "concentration" are used interchangeably. At this point, we want to make clear
the difference. Concentration is based on volume and is one way of expressing composition. The mass concentration is the
mass of a component per unit volume, similarly molar concentration is the moles per unit volume.

EXAMPLE: If I dissolve 1 g of salt in 1000 liters of water, what is the concentration of the mixture?

Assume additive volumes.

Concentration is grams solute divided by the volume of the mixture (water and solute).

To simplify the problem, notice that the volume of the salt is probably much much less than that of the water; consequently,
let's neglect the volume of the salt. WRITE DOWN "Assume volume of salt is negligible".
If this were an important problem, we would probably want to go back and justify our assumption by looking up the density
of salt and estimating how much the assumption changed the answer.

In the example, I assumed additive volumes. Generally speaking, if we add 1 m3 of component A to 1 m3 of component B,
we cannot be sure to get 2 m3 of the mixture. When it is true, we say that the "volumes add" or that "volume is additive".

Volumes are additive only if the mixture is "ideal". The details of ideality will be discussed in ChE thermodynamics, but for
the time being we will usually assume ideal solutions. This is probably ok if all components are similar and if the
temperatures and pressures are not extreme, but the assumption of ideality needs to be stated.

When concentration is calculated in terms of gmol/liter, it is called Molarity, abbreviated M.

EXAMPLE: How much KOH is in 5 ml of a 2 M solution?

Concentration is grams solute divided by the volume of the mixture (water and solute).

You MUST be able to switch between volumetric, mass, and molar compositions and flows quickly and without struggle.
Otherwise all the problems in this class will take a lot longer than they should.

The smart engineer will usually work problems in mass or mole units, converting in and out of volume units if necessary.
Trying to work problems primarily in volume units is often a source of problems.

References:

1. R.M. Felder & R.W. Rousseau, Elementary Principles of Chemical Processes (2nd Ed.), John Wiley, 1986, pp. 50-55.
2. D.M. Himmelblau, Basic Principles and Calculations in Chemical Engineering (6th Ed.), Prentice Hall, 1996, pp. 16-
17, 22-26.

R.M. Price
Original: 6/2/94
Modified: 8/24/95, 8/14/96, 8/26/98; 5/24/2004

Copyright 1998, 2004 by R.M. Price -- All Rights Reserved