Exploring Engineering

Chapter 6
Chemical Engineering
What You Will Learn
Chemical formulae
Atomic and molecular masses
The mole and Avogadros number
Stoichiometry
Tabular method of determining
stoichiometric cfts.
Basic combustion reactions and a
tabular method for energy released
Distillation

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The Mole Concept
Atoms are the building blocks of matter.
A molecule is the smallest possible piece of a
chemical compound.
Molecules are made of atoms.
In chemical changes, the identity and number of
atoms remains constant
E.g., S + O2 SO2
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The Mole
The gram mole (units mol) is the amount of
substance containing as many "elementary entities" as
there are atoms in exactly 0.012 kg of pure carbon-12.
(The kg mole is a factor 10
3
larger)
1 mol = 6.0221367 10
23
elementary entities. This is
known as Avogadros number
1 kmol = 6.0221367 10
26
elementary entities.
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Avogadros Number
Avogadros number is to moles as a dozen eggs is
to 12 eggs - a shorthand notation.
Just as a dozen eggs may include 5 turkey and 6
chicken eggs and 1 dinosaur egg, the
elementary entities can include mixtures of
molecules, atoms, electrons, ions, neutrons, etc.
Relative masses of elements on C-12 scale:
H = 1.00, He = 4.00, C =12.0, O = 16.0, N = 14.0,
S = 32.1, Cl = 35.5, Ar = 40.0 etc. (to three
significant figures).

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The Periodic Table
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Example
How many kg are there in 1.00 kg mole of CO
2
?
How many kg moles, gram moles and pound moles
(lbm moles) are there in 11.0 lbm of CO
2
?

Need: m (mass) and n (moles) in specified CO
2
Know: Atomic masses of C = 12.0, O = 16.0; 11.0 lbm =
5.00 kg. (again, courtesy of Convert)
How: n = m/M where M = molecular mass of CO
2
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Example: Concluded
Solve: M for CO
2
= 12.0 + 2 x16.0 = 44.0 kg/kg mole or 44.0
kg/kmol or lbm/lbm mole etc.
Thus 1.00 kg CO
2
= 1.00/44.0 [kg][kmol/kg]
= 2.27 10
-2
kmol (or kgmole)
5.00 kg into kg moles, n = 5.00/44.0 [kg][kmo/kg]
= 0.114 kmol = 114 mol
11.0 lbm into lbm moles is
n = 11.0/44.0 [lbm][lbm mole/lbm] = 0.250 lbm moles.

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Stoichiometry
How much of A reacts with B according to a
stipulated chemical reaction?
Need valE.g., C
2
H
5
OH + aO
2
bCO
2
+ cH
2
O
C
2
H
5
OH is called ethanol or ethyl alcohol and
popularly just plain alcohol.
We are completely combusting it to carbon dioxide and to
water (vapor) in this example.
Use a,b & c that satisfy left and right hand sides of
this equation preserving the number of C, H and O
atoms
This leads to three equations and three unknowns.
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The Tabular method
This tabular method is used in this course:
Atoms LHS RHS Solution
C 2 b b = 2
H 6 2c c = 3
O 1 + 2a 2b + c a = 2 + 3/2 -
1/2 = 3
Therefore, C
2
H
5
OH + 3O
2
2CO
2
+ 3H
2
O
Visually check that this is correct!
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Stoichiometry
To combust a fuel properly you must use the
correct amount of accompanying air.
Too much air or too little and the fuel will not burn.
The air-to-fuel ratio is the key variable. For
stoichiometric combustion account for the inert 3.76
mols of N
2
as well as the 1.00 mols of O
2
in air. Hence,
using the tabular method, for CH
4
(methane or natural
gas) combustion:

CH
4
+2(O
2
+ 3.76 N
2
) = CO
2
+ 2H
2
O+ 7.52N
2

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Stoichiometry
Mols of air/mol of fuel = 2(O
2
+ 3.76 N
2
)/1
Mass of air/mass of fuel
= 2(1 32.0 +3.76 28.0)/16.0
= 17.2 lbm air/lbm fuel
or equally 17.2 kg air per kg of methane.
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Combustion Energetics
How much heat is produced when a chemical is
combusted?
C
2
H
5
OH + 3O
2
2CO
2
+ 3H
2
O + Heat
Every compound takes energy or gives energy to
make a new one.
Each compound has an heat of formation.
Tables are widely available in reference books and
on the net (check the reliability of such sources!)

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Combustion Energetics
Heats of Formation of Various Fuels
Substance kJ/kg
Carbon, C (s) 0
Nitrogen, N
2
(g) 0
Oxygen, O
2
(g) 0
Hydrogen, H
2
(g) 0
Carbon Monoxide, CO (g) 3,946
Carbon Dioxide, CO
2
(g) 8,942
Water, H
2
O (g) 13,423
Methane, CH
4
(g) 4667
Acetylene, C
2
H
2
(g) +8,720
Hexane, C
6
H
14
(g) 1,945
Ethanol, C
2
H
5
OH (l) 5,771
Benzene, C
6
H
6
(l) +629
Combustion Heating Value
Use another tabular model: Keeps the signs straight!
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Heating Value = Energy in Fuel and Oxidizer Energy in the Products of Combustion
Heating Value = 5,771+ 0.000 (17,10615,759) = + 27,100 kJ/kg
Heating Value Method
Item LHS LHS RHS RHS
Molar quantities C
2
H
5
OH(l) O
2
(g) CO
2
(g) H
2
O(g)
Mass, kg 46.0 3 32.0 2 44.0 3 18.0
Mass m, kg/kg of fuel 1.00 2.087 1.913 1.174
H
f
, kJ/kg 5,771 0.000 8,942 13,423
m H
f
kJ/kg of fuel 5,771 0.000 17,106 15,759
HOW DO YOU MAKE CHEMICAL
FUELS?
Raw petroleum is
a toxic, corrosive,
foul smelling
viscous liquid.
For use it is
refined, the first
step of which is
to distill out the
valuable light
liquids fuels.
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Figure 5: Schematic of a typical distillation column
Vapor
Liquid
Overheads
Reflux Condenser
Reboiler
Bottoms
Distillation
tray
Condensed
volatiles
Crude
Pre-heater
Vapor
Liquid
Overheads
Reflux Condenser
Reboiler
Bottoms
Distillation
tray
Condensed
volatiles
Crude
Pre-heater
Figure 5: Schematic of a typical distillation column
Vapor
Liquid
Overheads
Reflux Condenser
Reboiler
Bottoms
Distillation
tray
Condensed
volatiles
Crude
Pre-heater
Vapor
Liquid
Overheads
Reflux Condenser
Reboiler
Bottoms
Distillation
tray
Condensed
volatiles
Crude
Pre-heater
HOW DO YOU MAKE CHEMICAL
FUELS?
A crude oil contains three components by mass: 10.%
asphaltenes (C
38
H
16
), 5.0% light gases, 40. % isooctane (C
8
H
18
),
and 45.% cetane (C
16
H
34
). An input stream of 1.00 10
4
kg/hr of
this crude oil is fed to a distillation column in an oil refinery.
Assume the distillation process separates out a top and a
bottom stream. If the bottom stream consists of 100%
asphaltenes, what are the flow rates and composition of all of
the process lines?
This is a physical process and no new molecules are made and
none are lost
Therefore the methods are based on simple mass balances.
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HOW DO YOU MAKE CHEMICAL
FUELS?
Need: Composition and rate of flow of each component in each
line.
Know: Principle of conservation of mass across control volume.
Also that the distillation process is a physical one and therefore
the type and quantities of molecules are preserved.
How: Use a process diagram showing inputs and outputs of each
stream and calculate the required unknowns.
Solve: Since we know the mass flow rate of the input stream is
1.00 10
4
kg/hr of crude oil, we can easily calculate the amount
of each component in the feed.

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HOW DO YOU MAKE CHEMICAL
FUELS?
Overheads are 1.0 10
4
1.0 10
3
= 9.0 10
3
kg/hr
Inlet mass flow rate of light gases
= (5.0/100) 1.00 10
4
= 5.0 10
2
kg/hr
Inlet mass flow rate of isooctane
= (40./100) 1.00 10
4
= 4.0 10
3
kg/hr
Inlet mass flow rate of cetane
= (45./100) 1.00 10
4
= 4.5 10
3
lb/hr
Inlet mass flow rate of asphaltenes
= (10./100) 1.00 10
4
= 1.0 10
3
kg/hr
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HOW DO YOU MAKE CHEMICAL FUELS?


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Flow Stream
Light
Gases
Isooctane Cetane Asphaltenes
Percent by Mass
Inlet 5.0 % 40. % 45. % 10. %
Overheads 5.6 % 44. % 50. % 0 %
Bottoms 0 % 0 % 0 % 100 %
Flow Rate, kg/hr
Inlet 500 4,000 4,500 1,000
Overheads 500 4,000 4,500 0
Bottoms 0 0 0 1,000
Summary
Elementary entities means atoms, molecules, even
sub-nuclear particles
Every mole has the same enormous number of such
particles (Avogadros number)
Includes mixtures of molecules such as air
Stoichiometry based on conservation of atoms in a
reacting mixture
Tabular method given to allow solution of stoichiometric
coefficients.
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Summary
To calculate heat from a fuel use stoichiometry
tables first, then the heat of formation also in a
tabular form.
Both table forms are convenient, easy, and useful
and are required in this course.
To make a fuel from petroleum the first step is
distillation, a process that preserves the
molecular identity of the constituents.
Analysis is based on conservation of the molecules
in the oil.

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