1.

0 Introduction

Mass and energy balances are fundamental principles behind the design and analysis of
all chemical processes. Mass and energy balances are based on the principles of

• Conservation of mass (material balances)

• Conservation of energy (heat balances)

In chemical processes, material and energy balances are a useful tool for product
formulation, process design, cost estimation and process efficiency calculation. Material
balance is the tracking of the inflow and outflow of material in a process and the
accumulation amount of the product. The selection and sizing of process equipment is
made based on the material balance.

Energy balances provide information on energy inflow, out flow and loss or conversion.
Thus, energy balances enable us to design a process in terms of thermal, mechanical
energy and to select the suitable source of energy for the process of concern. Moreover,
we gain insight about where loss of energy is taking place and find out the alternative
ways to remedied it.

1.1 Types of processes

A particular process can be:

• Continuous process: here feed enters, and products leave continuously.

 It will be easy to analyse such a process if it is at steady state (i.e.,
when the flows and compositions are independent of time).

 It will be complicated if there are time dependencies (e.g., transient

behaviour during start-up and shutdown)

• Batch process: here material is charged into a vessel, a reaction (or other
operation) is then performed, and then the product is withdrawn.

 This is less efficient use of time than continuous process, but it is used for
products of high value where purity is very important e.g.,
pharmaceuticals

• Semi-batch process: term used to describe processes that operate in batch

mode, but with slow continuous addition of feed (or slow continuous withdraw of
product)

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A schematic of a sample simple continuous plant:

 Each box in the diagram represents one or more-unit operations

 Unit operations include heaters, mixers, reactors, filters, distillation columns, etc.

For example, consider a problem in crystallization.

The problem may be simply stated:

Determine the amount of sugar (water-free basis) that can be produced from 100 kg of
sugar solution that contains 20% by weight of sugar and 1% of a water-soluble
uncrystallizable impurity. The solution is concentrated to 75% sugar, cooled to 20 oC,
centrifuged, and the crystals dried.

The problem statement is indeed adequate to draw a process flow diagram, as shown
below.

A block diagram showing the basic process unit is called a process flowsheet.

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In a full process flow diagram (PFD), the diagram will include valves and pumps and a
table of stream

 Flowrates, composition,
 temperatures
 pressures.

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1.2 Notation
• In a batch process, we will normally be interested in the amount of a particular
substance present.
• In a continuous process, we will more commonly be talking about the flowrates of
species present.
• In both cases, we need to be able to use mass and molar units as appropriate.

1.2.1 Amount of substance

Amount Flowrate
•
• Mass M (kg) M (kg/s)
•
• Moles N (kmol) N (kmol/s)
•
• Volume V (m3) V (m3/s)

These are related by:

• Mass density ρ = M/V (kg/m3)
• Molar density ρm = N/V (kmol/m3)
• Molar mass m = M/N (kg/kmol)

1.2.2 Composition

When more than one species is present, we shall use subscript i’s to denote the individual
•
components, e.g., M i is the mass flowrate of species i (kg/s).

• Concentration Ci = Ni/V (kmol/m3)

i.e., the number of moles of species i/volume of mixture.

Provided all components are moving at the same velocity, then:

• •
• Concentration Ci = N i / V (kmol/m3)

Hence, we can obtain the molar flow of species from the overall volumetric flowrate
and concentration.

• •
• Mass fraction: wi = M i / M = M i / M
i.e., the mass of the species i/mass of mixture.

Mass fractions are often quoted in a percent basis as wt% or %w/w.

Another “unit” which is used to express mass fractions of low concentration species
(particularly in liquids) is “parts per million” (ppm), where ppm = 106 wi.

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 • •
• Molar fraction: xi = N i / N = N i / N
i.e., the number of moles of species i/number of moles of mixture.

When liquid and vapour phases are simultaneously present, it is common to use:
⇒ xi to denote mole fractions in the liquid phase
⇒ yi to denote mole fractions in the vapour phase

Mole fractions are normally quoted as mol%. Occasionally ppm units on a molar
basis are used (particularly for gases).

• Volume fraction = Vi/V

Note that this equals the molar fraction, xi, for an ideal gas.
Volume fractions are sometimes quoted in percent basis as vol% or %v/v

M
• We may also use the mean molar mass for a mixture m = = ∑ xi mi
N i

xm
• This enables the conversion between mass and molar fractions: wi = i i
m

1.2.3 Symbols for intensive and extensive properties

1) INTENSIVE properties are those that are independent of the amount of substance.
Thus, we can simply use P and T to denote pressure and temperature, respectively.

2) EXTENSIVE properties depend on the amount (or “extent”) of substance (e.g.,

volume). We shall follow the following nomenclature:

• V to denote the total volume

• V to denote the molar volume, i.e., in m3/mol
∧
• V to denote the specific volume, i.e., in m3/kg

Thus, we can write the IDEAL GAS number of ways:

• PV = RT which implies PV=NRT
∧ ∧ ∧
• PV = R T which implies PV = M R T

The universal gas constant R=8.3145 J mol-1 K-1 or 8314.5 J kmol-1 K-1, for all gases.
∧ ∧
Note that the gas constant in mass units, R = R / m depends on the gas (e.g., R =287 J kg-1
∧
K-1 for air; R =2079 J kg-1 K-1 for helium).

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The ideal gas law (when it holds) can be used to obtain concentrations and/or densities:

• P = CRT and Pi = Ci RT where Pi is the partial pressure of species i.

∧
• P=(ρ/m) RT or equivalently P = ρ R T

1.2.4 A word on units

• Be careful not to mix up molar and mass units in the same equation
• Be careful not to mix up “mol” and “kmol” in the same equation
• Be careful to distinguish between pressures quoted in “bara” (bar absolute) and
“barg” (bar gauge).
• Be careful to distinguish between temperatures in Kelvin and oC. In
thermodynamics, the symbol T implies temperatures in Kelvin.
• We shall often use the SI system, but it is essential that you can deal with other
units. Conversion units can be found in many places (e.g., inside cover of
Sandler’s book, or Perry’s Chemical Engineers’ Handbook).
• Note that concentrations may also be expressed in other units e.g., molarity,
molality, normality (less popular). You must be able to convert between these
units.

1.2.5 Example

A 5 wt% aqueous solution of NaOH has a density of 1.0554 g/mL. What is the mole
fraction of NaOH and its molar concentration?

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