CET I PROCESS CALCULATIONS

1. INTRODUCTION

 Chemical engineers are concerned with making processes useful (profitable, safe,
environmentally friendly...).
 For this reason, this course is called PROCESS CALCULATIONS. It covers some fundamental
principles that are behind all processes.
 The usual name of the science underpinning these principles is THERMODYNAMICS.
 We are thus going to revise (or learn!) some basic thermodynamics and use it in a useful
way to do calculations on processes.
 This course is largely based on the principles of:
o
o
 We will not discuss the conservation of momentum (which is the fundamental principle
behind the subject “fluid mechanics”).

1.1 Types of Process

 A particular operation can be continuous, batch, or semi-batch.

 CONTINUOUS PROCESS: here feed enters and products leave continuously.
 This process will be easy to analyse if at STEADY STATE (i.e. when the flows and
compositions are independent of time).
 It will be more complicated if there are time dependencies (e.g. transient behaviour
during start-up and shut-down)
 BATCH PROCESS: here material is charged into a vessel, a reaction (or other operation) is
then performed, and then the product withdrawn.
 This is less efficient use of time than a continuous process, but is used for products of
high value where purity is important (e.g. pharmaceuticals).
 The term SEMI-BATCH PROCESS is sometimes used for those processes which operate in
batch mode but with slow continuous addition of feed (or slow continuous withdrawal of
product).
 Here is a schematic of a simple continuous plant:

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 Each box in the diagram represents one (or more) UNIT OPERATIONS.
 Unit operations include heaters, mixers, reactors, filters, distillation columns, etc. (These
will mainly be covered in other courses).
 A block diagram showing the basic process units is called a PROCESS FLOWSHEET. (This
will mainly be covered in this course).
 In a full PROCESS FLOW DIAGRAM (abbreviation: PFD), the diagram will include valves
and pumps and a table showing, for each process stream, the:
 temperature
 pressure
 flowrate
 composition
 The purpose of this course is the calculation of these quantities.

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Figure: Example PFD (from Towler & Sinnott “Chemical Engineering Design”)

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1.2 Notation

 In a batch process, we are interested in the AMOUNT of each substance present.

 In a continuous process, we are interested in the FLOWRATES of each 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) 𝑀̇ (kg/s)

Moles 𝑁 (kmol) 𝑁̇ (kmol/s)

Volume 𝑉 (m3) 𝑉̇ (m3/s)

 These properties are related by:

Mass density (kg/m3) 𝜌 = 𝑀 ⁄𝑉 𝜌 = 𝑀̇⁄𝑉̇
Molar density (kmol/m3) 𝜌m = 𝑁⁄𝑉 𝜌m = 𝑁̇⁄𝑉̇
Molar mass (kg/kmol) 𝑚 = 𝑀 ⁄𝑁 𝑚 = 𝑀̇⁄𝑁̇

1.2.2 Composition

 When more than one species is present, we shall use subscript 𝑖 to denote an individual
components, so 𝑀̇𝑖 is the mass flowrate of species i (kg/s).

Concentration
 Concentration of a species for a batch process:
 Concentration of a species for a continuous process:
 This assumes all components are moving at the same velocity.
 Note that we can obtain the molar flow of a species from the overall volumetric flowrate and
concentration.

Mass fraction
 Mass fraction for a batch process:
 Mass fraction for a continuous process:
 Mass fractions are often quoted in a percent basis as wt% or %w/w.

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 For low concentration species (particularly in liquids), mass fractions may be quoted using
parts per million (ppm) “units”, where ppm = 106 𝑤𝑖 .

Mole fraction
 Mole fraction for a batch process
 Mole fraction for a continuous process
 When liquid and vapour phases are simultaneously present, it is common to use:
o 𝑥𝑖 to denote mole fractions in the liquid phase;
o 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, where ppm = 106 𝑥𝑖 .

Volume fraction
pure
 Volume fraction = 𝑉𝑖 ⁄𝑉
pure
 Here 𝑉𝑖 is the volume that species 𝑖 would have if it was pure (rather than being in a
mixture).
 Volume fractions are sometimes quoted in a percent basis as vol% or %v/v.
 Note that volume fractions are equivalent to mole fraction for an ideal gas mixture.
 For low concentration species (particularly for gases), ppm units on a volume basis are
quoted – these are assuming the ideal gas law and so correspond to ppm units on a molar
basis.

Mean molar mass

 The mean molar mass 〈𝑚〉 (in kg/kmol) of a mixture is:

 The mean molar mass enables mass and mole fractions to be interconverted:

1.2.3 Intensive and extensive properties

 INTENSIVE properties are those that are independent of the amount of substance. Examples
are pressure 𝑃 and temperature 𝑇.

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 EXTENSIVE properties depend on the amount (or “extent”) of substance. An example is
volume 𝑉.
 We shall follow Sandler’s notation and use:
 𝑉 to denote the total volume (an extensive property)
 𝑉 to denote the molar volume, i.e. in m3/mol (or m3/kmol) (an intensive property)
 𝑉̂ to denote the specific volume, i.e. in m3/kg (an intensive property)

1.2.4 The ideal gas law

 We can write the IDEAL GAS LAW in a number of ways.


 The universal gas constant R = 8.3145 J mol–1 K–1, or 8314.5 J kmol–1 K–1, for all gases.


 The gas constant 𝑅̂ in mass units (J kg–1 K–1) depends on the gas by 𝑅̂ = 𝑅⁄𝑚
 For instance: 𝑅̂ = 287 J kg–1 K–1 for dry air; 𝑅̂ = 2079 J kg–1 K–1 for helium.
 In a continuous flowing system:


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

 In a mixture of ideal gases:



1.2.5 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 (K) and °C. In thermodynamics, the
symbol T implies temperatures in kelvin.
 We will normally use the SI system, but be aware that non-SI units exist as well.
 A list of units is given on Page 3 of the Data Book, with SI prefixes given on Page 2.

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