Department

Of
Chemical Class
Engineering
Notes

Chemical Engineering 113/123

CIR 113/123
 Table of content
CLASS NOTES FOR CIR113 ....................................................................................................... 1
1. Dimensions, units and their conversion .............................................................................. 1
1.1. Conversion .................................................................................................................. 1
Dimensional Consistency ............................................................................................ 5
Significant Figures....................................................................................................... 5
2. The mole unit, density, concentration, temperature, pressure ............................................ 6
The mole unit .............................................................................................................. 6
Density and SG of solids/liquids .................................................................................. 7
Temperature and pressure standards ....................................................................... 10
Density and SG of gases........................................................................................... 11
Flow rate ................................................................................................................... 13
Concentration ............................................................................................................ 13
Temperature ............................................................................................................. 17
Pressure and hydrostatic head .................................................................................. 18
Buoyancy and flotation .............................................................................................. 21
3. Empirical formulae ........................................................................................................... 23
Introduction to empirical formulae ............................................................................. 23
Conversion of an empirical formula ........................................................................... 25
4. Introduction to basic processes ........................................................................................ 27
Fundamental process descriptions ............................................................................ 27
Process flow diagrams and block diagrams............................................................... 31
5. Introduction to material balances ...................................................................................... 35
Basic introduction ...................................................................................................... 35
Solving material balances ......................................................................................... 36
6. Basic material balances ................................................................................................... 44
Tie elements or tie components ................................................................................ 44
Mixing streams .......................................................................................................... 44
Splitting streams........................................................................................................ 47
Linear interpolation .................................................................................................... 48
Multi-unit processes .................................................................................................. 49
CLASS NOTES CIR123 ............................................................................................................. 53
7. Material balances without reaction ................................................................................... 53
Crystallisation and mixing .......................................................................................... 53
8. Chemical reaction and stoichiometry ................................................................................ 55
Stoichiometry ............................................................................................................ 55
Extent of reaction ...................................................................................................... 55
Limiting and excess reactants ................................................................................... 56
Conversion or degree of conversion .......................................................................... 58
Selectivity .................................................................................................................. 59
Yield and percentage yield ........................................................................................ 59
9. Material balances with chemical reactions........................................................................ 62
Species mole balance ............................................................................................... 62
Element material balance .......................................................................................... 62
10. Fuel and combustion .................................................................................................... 68
Coal ....................................................................................................................... 68
Coal analysis methods........................................................................................... 69

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 Combustion ........................................................................................................... 74
Combustion terminology ........................................................................................ 75
Combustion calculations ........................................................................................ 76
11. Material balances with recycle streams, bypass streams and purge streams................ 87
Recycle systems.................................................................................................... 87
Bypass and purge streams .................................................................................... 93

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 CLASS NOTES FOR CIR113
1. DIMENSIONS, UNITS AND THEIR CONVERSION

To define the physical properties of any entity (e.g. their size, position, energy content, etc.),
primary dimensions consisting of mass, length, time, and temperature are used. These primary
dimensions can then be used to define secondary attributes such as viscosity, density, pressure,
etc.

1.1. Conversion

Due to the lack of published data, it is not always possible to use units of the SI system. Therefore,
a thorough knowledge of the other systems is necessary.
Table 1: Unit comparison of the three most used unit systems.

Secondary Symbol CGS Units British Units SI Units

properties
Area A cm2 ft2 m2
Volume V cm3 ft3 m3 and litre (L)
pound force (lbf) and Newton (N)
Force F dyne
poundal (lbm·ft/s2) (kg m/s2)
Work W calorie ft·lbf and BTU Joule (J) Nm
Energy, Heat Q calorie ft·lbf and BTU J
Density  g/cm3 lbm/ft3 kg/m3
Watt (W)
Power cal/sec BTU/sec and hp
J/s
Specific volume Vˆ cm3/g ft3/lbm m3/kg
Molar volume Vˆ cm3/gmol ft3/lbmol m3/kmol
Pascal (Pa)
Pressure P dyne/cm2 lbf/ft2
N/m2
Velocity u and v cm/sec ft/sec m/s
Acceleration a cm/sec2 ft/sec2 m/s2
Acceleration
g cm/sec2 ft/sec2 m/s2
due to gravity
Gravitational g m  cm lbm  ft
gc Not defined
constant g f  sec 2 lb f  sec 2
Poise
Viscosity   g  lbm/ft·h N·s/m2
=Pa·s
  = kg/m·s
 cm  sec 
Thermal  C  F
k cal / cm2 ·sec   BTU/ft2·h W/m·K
conductivity  cm  ft
Heat capacity Cp and Cv cal/g·°C BTU/lbm·°F J/kg·K
Molar heat
Cp and Cv cal/gmol·°C BTU/lbmol·°F J/kmol·K
capacity
Heat transfer
h cal/cm2·s·°C BTU/h·ft2·°F W/m2·K
coefficient

To move from one-unit system to another, conversion factors are used. The tables on the inside
of the Himmelblau cover summarise some of the most common conversion factors.

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 USE OF CONVERSION FACTORS

The viscosity of a liquid is 1 Poise. What is the viscosity in lbm/ft·h and N·s/m2?

1g lbm 2.54 cm 12 inch 3600 s lbm

1 Poise = cm s 453.6 g inch ft h = 241.9
ft  h

1g kg 100 cm kg
1 Poise = = 0.1
cm s 1000 g m ms

 kg  m  s  N s
= 0.1 
kg m s 
 = 0.1  2  2  = 0.1
 ms m s  s  m  m2
Refer to Examples 2.1 – 2.3 in Himmelblau (pp. 20-21).

TUTORIAL 1

Note: Various sources can be scoured and used to aid in conversion calculations. Perry’s
Chemical Engineering’s Handbook (mentioned in the study guide) contains a vast collection of
conversion factors. Electronic sources such as Microsoft Excel and Google can also be used.

Conversions in Excel
Conversion calculations can
be performed in Excel by using
the CONVERT function. Refer
to the following link for more
information on how to use the
function:
https://exceljet.net/excel-
functions/excel-convert-
function

Conversion using Google

Conversion factors and basic
calculations can be performed
straight in the google search
bar.

NB: During semester tests and exams the data sheet below will always be provided. It is
recommended that you use these conversion factors when studying.

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 Datasheet
Conversion factor

1 inch = 2.540 cm 1 m3 = 1000 L

1 lbm = 0.4536 kg 1t = 1000 kg
1 lbm = 16 oz 1 BTU = 1055 J
1 ft = 12 inch 1 cal = 4.187 J
1 ft = 0.3048 m 1h = 3600 s
1 mile = 1.609 km 1 min = 60 s
1 lbf = 4.448 N 1 hp = 0.7457 kW
1 US gallon = 0.8327 Imp gall. 1 bbl (oil) = 42 US gallon
1 Imp gallon = 4.545 L 1 US gallon = 3.785 L

1 atm = 14.696 lbf/inch2 = 33.91 ft H2O = 760 mm Hg =101.325 kPa

= 29.92 inch Hg
1 bar = 100 kPa
R = 8.314 kJ/kmol·K
g = 9.807 m/s2 = 32.17 ft/s2
lbm ft Δ(1°C) = Δ(1.8°F)
gc = 32.17 K = °C + 273
lb f s 2
(273.15)
At NTP Ideal gas Vˆ = 24.05 nm3/kmol °C = (5/9)*(°F-32)
°R = °F + 460
At STP Ideal gas Vˆ = 22.71 sm3/kmol (459.67)

Atomic mass

O = 16 H =1 C = 12
Na = 23 S = 32 Cℓ = 35.5
N = 14 Ca = 40 Cu = 63.5
Sb = 121.8 Fe = 55.8 Aℓ = 27
Cr = 52 K = 39 Mg = 24.3
Zn = 65.4 Mn = 55 Ag = 108
Pb = 207 F = 19 P = 31
Ba = 137.3 Si = 28.1 I = 127

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The use of gc in the British system and the American Engineering (AE) system

Study Himmelblau (8th edition), Chapter 2 from Eq. 2.1 on pp. 21 up to the end of example 2.4 on
pp. 23. [7th edition, Chapter 1.3, Eq. 1.1 up to the end of Example 1.4]

Just like there exist a difference between the definitions of mass and weight in the SI unit system,
there exists a difference between pound-mass and pound-force in the British and AE systems.
Please be aware that the concept of kilogram-force does not exist in the SI unit system.
SI-Units British and AE system
Mass kg Pound-mass lbm
Weight N Pound-force lbf

In the SI unit’s system, g (9.807 m/s2) is used to convert mass values to weight values in order to
take the effect of gravitational acceleration into account when performing force calculations.

The same concept can be applied to gc when considering the British and AE unit systems,
HOWEVER, here we are NOT converting pound-force to pound-mass BUT pound-force to
poundal!

POUNDAL DEFINITION ORIGIN

What is the weight of a mass of 15 lbm?

From F = mg
= m·gc
= 15 (32.17) = 482,6 lbm·ft/s2

Just like (in SI) the combination of units kg·m/s2 is called a Newton, the combination lbm·ft/s2 is
called a poundal.
1 poundal = 1 lbm·ft/s2

The weight of the 15 lb mass can now be reported as 482.6 poundal or it can be converted as
follows:
 lb  ft   1 
Weight =  482.6 m 2    
 s   gc 
482.6 lbm  ft lb f  s
2

= 
32.17 s2 lbm  ft
= 15 lbf

From the above, it should be clear that

482.6
482.6 poundal = lbf = 15 lbf
32.17
and a new identity is created

1 lbf = 32.17 pndl

which effectively eliminates the necessity ever to use gc for conversions.

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 Dimensional Consistency

Any equation can only be deemed valid if it conforms to one of the most basic principles: that all
equations should be dimensionally consistent. In layman’s terms, you cannot sum apples and
oranges and expect your answer to be in pears. In the same way, you cannot sum values that
are in SI and British and expect your answer to be sound. Therefore, it is always good practice
to convert all values to the same unit system before manipulation.

Study Himmelblau (8th ed), Chapter 2.3 from pp.25 to pp.29 (Ignore example 2.5). [7 th edition,
Chapter 1.4, pp.21 to 24 (Ignore example 1.6)]

Do the self-assessment test in Himmelblau (8th edition). pp.27 & 28. [7th edition pp.23-24]. Note
that the answers to these self-assessment tests appear in Appendix A in Himmelblau (8th
edition). (pp.829). [7th edition, pp.998]

Dimensionless groups:
uD
Reynolds number Re =

hD
Nusselt number Nu =
k
Cp
Prandtl number Pr =
k
etc.
Refer to the following website for a list and a simple description of all of the dimensionless
numbers: https://en.wikipedia.org/wiki/List_of_dimensionless_quantities
Page 3-88 in Perry’s Chemical engineers’ handbook (8th edition)

Significant Figures

As engineers, we should always be aware of the accuracy and estimated percentage error that
accompanies most of our calculations. The number of significant figures for a number is a direct
indication of its accuracy. It is important to consider the significant figures of all the values that
are given/used in calculations and present your answers in a form that is sensible.

Study Himmelblau (8th edition) Chapter 2.4, pp.29 to pp.35. Especially Table 2.5 (pp.30) and
example 2.7 (pp.31). [7th edition, Chapter 1.5, pp.24-29, example 1.8]

Review Chapter 2.5 (8th edition) (pp.36 to pp.37). [7th edition, Chapter 1.6 pp.30-31]

TUTORIAL 2

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2. THE MOLE UNIT, DENSITY, CONCENTRATION, TEMPERATURE, PRESSURE

The mole unit

Study paragraph 2.6 in Himmelblau (8th edition) pp.37-43. Ignore example 2.12. [7th edition,
paragraph 2.1 pp.43-47, Ignore example 2.1]

Mole mass (or molar mass or molecular mass) is generally accepted as a dimensionless
quantity. This is however strictly speaking not true. If we say the mole mass of water is 18,
then we mean that 18 grams water is one gram mole water, i.e. the mole mass of water is:

18 g/gmol or 18 lb/lbmol or 18 kg/kmol

Note that a mole unit is essentially a mass unit. Consider e.g. the units of heat capacity,
kJ/kg·K, which can also be given in kJ/kmol·K.

• Average mole mass ((8th edition), Chapter 2.6, pp.39-41) [7th edition, Chapter 2.1
pp.43-47]

Please refer to examples 2.11 and 2.12 on pp.40-41 in Himmelblau (8th edition). [7th edition,
example 2.1] Himmelblau

The average mole mass of a mixture is the sum of the individual mole fractions multiplied by the
individual mole masses.

n
i.e. (MM)av = 
i = 1
xi (MM)i

with xi = mole fraction of component i if n components are present

(MM)i = mole mass of component i.

Note the units in this calculation. If two compounds A and B are mixed to give mole fractions xA
and xB, then if T denotes TOTAL:

MM)av = xA  MM A + xB  MM B

kmol A kg A kmol B kg B
 + 
kmol T kmol A kmol T kmol B

kg A + kg B kg T
= = = MM of the total mixture
kmol T kmol T

• Mass and mole fraction ((8th edition), Chapter 2.6, pp.41-42) [7th edition, Chapter
2.5 pp.57-59]

The mass and mole fraction of a certain component in a system is never the same and should
never be used interchangeably. This is indicated clearly in example 2.13 (pp.42) [7 th edition,
example 2.6, pp.57].

NB: Mole fraction cannot be converted to a mass fraction by multiplying with the molecular mass
of that particular species, and vice versa!!
6|Page
 • Choosing a basis ((8th edition) Chapter 2.7 pp.44-48) [7th edition, Chapter 3,
pp.78-87]

When information of the analysis of a solid, liquid, or gas is given, knowledge must first be
obtained about the basis of the analysis, e.g. is the analysis on a mass basis, mole basis, volume
basis, etc. Generally, it is assumed that solids and liquids are always on a mass basis and gasses
on a mole basis or volume basis unless stated otherwise. If the Ideal gas law is applicable, a gas
analysis on a volume basis is exactly the same as an analysis on a mole basis.

CHOOSING A BASIS

A solution of methanol, ethanol, and water has the following analyses:

Ethanol = 30 %; Methanol = 45 %; Water = 25 %

What is the analysis on a mole basis?

First, a suitable basis should be selected. The basis can be of any value that would simplify the
calculation.

Basis: 100 kg solution

Component MMw kg kmol Mole%

C2H5OH 46 30 0.6522 18.92
CH3OH 32 45 1.4063 40.79
H2O 18 25 1.3889 40.29
100 3.4474 100

NB: Only one basis can be selected for a system at a time. For instance, in the example above,
we selected a basis of 100 kg total solution, however, we could also have selected a basis of
100 kg methanol. Both bases are correct; however, we cannot use both bases in the same
calculation.

Density and SG of solids/liquids

Study (8th edition) Himmelblau Chapter 2.8 pp.49-54. [7th edition, Chapter 2.2 & 2.3, pp.48 – 56]
Note the concepts density, specific volume, bulk density, molar density, molar volume, and
solution.

• The density of solids and liquids

Bulk density is a variable that depends on the SG (or real density) and on the particle size and
porosity of the material. It may happen that a material with an SG of 2.6 (in other words a density
of 2600 kg/m3) can be chopped into small pieces. If the fine pieces are now placed in a volume
of 1 m3, it will not be possible to fit 2600 kg of material into the 1 m3 volume, because the particles
will settle in the container in such a manner that openings will exist between them. If it is then
possible to pack e.g. 1800 kg of the particles into a 1 m3 volume, we say the bulk density of the
material is 1800 kg/m3.

It ought to be clear that the bulk density of liquids is the same as the true density while the bulk
density of solid particles will always be lower than the true density of the solid.
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 • SG

Specific gravity is commonly reported and thought of as a dimensionless ratio, however, it is a

ratio of two densities: that of the substance of interest (A) and that of a reference substance.

(g / cm ) 3
(kg / m ) 3
(lb / ft )3

(g / cm )ref (kg / m )ref (lb / ft )ref

A A A
SG of A = 3
= 3
= 3

Generally, the reference substance for liquids is water with a density of 1 g/cm3; 1000 kg/m3; or
62.43 lb/ft3.

• Ideal mixing

Liquid A and liquid B is mixed to produce mixture C. If it is assumed that the liquids mix ideally,
then the volume of mixture C can be calculated by summing the volumes of A and B.
VA + VB = Vc

DENSITY CALCULATIONS

A liquid of density 1630 kg/m3 must be prepared by mixing clay with water. How much clay
(SG = 2.1) must be added to 100 kg of water to achieve the required density?
Assume mixing is ideal

Basis: 100 kg water

Let X kg clay be required with 100 kg H2O.

Mass X kg X
Volume of the clay = = = = m3
Density 2100 kg / m3 2100
Mass 100
Volume of the water = = = 0.1 m3
Density 1000
X
i.e. final volume = (0.1 + ) m3 = V
2100
X + 100
= 1630  3 
Mass kg
and final density = =
Volume V  m 
X + 100
i.e. = 1630 from which follows: X = 282 kg
X
0.1 +
2100

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 DENSITY OF LIQUID MIXTURES

A mixture of liquids A and B contains 40% A (i.e. x A = 0.4; xB = 0.6). The SG of A is 1.4 and the
SG of B is 2.1. Assume that the liquids form an ideal mixture and calculate the SG of the mixture.

Like the method of calculating MM)av as MM)av =  xi(MM)i

it is frequently assumed in error that:

 av =  xi  i = 0.4(1400) + 0.6(2100) = 1820 kg/m3

This is WRONG. Note the units

kg A kg A kg B kg B
 xi  i : . + .
kg mixture m3 A kg mixture m3 B

The units are not the same and the two terms cannot be added!

Solution: Consider one kg mixture, i.e. 0.4 kg A and 0.6 kg B

Volume A = mass/density = (0.4 / 1400) m3

Volume B = mass/density = (0.6 / 2100) m3
Volume mixture = Volume A + Volume B (If ideal mixing can be assumed)
= (0.4 / 1400 + 0.6 / 2100) m3
Mass mixture = 1 kg

1
* Density mixture = Mass/volume = = 1750 kg/m3
0.4 / 1400 + 0.6 / 2100
1
From * it follows: m = with xi = mass fraction
 ( xi / i )
1 1 xA xB xC
or =  ( xi / i ) i.e. = + +
m m A B C

Now note the units

kg A m3 A kg B m3 B
 (xi/  i): . + .
kg mixture kg A kg mixture kg B

m3 A + m3 B m3 mixture 1
= = =
kg mixture kg mixture m

What about the density of gas mixtures if xi = mole fraction?

TUTORIAL 3

9|Page
 Temperature and pressure standards

By now it should be clear that temperature and pressure affect almost all the physical properties
of matter. To ensure that all the physical and experimental data measured all over the world can
be compared; sets of standard conditions have been established.

2.3.1. Standards for solids and liquids

Standard state (ST) conditions are strictly used for liquids and solid only. For a given material,
the standard state is the reference state for the material’s thermodynamic state properties such
as enthalpy, entropy etc. The reference state of the properties of a material is determined at a
standard state of 25°C and 1 atm.

2.3.2. Standards for gases

Just as there are several accepted unit systems used all over the world; there are several
standard reference conditions in use for gases. The most used standards are those of the
International Union of Pure and Applied Chemistry (IUPAC) and the National Institute of
Standards and Technology (NIST), although these are not universally accepted standards. The
most used standards for gases are:

• Standard conditions (SC)

• Standard temperature and pressure (STP)
• Normal temperature and pressure (NTP)

The difference between these three sets of standards is the specified temperature and pressure.
However, over time the accepted standard temperature and pressure associated with each of
these standards have changed, with the last most notable change being in 1982. In 1982 the
pressure of STP was changed to be the same as that of SC, hence SC and STP can now be
considered to be the same thing. However, there are still some books and literature that use the
old definition of STP, for instance, in Himmelblau (8th edition) pp.70 [7th edition, pp.107] the
standard pressure is defined at 1 atm (101.325 kPa) at 0°C, where it should be 1 bar (100 kPa)
at 0°C. The same mistake can be seen in the table on pp. 353 (8th edition, Himmelblau) [7th
edition, pp.404] with the specification of the SI and Universal Scientific standard pressure as
101.325 kPa and 760mm Hg respectively. The correct values should be 100 kPa and 750.06 mm
Hg.
Table 2: Standard conditions for gases.

Before 1982 After 1982

SC STP NTP SC STP NTP
Temperature 0°C 0°C 20°C 0°C 0°C 20°C
Pressure 1 bar 1 atm 1 atm 1 bar 1 bar 1 atm

It is important to note that various industries prefer to use their own specified standards that could
differ from the standards that you are use to. It is your job as an engineer to make sure that you
specify the standards that you used for your calculations clearly so that other people know exactly
how to replicate your work. For the purposes of this module, the new definition of STP will be
used (0°C; 1 bar).

10 | P a g e
 2.3.3. Ideal gas law

The ideal gas law, also called the general gas equation, is the equation of state of a hypothetical
ideal gas. All the properties that describe the behaviour of a gas, i.e. temperature, pressure,
volume, and mole, is related by this simple equation.
𝑃𝑉 = 𝑛𝑅𝑇
With P – Absolute pressure of the gas
T – Absolute temperature of the gas
V – Total volume occupied by the gas
n – number of moles of the gas
R – the ideal (universal) gas constant

It is very important to note that if any three of the variables (P, V, n, T) are specified then the other
non-specified variable is fixed due to the relationship imposed by the equation. Hence, if it is
specified that a gas fills a 1 L container and the container is kept as 100 °C and 200 kPa; we
cannot decide to select a basis of 100 moles since the number of moles of gas would be fixed by
the equation. Therefore, when information for a gas is given always check whether the rest of
the variables can be calculated using the ideal gas law equation.

2.3.4. Standard volume of a gas

The standard molar volume ( Vˆ ) of a gas is the volume that one mole of gas occupies at specified
reference conditions. This reference condition can be STP, NTP or any other specified conditions.
However, in most cases, STP is used. Hence, the Vˆ of a gas at STP is calculated as:
𝑉 𝑅𝑇 (8.314)(273.15) 𝑠𝑚3
= Vˆ = = = 22.71
𝑛 𝑃 (100) 𝑘𝑚𝑜𝑙
ˆ
The units of V at STP is defined as standard cubic meters per kilomole (sm3/kmol).
The units of Vˆ at NTP is defined as normal cubic meters per kilomole (nm3/kmol).

Density and SG of gases

• Density

The calculation of gas density is not well covered in Himmelblau; however, it is covered in detail
in the prescribed textbook for CYM171 (Refer to the study guide pp.2).
Study (8th edition) Himmelblau Chapter 7.1 (pp.350-357) [7th edition, Chapter 13 pp.401-414] for
single component gases and Chapter 7.1 (pp.360-366) for multi-component gases.
m PM
= =
V R T

• SG of gases

Gas SG sometimes creates problems. SG is always a ratio of densities, but unlike the case for
liquids, where the reference density is always the density of water at 4°C, the reference gas must
be specified together with its temperature and pressure.

• If no reference is given for gas density, it is assumed to be air at STP.

• The reference gas (and condition) is frequently written as follows, e.g. for N2 at 300 kPa
and 600 K
SG (N2 300 kPa 600 K) = 1.18 (O2 at STP = 1.00)
11 | P a g e
This means the SG of N2 at the pressure and temperature indicated was calculated relative to the
density of O2 at STP.
PM 300 (28)
 N 2 (300 kPa 600 K) = = = 1.684 kg/m3
RT 8.314 (600)
100(32)
O 2 at STP = = 1.409 kg/m3
8.314(273.15)
1.684
Then SG = = 1.195
1.409
The sm3 unit is used to indicate the volume the gas would have occupied if the conditions were
changed to 1 atm and 0°C. sm3 is then really an indication of the number of kmol because all
ideal gases at STP have a specific volume of 22.71 sm3/kmol. If a gas flow rate is given as 6000
sm3/h, the flow rate is
sm3 kmol
6000 = 267.2 kmol/h
h 22.71 sm3
and the real volumetric flow rate will depend on the temperature and pressure of the gas.

• Ideal gas mixtures Dalton and Amagat’s law

Partial pressure is defined as the pressure that would be exerted by a single component in a
gaseous mixture if it existed alone in the same volume as that occupied by the mixture and at
the same temperature:

piVTotal = ni RTTotal

Here pi is the partial pressure of component i, and ni is the number of moles of that component
in the mixture.

This same method can be used to determine the partial volume of a specific component in a
mixture:
PTotalVi = ni RTTotal

For the total mixture the following equation holds true:

PTotalVTotal = nT RTTotal

where nT refers to the total mole of all components present in the mixture.

The mole fraction of a specific component can also be used to determine the partial pressure:
pV
ni = i
RT
pi n
p1 + p 2 + .... + pi = PTotal = 1
p2 n2
pi ni
= = yi i.e. pi = yi P
P nT

And in the same way the partial volume of a single component:

PVi
ni = with Vi = partial volume of component i
RT

12 | P a g e
 Vi n1
V1 + V2 + ... + Vi = VTotal =
V2 n2
Vi ni
= = yi i.e. V i = yi V
V nT

However, the partial pressure and partial volume of a single component can NEVER be used to
determine the ni of a component.

pi Vi
WRONG ! ni =
RT

Flow rate

Study Himmelblau (8th edition), Chapter 2.12 on pp.78. [7th edition, Chapter 2.4 pp.56].
Flow rate is defined as the mass of material (e.g. kg/s) moved in a certain amount of time. This
mass flow rate can be converted to a molar flow rate by dividing with the molecular weight. The
mass flow rate can also be converted to a volumetric flow rate by using the density of the material.

• Linear velocity of flow

If a fluid flows in a duct (pipeline etc) at a volumetric flow rate of Q [m3/s] and the cross-sectional
area of the duct is A [m2], then the linear velocity is
 m3 1 
u = Q/A   2 = m/ s
 s m 
 
This is frequently used in the calculation of Reynolds numbers.
TUTORIAL 4

Concentration

Study Himmelblau (8th edition), Chapter 2.9, pp.55 to pp.59. [7th edition, Chapter 2.7, pp.62-66]

Concentration is normally expressed in terms of a certain quantity (mass, mole or volume) of a

material (the solute or dissolved material) per given quantity (mass, mole or volume) of the
solvent or of the solution. The following ways to express concentration are generally used:

Note Himmelblau’s use of L for litre. The ℓ or l are also commonly used.

• Mass per unit volume of solution

kg/m3; lb/ft3; g/m3; kg/L; etc.

In the case of a solution of salt in water this can, for example, be 200 kg salt per m3 of the salt
solution or 0.2 kg salt per litre solution, etc. Mass per unit volume must not be confused with
density.

13 | P a g e
 • Mass per unit volume of solvent

kg/m3; kg/L; etc,

However, here we have a concentration that is kg salt per m3 of water (or solvent) and not kg salt
per m3 salt solution.

• Mole per unit volume of solvent

gmol material A kilomol A

or
litre of solvent B m3 of solvent

or kmol salt/m3 water.

• Parts per million:

This is always expressed on a mass basis. If it is said that a solution contains 40 ppm solid, then
it contains 40 mass parts of solid per million mass parts of the solution. Sometimes (for gases) it
is expressed on a mole basis.

PART PER MILLION

One gmol NaCl (MM = 58.5) is dissolved in 1 m3 water. What is the concentration in ppm?

Basis: 1 m3 water

Mass water (1000 L and density 1 kg/L) = 1000 kg

1 gmol NaCl = 58.5 g
Mass solution = 1000 kg + 58.5 g = 1 000 058.5 g
In 1 000 058.5 g solution is 58.5 g NaCl
1 000 000
i.e. in 1 000 000 g solution is (58.5) g NaCl
1 000 058.5
= 58.4966 g NaCl

i.e. concentration is 58.4966 ppm

Note: The concentration is 58.5 g/1000 L = 58.5 mg/L

For dilute solutions in water, the concentration in ppm is the same as the concentration in mg/L.

• Molarity:

The number of gmols of the dissolved solid per litre of the solution is called the molarity of the
solution (gmol/L).

• Normality:

This is the number of gram equivalents of the dissolved material per litre of solution (geq/L or
ge/L).
(Self-study assignment: Find out how the normality of a solution is calculated)

14 | P a g e
(For a brief summary of Normality go to the following link: https://www.thoughtco.com/definition-
of-normality-in-chemistry-605419)
𝑔𝑚𝑜𝑙 𝑔𝑒
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 ≡ 𝑔𝑚𝑜𝑙 𝑔𝑒 𝑔𝑒 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 ≡
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ∙ = 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑔𝑚𝑜𝑙 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

NORMALITY TO MASS FRACTION

A solution of Na2CO3 (MM = 106) in water has a normality of 7.6. The density of the solution is
1.15 kg/L. What is the mass fraction Na2CO3 in the solution?

Concentration = 7.6 N = 7.6 ge/L

= 3.8 gmol Na2CO3 106 g L soln kg Na2CO3
L soln gmol 1.15 kg soln 1000 g

= 0.35 kg Na2CO3 /kg soln

= 0.35 mass fraction

NORMALITY

To neutralise a tank of an acid solution requires 30 L of a 6.0 N NaOH solution. How many litres
of the following is required?
(a) 0.48 N NH4OH soln
(b) 1.2 M KOH soln
(c) 0.52 M Al(OH)3 soln
(d) 0.2 N Ca(OH)2 soln

6.0 N NaOH-soln contains 6 ge/L soln

To be neutralised = 30 (6) = 180 ge
(a) 0.48 N NH4OH soln contains 0.48 ge/L soln

Vol. reqd = 180 ge = 375 L

0.48 ge/L

(b) 1.2 M KOH soln contains 1.2 gmol/L = 1.2 ge/L

Vol. reqd = 180 ge = 150 L

1.2 ge/L

(c) 0.52 M Al(OH)3 soln contains 0.52 gmol/L = 0.52(3) = 1.56 ge/L

Vol. reqd = 180 ge = 115.4 L

1.56 ge/L
(d) 0.2 N Ca(OH)2 soln contains 0.2 ge/L

Vol. reqd = 180 ge = 900 L

0.2ge/L

15 | P a g e
 • Molality:

This is the number of gmols of the dissolved material per 1000 g of solvent. NB: The base is a
1000 g solvent and NOT 1000 g solution!!

• Other

Mass fraction, mole fraction, mass percentage, and mole percentage can all be used to describe
the concentrations of a mixture.

CONCENTRATION

A solution of water contains 0.24 kg Na2SO4 per kg water. Express this concentration as

(a) kg Na2SO4 per kg solution.

(b) Mass fraction.
(c) Mole percentage.

The mole mass of Na2SO4 is 142.

Basis: 1 kg water.
It contains 0.24 kg Na2SO4.
Mass solution = 1.24 kg.
0.24
(a) kg Na2SO4/kg solution = = 0.194 kg Na2SO4/kg solution.
1.24
(b) Mass fraction Na2SO4 = 0.24/1.24 = 0.194
Mass fraction H2O = 1/1.24 = 0.806

(c) kmol Na2SO4 = 0.24/142 = 1.690 x 10-3

kmol H2O = 1/18 = 5.556 x 10-2
-2
Total: 5.725 x 10 kmol

mol % Na2SO4 = (1.690 x 10-3/5.725 x 10-2) 100 = 2.95%

mol % H2O = (5.556 x 10-2/5.725 x 10-2) 100 = 97.04%

16 | P a g e
 DIFFERENT FORMS OF CONCENTRATION

A starting stock solution has an SG of 1.075 and contains 12.7wt% sugar. If all the sugar is
assumed to be C12H22O11, determine

a) kg sugar/kg H2O
b) lb solution/ft3 solution
c) g sugar/L solution

Solution

Basis: 100 kg starting stock solution

a)
12.7 kg sugar 100 kg solution
=0.145 kg sugar/kg H2O
100 kg solution 87.3 kg H2O

b)
1.075g sol./cm3 1.0 g H2O/cm3 1 lb 2.832x104 cm3
=67.1 lb sol./ft3 sol.
1.0 g H2O/cm3 4536 g ft3
c)
1.075g sol./cm3 1.0 g H2O/cm3 12.7 g sugar 1000 cm3
=136.53 lb sol./ft3 sol.
1.0 g H2O/cm3 100 g sol. L

TUTORIAL 5

Temperature

Study Himmelblau (8th edition), Chapter 2.10, from pp.59 to pp.65. Study example 2.21 pp.63.
Ignore example 2.22 and the self-assessment Problem 2 pp.64.
[7th edition, Chapter 4, pp.89-95. Study example 4.1 (pp.92), ignore example 4]

The Celsius and Fahrenheit temperature scales are relative and arbitrary. It is often necessary
to work with absolute temperatures. Absolute scales have their zeros at the lowest temperature
which can exist from consideration of the laws of Thermodynamics. The absolute scale which
corresponds with the Fahrenheit scale in size of the unit is the Rankine scale and that which has
the same unit size as the Celsius scale is the Kelvin scale. The Kelvin scale is the accepted scale
for the SI system. From the above equal unit size follows:
 °F =  °R
 °C =  K

Further, from the definition of the Celsius and Fahrenheit scales, the following ratio exists
between the unit size of °F and °C:

Between the freezing point and the boiling point of water, there are 212 - 32 = 180 units on the
Fahrenheit scale and 100 units on the Celsius scale; a ratio of 1.8. Conversions can, therefore,
be done with this factor and the necessary zero reference point adjustments. It is clear that the
same ratio will exist between °R and K.

17 | P a g e
The absolute zero on the Rankine scale is at -459.58 °F (rounded off to -460 °F) and the absolute
zero on the Kelvin scale is at -273.15 °C (rounded off to -273 °C).

NOTE: In properties such as heat capacity, (kJ/kg·K), heat transfer coefficient (W/m2·K) etc,
all temperatures refer to a temperature difference of 1 K (or 1°C). If conversion of this type of
unit must be done, no reference point adjustment is necessary. Only the following identity will
be used:
 1 °C =  1.8 °F

which is generally written as °C = 1.8 °F or K = 1.8 °R or even °C = 1.8 °R or K = 1.8 °F.

TEMPERATURE CONVERSIONS

The heat capacity of water is 4.187 kJ/kg·°C. What is the heat capacity in

(a) kJ/kg K (b) kJ/kg·°F (c) BTU/lb·°F

(a) 1°C temperature difference is the same as 1 K temperature difference

kJ 1C kJ
4.187 kJ/kg·°C = 4.187 = 4.187
kg  C 1 K kg  K
(b) 1°C temperature difference is the same as 1.8°F difference

kJ 1C kJ
4.187 kJ/kg·°C = 4.187 = 2.33
kg  C 1,8 F kg   F
kJ 1C BTU 0,4536 kg
(c) 4.187 kJ/kg·°C = 4.187
kg  C 1,8 F 1,055 kJ lb

= 1.0 BTU/lb·°F

Pressure and hydrostatic head

Study Himmelblau (8th edition), Chapter 2.11, from pp.65 to pp.76. [7 th edition, Chapter 5 pp.99-
114]

Pressure, just like temperature, can also be expressed on an absolute or relative basis. Pressure
is defined as force per unit area. Note that kg/m2 indicates a mass distribution and not a pressure.

PRESSURE DUE TO GRAVITY

What is the pressure (in kPa) exerted by a 10 ft column of water at 60°F only due to gravity? The
density of water at 60°F is 62.4 lbm/ft3.

10 ft 0.3048 m
Column height = = 3.048 m
ft
3
lb 0.4536 kg  ft 
Density = 62.4 m3   = 1000 kg/m3
ft lbm  0.3048 m 

18 | P a g e
 Pressure due to gravity is expressed as:

P =  gH

P = 1000(9.807)(3.048)  3  2  m = 2 
kg m N
then
m s m 
= 30000 N/m2 = 30000 Pa = 30 kPa
P =  gh
If the formula is not known, the pressure can be calculated from first principles,
as follows:

Let the column cross-sectional area be A [m2] i.e. column volume = 3.048 A [m3] and the mass of
water in the column (mass = density x volume)

= 1000 (3.048·A)  3  m 3 = kg 
kg
 m 

The force exerted by this mass is

F = ma
= 1000 (3.048·A)·9.807  kg  2 = N 
m
 s 
i.e. the pressure P = force/area

1000 (3.048  A)  9.807  N 

i.e. P =  2 = Pa 
A  m 
= 30 000 Pa

• Gauge pressure and absolute pressure

Most pressure measuring devices measure gauge pressure. If atmospheric pressure is also
brought into account an absolute pressure is obtained.

Pabs = Pg + Patm

Absolute pressure = Gauge pressure + Atmospheric pressure

The atmospheric pressure is not necessarily one atmosphere – but varies depending on the
height above sea level and meteorological conditions. On the Witwatersrand, the average
atmospheric pressure is 83 kPa. In Pretoria, it is 87 kPa. Atmospheric pressure is also
sometimes called barometric pressure. The standard atmosphere is defined as the pressure
equivalent to 760 mm Hg in a standard gravitational field or

19 | P a g e
 1 atm = 760 mm Hg = 14.696 lbf/inch2 = 101325 N/m2
= 101325 Pa = 1.013 bar = 101.3 kPa
= 29.92 inch Hg = 33.91 ft H2O

NOTE: A vacuum must be seen as a negative gauge pressure.

In cases where confusion is possible it is advisable to distinguish between absolute and gauge
pressure as follows: kPaa, kPag, psia, psig, etc.

PRESSURE

An obsolete pressure gauge shows a reading of 1 kgf /cm2. What is the pressure?
The concept kgf is not defined. Like lbf the following can be assumed

1 kgf = 1(g)N = 9.807 N with g = 9.807 m/s2

2
N 100 cm  kN
1 kgf /cm2 = 9.807  = 98.07 kPa
cm 2  m  1000 N

VACUUM PRESSURE

A vacuum of 4 inches water is measured in a gas pipeline. If the atmospheric pressure is 730
mm Hg, calculate the absolute pressure in the pipeline in inches Hg and in N/m 2.

730 mm Hg atm 29.92 inches Hg

Patm= = 28.739 inches Hg
760 mm Hg atm

4 inches H 2 O ft H 2 O 29.92 inches Hg

PVac= = 0.294 inches Hg
12 inches H 2 O 33.91 ft H 2 O

Pabs = Patm + Pg = Patm + (-Pvac) = 28.739 + (-0.294) = 28.445 inches Hg

or
inches Hg 101325 N / m 2
Pabs= 28.445 = 96330 N/m2
29.92 inches Hg

GAUGE PRESSURE

The gauge pressure on a gas cylinder in Pretoria (atm pressure = 87 kPa) is 300 kPa. The
cylinder is transported to a campsite at the coast (atm pressure = 1010 millibar). What will the
gauge pressure on the cylinder be? Assume the temperature stays constant.

Pretoria: Pabs = 300 + 87 = 387 kPa

1010 bar 100 kPa

Coast: Patm = = 101 kPa
1000 bar

20 | P a g e
The absolute pressure in the cylinder cannot change without changing the number of moles of
gas in the cylinder, i.e. at the coast, if the temperature remains constant, the absolute pressure
will remain constant and

Pabs = 387 kPa and Pg = Pabs – Patm = 387 – 101 = 286 kPa

TUTORIAL 6
• Differential pressure

Study Himmelblau (8th edition). paragraph 2.11 pp.65-75. [7th edition, Chapter 5.3 pp.114-117]

TUTORIAL 7

Buoyancy and flotation

The well-known Archimedes principle can be stated as follows:

If a body is wholly or partially submerged in a liquid, an apparent loss of weight of the body will
be observed. The apparent weight loss is equal to the weight of the liquid displaced by the body.

In the case of a floating body, such as a piece of wood or a ship, the apparent weight of the
floating body is zero, which means that the floating body has lost all its weight. In this case, the
total weight of the body is equal to the weight of the water displaced. This means that the heavier
the floating body, the more liquid it must displace to enable it to float, which explains why empty
ships float “higher” in the water than fully laden ones.

If the immersed body does not float, the weight loss is not total but is still easily determined by
means of a scale. If the body is fully immersed, the volume of water displaced is equal to that of
the body itself, and the apparent weight loss can be used to calculate the density of the body or
its volume.

BUOYANCY

An irregular shaped object has a mass of 4.0 kg and it is necessary to find its volume and density.
The object is immersed in water (SG = 1.0) and is then found to have a “weight” of only 2.3 kg.

Solution: Weight of body = 4.0 x 9.8 [kg x m/s2 = N]

“Weight” of body in water = 2.3 x 9.8 [kg x m/s2 = N]
Apparent weight loss = 4.0 x 9.8 – 2.3 x 9.8
= 16.68 N

This apparent weight loss is known as the buoyant force exerted by the liquid on the body. The
body is pushed up or buoyed by the liquid and the body, therefore, seems to be “lighter” than it
really is.
According to the Archimedes principle, the buoyant force is equal to the weight of the water, which
is displaced, i.e.
21 | P a g e
Weight of water displaced = 16.68 N
= mass of water displaced x g

i.e. Mass of water displaced = 16.68/9.81 = 1.7 kg

and since the density of water =mass of water /volume of water

it follows that the volume of the water which was displaced

= mass of water/density of water
= 1.7/1000 = 0.0017 m3

Since the whole body was immersed, this is also the volume of the body i.e.
Volume of body = 0.0017 m3 = 1.7 litre

The density of the body is calculated from :

Density = Mass/Volume = 4.0/0.0017 = 2350 kg/m3

SG of the body = Density of body/Density of water = 2350/1000 = 2.35 →

Note that if the body floats, the mass of the body is equal to the mass of the liquid displaced, i.e.
total “weight loss”.

FLOTATION

A glass hydrometer is made by putting a lead shot into a glass bulb and adding a stem as shown
in the sketch. The volume of the bulb is 50 cm3 and the stem has an outside diameter of 12 mm.
The total mass of the hydrometer is 65 g. It is found to float in a liquid as detailed in the sketch.
What is the density of the liquid?

22 | P a g e
Solution
The mass of the hydrometer is 65 g and it floats. This means that the mass of the liquid displaced
is also 65 g and if one can find the volume of the liquid displaced, it is possible to calculate the
density.

The bulb displaces 50 cm3 of liquid. The volume of liquid displaced by the stem is equal to the
volume of the stem below the liquid surface, i.e.  /4 d2 x depth.

Stem volume below surface =  /4 x (12/10)2 x 60/10 = 6.79 cm3

Density = 65/(50 + 6.79) = 1.14 g/cm3 →

3. EMPIRICAL FORMULAE

Introduction to empirical formulae

Formulae derived from basic principles are valid, regardless of the system of units in use.

Take for example: speed = distance/time

u = s/t

If s is measured in kilometres and t in hours, u will be calculated in km/h. Confirmation that it is a

basic formula can be done by doing dimension comparison:

U is a speed :[length/time]
s
s is a distance or length :[length] i.e. = [length/time]
t
t is time :[time]

In other words, the net dimension on the left-hand side is the same as the net dimension on the
right-hand side.

It is, however, not always so simple; consider for example

ud1/ 4 = D1/2g1/ 4

with u = speed (e.g. m/s)

d = diameter (e.g. m)
D = diffusivity (e.g. m2/s)
g = gravitational acceleration (e.g. m/s2)

The dimensional correctness of the equation can be tested by ensuring that the net dimension on
the LHS = to that on the RHS.

m 
LHS :  m1 / 4 = m5 / 4 s −1 
s 

 m 2 1 / 2  m 1 / 4 m m1 / 4 
RHS :    2  = = m5 / 4 s −1 
 s   s  s1 / 2 s1 / 2 

23 | P a g e
The equation is dimensionally correct and if it is for example required to calculate u in ft/s, it will
only be required to set d in ft, D in ft2/s and g in ft/s2 in the equation.

1,08 k
Consider also the equation: u=
Cp 
Which holds true, on condition that u in ft/s, k in BTU/ft h°F, Cp in BTU/lb°F and  in lb/ft3 are
set in the equation.

 BTU lb F ft 3 ft 2 
Lhs = [ft/s] Rhs =    = 
 ft h F BTU lb h 

The equation is not dimensionally correct, in other words, it is valid only if u is in ft/s, k in BTU/fth°F,
etc.

If such an equation must be used, care must be taken that the correct units are used for which
the equation was designed.

Such a formula is known as an empirical formula.

If it is necessary to calculate (with this formula) u in m/s, it will be necessary to write all the data
(k, Cp and  ) in units of the British system; calculate u (in ft/s); and then convert the final answer
to units of m/s.

EMPIRICAL FORMULAE

Use the formula:

1,08 k
u = ,
Cp 
to calculate u in m/s if k = 0.1 W/m·K; Cp = 5.2 kJ/kg·K;  = 1200 kg/m3

J BTU 3600 s 0.3048 m K

k = 0.1 W/m·K = 0.1
smK 1055 J h ft 1.8 F

= 0.05778 BTU/h ft°F

J BTU 0.4536 kg K
Cp = 5.2 kJ/kg·K = 5200
kgK 1055 J lb 1.8 F

= 1.242 BTU/lb·°F

3
kg lb  0.3048 m 
 = 1200 kg/m3 = 1200 3   = 74.91 lb/ft3
m 0.4536 kg  ft 

1.08 (0.0578)
i.e. u = = 6.71 x 10-4 ft/s
1.242 (74.91)

24 | P a g e
 ft 0.3048 m
u = 6.71 x 10-4 = 2.04x10-4 m/s
s ft

Conversion of an empirical formula

If calculations of this type must be done regularly with the same formula it will be time-consuming,
to convert all the data and then again convert the final answer. In such instances, it is handy to
rewrite the empirical formula for direct application in the system of units in which it is required.

If this must be done, the constant in the equation, (in the above case the constant 1,08) is seen
as if it has units and that the units of the constant are such that the equation is dimensionally
correct. Only the constant is then converted to units which correspond to those required for the
new calculation.

CONVERSION OF EMPIRICAL FORMULAE

1,08 k
The formula u = is valid on condition that k, Cp and  are in British units and it can then
Cp 
be used to calculate u in ft/s. Rewrite the formula for direct application with units of the SI system
and calculate u in m/s if k = 0.1 W/m·K, Cp = 5.2 kJ/kg·K and
 = 1200 kg/m3.
u  C p     ft BTU lb ft  h   F   h 
The units of 1.08 are:   =    3  =  
 k   s lb   F ft BTU   ft  s 

h h 3600 s ft
1.08 = 1.08 = 12 756 m-1
ft  s ft  s h 0.3048 m

The SI formula is therefore

k 1 J kg  K m 3 m 
u = 12 756     = 
Cp   m s  m  K J kg s

For application in this formula, k = 0.1 W/m·K, Cp = 5200 J/kg·K,  = 1200 kg/m3

12756 (0.1)
u= = 2.04 x 10-4 m/s
5200 (1200)

REWRITING EMPIRICAL FORMULAE

The heat capacity (Cp) of sulphur is given by

Cp = 3.63 + 0.640 T with Cp in cal/gmol·K and T in K

NOTE: In the eq Cp = 3.63 + 0.640 T, T is a real temperature and not a temperature difference.
In the units of Cp (cal/gmol·K) the K denotes a temperature difference in K (or in other
words °C).

25 | P a g e
Rewrite this formula to the form:
Cp = a + bt

to calculate Cp directly in cal/gmol·°F if t in °F is set into the new formula.

Let t be the temperature in °F, i.e.
 t − 32  cal
Cp = 3.63 + 0.640  + 273 with t in °F
 1.8  gmol  K
Cp = 166.97 + 0.35556 t with Cp in cal/gmol K; t in °F

Note that the units of Cp are still not right. It is usually advisable to test the formula at this stage.
Test at 32°F (273 K)

Cp = 3.63 + 0.640 (273) = 178.35 cal/gmol·K

or Cp = 166.97 + 0.35556 (32) =178.35 cal/gmol·K

To correct the units of Cp : [Cp = 166.97 + 0.35556 t]

The units of the 166.97 are cal/gmol·K

cal K
166.97 = 92.76 cal/gmol·°F
gmol  K 1.8   F

The units of the 0.35556 are cal/gmol·K·°F

cal K
0.35556 = 0.1975 cal/gmol·°F·°F
gmol  K   F 1.8   F
cal
i.e. Cp = 92.76 + 0.1975 t in with t in °F
gmol F

Test again at 32°F:

Cp = 92.76 + 0.1975(32) = 99.08 cal/gmol·°F

= 99.08 (1.8) = 178.35 cal/gmol·K

Also, study (8th edition) Himmelblau Example 2.22, pp.63 and the self-assessment Problem 2 on
p. 64. [7th edition, example 4.2 pp.93]

TUTORIAL 8
and
TUTORIAL 9

26 | P a g e
4. INTRODUCTION TO BASIC PROCESSES

Fundamental process descriptions

Chemical engineers use various processes and methods to convert low-cost raw material into
highly valuable and useful products. In this chapter, a basic overview of some of the most
fundamental processes will be provided.

4.1.1. Filtration and crystallisation

Filtration is a separation process where a specific component or components are removed from
another mixture. Filtration can be performed in both liquid-solid systems and gas systems. In
this subject, the main focus will be on filtering solids from liquids. The process of separating solids
and liquids is presented visually Figure 1. Generally, the slurry or solution is fed into the process.
The solids collect on the filter membrane to create a filter cake. The liquid collected at the bottom
is collectively called the filtrate.

Figure 1: Filtration process explained.

• Filtration of slurries

The simplest description of slurry filtration is the filtration of sand out of a sand-water mixture, also
called a slurry. Hence, this process mainly refers to solids that do not dissolve in the carrier liquid.
The sand collects on top of the filtration membrane and is collectively called the filter cake. The
water collected at the bottom of the filter is referred to as the filtrate or simply as the pure liquid.
It should be clear that when the filter cake is removed from the filter, it will still be wet, as a small
amount of water is still trapped in the sand.

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 Figure 2: Block diagram of slurry filtration.

• Filtration of solutions

Filtration can also be used to remove crystals and dissolved salts from the water. For instance,
if a saturated salt solution is cooled down, some of the salts will start to crystallise from the
solution. This mixture of crystals and salt solution is fed into a filter to remove the crystals. The
crystals collect on top of the membrane to produce a filter cake, and the salt solution is extracted
at the bottom. The salt solution extracted at the bottom of the filter is referred to as a mother
liquor or filtrate. As with the sand-water solution, the filter cake will be wet upon removal from
the filter and will still contain some small amount of mother liquor (that consist of water and
dissolved salt). Upon drying, all the dissolved salts in the mother liquor will crystallise and collect
with the filter cake.

Figure 3: Block diagram describing a solution filtration system.

4.1.1. Decanters/Thickeners/Settling tanks/Clarifier

In all three of the processes: Decanters, thickeners and settling tanks; solids are separated from
an associated solution by various methods. These processes basically utilise gravity
sedimentation, where the solution is left in a tank over time and the solids settle to the base of the
tank. The solids are then removed from the bottom of the tank and the liquids are removed from
the side, above the solid level.

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 Figure 4: (Left) Settling tank illustration of the process, (Right) Settling tank block diagram.

a. Heat exchangers/Evaporator/Condenser

Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion,
and exchange of thermal energy (heat) between physical systems. Heat exchangers are probably
one of the most used chemical engineering processes. Heat exchangers are used to transfer
heat between either a solid and a liquid, or between two liquids. A wide array of different types
of heat exchangers are available to be used depending on the process requirements. Figure 5
below is a very simple depiction of a one-pass shell a tube heat exchanger. The hot liquid flowing
in the pipes of the heat exchanger is cooled down by the cold liquid flowing in between the pipes.
The one advantage of heat exchangers is the fact that liquids can be cooled and/or heated without
direct contact between the two liquids. This same process can be used to evaporate or condense
liquids. The degree of cooling/heating achieved in these processes is determined by the heat
transfer capacity of the two liquids and the material of construction of the pipes. This topic will be
explored in more detail later in your studies. For this course we will assume that the flow rate
and/or composition of any stream entering a heat exchanger does not change, hence, stream A
(Figure 5) will be equal to stream B, and stream C will be equal to stream D.

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 Figure 5: (Above) One-pass shell and tube heat exchanger (Below) Simple block diagram of a heat exchanger.

4.1.2. Distillation column

Distillation columns are used to separate light components from heavier components by taking
advantage of the difference in boiling point temperatures of the components. The lighter
components have a lower boiling point and thus will evaporate first and leave the top of the
column, whilst the heavier components will flow down to the bottom of the column. To make sure
that separation is efficient the vapour flowing up and the liquid flowing down is brought into contact
by using trays or column packing. Distillation columns make up over 95% of the separation
systems in the chemical engineering industries.

Figure 6: (Left) Basic distillation process; (Right) Distillation block diagram (excluding reflux)

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 4.1.3. Flash drum

A flash drum is another separation process that is used to separate vapour-liquid mixtures. A
vapour-liquid separator may also be referred to as a breakpot, knock-out drum or knock-out pot,
compressor suction drum or compressor inlet drum. The most common variety of flash drum
makes use of gravity to separate the feed if the feed is already a mixture is vapour and liquid.
Other types of flash drums may also be used to partially or totally flash (evaporate) a liquid feed
stream into a vapour and liquid as it enters the separator. Total (or partial) flash evaporation
occurs when a saturated liquid stream undergoes a sudden reduction in pressure when passing
through a throttling valve or other throttling device. A common example of this process is the way
a deodorant can works.

Figure 7: (Left) Detailed flash drum illustration, (Right) Flash drum block diagram.

Process flow diagrams and block diagrams

Two of the primary functions of a chemical engineer is:

• To develop and design processes to convert raw materials into useful products
• To improve and operate existing processes so that they are as safe, reliable, efficient
and economical as possible.

To carry out these duties, knowledge of the chemical reactions and physical processes that are
taking place in the process must be available. The chemical engineer interprets and processes
this information and makes recommendations on the findings. An essential part of the information
about a process is the process flow diagram. A process flow diagram is a graphical representation
of a process. These flow diagrams always describe the process in enough details that you can
use it to formulate material and energy balances. As seen in Figure 8, all the necessary
information for each individual stream is displayed on the diagram.

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Figure 8: Process flow diagram of an ethylbenzene production process

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Two different process flow diagrams can be used: illustrated flow diagrams (represented in Figure
8) and the much simpler block flow diagrams. Block flow diagrams are much simpler to create
than illustrated diagrams as each processing step can be represented by a block instead of a
detailed symbol (Refer to Figure 9).

Figure 9: (a) Process flow diagram of an ammonia production plant; (b) The block flow diagram for the same
process. (Himmelblau (8th ed.) pp.269)

Even though block diagrams look much easier, illustrated flow diagrams that use standard
symbols to represent each of the processing steps usually makes the diagram much easier to
read and understand. There exist a few standard symbols for various processes and a few of
these symbols (available in Microsoft Visio) are illustrated below. A wide variety of further
symbols are used to provide information on the flow diagram. The examples shown are typical
(Figure 10). Each designer or institution will develop its own symbols.

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 Heat
exchanger
(General) Tray
distillation
Shell and tube
column
heat
exchanger

Shell and
tube: kettle Tray
reboiler distillation
column
Air-blown (general)
cooler

Plate and
frame heat Fluid contact
exchanger vessel or
packed
Double pipe distillation
type heat column
exchanger

Fired heater /
boiler Reactor or
absorption
vessel
In-line pump

Centrifugal
pump
Auroclave
Positive
displacement
pump

Screw
conveyor Open tank
(left) closed
tank (right)
Crusher

Ball mill

Mixer

Tank

Figure 10: Examples of the standard flow diagram symbols used in industry.

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5. INTRODUCTION TO MATERIAL BALANCES

Basic introduction

A material balance is an exact version of all material entering, going out, generated, consumed
or accumulating in a system, in any given time period or on any chosen basis. The first principle
of a material balance is the law on mass conservation. In general, for any material balance:
In – Out + Generated – Consumed = Accumulated
If there is no material being generated or used (i.e. chemical reactions) then:
In – Out = Accumulated
If Out > In, then Accumulation will be negative. Further, if there is no accumulation in the system,
then:
In – Out + Generated – Consumed = 0
This equation is generally referred to as the “steady-state” equation. In this course, we will only
be working with steady-state systems.

1. BASIC MASS BALANCE (HIMMELBLAU EXP. 3.1)

Figure 11: Examples 3.1 in Himmelblau (8th edition) pp.106-107.

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 BASIC MASS BALANCE (HIMMELBLAU EXP. 3.2)

Figure 12: Examples 3.2 in Himmelblau (8th edition) pp.107.

Solving material balances

5.2.1. Degrees of freedom

Study point nr.7 and 8 (pp.132-140) in Chapter 3.2 (8th edition). [7th edition, Chapter 3.2, point
nr.7&8, pp.174-184]

One of the most important aspects of material balances is how to ensure that the process
equations or sets of modules are determinate, that is, have at least one solution, and ideally no
more than one solution. The question is: How many variables are unknown and consequently
must have their values specified in any problem? The number of degrees of freedom is the
number of variables in a set of independent equations to which values must be assigned so that
the equation can be solved.
The degrees-of-freedom of a system is determined using:
ND = NU - NE
With ND – Degrees of freedom
NU – Number of unknowns
NE – Number of independent equations

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Therefore, we can conclude that NU – NE variables must be specified as long as the NE equations
are still independent. During the analysis you do not have to write down the equations but just
identify them.

Case ND Classification of Solution

NU = NE 0 Exactly specified; a solution exists
NU > NE > 0 >0 Underspecified; more independent equations required
NU < NE < 0 <0 Over specified, in general, no solution exists unless
some constraints are eliminated, or some additional
unknowns are included in the problem

Note, that the term independent equations is used in the statement above. An independent
equation is an equation in a system of several equations which cannot be derived algebraically
from the other equations. As an example, consider the following:

A solution of NaOH and H2O is fed into a separation unit. For this system we can set-up the
following mass balances:

Overall mass balance: F=P+W

NaOH mass balance: FNaOH = PNaOH + WNaOH
H2O mass balance: FH2O = PH2O + WH2O

We can define this system with three total equations, however only two of the equations can be
independent since the NaOH and H2O equations can be added to produce the overall mass
balance equation. Any two of the three equations can be used in the calculation of the degrees
of freedom. Hence, these equations can only be used to determine the unique solution for two
separate unknown variables and not three. A golden rule to follow is the following: for every
unknown variable that must be calculated, there should be an independent equation. If not, the
system is not solvable, and the selection of a basis should be considered to decrease the number
of unknowns. Figure 3.8 in (8th edition) Himmelblau (pp.134) [7th edition, figures 7.1 and 7.2,
pp.176 - 177] provides a very good visual explanation of the relationship between the number of
unknown variables and the number of independent equations specified.

What kind of variables would you consider? The typical variables are:

1. Temperature
2. Pressure
3. Total stream mass/mole/volumetric flowrate
4. Component mass/mole/volumetric flowrate per stream
5. Elemental mass/mole/volumetric flowrate per stream
6. Mass/mole/volume percentages
7. Stream specifications (splitting/recycle ratios etc.)
8. Extent of reaction or fraction conversion (To be considered in CIR123)

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What kinds of equations are involved in the analysis of the degree of freedom?

1. Overall mass balance equations

2. Component balances
For example: Imagine that there is xi% NaOH and yi% H2O in the feed and the rest of the
process streams in Figure 13:

Mass balance: FFeed = FProd1 + FProd2 + FPurge

NaOH balance: x1FFeed = x2FProd1 +x3FProd2 + x4FPurge
H2O balance: y1FFeed = y2FProd1 +y3FProd2 + y4FPurge
3. Elemental mole balances

F W P
x1% CO2 x2% CO2 y2% CO
y1% CO z2% N2
z1% N2

C balance: x1F + y1F = y2P + x2W

N balance: 2z1F = 2z2W
O balance: 2x1F + y1F = 2x2W + y2P
4. Energy balances (to be cover in second year)
5. Phase equilibria relations, that is, equations that give the compositions between one species
that exists in two (or more) phases
6. Chemical equilibrium
7. Implicit relations, such that the concentration of a species is zero in a stream or especially,
the sum of mass or mole fractions, which should always equal one.
e.g. in FFeed: x1NaOh + y1H O = 1
2

8. Explicit relations, such that a given fraction of a stream condenses

FPurge
e.g. the flow rate ratio for the process in Figure 19: = 0.24
FRe cycle

9. Extent of reaction or fraction conversion specified (CIR123)

Figure 13: Basic multi-system process.

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 Practice skills: Try to calculate the degrees-of-freedom for the scenarios described
in Examples 3.8 and 3.9 (Himmelblau (8th edition). pp.135 – 138) before looking at the
solutions. [7th ed. Example 7.4 pp.180-181]

DETERMINING THE DEGREES-OF-FREEDOM

Determine the degrees-of-freedom for the following process. Is there a unique solution? If not,
how can it be changed to give a unique solution?

Figure 14: Process where streams A and B is mixed in a certain ration to provide stream C.

Solution

Total number of variables: Each stream has 3 variables => (3)(3) = 9 variables
Total number of unknown variables: 6 variables specified in system => 9 – 6 = 3 unknowns.
Total number of equations: 3 equations

N2 balance: 0.9A + 0.3B = 0.65C

R balance: 0.1A + 0.7B = 0.35C
Total balance: A+B=C

Only two of the equations are independent.

ND = NU-NE
=3–2
=1
Problem under specified, hence, no unique solution

In order to get a unique solution for the problem, we need to reduce the number of unknowns.
Choosing a basis is one of the methods used to reduce the number of unknowns. If we select a
basis of 100 kmol of A, the degrees-of-freedom for the solutions decreases to 0.

The example above is just one of the simple methods of calculating the degree of freedom for a
system. But how do we determine the degrees of freedom for a system with more than one unit-
operation in the process. One of several methods can be used however, the two most used
methods are demonstrated below.

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 DEGREE OF FREEDOM WITH MULTI UNIT SYSTEMS: SYSTEMATIC
DETAILED APPROACH

Consider the following process which consist of two unit-operations:

The first step in the analysis is to determine the total number of variables in the system. When
determining the degrees of freedom, do not select a basis first. Always do the degrees of freedom
and then decide, based on the results, if a basis should be selected. With the systematic detailed
approach, we set up a table (below) and analyse each stream in detail. For this example, we are
only going to focus on the component balances. To complete the table, each stream is analysed
to determine the total number of valid independent variables that define that stream. For instance,
stream A has 9 global variables (1 total stream flowrate, 4 component flowrates and 4 component
percentages) however, the stream can have only 5 (1 total stream flowrate and 4 component
flowrates or 1 total flowrate and 4 component percentages) valid independent variables. It is
important to note that we cannot include all 9 of stream A’s variables since the one can use the
total stream flowrate and the component percentages to calculate the component percentages
and visa versa. Hence, stream A will only have 5 total variables in the table.

Total known
Streams Total variables
variables
Total + 4 component % 4 comp %
A
5 4
Total + 2 comp % 2 comp %
B
3 2
Total + 5 comp % None
C
6 -
Total + 3 comp % 3 comp %
D
4 3
Total + 3 comp % 3 comp %
E
4 3
Total + 5 comp % 1 total + 5 comp %
F
6 6

Total 28 18

By subtraction the known variables from the total we now know that we have a total of 10
unknowns in the system. Hence for this system to have a unique solution we should be able to
set up 10 independent equations.

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To determine the equations, we can either look at the system as a whole or divide the system into
the two individual unit operations. Let us set the first unit operation as System I and the second
unit as System II. Now we look at each system individually to determine the independent
equations.

System I System II
Total global equations: 9 Total global equations: 9
• 1 Total mass balance: A + B = C • 1 Total mass balance: C + D + E = F
• 5 Component mass balances • 5 Component mass balances
• 3 Percentage equations (the sum of • 3 Percentage equations (the sum of
component % in each stream equals 1) component % in each stream equals 1;
percentage equation (stream C) can
only be used once)
Total independent equations: 6 Total independent equations: 5
• 5 component balances • 5 component balances
• 1 percentage equation (stream C)
Total global equations for entire system: 18
Total independent equations for the entire system: 11
Note that in System I and System II only the percentage equation for stream C was considered to be an important
independent equation. It would be pointless to include the other percentage equations since all the individual
component percentages for streams A, B, D, E and F are known and do add up to 1. Therefore, it is important to
note that a degrees of freedom analysis is very system specific and each system should be treated as a completely
new problem, there are no easy plug and play methods of determining the degrees of freedom.

The degrees of freedom for this system can now be determined according to the equation:
ND = NU - NE
ND = 10 - 11
= -1
The system is over specified; hence no unique solution exists without eliminating some variables.

DEGREE OF FREEDOM WITH MULTI UNIT SYSTEMS: NODAL

APPROACH

Another method of determining the degrees of freedom is the nodal approach. This method
makes the analysis of large multi-unit systems much easier. To use this method, the system is
broken down and each unit operation is replaced by a node. A unit-operation refers to any place
where the stream composition and/or flowrate changes, hence stream splitters and mixers will
also be a node. Each unit operation is replaced with a dot that represents a node. As an example,
we are going to repeat the previous example.

Actual system

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 System converter into nodes

Now it is easy to see that the system consists of:

• 2 nodes
• 6 streams
• 5 components in total
To determine the total number of variables we assume that every stream has all five components:
6 total stream flowrates + 6streams × 5componets = 36 total variables.

To determine the known variables, each stream is analysed individually:

Total
Streams known Explanation
variables
4 given component percentages and one self-specified
A 5 percentage
(inert % = 0)
2 given component percentages and 3 self-specified
B 5 percentage (NaCL %, HCL %, H2SO4 % = 0)
C - None
3 given component percentages and 2 self-specified
D 5 percentage (NaCL %, inert % = 0)
3 given component percentages and 2 self-specified
E 5 percentage (NaCL %, inert % = 0)
5 given component percentages and 1 total stream
F 6 flowrate
Total 26
Note: We assumed that all the components are present in each of the streams, however, in reality there are certain
components that are not present in certain streams. This is considered when determining the total number of known
variables (e.g. it is known that the percentage of inerts present in stream A is zero)
The total number of independent equations is: 5components × 2nodes = 10 independent equations plus
the 1 percentage equation (stream C). Hence, according to the degrees of freedom equations:
ND = NU - NE
ND = (36 - 26) - 11
= -1
The system is over specified; hence no unique solution exists without eliminating some variables.

5.2.1. Solution strategies and hints

Study the whole of Chapter 3.2 in (8th edition) Himmelblau, pp.123 to pp.143. Focus on
understanding the solution strategy presented. [7th edition, Chapter 7 pp166-186]
Revise Chapter 2.7 (pp.44-49) on choosing a basis. [7th edition, Chapter 3, pp.78-87]
42 | P a g e
A summary of the solution strategy is located on page 142 (8th edition). [7th edition pp.186]

The following additional tips will help in solving material balances:

• If no chemical reaction occurs in the system, the mass balance is performed on the
compounds and not the elements – or on the solid products even if they are not pure
compounds. Mass or mole units can be used.
• If chemical reactions do occur, mass balance calculations are performed in terms of the
elements and /or radicals and/or substances that do not change chemically.
• Where more than the required number of independent balances can be set, the balance
based on components that make up the bulk of the total mass will be the most reliable.
• If two or more components are found in a definite relationship in each stream where they
are present, only one independent balance for these components can be set up.
• A component or element that is only found in an inlet and exhaust stream is used as a tie
component or element. It immediately determines the mass of the one stream relative to
the other.

TUTORIAL 10

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6. BASIC MATERIAL BALANCES

Read Himmelblau (8th edition), Chapter 4 (pp.159-178) [7th edition, Chapter 8, pp.196-215] to get
a basic understanding of the practical application of the solution strategies. The concepts of
mixing, splitting and separation streams are not covered clearly in Himmelblau but are mentioned
in detail in the class notes.

Tie elements or tie components

A tie element or tie compound is one which passes unchanged from one stream to another.

Often more than one tie element will be present, in which case the one present in the greatest
quantity will give the best results in calculations.

Tie elements are useful even if the masses and compositions are not known because it enables
one to place two streams on the same basis.

TIE ELEMENTS

32% H2O NaHCO3

68% NaHCO3 B
A
48% H2O
NaHCO3
C

Determine the flow rates of B and C.

Solution

Basis: 100 kg A

In A 32 kg H2O
68 kg NaHCO3
H2O is the tie element since it only exits the system in stream C. Hence:
0.48C = 32 kg
C = 66.67 kg
NaHCO3 in C: (1-0.48)C = 34.67 kg
Hence: B = 68 – 34.67
= 33.33 kg

Mixing streams

The mass balance for mixing streams are straightforward. What goes in must come out. The sum
of flow rates A and B equal C. However, if both A and B have different compositions, then C’s
composition will be different. If A and B have exactly the same compositions, then C will have
the same compositions, just a different flow rate.

Overall mass balance: A+B=C

Component balance: xiA + yiB = ziC

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 Figure 15: Flow diagram (Left) and block diagram (Right) depicting a mixing process.

MIXING REQUIREMENTS
100kg
Na2CO3·10H2O
A
68% H2O 14% Na
32% Na2SO4
Mixer C
B

What mass of stream B is required to give a mass percentage of 14% Na in stream C? What is
the % Na2CO3 in C?

Solution

Basis: 100 kg A. Set x = kg B.

Mol mass Na = 23 Na2CO3 = 106 Na2SO4 = 142 H2O = 18

% Na in Na2CO3∙10H2O = 46/(106 + 180) = 16.08 %

% Na in Na2SO4 = 46/142 = 32.39 %
Na-balance = 0.3239(0.32x) + 0.1608(100) = 0.14(100 + x)
x = 57.22 kg
106
( )100
106+180
% Na2CO3 in C = [ (100+57.22) ] 100 = 23.57 %

MULTIPLE STREAMS

CuS
A
CuSO4 Mixer 10% S
B Mixer 150 kg mixture
D
NaCl (100 kg)
C

How much of streams A and B should be mixed with stream C in order to achieve a mass fraction
of 0.1 S in stream D?

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Solution

Basis: 150 kg mixture

Say x kg CuS, then (50 – x) kg CuSO4
CuS contains 33.51 % S
CuSO4 contains 20.06 % S

S – balance:
0.3351x +0.2006(50 – x) = 0.1(150)
⇒ x = 36.95 kg
i.e. CuS = 36.95 kg
CuSO4 = 13.05 kg

MULTIPLE OUTCOME NEEDS

What masses NaOH (MM = 40), CaCO3 (MM = 100) and MnSO4 (MM = 151) must be mixed to
give 100 kg of a mixture to contain 15 % Na and 20 % Ca?

Solution

Basis: 100 kg mixture

Let x kmol NaOH, y kmol CaCO3, and z kmol MnSO4 be required

40x + 100y + 151z = 100 (TOTAL)

23x/100 = 0.15 (Na)
40y/100 = 0.2 (Ca)

⇒ x = 0.652 y = 0.5 z = 0.158

Then NaOH = 26.1 kg
CaCO3 = 30.0 kg
MnSO4 = 23.9 kg

MIXING MASS BALANCE

160 kg/h
10% H2SO4 6% H2SO4
A 8% HNO3
86% H2O
30% HNO3 D
B
H2O
C

Solution

Basis: 160 kg/h stream A

H2SO4 in D = 0.1 (160) = 16 kg/h and that is 6% of D

 0.06 D = 16  D = 266.7 kg/h

HNO3 in D = 0.08 (266.7) = 21.33 kg/h

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And that is 30% of stream B
0.3 B = 21.33  B = 71.1 kg/h

Total mass balance

A + B + C = D
160 + 71.1 + C = 266.7
 C = 35.6 kg/h →

Check : Water balance :

0.9 A + 0.7 B + C = Water in D
0.9 (160) + 0.7 (71.1) + 35.6 = 229 kg/h
And water in D = 0.86 (266.7) = 229.4 kg/h

DISSOLUTION

The following two requirements must be met (at the same time) by a solution of NaCℓ and CuSO 4
in water.
• The solution must contain 30,0% dissolved solids
• The solution must contain 5,0% (mole basis) NaCℓ
What masses NaCℓ and CuSO4 must be dissolved in 100 kg water?

Solution

Basis: 100 kg H2O: x kg NaCℓ and y kg CuSO4

x y
kmol: 100/18 = 5.55 kmol H2O: kmol NaCℓ : kmol CuSO4
58.5 159.5
x+ y
30% solids: = 0.3 …………...…………………….…………. (1)
x + y + 100
x / 58.5
Mole % NaCℓ: = 0.05 ……………….……… (2)
5.55 + x / 58.5 + y / 159.5

From (1) and (2): x = 17.59 kg NaCℓ : y = 25.27 kg CuSO4

Splitting streams

The compositions of streams B and C will always be the same as stream A. When streams are
split, the only change that occurs is the flow rate of the individual streams. Unless a split ratio is
specified there is no way of guessing the how much of A went into B or C. If A had the following
composition: 24% H2O; 53% NaOH; 23% Na2CO3

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 Overall mass balance: A=B+C
Component balance: xiA = yiB + ziC With xi=yi=zi

Figure 16: Block diagram depicting a splitting stream.

SPLITTING STREAMS COMPOSITION

Stream A has the following composition and flow rate: 24% H2O; 53% NaOH; 23% Na2CO3; 128
kg/min. If it is known that the split ratio between B and C is 2/3, what are the flow rates and
compositions of B and C?

B= 2/3A = 85.33 kg/min

C= 1/3A = 42.67 kg/min

Because it is a splitting stream, we can assume that both stream B and C will have the same
composition of A:

Composition of B Composition of C
H2O: 0.24(85.33) = 20.48 kg/min H2O: 0.24(42.67) = 10.24 kg/min
NaOH: 0.53(85.33) = 45.22 kg/min NaOH: 0.53(42.67) = 22.62 kg/min
Na2CO3: 0.23(85.33) = 19.63 kg/min Na2CO3: 0.23(42.67) = 9.81 kg/min

Linear interpolation

Linear interpolation is a mathematical method that is used to construct new data point within the
range of a discrete set of known data points.

Figure 17: Linear extrapolation explained visually. The data points on the curve are the actual known values.

In Figure 17 the process of linear extrapolation is represented. Data points (y1,x1) and (y2,x2) are
the known data points. To determine the value of y3 at point x3 without any information regarding
the curve we use the following:

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 𝑦3 − 𝑦1 𝑦2 − 𝑦1
=
𝑥3 − 𝑥1 𝑥2 − 𝑥1
𝑥3 − 𝑥1
𝑦3 = 𝑦1 + (𝑦 − 𝑦1 )
𝑥2 − 𝑥1 2

From the graph, there is always a certain amount of error associated with linear extrapolation. To
minimise the error, we only extrapolate between two adjacent points.

LINEAR EXTRAPOLATION

C 130 140 155 148 144

T 10.8 18.4 24.2 30.7 38.1

(b) What is C at T = 35?

(c) What is C at T = 8,7?
(d) At what T is C = 150? (Try at home)

Solution:
(a) At T = 35.0
35 − 30.7
𝐶 = 148 + (144 − 148)
38.1 − 30.7
𝐶 = 145.7
(b) At T = 8.7
10.8 − 8.7
𝐶 = 130 + (140 − 130)
18.4 − 10.8
𝐶 = 127.2

Multi-unit processes

6.5.1. Mass balances over multi-unit processes

Material balances are not only performed over individual pieces of apparatus, but more generally
on combinations of equipment which form part of a larger process. Multiple mass balance
calculations are performed daily to monitor the operation of industrial processing plants. For
example, the process below (Figure 18) that produces ethylbenzene. Several mass balances will
be performed for this system in order to determine the details of each of the individual streams.

The mass balance principles that were used to solve a single unit system stay the same for the
whole process.

49 | P a g e
 Figure 18: A simple process flow diagram of the ethylbenzene production process from benzene and ethylene.

6.5.2. Multi-system process

In order to perform all the mass balance calculations for a total process, the process is broken
down into systems. The word system refers to any process or part of a process selected by the
engineer to analyse. For example, Figure 19 shows how a simple block diagram of a process
can be broken down into several different systems. A mass balance can be performed over each
of these systems in order to define the whole process.

Figure 19: A basic chemical process broken down into 6 different systems.

The same solution strategies mentioned in section Example 5.2.2 on page 39 are used to solve
mass balances of multi-unit systems. Example 6.5.2 explains how to determine the number of
independent equations in a multi-unit process, which can be used to determine the degrees-of-
freedom for the entire system.

50 | P a g e
When solving a multi-unit system always:

• Make sure that you have accounted for all the variables involved in the problem and not
included irrelevant ones. Look for:
o Flow variables entering and leaving each system
o Species or components entering and leaving for each system.
o Reaction variables and extent of reactions. (Mass balances with chemical
reactions are not part of the scope for CIR113, but is part of CIR123 next
semester)
• Make sure that you have not missed any of the information in the problem that should be
included as an equation. Look for:
o Selection of a basis for a system or the overall process.
o Material balances for each species, element, or component in each system and
the overall process.
o Specifications for a system and the overall process that can be used to assign
values to variables or add equations to the solution set.
o Implicit equations (sum of mole or mass fractions) used explicitly or implicitly.

TUTORIAL 11
and
TUTORIAL 12

DETERMINATION OF THE NUMBER OF INDEPENDENT MATERIAL

BALANCES IN A MULTI-UNIT PROCESS

Figure 20: Example 6.1 Himmelblau (8th edition) pp.274. [7th edition, example 11.1 pp.311].

51 | P a g e
 Figure 21: Example 6.1 Himmelblau (8th edition) pp.275-276. [7th edition, example 11.1 pp.312].

52 | P a g e
 CLASS NOTES CIR123
7. MATERIAL BALANCES WITHOUT REACTION

TUTORIAL 13 : Revision of CIR113

Crystallisation and mixing

When dissolving any salt in a solvent, a point is reached (the saturation point) where no more salt
will dissolve and it starts to settle at the bottom of the container. The saturation point can be
shifted by heating the solution, causing more salts to dissolve. However, as the solutions starts
to cool down, the extra salt that dissolved at a higher solution temperature will start to crystallise.
This behaviour of salts dissolving in solvents is described by their solubility curves as indicated in
the diagram below.

Saturated solutions of the salts are represented by the curves for each of the salts on the
Figure 22: The typical solubility curves of inorganic salts in water.

diagram. Any point above the salt’s saturation curve represents a solution consisting of a
saturated solution together with salt crystals that did not dissolve. A solution that is at any point
below the curve will not be saturated and will have no crystals. The curves for K2SO4, NaCl and
Na2SO4·10H2O show that if saturated solutions of these salts are cooled, crystals of the salts will
be formed so that the salt concentration in the final cooled (saturated) mother liquor, will be lower
than in the original saturated solution. The crystal yield can be determined by means of simple
mass balance calculations.

CRYSTALLISATION

The solubility of NaCl in water at 100° C is 28.5% and at 0 °C it is 26.3 %. What is the percentage
yield of NaCl crystals if a saturated solution at 100 °C is cooled to 0 °C.
Saturated solution
Saturated solution 0 °C
Cooling
100°C NaCl crystals

53 | P a g e
Solution

Basis: 100 kg saturated solution at 100 °C

NaCl in = 0.285(100) = 28.5 kg

Let x kg NaCl crystals be formed, i.e. (100-x) kg saturated solution at 0 °C.

NaCl-balance: 28.5 = x + 0.263(100-x) i.e. x = 2.99 kg

2.99
%Yield = ( ) 100 = 10.5%
28.5
INTERPOLATIONS OF SOLUBILITY DATA

500 kg of a solution, saturated with NaHCO3, at 60 °C, is cooled to 10 °C. What is the crystal
yield in kg? Solubility data are as follows:

Temperature (°C) 60 40 30 20 10
g NaHCO3 per 100 g H2O 16.4 12.7 11.1 9.6 8.15

Solution

Basis: 500 kg saturated solution at 60 °C.

16.4 g NaHCO3 16.4

60 °C saturated: % NaHCO3 =( ) 100 = 14.09 %
100 g H2 O 16.4+100

8.15
10 °C saturated: % NaHCO3 = (
108.15
) 100 = 7.536 %

Let x kg crystals be formed:

NaHCO3 balance
0.1409 (500) = x + (500 – x) (0.07536)
i.e. x = 35.44 kg

54 | P a g e
 DISSOLUTION

A 30 % solution of Na2CO3 in water is made by dissolving crystals of Na2CO3·10H2O in a 10 %

solution of Na2CO3 in water. What mass of crystals must be dissolved in 100 kg of the 10 %
solution to achieve the required 30 % Na2CO3 in the final solution?

Solution

Na2CO3·10H2O

x kg
30 % Na2CO3 solution

10 % Na2CO3 solution
100 kg

Set x = kg Na2CO3·10H2O
Basis: 100 kg 10 % solution
Mass fraction Na2CO3 in Na2CO3·10H2O
= 106/(106 + 180) = 0.3706
Na2CO3 balance: 0.3706 x + 0.1(100) = 0.3 (100 + x)
 x = 283.3 kg of Na2CO3·10H2O →

TUTORIAL 14

8. CHEMICAL REACTION AND STOICHIOMETRY

Stoichiometry

The stoichiometric coefficients in the chemical reaction equation tell you the relative amounts of
moles of chemical species that react and are produced by the reactions.

Extent of reaction

• Extent of reaction (𝝃):

Refers to a value based on a specific stoichiometric equation and denotes how much reaction
occurs. Has units of “moles reacting”.

The extent of reaction for a reaction is defined as follows for a single reaction involving component
i:
ni − ni0
ξ=
vi
where ni = moles of species i present in the system after the reaction occurs
nio = moles of species i present in the system when the reaction starts
νi = stoichiometric coefficient for species i in the specified chemical reaction equation
(moles of species per moles reacting)
ξ = extent of reaction (moles reacting according to the assumed reaction stoichiometry)

55 | P a g e
Note: in order to distinguish between the reactants and the products the following rules are always
followed:

1. The stoichiometric coefficients value used for reactants are always

entered as a negative value into the equation above.
2. The stoichiometric coefficient value used for the products are always
entered as a positive value into the equation above.

The main reasoning behind this is to ensure that the extent of reaction value remains positive.

for the NH3 reaction

νNH3 = 2
νH2 = –3
νN2 = –1
and the extent of reaction calculation via any of the species is:

nout
NH3 − nNH3
in
6−0
ξ= = =3
vNH3 2
nout in
H2 − n H2 9 − 18
ξ= = =3
vH2 −3
nout in
N 2 − nN 2 12 − 15
ξ= = =3
vN2 −1

Limiting and excess reactants

• Limiting component:

Refers to limiting reactant and is the component which is added in less than the stoichiometrically
required quantity. To determine the limiting component the maximum extent of reaction is used.
The maximum extent of reaction is determined for each of the reagents by assuming that the
reagent reacts completely. For example, refer to the reaction illustrated below. 20 kmol of A, and
65 kmol of B is fed into the reaction.
1
2A + 3 B → 4C + D
2
𝑛𝑜𝑢𝑡 − 𝑛𝑖𝑛 0 − 20
𝜉𝑚𝑎𝑥𝐴 = = = 10 𝑘𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
−𝑣 −2

𝑛𝑜𝑢𝑡 − 𝑛𝑖𝑛 0 − 65
𝜉𝑚𝑎𝑥𝐵 = = = 18.57 𝑘𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
−𝑣 −3.5

From the calculations above, reagent A has a smaller 𝜉𝑚𝑎𝑥𝐴 than reagent B, hence reagent A is
limiting.

56 | P a g e
 • Excess reactant:

The quantity of reactant present over and above that necessary to react fully with the limiting
reactant. The %excess can be calculated and represented in one of two ways. The first method
is to determine the %excess with equation 1 as represented below.

Number of mol in excess

% Excess = × 100
Number of mol required for complete
reaction with the limiting reactant
Equation 1
mol charged − mol theoretically required
% Excess = × 100
mol theoretically required

The number of mole in excess is calculated as the total mole present minus the mole required for
complete reaction with the limiting reactant. Even if in reality only a part of the limiting reactant
reacts, the required and excess reactant are still calculated on the basis of complete reaction with
the limiting reactant.

When limiting reactant and % excess is calculated, only the reactants charged are considered.
The actual conversion (if at all) does not figure in the calculation.
Note that % excess is dimensionless.
1
e.g. 2A + 3 2 B → 4C + D
20 kmol of A, and 65 kmol of B is fed into the reaction. Reagent A is limiting, hence reagent B is
in excess.
3.5
mol𝑖𝑛 − mol𝑡ℎ𝑒𝑜𝑟 65 − 20( 2 )
% Excess B = × 100 = 100 ( ) = 85.71% in excess
mol𝑡ℎ𝑒𝑜𝑟 3.5
20( 2 )

From reagent A we know that 35 kmols of B is theoretically required. This means that 35 kmols
of B would be 100 % of what is required. But there is (65-35) = 30 kmols of reagent B extra in
the reactor which is 85.71 % more than is required. Hence we can say that the 65 kmols of B
accounts for 185.71 %. When calculating the %excess using equation 1 it is important to
remember that the answer should always be displayed as “85.71 % in excess”, to indicate that
the 85.71 % is the percentage above the 100 % of reagent B required. Alternatively the %excess
can be given as “185.71 %”, which automatically indicates that the reagent is in excess as the
percentage is more than 100 %. This is the second way of displaying %excess and is calculated
using equation 2.

Number of mol charged

% Excess = × 100
Number of mol required for complete
reaction with the limiting reactant
Equation 2
mol charged
% Excess = × 100
mol theoretically required
1
e.g. 2A + 3 B → 4C + D
2
20 kmol of A, and 65 kmol of B is fed into the reaction. Reagent A is limiting, hence reagent B is
in excess.

57 | P a g e
 mol𝑖𝑛 65
% Excess B = × 100 = 100 ( ) = 185.71 %
mol𝑡ℎ𝑒𝑜𝑟 3.5
20( 2 )

Using equation 2 the %excess is represented as “185.71 %” only, and it is not needed to specify
that it is “in excess”.

The %excess as calculated using equation 1 and equation 2 can also be determined using the
1
concept of extent of reaction. e.g. 2A + 3 2 B → 4C + D
20 kmol of A, and 65 kmol of B is fed into the reaction. Reagent A is limiting, hence reagent B is
in excess.
𝑛𝑜𝑢𝑡 − 𝑛𝑖𝑛 0 − 20
𝜉𝑚𝑎𝑥𝐴 = = = 10 𝑘𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
−𝑣 −2
𝑛𝑜𝑢𝑡 − 𝑛𝑖𝑛 0 − 65
𝜉𝑚𝑎𝑥𝐵 = = = 18.57 𝑘𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
−𝑣 −3.5

Equation 1 in terms of extent of reaction Equation 2 in terms of extent of reaction

% Excess 𝜉𝑚𝑎𝑥𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠
𝜉𝑚𝑎𝑥𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠 − 𝜉𝑚𝑎𝑥𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 % Excess = 100 ( )
= 100 ( ) 𝜉𝑚𝑎𝑥𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡
𝜉𝑚𝑎𝑥𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡

18.57 − 10 18.57
% Excess = 100 ( ) = 85.71 % % Excess = 100 ( ) = 185.71 %
10 10

Conversion or degree of conversion

• Conversion or degree of conversion:

Can refer to any component but usually refers to the limiting component. Different bases for
conversion can be defined. The most common is the percentage of the limiting reactant which
did in fact react (to form any product). Percentage conversion of the limiting reactant is also
known as the degree of completion of the reaction. Conversion and degree of completion are
dimensionless.

If the extent of reaction is given the degree of conversion or fractional conversion of the limiting
reactant can be calculated with the following equation:

(−ƒ) ∙ nin
limiting reactant
ξ=
−vlimiting reactant

where n = moles of the limiting reactant into the system

νi = stoichiometric coefficient of the limiting reactant
ξ = extent of reaction (moles reacting according to the assumed reaction
stoichiometry)
ƒ = fractional conversion of the limiting reactant

58 | P a g e
 Selectivity

Selectivity: is the ratio of the net number of mole of the required product produced to the net
number of mole of the unwanted product or products produced in the reactor.
Consider e.g. the hypothetical reaction:

A B C With B the desired product and C not wanted

C
net mol B produced
Selectivity = net mole C produced

Yield and percentage yield

Yield: is the quantity of product produced divided by the quantity of reactant fed. If more than one
product or reactant are involved, the basis must be specified. It can be calculated on a mass
basis, a mole basis or a volume basis. For solids and liquids, it is usually on a mass basis. Yield
is not dimensionless.

Percentage yield: is an indication of the conversion of the limiting reactant to the required product.
(Note the difference between % yield and % conversion or degree of completion).

% Yield = 100 × [Mass or mole formed/Mass or mole theoretically possible]

net mol B produced net mol B produced

% Yield of B = net mol B theoretically possible =
mol A introduced

Note that due to stoichiometric considerations this calculation cannot be done in terms of mass
of product and mass of reactant.

59 | P a g e
 CALCULATION OF VARIOUS REACTION TERMS

Figure 23: Himmelblau (8th edition Hardcover) Example 5.6 on pp.205

60 | P a g e
 TUTORIAL 15

61 | P a g e
9. MATERIAL BALANCES WITH CHEMICAL REACTIONS

Species mole balance

One mass balance equation is set-up for each species or molecule present in the process.

Element material balance

SOLVING THE MASS BALANCE WITH AN ELEMENTAL BALANCE

A solution of Na2CO3 in water is treated with dry partially slaked lime powder. The lime contains
CaCO3 as impurity. The Na2CO3 solution contains a small amount of NaOH and the analysis of
the solution is as follows:

NaOH = 0.59 %: Na2CO3 = 14.88 %; H2O = balance.

The product from the reaction tank shows the following analysis

CaCO3 = 13.48 % Na2CO3 = 0.61 %

Ca(OH)2 = 0.28 % NaOH = 10.36 %
H2O = 75.27 %

Calculate the mass balance of the process on the basis of 100 kg of product from the reaction
tank. What is the analysis of the partially slaked lime powder? The following reactions take place
in the reaction tank:

CaO + H2O → Ca(OH)2

Ca(OH)2 + Na2CO3 → CaCO3 + 2NaOH

Atomic masses: Ca = 40.1 Na = 23 C = 12

Solution

NaOH = 0.59 % x kg CaCO3 = 13.48 %

Na2CO3 = 14.88 % z = 100 kg Ca(OH)2 = 0.28 %
H2O = 84.53 % Na2CO3 = 0.61 %

CaO = ? NaOH = 10.36 %

Ca(OH)2 = ? y kg H2O = 75.27 %
CaCO3 = ?

62 | P a g e
Basis: 100 kg product from reaction tank
Product stream

Component kg MM kmol kmol Na kmol C

CaCO3 13.48 100.1 0.1347 - 0.1347
Ca(OH)2 0.28 74.1 0.00377 - -
Na2CO3 0.61 106.0 0.00575 0.0115 0.00575
NaOH 10.36 40.0 0.2590 0.2590 -
H2O 75.27 - -
TOTAL 0.2705 0.14045

Assume x kg alkaline solution:

Component kg MM kmol kmol Na kmol C

NaOH 0.0059x 40 0.000148x 0.000148x -
Na2CO3 0.1488x 106 0.001404x 0.002808x 0.001404x
H2O 0.8453x - -
TOTAL 0.002956x 0.001404x

Na balance: 0.2705 = 0.002956 x i.e. x = 91.5 kg

Total mass balance: y = 100 – x i.e. y = 8.5 kg

C-balance: Let stream y contain m kg CaCO3

0.14045 = 0.001404x + m/100.1 with x = 91.5 kg: m = 1.2 kg
i.e. CaO + Ca(OH)2 in the powder = 8.5 – 1.2 = 7.3 kg

Water balance:
Mass water in with x = 0.8453 x = 0.8453 (91.5) = 77.34 kg
Water used in slaking reaction = (77.34 – 75.27) = 2.07 kg
= 2.07/18 = 0.115 kmol H2O

kmol CaO slaked = 0.115 kmol CaO

mass CaO slaked = 0.115(56.1) = 6.45 kg CaO

i.e. mass Ca(OH)2 in the lime = 7.3 – 6.45 = 0.85 kg Ca(OH)2

Lime analysis: CaCO3 = (1.2/8.5)(100) = 14.1%
CaO = (6.45/8.5)(100) = 75.9%
Ca(OH)2 = (0.85/8.5)(100) = 10%

63 | P a g e
 SOLVING EXAMPLE 9.2.1 USING EXTENT OF REACTION

A solution of Na2CO3 in water is treated with dry partially slaked lime powder. The lime contains
CaCO3 as impurity. The Na2CO3 solution contains a small amount of NaOH and the analysis of
the solution is as follows:

NaOH = 0.59 %: Na2CO3 = 14.88 %; H2O = balance.

The product from the reaction tank shows the following analysis

CaCO3 = 13.48 % Na2CO3 = 0.61 %

Ca(OH)2 = 0.28 % NaOH = 10.36 %
H2O = 75.27 %

Calculate the mass balance of the process on the basis of 100 kg of product from the reaction
tank. What is the analysis of the partially slaked lime powder? The following reactions take place
in the reaction tank:

CaO + H2O → Ca(OH)2

Ca(OH)2 + Na2CO3 → CaCO3 + 2NaOH

Solution

NaOH = 0.59 % x kg CaCO3 = 13.48 %

Na2CO3 = 14.88 % z = 100 kg Ca(OH)2 = 0.28 %
H2O = 84.53 % Na2CO3 = 0.61 %

CaO = ? NaOH = 10.36 %

Ca(OH)2 = ? y kg H2O = 75.27 %
CaCO3 = ?

CaO H2O Ca(OH)2 CaCO3 Na2CO3 NaOH

a 0.8453x b c 0.1488x 0.0059x
In
56.1 18 74.1 100.1 106 40

Cons(1) -ξ1 -ξ1 - - - -

Prod(1) - - ξ1 - - -

Cons(2) - - -ξ2 - -ξ2 -

Prod(2) - - - ξ2 - 2ξ2

0.7527(100) 0.0028(100) 0.1348(100) 0.0061(100) 0.1036(100)

Out 0
18 74.1 100.1 106 40

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 0.1488x 0.0061(100)
Na2CO3: − ξ2 =
106 106

0.0059x 0.1036(100)
NaOH: + 2ξ2 =
40 40

Solving for x and ξ2: x = 91.5 kg

ξ2 = 0.123 kmol reacting

c 0.1348(100)
CaCO3: + ξ2 =
100.1 100.1
c =1.17 kg

0.8453(91.5) 0.7527(100)
H2O: − ξ1 =
18 18
ξ1 = 0.115 kmol reacting
a
CaO: − ξ1 = 0
56.1
a = 6.45 kg
b 0.0028(100)
Ca(OH)2: + 𝜉1 − 𝜉2 =
74.1 74.1
b = 0.87 kg

Lime analysis: CaCO3 = (1.17/8.5)(100) = 13.76%

CaO = (6.45/8.5)(100) = 75.88%
Ca(OH)2 = (0.87/8.5)(100) = 10.36%

Assignment:
(Himmelblau 8th edition): Attempt example 5.7 (pp. 214) and example 5.8 (pp. 218)
(Himmelblau 7th edition): Attempt example 10.1 (pp. 264) and example 10.3 (pp. 270)

TUTORIAL 16

65 | P a g e
 SELECTIVITY WITH TABLE METHOD

Consider a continuous, steady-state process in which the following two reactions take place:
C6H12 + 6H2O → 6CO + 12H2 (1)
C6H12 + H2 → C6H14 (2)
In the process 250 moles of C6H12 and 800 moles of H2O are fed into the reactor each hour. The
yield of H2 is 40.0 % and the selectivity of the first reaction compared to the second reaction is
12.0. Calculate the molar flow rates of all five components in the output stream.

Solution
First step is to set up a table to specify each of the components. Let x be the mol C6H12 reacted
in reaction (1) and y be the mol C6H12 reacted in reaction (2).
C6H12 H2O H2 CO C6H14
Total mol in 250 800

Reacted in Rx(1) -x -6x - - -

Produced in Rx(1) - - 12x 6x -

Reacted in Rx(2) -y - -y - -
Produced in Rx(2) - - - - y
Total 250-x-y 800-6x 12x-y 6x y

Determine the limiting reagent:

H2O required to react all C6H12 (Rx(1)) = (250)(6) = 1500 mol
C6H12 required to react all H2O (Rx(2)) = (800/6) = 133.33 mol

H2O is limiting reagent.

H2 theoretically possible Rx(1) = (800/6)(12) = 1600 mol
But H2 yield is only 40 %: H2 actually produced = (1600)(0.4) = 640 mol
Therefore, H2 component equation: 12x-y = 640 mol

Selectivity of Rx(1):Rx(2) = 12:1

x:y = 12:1
Hence, x = 12y

Then 12(12y) – y = 640

y = 4.48 mol
x = 53.71 mol

C6H12 H2O H2 CO C6H14

(mol) (mol) (mol) (mol) (mol)
Total 191.81 277.74 640 322.26 4.48

66 | P a g e
 SELECTIVITY WITH EXTENT OF REACTION

Example 9.2.3 can also be solved by using the extent of reaction instead of using variables.
Consider a continuous, steady-state process in which the following two reactions take place:
C6H12 + 6H2O → 6CO + 12H2 (1)
C6H12 + H2 → C6H14 (2)
In the process 250 moles of C6H12 and 800 moles of H2O are fed into the reactor each hour. The
yield of H2 is 40.0 % and the selectivity of the first reaction compared to the second reaction is
12.0. Calculate the molar flow rates of all five components in the output stream.

Solution
First step is to set up a table to specify each of the components.
C6H12 H2O H2 CO C6H14
Total mol in 250 800

Reacted in Rx(1) -ξ1 -6ξ1 - - -

Produced in Rx(1) - - 12ξ1 6ξ1 -

Reacted in Rx(2) -ξ2 - -ξ2 - -

Produced in Rx(2) - - - - ξ2
Total 250-ξ1-ξ2 800-6ξ1 12ξ1-ξ2 6ξ1 ξ2

Determine the limiting reagent:

0−800
Assume all of the water reacts: ξ𝑚𝑎𝑥𝐻2 𝑂 = −6 = 133.33 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
0−250
Assume all of the C6H12 reacts: ξ𝑚𝑎𝑥𝐶6𝐻12 = = 250 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔
−1

ξ𝑚𝑎𝑥𝐻2 𝑂 < ξ𝑚𝑎𝑥𝐶6𝐻12 Therefore, H2O is limiting.

H2 theoretically possible Rx(1) = (800/6)(12) = 1600 mol

But H2 yield is only 40 %: H2 actually produced = (1600)(0.4) = 640 mol
Therefore, H2 component equation: 12ξ1-ξ2= 640 mol

Selectivity of Rx(1):Rx(2) = 12:1 Then 12(12ξ2) – ξ2 = 640

ξ1: ξ2 = 12:1 ξ2 = 4.48 mol
Hence, ξ1 = 12ξ2 ξ1 = 53.71 mol

C6H12 H2O H2 CO C6H14

(mol) (mol) (mol) (mol) (mol)
Total 191.81 277.74 640 322.26 4.48

TUTORIAL 17

TUTORIAL 18

67 | P a g e
10. FUEL AND COMBUSTION

Coal

Coal is a combustible black or brownish-black

sedimentary rock that occurs naturally in the earth’s
crust in coal beds or coal seams. Coal is considered a
fossil fuel that forms when dead plant matter decays and
is exposed to very high temperature and pressure over
millions of years. In our industry today, coal is mainly
used as a fuel source either in the petrochemical or
electrical industry.
The physical and
chemical structure of
coal is highly dependent
on the geographical
location and biological
matter that the coal is
made of. The figure on
the left represents just
one of the different
structures of coal that
can occur. However,
one thing that all of them
have in common is the
fact that coal is
composed primarily of
five elements:
Carbon, Hydrogen,
Oxygen, Sulphur and
Nitrogen.
Figure 24: An example of the chemical structure of coal.

The largest concentration of coal is carbon, as

can be seen on the pie graph on the right.
Another constituent of coal that is not show in
the structure above is ash. Ash is a collective
name for all of the minerals and metals (e.g.
potassium carbonate) that was present in the
plant material. Ash is generally considered to
be inert and does not take part in any
combustion reaction. Since the structure of
coal varies it is clear that the elemental
analysis if coal will vary as well. If coal is to be
used in a controlled combustion reaction it is
very important to know exactly what the coal
elemental analysis is so that the correct
amount of air can be supplied. Figure 25: A general elemental analysis of coal.

68 | P a g e
 Coal analysis methods

As mentioned previously, coal is mainly used in industry as a fuel source for combustion reactions.
Chemical engineers are required to make sure that these combustion reactions can be controlled
and optimised to get the most out of each piece of coal. For this to be possible, we need to know
exactly what the coal we are working with looks like on an elemental level. Two of the main
methods used to determine the composition of coal are discussed below.

• Coal content

Before we look at the analysis methods, what information of coal do we need to know with regards
to combustion reactions?

(a) Free water or moisture – This refers to any water present as H2O. Free water or moisture can be
subdivided onto two categories: 1) Surface moisture – water present on the surface from e.g. being
left in the rain; 2) Hygroscopic or inherent moisture – This is water that is held by capillary action
within the microfractures of the coal. It can also include the water held within the coal’s
decomposed organic compounds. The important thing to remember is that the free water or
moisture is physical H2O molecules present which can be removed by heating the coal to above
100 °C.

(b) The total carbon content – This is all of the carbon present in the coal. This can be pure carbon
(fixed carbon) or carbon that is bound to hydrogen (volatile carbon) (refer to Figure 24).

(c) The oxygen – This represents all of the oxygen that is present in the coal. Oxygen gives us an
idea of the bound water content in the coal. But what is bound water? And what is the difference
between bound water and free water? Free water is physical H2O molecules that are present on
the surface or inside of coal. Whereas, bound water can be thought of as future potential water
molecules that does not exist yet. What? Well, if we look at the structure of coal in Figure 24,
there is two hydrogen atoms and one oxygen atom that is collectively called bound water.
Hydrogen and oxygen are highly reactive and will always react very fast. Therefor, during a
combustion reaction we can assume that all of the oxygen present in the coal will react with some
of the hydrogen present to produce water, which we refer to as the bound water.

(d) The hydrogen content– This includes all of the hydrogen present in the coal. The hydrogen content
can be divided into two main sections: 1) the hydrogen needed to react with all of the oxygen in
the coal to produce bound water and 2) all of the hydrogen left after the bound water is produced,
this is referred to as the available hydrogen. Available hydrogen can hence be seen as all of the
hydrogen that will react with and external air supply.

(e) Sulphur – All of the sulphur present in the coal. During combustion all of the Sulphur will react to
produce SOx (this includes SO2 and SO3). For the purposes of this module it will always be
specified to which SOx the sulphur reacts to.

(f) Nitrogen – This is all of the nitrogen that is physically bound in the structure of the coal. During
combustion all of the nitrogen will react to produce NOx (this includes NO2 and NO3). For the
purposes of this module it will always be specified to which NOx the sulphur reacts to.

69 | P a g e
 • Coal presented for analysis

The one thing that has a huge effect on any coal analysis is the water content. The water content
will not only affect the values determined during analysis but will also reduce the heat of
combustion of the coal. Therefor, it is important to understand the following specifications for
coal:

1. “As received coal” – Coal that contains surface water, inherent water and bound water.
Hence, no attempt has been made to alter the water content of the coal.
2. “Air dry coal” – Coal that has been exposed to the atmosphere so that all the surface and
a little bit of the inherent moisture has already evaporated. Hence, it will still contain some
inherent moisture and all of the bound water.
3. “Dry coal” – Only contains bound water. This coal has been exposed to a temperature of
at least 100 °C for an extended period of time to evaporate any free and inherent moisture.
4. “Moisture less coal” – Here we can assume that the coal does not contain any moisture,
not even bound moisture.

Always keep there four types of coals specifications into account when considering the coal
analysis results given. The following description of the coal analysis methods is for “As received
coal”, hence, the according adjustments should be made to take the changes in moisture level
into account.

Generally, only two types of analysis methods are performed on coal: The ultimate analysis and
the proximate analysis.

• Ultimate analysis

The ultimate analysis is also known as the elemental analysis, it is a method to determine the
carbon, hydrogen, nitrogen, sulphur and oxygen content present in the solid fuel. A typical
ultimate analysis will look like this:

Ultimate analysis

C 79.90 %
H 4.85 %
S 0.69 %
N 1.30 %
Ash 6.50 %
O (Difference) 6.76 %

100 %

Generally, the mass percentage composition of all of the elements will be determined excluding
oxygen. The oxygen content will be determined by calculating the difference. Hence, it should
always be kept in mind that the oxygen content is not always explicitly given and should be
calculated by subtracting the percentages of the other elements from 100 %. It is important to
note that all of the values present for the elements refer to the monoatomic form of the element
i.e. there is 4.85 % hydrogen (H) in the coal and not H2.

The values in an ultimate analysis represents the following:

70 | P a g e
 1. Carbon (C – 79.9 %): This value represents ALL of the carbon present in the coal. It
includes all of the carbon that is pure (fixed carbon) as well as the carbon that is bound to
hydrogen (volatile carbon).
2. Hydrogen (H – 4.85 %): This value for hydrogen represents ALL of the hydrogen present
in the coal. This includes: a) all of the hydrogen present in the free water surrounding the
coal if the coal has not been dried; b) all of the hydrogen present as bound water; and c)
all of the available hydrogen that can react during combustion.
3. Sulphur (S – 0.69 %): All of the sulphur in the coal that will combust to SOx.
4. Nitrogen (N – 1.3 %): All of the nitrogen present that will combust to NOx.
5. Ash (Ash – 6.5 %): All of the inert ash present in the coal.
6. Oxygen (O – 6.67 %): This is all of the oxygen present in and around the coal. This
includes the oxygen present as a) free and inherent water in and on the surface of the coal
and b) the oxygen present as bound water in the coal.

NOTE: Sulphur and nitrogen are often ignored if they are present in percentages lower than 1 %.
At these low concentrations they will have a negligible effect on the overall combustion reaction.
Hence if the ultimate analysis does not indicate the presence of sulphur of nitrogen it can be
assume that there is nothing in the coal.

• Proximate analysis

Proximate analysis

Free moisture 3.2 %

Fixed carbon 69.3 %
Volatile matter 21.0 %
Ash 6.5 %

100 %
The proximate analysis is known as the quick summary analysis. It only provides a very basis
summary of everything in the coal:

1. Free moisture – This value only takes the free surface moisture and inherent moisture
into account and not the bound moisture.
2. Fixed carbon – Fixed carbon can be seen as large pure carbon structures (e.g. graphite)
present in the coal. This can also be represented by the benzene rings present in Figure
24 (page 68). The bonds between the carbon atoms in these structures are very strong
and need a lot of energy to be broken. The carbon that counts as volatile carbon is usually
long polymer strings bound to hydrogen with weaker bonds that can be broken more easily.
Hence, at the start of combustion all of the volatile material will be burned off first leaving
the more difficult pure carbon behind to burn last. These pure carbon spaces usually also
make up most of the weight of the carbon, hence the mass lost noticed during carbon can
be attributed to the fixed carbon.
3. Volatile matter – This is the collective name for all of the combustible elements present in
the coal excluding the fixed carbon. This will include all of the volatile carbon, all of the
hydrogen (including the available hydrogen and the bound water hydrogen); oxygen
(from the bound water), and if present all of the nitrogen and sulphur. The volatile matter
of coal is determined by the mass loss of coal when powdered coal is heated at 1200 K in
the absence of air (oxygen). In combustion processes the volatile matter causes the

71 | P a g e
 formation of smoke which is why it is important to consider the volatile matter in processes
where the gas production is most important.
4. Ash - This is the incombustible residue after the coal has been fully burned. The ash
consists of the incombustible minerals which are present in the coal, like silica, iron oxides,
gypsum, etc.

• Determining the relationship between the two analyses

It should be clear that each of the analysis methods have their own significance depending on
what the main objective of the process is. However, usually both if the analysis will be performed
and the results combined to give a very clear picture of what the coal looks like. In processes
where the volatile gas production part of combustion is significant it would be wise to use the
proximate analysis to provide a clear idea of how much volatiles there are in the coal. The ultimate
analysis does not provide a distinction between the carbon present as volatile carbon or as fixed
carbon. The following example illustrates the use of both of the coal analyses.

A proximate and ultimate analysis on a sample of coal provided the following results. It is
important to note that the coal was air dried before the analysis.

Proximate analysis Ultimate analysis

Free moisture 3.2 % C 79.90 %

Volatile matter 21.0 % H 4.85 %
Fixed carbon 69.3 % S 0.69 %
Ash 6.5 % N 1.30 %
Ash 6.50 %
O (Difference) 6.76 %
100 % 100 %

Firstly, what effects will the coal being air dried have on the analysis? When coal is air dried all
of the surface moisture and some of the inherent moisture is removed. Hence, we can assume
that any and all of the oxygen present in the analysis will be due to some of the inherent moisture
and all of the bound water.

Basis: 100 kg of coal

The proximate analysis reports a fixed carbon percentage of 69.3 %. This means that there is a
total of 69.3 kg of fixed carbon in the coal. However, the ultimate analysis reports a total of 79.9 kg
of carbon. Why the difference? The fixed carbon mentioned in the proximate analysis does not
take the volatile carbon (bound to hydrogen) into account, hence, the difference, 79.9 kg – 69.3 kg
= 10.6 kg, is all of the volatile carbon present in the 21 kg of volatile matter (proximate analysis).
The rest of the volatile matter will include the available H, the S, N and bound H 2O. Notice that
the volatile matter will not include the inherent moisture as this is measured separately and
reported as 3.2 kg free moisture.

Now the next step would be to distinguish between the bound water hydrogen and the available
hydrogen (available for combustion).

The difference calculated in the ultimate analysis refers to the oxygen content in the coal. All of
this oxygen is bound to hydrogen as bound water. Hence, this oxygen % can be used to
determine the total amount of hydrogen that is free for combustion:

72 | P a g e
Basis: 100 kg Coal: Ultimate analysis

Hydrogen (H) = 4.85 kg = 4.85 kmol Oxygen (O) = 6.76 kg = 0.4225 kmol
4.85 0.4225
(H2) = 2 =2.425 kmol (O2) = 2 = 0.2115 kmol

The H required to bond with all of the oxygen in the coal: (0.4225)(2) = 0.845 kmol
= 0.845 kg
Hence, the hydrogen (H) available to react: 4.85 – 0.845 = 4 kmol H
= 2 kmol H2
= 4 kg H2
The total amount of water produced: (0.4225)(18) = 7.61 kg H2O
Which should be equal to the mass of oxygen and hydrogen reacted: 6.76 + 0.845 = 7.61 kg
This water constitutes the free moisture and the bound moisture in the coal.
The H2 and O2 elements of the ultimate analysis can therefore be replaced with:

Available H2 = 4.0 %) cf. 4.85 total H2 and

Total H2O = 7.61 %) 6.76 total O2

According to the proximate analysis there is 3.2 kg free moisture, so the bound moisture = 7.61
– 3.2 = 4.41 kg. This is of course the bound water in the volatile matter.
The volatile matter analysis can now be done:

Volatile matter (Total 21 kg)

C = 10.6 kg
Bound water H2O = 4.41 kg
Hydrogen = 4.0 kg
S = 0.69 kg
N = 1.3 kg
21.0 kg

For calculation purposes the coal analysis can now be written as:
Coal analysis
Free moisture 3.20
Bound moisture 4.41
Carbon 79.90
Available hydrogen 4.00
Sulphur 0.69
Nitrogen 1.30
Ash 6.50

100.00 %

TUTORIAL 19

73 | P a g e
 Combustion

We have all been exposed to combustion reaction from a very young age and we all know the
three most important elements to any combustion reaction: fuel, air and heat. Remove any one
of these and combustion reaction will suffer or will not occur.

Any combustion process can typically be broken down into five fundamental reactions:

1
1) 𝐻2 + 𝑂2 → 𝐻2 𝑂
2
1
2) 𝑆 + 𝑥𝑂2 → 𝑆𝑂𝑥
2
1
3) 𝑁 + 𝑦𝑂2 → 𝑁𝑂𝑦
2
1
𝐶 + 𝑂2 → 𝐶𝑂

}
4) Collectively summarised as:
2
1
5) 𝐶𝑂 + 𝑂2 → 𝐶𝑂2 𝐶 + 𝑂2 → 𝐶𝑂2
2
The order of these reaction (ranked from 1 to 5) typically also represents the priority of each of
the reactions. You can think of it as the following: If combustion occurs and there is enough heat
and oxygen present, all of the hydrogen will react first to produce water; sulphur will react to
produce SOx and all of the nitrogen in the fuel (not N2 from the air) will be converted to NOy.
Carbon will first react to form CO, and if there is enough oxygen left all of the CO will be converted
to CO2. If there is not enough oxygen only a part of the CO will be converted to CO2. This will be
cover in more detail in the sections to come.

It is very important to distinguish between the nitrogen that is present in the coal or fuel source
and the nitrogen gas that is present in the air. All of the nitrogen present in the fuel is usually
bound within the physical structure of the fuel as N+ or 𝐍𝐇𝟑+ etc. When combustion occurs, these
ions are released and will be able to react with oxygen e.g.:

4𝑁𝐻3+ + 5𝑂2 → 4𝑁𝑂 + 6𝐻2 𝑂

2𝑁 + 𝑂2 → 2𝑁𝑂
𝑁 + 𝑂2 → 𝑁𝑂2
4𝑁 + 5𝑂2 → 2𝑁2 𝑂5
4𝑁 + 3𝑂2 → 2𝑁2 𝑂3

However, nitrogen gas (N2) is an inert gas and will never take part in a combustion reaction.
𝑁2 + 𝑂2 → 𝑁𝑂𝑥

NOTE: Sometimes when N is present in very low concentrations in the fuel, it is assumed that
the effect of the reaction between N and O2 on the overall energy requirements for combustion is
so small that the reaction is ignored. It is then assumed that all of the N coming in with the fuel
leaves the system as N2 gas. This is why there are not NOx gasses leaving the system in Example
5.14 (Himmelblau 8th edition pp.240 – 241). For the purpose of this module this assumption will
not be used and it will be assumed that all of the N in the fuel will combust to produce NOx (which
will always be specified).

74 | P a g e
 Combustion terminology

10.4.1. Flue gas, stack gas or exhaust gas:

All of these terms refer to the gas that is produced during combustion. This will include
CO2, CO, SOx, H2O, NOy possible unreacted hydrocarbons, free O2 and free N2. Since this
includes the water vapour present in the gas, it can also be known as a wet basis. To distinguish
between a flue gas that includes the H2O and flue gas without H2O we would refer to the gas as
on a wet or dry basis. Hence, flue gas on a dry basis will include all of the product gases accept
the water vapour.

10.4.2. Product gas analysis methods

Just like the two analysis methods for coal, there are various methods to determine the
combustion product gas composition.

75 | P a g e
 • Orsat analysis method

An Orsat gas analyser is a piece of laboratory equipment that is used to analyse a gas sample
for its N2, O2, CO, CO2, and SOx content. It is important to note that the Orsat apparatus cannot
account for any NOx gas present in the product gas. In order to analyse the product gas all of the
water vapour is condensed and not measured, hence, an Orsat analysis is always on a moisture
free or dry basis.

Product gas analysis results can be presented in various forms, the three main forms being
represented in the figure below.

Figure 26: The difference between the three main combustion gas analyses.

• Other types of analysis methods

The Orsat analysis method is one of the standard analysis methods used in industry to determine
the composition of gas streams, however, this method is not always as accurate and has the
drawback that it cannot detect any NOx gases present in the product. There are a few other more
accurate methods that can be used to determine the composition including the NO x concentration,
namely: Fourier transform infrared spectroscopy (FTIR); Gas chromatography – Mass
spectrometry (GC-MS) and Gravimetric analysis.

Combustion calculations

Combustion calculations entail the material and energy balances of a combustion process.

• Complete combustion:

Complete combustion occurs when ALL of the combustibles in the fuel is converted to its highest
level. The combustibles are C, H, N, S. As mentioned in section 10.3, firstly all of the hydrogen
will be converted to water, sulphur will be converted to SO x, and all of the nitrogen will be
converted to NOy. All of the carbon will be converted to CO2 with completed combustion. (Note:
For the purpose of this module it will always be specified to which level of SOx and NOy, S and N
will combust.)

• Theoretically required air (or oxygen):

The amount of air (or oxygen) that is required to ensure complete combustion of all of the fuel
sources in the fuel. For calculation of the theoretical oxygen required, combustion of C, H, N and
S to CO2, H2O, NOy and SOx is assumed. The theoretical quantity of oxygen required is calculated
without considering the real degree of completion of the combustion - even if the real combustion
is only 90 % complete, the theoretical oxygen required is still calculated as if the combustion will
proceed 100 %.

76 | P a g e
 CALCULATION OF THEORETICALLY REQUIRED AIR

A gas has the following composition:

C2H6 = 15 % H2 = 28.2 % S = 26.4 %

CH4 = 3.5 % CO = 17.5 % O2 = 9.4 %

If all of the S burns to SO2 and N burns to NO3, determine the theoretically required oxygen that
should be fed in with the air.
2N + 3O2 → 2NO3
Basis: 100 kmol fuel gas

kmol kmol Theoretically

Component kmol kmol C kmol S
H2 O2 required O2
C2H6 15 30 45 30+45/2 = 52.5
CH4 3.5 3.5 7 3.5+3.5 = 7
H2 28.2 28.2 28.2/2 = 14.1
CO 17.5 17.5 8.75 17.5 – 8.75 = 8.75
S 26.4 26.4 26.4
O2 9.4 9.4 -9.4
TOTAL 100 51 80.2 18.15 26.4 99.35

Hence, when determining the theoretically required air the should be fed for a fuel that contains
oxygen; the oxygen in the fuel will be subtracted.

• Excess air (oxygen):

The excess air is the amount of air (or oxygen) in excess of the theoretical air (oxygen) required
for complete combustion.

As is known, any chemical reaction in real life never really reacts to completion, however, by
adding an excess of one of the reactants it is possible to increase the degree of completion of the
reaction. Hence, in industry it is customary to supply an excess amount of air (oxygen) into the
combustion reaction in order to increase to degree of completion.

Excess air is given as a percentage of the theoretically required air, i.e.

O2 in − O2 required for complete combustion

% excess O2 = 100 × [ ]
O2 required for complete combustion

The excess O2 normally used for different fuels is:

Coal: 20 – 50 % Oil: 15 - 25 % Gas: 10 – 20 %

For purposes of calculation it is assumed that air contains 21 % O2 and 79 % N2. The mole ratio
of N2:O2 in air is therefore 79 / 21 = 3.762

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 COMBUSTION CALCULATION

A hydrocarbon gas has the following composition

C2H4 = 16.6 % H2 = 32.1 % CO2 = 3.0 %

CH4 = 19.8 % CO = 26.1 % N2 = 2.4 %
The exhaust gas shows the following Orsat analysis

CO2 = 12.2 % O2 = 4.0 %

CO = 0.4 % N2 = 83.4 %

Calculate:

i. The kmol exhaust gas formed per kmol of fuel gas.

ii. The volume air supplied per unit volume of fuel gas if the air and gas are at the same
temperature and pressure.
iii. The % excess air provided.
iv. The degree of completion of the carbon combustion.

Basis: 100 kmol fuel gas

kmol O2
Component kmol kmol C kmol H2 Theoretically
required
C2H4 16.6 33.2 33.2 49.8
CH4 19.8 19.8 39.6 39.6
H2 32.1 - 32.1 16.05
CO 26.1 26.1 - 13.05
CO2 3.0 3.0 - -
N2 2.4 - - -
TOTAL 100 82.1 104.9 118.5

Set x = kmol dry flue gas formed.

Component kmol kmol C kmol O2

CO2 0.122x 0.122x 0.122x
CO 0.004x 0.004x 0.002x
O2 0.04x - 0.04x
N2 0.834x - -
TOTAL X 0.126x 0.164x

Carbon balance: 82.1 = 0.126x then x = 651.6 kmol dry flue gas
And 104.9 kmol H2O formed by combustion.
Therefore, wet flue gas = 651.6 + 104.9 = 756.5 kmol wet gas.

78 | P a g e
Alternative
N2 in flue gas = 0.834(651.6) = 543.4 kmol N2,
N2 in as air = 543.4 – 2.4 = 541 kmol N2

Therefore, O2 in as air = (541/3.762) = 143.8 kmol O2

O2 in dry flue gas = 0.164(651.6) = 106.9 kmol O2 and O2 in with fuel gas as CO,
CO2 = (26.1/2) + 3.0 = 16.05 kmol O2

Therefore, O2 that reacted with H2 = 143.8 + 16.05 – 106.9 = 53 kmol O2

Therefore, kmol water formed in combustion = 106 kmol (cf. 104,9)
and wet flue gas = 106 + 651.6 = 757.6 kmol wet gas

Difference because of inaccurate analyses!!

kmol wet flue gas 756.5 kmol

(i) = = 7.57
kmol fuel gas 100 kmol

(ii) N2 in flue gas that is derived from air = 0.834(651.6) – 2.4 = 541 kmol N2
541
Therefore, O2 in as air = = 143.8 kmol O2
3.762

Air in = 541 + 143.8 = 684.8 kmol air

684.8 m3
Vol. Air/Vol. fuel gas = = 6.85
100 m3

(iii) O2 in as air = 143.8 kmol O2, O2 theoretically required = 118.5 kmol

143.8−118.5
% Excess O2 = ( ) 100 = 21.4 %
118.5

(iv) CO2 in flue gas = 0.122(651.6) = 79.5 kmol CO2

Therefore, CO2 formed by combustion = 79.5 – 3.0 = 76.5 kmol CO2  76.5 kmol C

kmol combustible C in fuel gas = 82.1 – 3.0 = 79.1 kmol C

76.5
Degree of completion = (79.1) 100 = 96.7% →

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 EXCESS AIR CALCULATION

Figure 27: Himmelblau (8th edition Hardcover) Example 5.12 on pp.235.

TUTORIAL 20

• Degree of completion of combustion:

The degree of completion in combustion calculation has a completely different definition than the
definition provided on page 58. Unless otherwise stated, it is always assumed that no unreacted
fuel (C, H, S, etc.) will be lost in the exhaust gas other than CO.

In combustion calculations it is always assumed that the first reaction to use oxygen will be
H2 + 0.5O2 → H2O, then all of the S will be converted to SOx and all of the N will be converted to
NOy. After all three these reaction, the remainder of the oxygen, if any, will be used to combust
C. If too little oxygen remains to burn all the carbon to CO 2, it is assumed that all of the C will
burn to CO and that part of the CO will then oxidise to CO2.

80 | P a g e
The degree of combustion can be given in one of two ways:

1. The degree of combustion is 90%. Here it is assumed that 90 % of all of the carbon
available in the fuel will be converted to CO2. Consider a fuel that contains the following:
15 % CO2, 27 % CO, 5 % C, and 53 % H2. Take a basis of 100 kmol gas.

Component In C O2 H2
(kmol) (kmol) (kmol) (kmol)
CO2 15 15 15
CO 27 27 27/2
C 5 5
H2 53 53
Total 100 44 28.5 53

From the table above it was determined that the fuel contains a total of 44 kmols of carbon.
This includes the carbon contained in the non-combustible CO2. Based on the degree of
completion 44(0.9) = 39.6 kmol of this carbon will react to produce CO2 and the rest
(4.4 kmol) will react to produce CO in the product gas. All of the hydrogen will react to
produce water.

2. The degree of completion based on the combustible carbon is 90 %. Now only the
combustible carbon is considered. Let us again look at a fuel that contains 15 % CO2,
27 % CO, 5 % C, and 53 % H2. The CO2 in the fuel cannot react any further, hence the
carbon contained in the CO2 is not considered as combustible carbon.

Combustible In C O2 H2
Components
(kmol) (kmol) (kmol) (kmol)
CO2 15 15 15
CO 27 27 27/2
C 5 5
H2 53 53
Total 85 32 13.5 53

Now based on the degree of completion given, the fuel only contains 32 kmols of
combustible carbon, hence 32(0.9) = 28.8 kmol will combust to produce CO2 and the rest
(3.2 kmol) will convert to CO. The product gas will thus contain 28.8 + 15 = 43.8 kmols of
CO2 and 3.2 kmol of CO.

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 ORSAT ANALYSIS DETERMINATION

Methane gas (CH4) is burned with 20 % excess air. If the degree of completion of the carbon
combustion is only 80 %, calculate the Orsat analysis of the flue gas and the total number of kmol
flue gas formed per kmol CH4.

CH4 Wet flue gas Dry gas

CO2
Air CO2 CO O2 CO
O2 H2O O2
N2 N2

H2O
Basis: 100 kmol CH4

CH4 + 2O2 → CO2 + 2H2O

O2 required for complete combustion = 200 kmol
O2 supplied = 1.2 (200) = 240 kmol
N2 in with air = (3.762) 240 = 903 kmol
The degree of completion of the C-combustion is 80 %

i.e. 80 kmol C → CO2

20 kmol C → CO
200 kmol H2 → H2O
20 200
+
Oxygen consumed: 80 + 2 2 = 190 kmol O2
i.e. free O2 in flue gas = 240 – 190 = 50 kmol O2

Note: Also O2 as CO2, CO, H2O, SO2 etc. in flue gas.

Flue gas: Orsat analysis

CO2 = 80 kmol 7.6 %

CO = 20 kmol 1.9 %
O2 = 50 kmol 4.75 % →
N2 = 903 kmol Orsat total = 1 053 kmol 85.75 %
H2O = 200 kmol
Total = 1 253 kmol
1253
Flue gas per kmol CH4 burned = 100 = 12.53 →

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 COAL COMBUSTION WITH ULTIMATE ANALYSIS

Figure 28: Himmelblau (8th edition Hardcover) Example 5.14 on pp.240

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84 | P a g e
 COAL COMBUSTION WITH PROXIMATE ANALYSIS

The flue gas from a steam boiler shows the following analysis on a water and SO2 free basis:
CO2 = 10.8 %; CO = 0.2 %; O2 = 9.0 % and N2 = 80,0 %

The proximate coal analysis is:

Free moisture 1.44 % Fixed C 57.77 %
Volatile matter 34.61 % Ash 6.18 %

Further coal analysis shows:

S = 0.78 %; N = 1.1 % and Total C = 78.76 %

The residue after combustion analyses:

Fixed C = 25 % and Ash = 75 %

The air in the boiler room contains 0.025 kmol water vapour per kmol dry air. Calculate:
(i) The percentage excess air provided.
(ii) The number of kmol moist air supplied per 100 kg coal.
(iii) The number of kmol water vapour in the exhaust gas per 100 kg coal charged.

SO2
H2O from air

Air (N2 O2) CO2

CO
Coal O2
Fixed C N2
Volatile matter
( C, H, S, N, H2O) H2O
Free water Residue from
Ash C; Ash Free water
Bound water
Air
Available H2
Basis: 100 kg Coal
Set x = kg residue formed

Ash Balance: 6.18 = 0.75x then x = 8.24 kg Residue

Carbon lost in residue = 0.25(8.24) = 2.06 kg
C in dry exhaust gas = 78.76 – 2.06 = 76.7 kg C = 6.392 kmol C

Set y = kmol dry exhaust gas formed: C-balance

0.108y + 0.002y = 6.392 i.e. y = 58.1 kmol dry gas

Exhaust gas (Dry, sulphur free)

CO2 (10.8 %) = 6.276 kmol  6.276 kmol O2

CO (0.2 %) = 0.116 kmol  0.058 kmol O2
O2 (9.0 %) = 5.229 kmol  5.229 kmol O2
N2 (80 %) = 46.48 kmol

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 1,1
N2 in as air = 46.48 - 28 = 46.44 kmol N2
Therefore, O2 in as air = 46.44/3.762 = 12.34 kmol O2
0,78
Total O2 out (as CO2; CO; O2 and SO2) = 6.276 + 0.058 + 5.229 + 32 = 11.59 kmol O2
Therefore O2  Avail H2 = 12.34 – 11.59 = 0.75 kmol O2  1.5 kmol H2O
 1.5 kmol Avail H2  3.0 kg H2 in Coal

(a) O2 required theoretically = (C) 78,76 + (H2)0.75 + (S) 0,78 = 7.34 kmol O2
12 32

And O2 in as air = 12.34 kmol O2

% excess O2 = (
12.34−7.34
)100 = 68.1 % →
7.34

(b) Dry air in = 46.44 + 12.34 = 58.78 kmol dry air

Water vapour in with air = 0.0250 kmol H2O / kmol dry air

Water vapour in with air = 0.025(58.78) = 1.47 kmol H2O

Moist air in = 58.78 + 1.47 = 60.25 kmol/100 kg coal →

(c) Water vapour in exhaust gas = water in air

+ free water in coal
+ bound H2O
+ H2O ex Avail H2

Consider the volatile matter in the coal:

Volatile matter

C = 78.76 – 57.77 = 20.99 kg

Avail H2 = = 3.00 kg
N2 = = 1.10 kg
S = 0.78 kg
Bound water (difference) 8.74 kg
Total: 34.61 kg

kmol H2O in exhaust gas

1,44 8,74
=1.47 + 18 + 18 + 1.5 = 3.54 kmol H2O/100 kg coal →

TUTORIAL 21

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11. MATERIAL BALANCES WITH RECYCLE STREAMS, BYPASS STREAMS AND PURGE
STREAMS

Recycle systems

• Recycle without reaction

Generally, recycle systems are used to improve some part of a process or industrial system.
Material balances that include recycle streams can be solved using all of the general methods
discussed in CIR113. A process that contains a recycle stream can be broken down into several
systems and a mass balance is done over each system.

FILTRATION WITH RECYCLE

Figure 29: Himmelblau (8th edition Hardcover) Example 6.5 on pp.294.

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88 | P a g e
 TUTORIAL 22
• Recycle with chemical reaction

The most common reason to add a recycle stream to a system where a chemical reaction occurs
is to increase the overall conversion achieved by recycling the unreacted reactants back into the
system. Hence, in systems where a recycle stream is present the following two types of
conversion can be referred to:

1. Overall conversion (ƒOA): The overall conversion is the conversion achieved over the
whole system. Hence, this is the conversion that will be determined if the system below
is analysed.

(moles of limiting reactant in F) − (moles of limiting reactant in P)

ƒOA =
Moles of limiting reactant in F

nFLR − nPLR
ƒOA =
nFLR

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If the extent of reaction of the system is known then the equation above can also be written as:
−𝑣𝐿𝑅 ∙ ξ
ƒOA =
nFLR

2. Single-pass conversion (ƒSP): This is the conversion that is achieved only in the reactor.

(moles of limiting reactant in B) − (moles of limiting reactant in C)

ƒSP =
Moles of limiting reactant in B

nBLR − nCLR
ƒSP =
nBLR
If the extent of reaction of the system is known then the equation above can also be written as:
−𝑣𝐿𝑅 ∙ ξ
ƒSP =
nBLR

Since the extent of reaction for a system always stays the same the overall conversion and single-
pass conversion can be related with the following:

ξ=ξ
Hence,
nF
LR ∙ƒOA nB
LR ∙ƒSP
=
−vLR −vLR
By simplification:
ƒSP nF
= nLR
B
ƒOA LR
From the system:

recycle
A mass balance over the mixer is: nBLR = nFLR + nLR
By substitution:
ƒSP nF
LR
= recycle
ƒOA nF
LR +nLR
Hence, the overall or single-pass conversion can be calculated by knowing the moles of limiting
reactant in the feed and recycle stream if the single-pass or overall conversion is known.

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 RECYCLE WITH REACTION

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 Figure 30: Himmelblau (8th edition Hardcover) Example 6.6 on pp.299.

OVERALL AND SINGLE-PASS CONVERSION

Examine the figure above (data for 1 hr).

(a) What is the single-pass conversion of H2 in the reactor?

(b) What is the single-pass conversion of CO?
(c) What is the overall conversion of H2?
(d) What is the overall conversion of CO?

Solution

−𝑣𝐿𝑅 ∙ ξ
(a) The equation for a single-pass conversion: ƒSP = 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑓𝑒𝑒𝑑
nLR

The single pass conversion based in H2 as the limiting reactant:

nout in
H2 − n H2 1.979 − 3.96
ξ= = = 0.99
vH2 −2
−(−2) ∙ (0.99)
ƒSP = = 0.5
3.96
nF −nP 1−0.01
(b) The overall conversion of CO is: ƒOA = = = 0.99
nF 1
−𝑣𝐿𝑅 ∙ξ −(−2)∙ξ
The extent of reaction of CO is: 0.99 = 𝑓𝑟𝑒𝑠ℎ𝑓𝑒𝑒𝑑 = 1.98
; ξ = 0.98
nLR

−𝑣𝐿𝑅 ∙ξ −(−2)(0.98)
Hence, ƒSP = 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑓𝑒𝑒𝑑 = 1.989
= 0.986
nLR

(c) Overall conversion of H2

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 nF P
LR −nLR 1.98−0
ƒOA = nF
= 1.98
=1
LR
or
−(−2)∙(0.99)
ƒOA = =1
1.98

(d) Overall conversion of CO

nF −nP 1−0.01
ƒOA = nF
= 1
= 0.99
or
−(−1)∙(0.99)
ƒOA = = 0.99
1

TUTORIAL 23

Bypass and purge streams

• Bypass streams

A stream that skips one or more steps is a process and goes directly to another downstream
stage.

• Purge stream

A stream bled off from the process to remove an accumulation of inerts or unwanted material that
might otherwise build up in the recycle stream with time of operation

OVERALL SYSTEM ANALYSIS WITH EQUATION

For the production of synthetic NH3 a mixture of N2 and H2 is charged to a reactor. The fresh feed
to the process contains 2 % Argon (the Ar is inert) and N2 and H2 in the correct stoichiometric
ratio.

The discharge from the reactor is condensed to remove the NH3 (which is condensable). The
incondensable gases (N2, H2 and Ar) are recycled to the reactor. A portion of the recycle stream
is purged to limit the Ar build-up in the system.

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Fresh Feed
F A C E
N2 Reactor NH3
Condenser
H2
Ar D

Recycle R Purge
P
Assume that the liquefied NH3 product stream (E) contains no N2, H2 or Ar and that the gas from
the condenser (D) contains no NH3. The maximum allowable Ar content in the feed to the reactor
(A) is 12 %. The conversion in the reactor is 25 %.
N2 + 3H2 → 2NH3

(a) What percentage of the gas stream (D) leaving the condenser must be purged?
(b) What is the conversion in the process?
Solution
Basis: 100 kmol/h fresh feed gas. Ar in fresh feed = 2 kmol/h

Then N2 + H2 in fresh feed = 98 kmol/h in ratio 1:3.

1
N2 in (F) = 4 (98) = 24.5 kmol/h
3
H2 in (F) = 4 (98) = 73.5 kmol/h N2 + H2 in (F) = 98 kmol/h
Set R = kmol/h total recycle gas
P = kmol/h total purge gas
x = mole fraction Ar in P, R and D

Ar balance total: 2 = xP …………………………………………………….. (1)

Ar in D = Ar in C = Ar in A = 0.12A = 0.12(100 + R) kmol/h

(N2 + H2) in A = 0.88(100 + R) kmol/h

(N2 + H2) in C = 0.75(0.88)(100 + R) kmol/h = (N2 + H2) in D

Total gas in D = 0.75(0.88)(100 + R) + 0.12(100 + R) = 0.78(100 + R) kmol/h

0.12(100+R)
Then mole fraction Ar in D = = 0.1538 = x = mole fraction Ar in R and P
0.78(100+R)
2+xR
Mole fraction Ar in A = 100+R = 0.12 and with x = 0.1538

R = 295 kmol/h
2
From (1) P = x = 13 kmol /h
And D = P + R = (13 + 295) kmol gas/h = 308 kmol/h
% purged = ( )100 = 4.2 % →
13
308

NH3 produced  25 % of the N2 in A.

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Total gas in A = (100 + R) = 395 kmol/h
(N2 + H2) in A = 0.88(395) kmol/h

1
N2 in A = 4 (0.88)395 = 86.9 kmol/h

NH3 in E = NH3 in C = 0.25(86.9)(2)

= 43.45 kmol NH3/h

𝑁𝐻3 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 43.45

Conversion in system = 𝑁𝐻 = [2(24.5)] 100 = 88.7 %
3 𝑡ℎ𝑒𝑜𝑟.𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒

Check: N2 in = 24.5 kmol/h: H2 in = 73.5 kmol/h

3
 
N2 out as NH3 = 43.45/2 = 21.7 kmol and H2 out as NH3 = 43.45  2  = 65.2 kmol/h
1
N2 out as purge = 4 (1 – 0.1538)(13) = 2.75 kmol/h and H2 out as purge = 3(2.75)
= 8.25 kmol/h

Total N2 out = 21.7 + 2.75 = 24.5 kmol/h

Total H2 out = 65.2 + 8.25 = 73.5 kmol/h (Equal to IN)

Conversion of H2 in the system

H2 in− H2 lost in purge 73.5−8.25
H in
= ( 73.5 ) 100 = 88.8 %
2
(Equal to the conversion in the system)

TUTORIAL 24
TUTORIAL 25
THE END

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