Topic 10: Reactive Systems

Three methods of analysis:

 Element (or atom)

 Component
 Total - this is usually for a final check: Mass IN=Mass OUT

You will practise these in tutorials 14 to 17

“Why use Element balances, when you can get
the same result by using component balances?”

 When you have more than one reaction, element

balances are easier to use than component
balances
 Very useful in combustion reactions (where the C
goes to CO2 or CO and the H goes to H2O)
 You might be asked to use element balances in an
test/exam question!
Why do we care about combustion reactions?
 Combustion Reactions
Combustion
 Fuel + O2(Air)  Products of Combustion + Energy

 Important reactions - release large

quantities of heat energy
 Heat then used to produce steam
2
 Steam drives turbines to generate
most of world’s electrical power
1
Combustion Reactions – role of chemical engineers
 Analyse combustion reactions & reactors
 Abatement and control of environmental pollution
caused by combustion products (SO2, NOx, … )

(1) Image Copyright Alan Murray-Rust. This work is licensed under the Creative Commons Attribution-Share Alike 2.0 Generic Licence.
(2) "Dampfturbine Laeufer01" by "Siemens Pressebild" http://www.siemens.com - Photo taken from [1] with the friendly permission of Siemens Germany by Christian Kuhna, E-Mail:
christian.kuhna/klammeraff/siemens/dot/com. Licensed under CC BY-SA 3.0 via Wikimedia Commons -
http://commons.wikimedia.org/wiki/File:Dampfturbine_Laeufer01.jpg#mediaviewer/File:Dampfturbine_Laeufer01.jpg
Combustion Terminology
Combustion Chemistry

Fuel:- Coal, gasoline, natural gas (CH 4), liquefied

petroleum gas (propane, butane)

Products of combustion:-
 Carbon reacts to form CO2 and CO
(CO formed - Incomplete Combustion)
 Hydrogen reacts to form H2O
 Sulphur reacts to form SO2

Let’s look at some examples (Class Activities - page 14 in

Semester 2 notes )
Air
 Common source of O2 in combustion reactions

Molar Composition of Dry Air:

N2 78.03%
O2 20.99%
Ar 0.94%
CO2 0.03%
H2, He, Ne, Kr, Xe 0.01%

 Acceptable to state 79% N2 & 21% O2 by moles

 NB for an ideal gas: mole fraction = volume fraction

 Combustion Terminology
Fuel + O2(Air)  Products of Combustion + Energy

Stack Gas or Flue Gas 1

Gas that leaves combustion chamber:
 Products of combustion: H2O, CO2 , CO
 Unreacted O2, unreacted fuel
 Tie element: N2 (goes through without any changes)

Composition on wet basis

 Used to denote component mole fractions of a gas including
water
Composition on a dry basis
 Used to denote component mole fractions of a gas ignoring
the presence of water

(1) Ref: http://commons.wikimedia.org/wiki/File:Air_.pollution_1.jpg

 Combustion Terminology

Orsat analysis: composition of flue gas on a dry basis

It measures the content of CO, CO 2, O2, and of N2 by difference

in a flue gas (after removal of water):

Class Activities page 15

Fig 22. http://www.gutenberg.org/files/22657/22657-h/chapters/fluegas.html#chapter_fluegas

 Class Activity Solution (1)

Wet
Dry
Basis:
basis
100 mols

N2 60% 70.6%

Check: 0.706+0.176+0.118=1

CO2 15% 17.6%

O2 10% 11.8%

H2O 15%
 Class Activity page 15 (2)
2. An Orsat analysis yields the following dry basis molar composition:
N2 65%, CO2 14%, CO 11%, O2 10%.
A humidity measurement shows that the mole fraction of H2O in the stack gas
is 0.07. Calculate the stack gas composition on a wet basis.
Dry Wet Basis:
On a wet basis, 7 % is water, 93 % is all the rest. basis 100 mols
Therefore in 100 mols of wet sample, 93 moles
will be “dry”. Of these 93, 65% are N2 , 14% are
CO2 , 11% are CO, 10 % are O2:

Mols in 100 mols of wet sample: 65%

N2 60.45%

N2: 0.65 x 93 = 60.45=60.45%

CO2: 0.14 x 93 = 13.02 = 13.02 %

CO2 14% 13.02%
CO: 0.11 x 93 = 10.23 = 10.23 %
CO 11% 10.23%
O2 : 0.10 x 93 = 9.3 = 9.30 %
O2 10% 0.93%
And 7 % is H2O 7% H 2O
Theoretical and Excess Air
Combustion:
Fuel + Air  Products of Combustion + Energy

Fuel is much more expensive than air:

 Practical to feed less expensive reagent (air) in excess
 Increase the yield w.r.t. expensive reactant
 Not enough O2 will cause formation of CO instead of CO 2
 Therefore run with more air than is needed to
supply O2 in stoichiometric proportion to fuel
Theoretical and Excess Air
Theoretical Oxygen
 Moles of O2 needed for COMPLETE combustion of ALL
the fuel assuming C  CO2 and H2  H2O

Theoretical Air
 Amount of air containing theoretical oxygen

Excess Air
 Amount by which air fed to reactor exceeds theoretical
air
Theoretical and Excess Air

air feed – air theoretical

% excess air = x 100
air theoretical

O2 feed – O2 theoretical
% excess O2 = x 100
O2 theoretical

Let’s look at an example (Class Activity Page 16)

 Class Activity Solution
100 mol/h of butane and 5000 mol/h of air are fed into a combustion reactor.
Calculate the % excess air. [HINT – Calculate theoretical air from butane feed
rate and the balanced equation for complete combustion of butane]
C4H10 + 6.5 O2 → 4 CO2 + 5 H2O
(O2)theoretical = mols (C4H10) x 6.5 = 100 x 6.5 = 650 mol/h
= mols O2 required for complete combustion

(Air)theoretical = (O2)theoretical x 100 mols air =650 x100/21=3095 mol/h

21 mols O2

(moles air)feed- (moles air)theoretical 5000- 3095

% excess air = x100 = x 100 =61.6 %
(moles air)theoretical 3095

 % excess air = 61.6 %

 The air feed is 161.6 % the theoretical air

 For you to do at home: Calculate excess O2. You will find out that:

 % excess O2 = % excess air (this is always true)

Theoretical/Excess Air – points of confusion
1. Theoretical O2 required to burn fuel does not depend
on how much is actually burning
 Fuel may not react completely
 May partially burn to CO & CO2
 But theoretical O2 still the same (i.e. that required to
react with ALL of fuel to form CO2 only)

2. Value of %XS depends only on theoretical amount &

air feed rate
 Not on how much O2 is consumed in the reactor
 Or whether combustion is complete (all CO 2) or
partial (some CO)
Main points
 Products of combustion, N2 is inert

 Going from composition on dry basis (Orsat analysis)

to wet basis

 Calculating theoretical air

 Understanding and using excess air

 Mini quiz

 Match the fuel to the usual amount of excess air used

gas 5-10 % Fuel Oil

liquid 10-20 % Coal

solid 30-60 % Natural Gas