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 103 larger)
1 mol = 6.0221367 1023 elementary entities. This is
known as Avogadros number
1 kmol = 6.0221367 1026 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 CO2?
How many kg moles, gram moles and pound moles
(lbm moles) are there in 11.0 lbm of CO2?

Need: m (mass) and n (moles) in specified CO2

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 CO2

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 Example: Concluded
Solve: M for CO2 = 12.0 + 2 x16.0 = 44.0 kg/kg mole or 44.0
kg/kmol or lbm/lbm mole etc.
Thus 1.00 kg CO2 = 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., C2H5OH + aO2 bCO2 + cH2O
C2H5OH 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, C2H5OH + 3O2 2CO2 + 3H2O
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 N2 as well as the 1.00 mols of O2 in air. Hence,
using the tabular method, for CH4 (methane or natural
gas) combustion:

CH4 +2(O2 + 3.76 N2) = CO2+ 2H2O+ 7.52N2

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 Stoichiometry
Mols of air/mol of fuel = 2(O2 + 3.76 N2)/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?
C2H5OH + 3O2 2CO2 + 3H2O + 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, N2 (g) 0
Oxygen, O2 (g) 0
Hydrogen, H2 (g) 0
Carbon Monoxide, CO (g) 3,946
Carbon Dioxide, CO2 (g) 8,942
Water, H2O (g) 13,423
Methane, CH4 (g) 4667
Acetylene, C2H2 (g) +8,720
Hexane, C6H14 (g) 1,945
Ethanol, C2H5OH (l) 5,771
Benzene, C6H6(l) +629
 Combustion Heating Value
Use another tabular model: Keeps the signs straight!
Heating Value Method
Item LHS LHS RHS RHS
Molar quantities C2H5OH(l) O2(g) CO2(g) H2O(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
Hf, kJ/kg 5,771 0.000 8,942 13,423
m Hf kJ/kg of fuel 5,771 0.000 17,106 15,759

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

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 HOW DO YOU MAKE CHEMICAL
FUELS?
Condensed
Raw petroleum is Overheads
Reflux Condenser
volatiles
a toxic, corrosive,
foul smelling Liquid

viscous liquid. Crude Vapor

For use it is
refined, the first Pre-heater

step of which is
to distill out the Distillation
tray
valuable light Reboiler
liquids fuels.
Bottoms

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 HOW DO YOU MAKE CHEMICAL
FUELS?
A crude oil contains three components by mass: 10.%
asphaltenes (C38H16), 5.0% light gases, 40. % isooctane (C8H18),
and 45.% cetane (C16H34). An input stream of 1.00 104 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
1.00 104 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 1.0 104 1.0 103 = 9.0 103 kg/hr
Inlet mass flow rate of light gases
= (5.0/100) 1.00 104 = 5.0 102 kg/hr
Inlet mass flow rate of isooctane
= (40./100) 1.00 104 = 4.0 103 kg/hr
Inlet mass flow rate of cetane
= (45./100) 1.00 104 = 4.5 103 lb/hr
Inlet mass flow rate of asphaltenes
= (10./100) 1.00 104 = 1.0 103 kg/hr

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 HOW DO YOU MAKE CHEMICAL FUELS?
Light
Flow Stream Isooctane Cetane Asphaltenes
Gases
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

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 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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