Module: CG5011 Principles of Chemical Engineering

Majority of text presented below was taken from

Felder R.M. and Rousseau R.W., Elementary Principles of Chemical Processes, John Wiley &
Sons, 2005.
recommended examples to self study:
Units
Mass balances Energy balances
conversion
4.1 to 4.25 7.15, 7.16,
2.1 to 2.10
4.29 to 4.40 7.19 to 7.28

other recommended handbooks:

Himmelblau D.M., Riggs J.B. Basic Principles and Calculations in Chemical Engineering,
Prentice Hall International Series in the Physical and Chemical Engineering Sciences, 2012

Sigurd Skogestad, Chemical and Energy Process Engineering, Crc Press, 2008, ISBN:
142008755X.

Duncan M. and Rei J., Chemical Process Design and Analysis, Cambrodge Univ. Press, 1998.

Field R.W., Chemical Engineering Introductory Aspect, MacMillan Education, 1988.

SI system of units

The basic quantities used in the SI system (International System of Units ) are as follows:
the unit of length is the meter (m); the unit of time is the second (s);
the unit of mass is kilogram (kg); the unit of temperature is the Kelvin (K);
the unit of an element in the mole (mol).
energy joule (J) kg·m2/s2 = N m
force newton (N) kg·m/s2
power watt (W) J/s = kg·m2/s3
pressure pascal (Pa) N/m2
frequency hertz (Hz) (cycles)·s-1
velocity m/s
density kg/m3
dynamic viscosity Pa·s kg/m·s
kinematic viscosity m2/s
surface tension N/m kg/s2

standard acceleration of gravity 9.81 m/s2 ; 1 atm = 1.0132·105 Pa ;

1 cSt = 10−2 stokes = 1 mm2/s

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 Units conversion

10 100 1000 106 109 1012 1015 1018 1021 1024

deka hecto kilo mega giga tera peta exa zeta yotta

10-24 10-21 10-18 10-15 10-12 10-9 10-6 0.001 0.01 0.1
yocto zepto atto femto pico nano micro milli centi deci

Example:
Unit conversion:
2 m/s = ? km/h

1 g/cm3 = ? kg/m3

5 g/(s·m) = ? Pa·s

1 lb/ft3 = ? kg/m3

1 lb = 0.4536 kg
1 ft = 0.3048 m

Speed of sound in air (15C) is 340 m/s, how much km/h and mile/h it is?

Units conversion

Convert liquid water fed at a rate of 20cm3/min to mol/min

MH2O= 18 g/mol

Table. Physical characteristic of water

Temperature Saturation Density Specific Specific Volume Dynamic Thermal
vapour enthalpy of heat heat viscosity conductivity
pressure liquid water capacity
C Pa kg/m3 kJ/kg kJ/(kg·K) kJ/m3 Pa·s W/(m·K)
0 611 999.82 0.06 4.217 4216.10 0.001792 0.5606
10 1227 999.77 1.001 4.192 4191.42 0.001308 0.5818
20 2337 998.29 83.95 4.182 4174.70 0.001003 0.6009
30 4242 995.71 125.75 4.178 4160.53 0.000798 0.6176
40 7375 992.25 167.54 4.179 4146.28 0.000801 0.6322
50 12335 988.02 209.33 4.181 4130.87 0.000547 0.6445
60 19919 983.13 251.16 4.185 4114.05 0.000467 0.6546
70 31161 977.63 293.03 4.190 4096.03 0.000404 0.6624
80 47359 971.60 334.96 4.196 4077.20 0.000355 0.6680
90 70108 965.06 376.96 4.205 4058.00 0.000315 0.6714
100 101325 958.05 419.06 4.216 4038.82 0.000282 0.6732

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 Chemical processes classification

Batch process. The feed is charged (fed) into a vessel at the beginning of the process and the
vessel contents are removed sometime later.
E.g.: Rapidly add reactants to a tank and remove the products and unconsumed reactants
sometime later when the system has come to equilibrium.

Continuous process. The inputs and outputs flow continuously throughout the duration of
the process.
E.g.: Pump a mixture of liquids into a distillation column at a constant rate and steadily
withdraw products streams from the top and bottom of the column.

Semibatch process. Any process that is neither batch nor continuous.

E.g.: Allow the contents of a pressurized gas container to escape to the atmosphere.

Steady state. If the values of all the variables in a process (i.e., all temperatures, pressures,
volumes, flow rates) do not change with time, except possibility of minor fluctuation about
constant mean values, the process is said to be operating at steady state.

Transient. If any of the process variables change with time, transient (unsteady-state)
operation is said to exist.

General balance equilibrium

Input + Generation - Output - Consumption = Accumulation

(enters (produced (leaves (consumed (build-up
through within through within within
system system) system system) system)
boundaries) boundaries)

Two types of balances may be written:

Integral balances, which describe what happens between two instants of time. Each term
of the equation is an amount of the balanced quantity.

Differential balances, which indicate what is happening in a system at an instant in time.

Each term of the balance equation is rate (rate of input, rate of generation, etc.) and has
units of the balanced quantity divided by a time.
Example
Each year 5000 people move into Limerick, 7500 move out, 2200 are born, and 1900 die.
How the population of the city change.
Solution
input + generation – output – consumption = accumulation

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 Continuous Steady State Processes

Distillation column Rectification column

Distillation column

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 Continuous Steady State Processes
Example
1000 kg/h of a mixture of benzene and toluene containing 50% benzene by mass is separated
by distillation into two fractions.
The mass flow rate of the top stream is 450 kg/h and that in the bottom stream is 550 kg/h.
The operation is at steady state.
Is it possible to calculate the unknown component concentrations in the output streams?
Solution:

Integral Balance on Bath Processes

Example
Two methanol-water mixtures are contained in separate flasks. The first mixture contains
40wt% methanol, and the second contains 70wt% methanol. If 200g of the first mixture is
combined with 150g of the second, what are the mass and composition of the product?
Solution:

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 Material Balances
Example
The labelled flowchart of a continuous steady-state two-unit process in shown below. Each
steam contains two components, A and B, in different proportions. Three streams whose
flow rates and/or compositions are not known are labelled 1, 2 and 3, calculate the unknown
flow rates and compositions of those streams.

Material Balances
Example
Three input streams are feed into an evaporation chamber to produce an output stream with
the desired composition.
Stream A: pure oxygen, with a molar flow rate one-fifth of the molar flow rate of stream B.
Stream B: Air (21 mole% O2, the balance N2).
Stream C: Liquid water, fed at a rate of 20cm3/min.
The output gas is analyzed and is found to contain 1.5mole% water. Draw and label a
flowchart of the process and calculate all unknown stream variables.
Solution:

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 Continuous Steady State Processes

Evaporation vapour

feed concentrate
(liquid) (liquid)

slurry, reagents,
Scrubbing
absorbents (liquid)

outlet gas

feed (gas/
exhaust steam)

outlet stream
(liquid)

Continuous Steady State Processes

Extraction
solvent
(liquid)

feed
(liquid)

(liquid)
rafinate
(liquid)

extract
(liquid)

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 Continuous Steady State Processes

Filtration (dead-end filtration)

feed, slurry
(liquid+solid) filter cake
(solid>>liquid)

filtrate
(liquid>>solid)

Membrane filtration

feed, slurry permeate

(liquid, gas) (liquid, gas)

retentate
(liquid, gas)

Material Balances
Example. A mixture containing 50wt% acetone and 50wt% water is to be separated into two
streams – one enriched in acetone, the other in water (according to the scheme). In a pilot-
plant study, for every 100kg of acetone –water fed to the first extraction stage, 100kg of methyl
isobutyl ketone (MIBK) is fed to the first stage and 75kg is fed to the second stage. The extract
from the first stage is found to contain 27.5wt% acetone. The second stage rafinate has a mass
of 43.1kg and contains 5.3wt% acetone, 1.6wt% MIBK, and 93.1wt% water, and the second
stage extract contains 9wt% acetone, 88wt% MIBK, and 3wt% water. The overhead product
from the distillation column contains 2wt% MIBK, 1wt% water, and the balance acetone.
Taking a basic of calculation of 100kg acetone-water feed, calculate the masses and
composition of the stage one raffinate and extract, the second stage extract, the combined
extract, and the distillation overhead and bottoms products.

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 Material Balances
Example. A stream containing 5.15 wt% chromium, is contained in the wastewater from a
metal finishing plant. The wastewater stream is fed to a treatment unit that removes 95% of
the chromium in the feed and recycles it to the plant. The residual liquid stream leaving the
treatment unit is sent to a waste lagoon. The treatment unit has a maximum capacity of 4500
kg wastewater/h. If wastewater leaves the finishing plant at a rate higher than the capacity of
the treatment unit, the excess (anything above 4500 kg/h) bypasses the unit and combines
with the residual liquid leaving the unit, and the combined stream goes to the waste lagoon.
(a) Without assuming a basis of calculation, draw and label a flowchart of the process.

Material Balances
Example. The flow chart of a steady-state process to recover crystalline potassium chromate
(K2CrO4) from an aqueous solution of this salt is shown below. 4500 kg/h of a solution that 1/3
K2CrO4 by mass is joined by a recycle stream containing 36.4% K2CrO4, and the combined
stream is fed into an evaporator. The concentrated stream leaving the evaporator contains
49.4% K2CrO4; this stream is fed into a crystallizer in which it is cooled (causing crystals of
K2CrO4 to come out of solution) and than filtered. The filter cake consist of K2CrO4 crystals and
a solution that contains 36.4% K2CrO4 by mass; the crystals account for 95% of a total mass of
the filter cake. The solution that passes through the filter, also 36.4% K2CrO4, is the recycle
stream. Calculate the rate of evaporation, the rate of production of crystaline K2CrO4, the feed
rates that the evaporator and the crystallizer must be designed to handle, and the recycle ratio
(mass of recycle/mass of fresh feed).

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 Integral Balance on Bath Processes
Example
Air is bubbled through a drum of liquid hexane at a rate of 0.15 kmol/min. The gas stream
leaving the drum contains 10mole% hexane vapour. Air may be considered insoluble in liquid
hexane. Use an integral balance to estimate the time required to vaporize 10m3 of the liquid.
Specific gravity of hexane is 659 kg/m3.

Continuous Transient Processes

Example
Water enters a 4 m3 tank at a rate of 6 kg/s and is withdrawn at a rate of 3 kg/s. The tank is
initially half full. How long will the tank take to overflow?
Solution:

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 Material Balances
Example. A stream of humid air enters a condenser in which 95% of the water vapour in the air
is condensed. The flow rate of the condensate (the liquid leaving the condenser) is measured
and found to be 225dm3/h. Dry air may be taken to contain 21mole% oxygen, with the balance
nitrogen. Calculate the flow rate of the gas stream leaving the condenser and the mole fractions
of oxygen, nitrogen and water in this stream. Is there enough data to solve the problem?
Solution:

Material Balances
Example. Calculate the amount of oxygen required to produce 1600kgS03/h in reaction
2 SO2 + O2  2 S03

Solution:

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 Material Balances
Example. Acrylonitrile is produced in reaction of propylene, ammonia, and oxygen:
C3H6 + NH3 + 3/2 O2  C3H3N + 3 H2O
The feed contains 10mole% propylene, 12mole% ammonia, and 78% air. Taking 100mol of feed
as basis, determine which reactant is limiting and the percentage by which each of the other
reactants is in excess.

Energy Balances
final system energy - initial system energy = net energy transferred to
the system (in - out)

U + Ek + Ep = Q-W

Potential energy, Ep: Energy due to the position of the system in a potential field
(such as a gravitational or electromagnetic field).
n m
E p   m i g h i   m j g h j
i1 j1

outlet inlet
components components

Kinetic energy, Ek: Energy due to the translational motion of the system as a whole
relative to some frame of reference (usually the earth's surface) or to rotation of the
system about some axis. 2
n 2
miui m m ju j
Ek   
i 1 2 j 1 2
outlet inlet
components components

u – linear velocity, m/s

g – gravitational acceleration, m/s2
m – flow rate, kg/s
h – height, m

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 Energy Balances
final system energy - initial system energy = net energy transferred to
the system (in - out)

U + Ek + Ep = Q-W

energy of the particles
Internal energy, U: All energy possessed by a system other than kinetic and movements
potential energy, such as energy due to the motion of molecules relative to the
center of mass of the system, to the rotational and vibrational motion and the
electromagnetic interactions of the molecules, and to the motion and
interactions of the atomic and subatomic constituents of the molecules.

H = U + Vp
Enthalpy (H) is the energy due to motion of molecules and their constituent
bond energy
parts plus the energy available to cause fluid flow.
Enthalpy depends on conditions of state (T, P, composition, phase)
n m
H   miHi   m jH j
i1 j1
outlet inlet
components components
V – volume, m3
p – pressure, Pa
m – mass flowrate, kg/s or kmol/s
H – enthalpy, kJ/kg or kJ/kmol

Energy Balances

Latent Heat
When a substance changes from one state to another, latent heat is added or released in the
process.
Latent heat: the energy required to change from one state to another at constant
temperature.

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 Energy Balances
final system energy - initial system energy = net energy transferred to
the system (in - out)

U + Ek + Ep = Q-W

Heat, Q: energy that flows as a result of temperature difference between a system and its surroundings.

The system is usually defined as the chemical reaction and the boundary is the container in which the
reaction is run. In the course of the reaction, heat is either given off or absorbed by the system.
Exothermic reaction
CH4 + 2O2 → CO2 + H2O - 889 kJ/mol methane combustion

Endothermic reaction
C + H2O ↔ CO + H2 + 131 kJ/mol water-gas reaction

Heat is defined as positive when it is

transferred to the system from the
surroundings.

Energy Balances
final system energy - initial system energy = net energy transferred to
the system (in - out)

U + Ek + Ep = Q-W

Work, W: energy that flows in response to any driving force other than a temperature difference, such as a
force, a torque, or a voltage.

E.g., if a gas in a cylinder expands and moves a piston

against a restraining force, the gas does work on the piston
(energy is transferred as work from the gas to its
surroundings, which include the piston).

Work is defined as positive when it is done by the system on the surroundings.

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 Energy Balances
final system energy - initial system energy = net energy transferred to
the system (in - out)

U + Ek + Ep = Q-W

Work, W: energy that flows in response to any driving force other than a temperature difference, such as a
force, a torque, or a voltage.

E.g., if a liquid in a reactor moves, the motor does work on

the fluid (energy is transferred as work from the motor to
the system).

Work is defined as positive when it is done by the system on the surroundings.

Energy Balances
Example. Two streams of water are mixed to form the feed to a boiler. Process data are as
follows: feed stream 1 - 120 kg/min at 30°C,
feed stream 2 - 175 kg/min at 65°C,
boiler pressure - 17 bar (absolute).
Calculate the required heat input to the boiler in kilojoules per minute (kJ/min) if the emerging
steam is saturated at the boiler pressure.
The exiting steam emerges from the boiler through a 6 cm ID pipe. Neglect the kinetic energies
of the liquid inlet streams.
Solution:
H + Ek + Ep = Q - W

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Table taken from Thermodynamic and transport properties of fluids – ‘Steam Tables’

Energy Balances

Q = m·cp·T
Q – heat, J
m – mass, kg
cp – specific heat, J/kg·K
T – temperature, K
Specific Heat, cp : the heat capacity of a substance per unit mass

Heat Capacity, H : ratio of the amount of energy absorbed to the associated temperature rise

substance specific heat,

kJ/(kg·K)
ice (0ºC) 1.960
water (0ºC) 4.217
water (10ºC) 4.192
water (20ºC) 4.182
water (34ºC) 4.179
water (100ºC) 4.216
water vapour (100ºC) 2.080
dry air 1.005
sandy clay 1.381
quartz sand 0.795

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 Energy Balances

Exercise: Which has the highest heat capacity:

a) 2 grams of pure water
b) 4 grams of ice at 0 °C
c) 10 grams of quartz sand

Exercise: Which will become warmer:

a) adding 500 Joules to 1 gram of water (0ºC)
b) adding 500 Joules to 1 gram of quartz sand
substance specific heat,
kJ/(kg·K)
ice (0ºC) 1.960
water (0ºC) 4.217
water (10ºC) 4.192
water (20ºC) 4.182
water (34ºC) 4.179
water (100ºC) 4.216
water vapour (100ºC) 2.080
dry air 1.005
hydrogen 14.30
quartz sand 0.795

Energy Balances
Table. Mean molar specific heat J/(mol·K) of gases between 298 and T (K) at 101.325 kPa

Exercise: The gas N2 at 1 atm pressure absolute is being heated in a heat exchanger. Calculate
the amount of heat needed to heat 3 gmol N2 in the following temperature ranges:
(a) 298 – 673 K (25 – 400°C); (b) 298 – 1123 K (25 – 870°C); (c) 673 – 1123 K (400 – 870°C)

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 Energy flow diagrams

Energy conversion efficiency (η) is the ratio between the useful output of an energy
conversion machine and the input, in energy terms.

E.g. battery operated drill machine

Battery Drill bit

100 J 28 J
chemical output
energy work
72 J
friction
and heat
h = 45%
28 J
Chemical energy is converted to 45 J mechanical
electrical
electrical energy energy
energy
(low speed)
29 J
mechanical
h = 65% energy h = 95%
(high speed)
The motors converts The rotational of the
electrical energy to motor is transferred to
mechanical energy the drill bit by gears

Overall efficiency of battery operated drill machine is 28%

Energy flow & Sankey’s diagrams

E.g. battery operated drill machine Battery Drill bit

100 J 28 J
chemical output
energy work
72 J
friction
and heat
h = 45%
28 J
45 J mechanical
electrical energy
energy
(low speed)
29 J
mechanical
h = 65% energy h = 95%
(high speed)

28 J
drill
Battery
100 J
1J

16 J
45 J

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 Energy Balances
Example. A liquid stream containing 60.0 wt% ethane and 40.0 wt% n-butane is to be heated
from 200 K to 300 K at a pressure of 10 bar. Calculate the required heat input per kilogram of
the mixture, neglecting potential and kinetic energy changes, using tabulated enthalpy data for
C2H6 and C4H1O and assuming that mixture component enthalpies are those of the pure species
at the same temperature.
Data in Perry’s Chemical Engineers’ Handbook
Solution:

Energy Balances
Example. At what rate in kilowatts (kW) must heat be transferred to a liquid stream of
methanol at its normal boiling point to generate 1500 g/min of saturated methanol vapour?

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 Energy Balances
if Ek , Ep , W = 0 or can be neglected, than from the first low of thermodynamic:

Q = H for open system

Q = U for closed system

For ideal gases:
T2 T2
for p=const H   c p (T )dT for V=const U   c v (T )dT
T1 T1

cp – specific heat (heat capacity) at p=const, J/kg·K

cp  c v  R R – gas constant
R = 8.314 J/(mol·K)
For solid or liquid: R = 0.08314 dm3bar/(mol·K)
T2

H  Vp   c p ( T )dT
T1

Example. Calculate the heat required (in J) to raise 200 kg of nitrous oxide from 20°C to 150°C
in a constant-volume vessel. The constant-volume heat capacity of N2O in this temperature
range is given by the equation
c v kJ /(kg·K )  0.855  9.42·10 4 T
where T is in °C.

Energy Balances
Example. Fifteen kmol/min of air is cooled from 430°C to 100°C. Calculate the required heat
removal rate using (1) heat capacity formulas from Table B.2 and (2) specific enthalpies from
Table B.8.

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 Energy Balances

Energy Balances
Example. Saturated steam at a gauge pressure of 2.0 bar is to be used to heat a stream of
ethane. The ethane enters a heat exchanger at 16°C and 1.5 bar gauge at a rate of 795 m3/min
and is heated at constant pressure to 93°C. The steam condenses and leaves the exchanger as a
liquid at 27°C. The specific enthalpy of ethane at the given pressure is 941 kJ/kg at 16°C and
1073 kJ/kg at 93°C.
(a) How much energy (kW) must be transferred to the ethane to heat it from 16°C to 93°C?
(b) Assuming that all the energy transferred from the steam goes to heat the ethane, at what
rate in m3/s must steam be supplied to the exchanger?
(c) Should the heat exchanger be set up for cocurrent or countercurrent flow. Explain. (Hint:
Remember that heat always flows from a higher temperature to a lower temperature.)

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