CHEMICAL REACTIONS

Fuels
Most fuels fall into one of three categories. They are, coal, liquid hydrocarbons
and gaseous hydrocarbons
Coal consists of the remains of vegetation deposits of the past geologic ages, after
subjection of biochemical actions, high pressure, temperature and submersion.
Coal sample analysis is performed by using two bases:
Proximate analysis “‫ ”التحليل المباشر‬gives the moister content, volatile matter, fixed
carbon and ash on mass base.
Ultimate analysis “‫ ”التحليل الكامل‬gives carbon, sulfur, hydrogen, nitrogen and oxygen on
mass base.
Most liquid and gaseous hydrocarbon fuels are a mixture of many different
hydrocarbons. For example, gasoline consists of a mixture of a bout 40 hydrocarbons
with iso-ocatian which is the main component.
:‫تسمية اﻻتحاد الدولي للكيمياء البحتة والتطبيقية )أيوباك( نظام معتمد من اﻷرقام كالتالي‬
1=Metha, 2=Etha, 3=Propa, 4=Buta, 5= penta, 6-=Hexa, 7=Hepta, 8=Octa,
9=Nona, 10=Deca
Hydrocarbon fuels are arranged in families:
Parafine family ends in “-ane” as (propane and ocatane). Cn H 2 n  2 chain
Olefin family ends in “-ene” or “-ylene” as propene and octene”. Cn H 2 n chain
Diolefine family ends in “-diene” as butadiene, Cn H 2 n  2 chain
Naphthene family starts by “cyclo-” as cyclopentane. Cn H 2 n ring 190
Some oh hydrocarbon families are saturated and others are not.
Definition of Saturated hydrocarbon:
Saturated hydrocarbons are compounds that contain carbon that are completely filled.
This means that they contain only single bonds. Chemically, they are strongly bonded
hence react slowly with other substances

Definition of Unsaturated hydrocarbon:

A hydrocarbon molecule containing one or more double or triple bonds, and can thus
absorb more hydrogen atoms

Examples:

Butane Butene Cyclobutane

191
General Formula of Some
hydrocarbon families

Examples of some hydrocarbon

fuels and their chemical
composition

192
The following table illustrates some famous gaseous fuels
The illustrated fuels are fossil fuels

Producer gas: Air is passed over the red-hot coal where carbon monoxide is produced. The
reaction is exothermic and proceeds as follows:
2C + O2 + 3.73 N2 → 2CO+ 3.73 N2
Water gas is made by passing steam over a red-hot carbon fuel such as coke:
H2O + C → H2 + CO ( this reaction needs energy of ΔH = +131 kJ/mol)
Coke-oven gas is manufactured by heating bituminous coal to temperatures of 900°C to
1000°C in a chamber from which air is excluded. 193
 Combustion Process:
The combustion process is a chemical reaction whereby fuel is oxidized, and energy
is released.

The oxidizer most often used in combustion processes is air. Why?

On a mole or a volume basis, dry air is composed of 20.9% O2, 78.1% N2, 0.9% Ar,
and small amounts of CO2, He, Ne, H2.
In the analysis of combustion processes, dry air is approximated as 21% O2 and
79% N2 by mole numbers.

The fuel must be brought above its ignition temperature to start the combustion.
The minimum ignition temperatures in atmospheric air are approximately 260°C
for gasoline, 400°C for carbon, 580°C for hydrogen, 610°C for carbon monoxide,
and 630°C for methane.
Fuel and air must be in the proper range for combustion to begin. For example,
natural gas does not burn in air in concentrations less than 5% or greater than
about 15%. This is called the flammability limit. 194
The mass (and number of atoms) of each element
is conserved during a chemical reaction.

The total number of moles is not conserved

during a chemical reaction.

Theoretical and Actual Combustion Processes

Complete combustion: If all the carbon in the fuel burns to CO2, all the
hydrogen burns to H2O, and all the sulfur (if any) burns to SO2.
Incomplete combustion: If the combustion products contain any unburned
fuel or components such as C, H2, CO, or OH.
Reasons for incomplete combustion: 1 Insufficient oxygen, 2 insufficient
mixing in the combustion chamber during the limited time that the fuel and the
oxygen are in contact, and 3 dissociation (at high temperatures).
Oxygen has a much greater tendency to combine with hydrogen than it does with
carbon. Therefore, the hydrogen in the fuel normally burns to completion, forming
H2O. 195
 Stoichiometric or theoretical air: The minimum amount of air needed for the
complete combustion of a fuel. Also referred to as the chemically correct amount
of air, or 100% theoretical air.
Stoichiometric or theoretical combustion: The ideal combustion process
during which a fuel is burned completely with theoretical air.

Air-fuel ratio: The number of moles of air used divided by the number of moles of fuel
fuel (kmolair/kmolfuel) . Or: The mass of air used divided by the mass of fuel (kgair/kgfuel).
Theoretical air-fuel ratio: The air-fuel ratio for the theoretical combustion.
Excess air factor: air-fuel ratio of the actual combustion divided by the air-fuel ratio of
the theoretical combustion AF)act/AF)th .
Excess air: The amount of air above the theoretical air.
Equivalence ratio: The ratio of the actual fuel–air ratio to the theoretical fuel–air ratio
FA)act/FA)th
50% excess air = 150% theoretical air
200% excess air = 300% theoretical air.
90% theoretical air = 10% deficiency of air 196
gas analyzer.
Predicting the composition of
the products is relatively
easy when the combustion
process is assumed to be
complete.
With actual combustion
processes, it is impossible to
predict the composition of
the products on the basis of
the mass balance alone.
Then the only alternative we
Determining the mole fraction of the CO2 in
have is to measure the
combustion gases by using the Orsat gas
amount of each component
analyzer.
in the products directly.
A commonly used device to
analyze the composition of
combustion gases is the gas
analyzer.
The results are reported on
a dry basis.
197
 Calculating the Theoretical Air-Fuel Ratio

Calculate the theoretical air-fuel ratio for the fuel CmHn.

Cm H n   O2  3.76 N 2   CO2   H 2O   N 2

Carbon Balance: m

Hydrogen Balance: n  2   n / 2

Oxygen Balance:     / 2  mn/4

Then : Cm H n  m  n / 4 O2  3.76m  n / 4 N 2  m CO2  n / 2 H 2O  3.76m  n / 4 N 2

A

ma 

m  n / 4  3.76m  n / 4M a

F th m f  1* M f
th

A 4.76m  n / 4* 28.96

 
F th m *12  n *1
198
Example:

Solution:
Then : C8 H18  2 * 8  18 / 4  O2  3.768  18 / 4  N 2 
 a CO2  b H 2O   dO2  e N 2
Carbon Balance: a 8
Hydrogen Balance: b  18 / 2  9
Oxygen Balance: d  2 * 8  18 / 4   a  b / 2  12.5
Nitrogen Balance: e  2 * 3.76 * 8  18 / 4   94

The total number of moles of products = 8+9+12.5+94=123.5

nco2 8 nH 2 O 9
yco2    0.06477  6.477% y H 2o    0.07287  7.287%
nT 123.5 nT 123.5
no212.5 nN 2 94
y o2    0.1012  10.12% yN2    0.7611  76.11%
nT 123.5 nT 123.5

Pv nH 2O Pv  7.287 kPa
From steam table at Pv , the dew point
  0.07287 temperature is 39.7 C 199
PT nT
 Example:

Solution: Table 14.2

From the table, the fuel composition is:

0.03CH 4  0.14 H 2  0.509 N 2  0.06O2  0.27CO  0.045CO2

200
Fuel  0.03CH 4  0.14 H 2  0.509 N 2  0.06O2  0.27CO  0.045CO2
Burning each component of the fuel
0.03CH 4  0.031  4 / 4O2  0.03CO2  0.06 H 2O
0.14 H 2  0.07O2  0.14 H 2O
0.27CO  0.27 / 2O2  0.27CO2
The required oxygen for combustion:=0.06+0.07+0.135=0.265 Kmol
The present oxygen in fuel=0.006 Kmol
The net required oxygen=0.265-0.006=0.259 Kmol
Air is used as a source of oxygen, then the corresponding amount of nitrogen is:
3.76*0.259=0.97384
Then the final theoretical equation is:
  fuel
 
0.03CH 4  0.14H 2  0.509 N 2  0.06O2  0.27CO  0.045CO2
theoretica

 
l air

 0.259O2  0.97384N 2 
 0.03  0.27  0.045CO2  0.06  0.14H 2O  0.509  0.97384N 2
 0.345CO2  0.2 H 2O  1.483N 2 201
As the excess air is 20%, the excess air factor is 1.2 and the final actual equation is:
  fuel
 
0.03CH 4  0.14 H 2  0.509 N 2  0.06O2  0.27CO  0.045CO2
 
actual air

 1.20.259O2  0.97384 N 2 
 0.345CO2  0.2 H 2O  1.483N 2  0.20.259O2  0.97384 N 2 
 0.345CO2  0.2 H 2O  0.0518O2  1.677 N 2
A 1.20.259  0.97384 kmol air
  1.4794
F 1 kmol fuel

A 1.20.259  0.97384* 28.96 kg air

  1.73
F 0.03 *16  0.14 * 2  0.509 * 28  0.06 * 32  0.27 * 28  0.04 * 44 kg fuel

202
Example:

Solution:

Assume 100 kmole of dry exhaust gases produced from combustion:

Then the combustion equation can be written as:

Make balancing equations for the elements:

203
 Compare between the two values of b

Then the combustion equation can be written as:

Dividing the equation by 10.53

The air-fuel ratio on mole bases is:

nair 2.2  8.27

AF   10.47 kmol air / kmol fuel
n fuel 1

The air-fuel ratio on mass bases is:

204
Theoretical air-fuel ratio can be calculated from theoretical combustion equation:

Then:

205
Example:
A fuel CxHy is burned with dry air, and the products of combustion is measured on dry
mole basis to be: 9.6% CO2, 7.3% O2and 83.1% N2. Find the fuel composition (x/y) and
the percent theoretical air used.
Solution:
Assume 1 kmole of dry exhaust gases produced from combustion:
Then the combustion equation can be written as:

C x H y  a O2  3.76a N 2  0.096 CO2  b H 2O  0.073 O2  0.831 N 2

Carbon Balance: x  0.096

Hydrogen Balance: y  2b

Nitrogen Balance: 3.76 a  0.831 a  0.221

Oxygen Balance: a  0.096  b / 2  0.073 b  0.104 Then y  0.208

Then : C0.096 H 0.208  0.221 O2  0.221* 3.76 N 2  0.096 CO2  0.104 H 2O  0.073O2  0.831 N 2

y / x  0.2166667 Then the fuel can be written as: CH 2.1667  C3 H 6.5  C12 H 26

This is a paraffin family fuel called Dodecane 206

 C0.096 H 0.208  0.221 O2  0.221* 3.76 N 2  0.096 CO2  0.104 H 2O  0.073O2  0.831 N 2

The air-fuel ratio on mass bases is:

A ma  0.221* 4.76 * 28.96

    22.4
F  act m f 
act
0.096 *12  0.208 *1

The Theoretical air-fuel ratio on mass bases is:

A ma  m  n / 4  3.76m  n / 4M a

  
F th m f  1* M f
th

A ma  0.096  0.208 / 4* 4.76 * 28.96  15

  
F th m f 
th
0.096 *12  0.208 *1
The excess air factor:

A A 22.4
     1.493
F  act F th 15

207
 Example:

Solution:

Assume 1 kmole of exhaust gas

flowing into the reactor,
Then the equation can be written as
follows:

 
Exhaust gas

0.1CO2  0.02CO  0.13 H 2O  0.03O2  0.72 N 2  aO2  3.76aN 2
 bCO2  0.13H 2O  eO2  dN 2
208
  
Exhaust gas

0.1CO2  0.02CO  0.13 H 2O  0.03O2  0.72 N 2  aO2  3.76aN 2
 bCO2  0.13H 2O  eO2  dN 2

Carbon Balance: b  0.1  0.02  0.12

Oxygen Balance: 0.1  0.02 / 2  0.13 / 2  0.03  a  b  0.13 / 2  e

Nitrogen Balance: 0.72  3.76 a  d

Oxygen Percentage: e  0.1* (b  0.13  e  d )

Solving these equations, results in: a  0.151 d  1.287 e  0.171

The required number of moles of air:

a  3.76a  0.718 kmol air / kmol exhaust gas
Air to exhaust gas ratio:
Air 0.718
  0.718 kmol air / kmol exhaust gas
Exhaust gas 1
209
Example:
Propane gas C3H8 is reacted with air such that the dry product gases are 11.5 percent
CO2, 2.7 percent O2, and 0.7 percent CO by volume. What percent theoretical air was
supplied? What is the dew point temperature of the products if the product pressure is
100 kPa?
Solution:
Assume 100 kmol of dry product gases:
Then, the combustion equation is:
X C3 H8  A (O2  3.76 N 2 ) 
. CO2  0.7 CO  2.7 O2  B H2 O  A(3.76) N 2
115
Make balancing for carbon, hydrogen, oxygen and nitrogen, results in:
C: X (3)  115 . (1)  0.7(1) X  4.07
H: X (8)  B(2) B  16.28
O: A(2)  115 . (2)  0.7(1)
 2.7(2)  B (1) A  22.69
N 2 : A(3.76)  85.31

Then, the combustion equation is:

4.07 C3 H8  22.69 (O2  3.76 N 2 ) 
115. CO2  0.7 CO  2.7 O2  16.28 H2 O  85.31 N 2 210
Dividing the equation by 4.07, yields:

C3 H8  557
. (O2  3.76 N 2 ) 
2.83 CO2  017
. CO  0.66 O2  4.0 H2 O  20.96 N 2

A ma  5.57 * 4.76 * 28.96

The actual air-fuel ratio is:     17.45
F  act m f 
act
3 *12  8 *1

The theoretical combustion equation is: C3 H8  5 (O2  3.76 N 2 ) 

3 CO2  4.0 H2 O  18.80 N 2

A ma  5 * 4.76 * 28.96
The theoretical air-fuel ratio is:     15.66

F th m f 
th
3 *12  8 *1
A A 17.45
The excess air factor:      1.11
F  act F th 15.66

The percent excess air is:   1*100  11%

211
Enthalpy of Formation
When a compound is formed from its elements (e.g., CO2, from C and O2), heat
transfer occurs. When heat is given off, the reaction is called exothermic. When
heat is required, the reaction is called endothermic. Consider the following.
For calculating the enthalpy of formation, some points must be noticed:

The chemical compound is formed from

its elements.
The entering elements to the reaction
and the outlet compound are at 100 kPa
and 25 C.
The enthalpy of formation of elements is
taken “zero”.
Then, the outlet or inlet energy to the
reactor is the enthalpy of formation.
 In the corresponding figure, C and O2
both at 100 kPa and 25 C are reacted
together to form CO2 at 100 kPa and 25 C.

212
 In the corresponding figure, C and O2
both at 100 kPa and 25 C are reacted
together to form CO2 at 100 kPa and
25 C.

The chemical reaction is:

Applying the first law of thermodynamics:

Using the moles of reactants and products. H R andH p can be written as :

The outlet energy from the reactor under these considerations is called the enthalpy
of combustion

Enthalpy of formation is designated as:

213
Hence, the enthalpy of the compound at Table A.10 gives values of enthalpy of formation
any another state of pressure and of some substances in kJ/kmol
temperature is calculated using the
enthalpy of formation as:

Where the term represents the difference

in enthalpy between any given state and
the standard state “100 kPa and 25 C”.

214
 First Law Analysis of Reacting Systems
For a steady state system having chemical reaction and both heat and work crossing
its boundary, The first law equation can be written as:

Qcv Wcv

Inlet and outlet from the chemical reaction systems conditions may have different
values of temperature and pressure than the standard conditions. Then the first law of
thermodynamics is:

215
Example:

Qcv Wcv
Solution:
1 kmol C8H18 (l)
Products
900 K and 0.1 MPa

The combustion equation:

First Law:

Reactants:
216
Products:

Wcv
wcv  kJ / kg
m
Wcv
Wcv  kJ / kg * M fuel kg / kmol   kJ / kmol fuel
m

217
Example:

Solution:

First law of thermodynamics for close system:

h  h f  h u  h  pv  h  R T
Then, for chemical compound the eternal energy can be written as:

u  h  pv  h f  h  R T

Then the first law is:

218
219
 Enthalpy and Internal Energy of Combustion
The enthalpy of combustion, hrp, is defined as the difference between the enthalpy
of products and the enthalpy of reactants when complete combustion occurs at
a given temperature and pressure.

Higher heating value (HHV): Or Higher

Calorific value(HCV): is defined as the heat
released when 1 kg of fuel is burned
completely in the presence of oxygen and H2O
in the products is in the liquid form.
Lower heating value (LHV): Or Lower
Calorific value(LCV): ): is defined as the heat
released when 1 kg of fuel is burned
completely in the presence of oxygen and H2O
in the products is in the vapor form.
 kg H 2O 
HCV  LCV  mH 2O  h fg
 kg 
 fuel  220
221
 u RP   ne h fo  h  R T p  ni h fo  h  R T R
p R

If the volume of liquid and solid constituents is negligible relative to the gaseous
constituents, then u RP can be written as:

u RP  hRP  R T ngaseous products  ngaseous reac tan ts 

222
Example:

Take the enthalpy of evaporation of propane 370 kJ/kg

Solution:
The enthalpy of evaporation of propane is 370 kJ/kg.
Then: h fg  h fg M  370 * (3 *12  8 *1)  16280 kJ / kmol

223
224
225
Example:

Solution:

226
Note that The difference between this value and the
previous value is small

227
 Adiabatic Flame Temperature

It is the temperature of the combustion products when no heat loss to the

surroundings (Q = 0).
It is called the adiabatic flame or adiabatic combustion temperature.

The adiabatic flame temperature of a fuel

depends on The temperature of a combustion
chamber becomes maximum when
(1) the state of the reactants combustion is complete and no heat is
(2) the degree of completion of the reaction lost to the surroundings (Q = 0).

(3) the amount of air used

For a specified fuel at a given pressure and
temperature the maximum adiabatic flame
temperature can be achieved when
theoretical combustion
228
Example:

Solution:

229
230
 Second Law Analysis of Reacting Systems
As we know, the reversible work for steady state process, can be written as:

 Vi 2   Ve2   To 
w rev
  hi   gzi  To si    he   gze  To se   q1  
 2   2   TH 
For a system having no changes in kinetic energy and potential energy and has no heat
transfer with other reservoirs except the surroundings, the reversible work can be
expressed as:

w rev
 hi  To si   he  To se 
Then, for the chemical reaction, the reversible work:

W rev   ni h fo  h  To s R  ne h fo  h  To s P
R P

231
The availability can be expressed as:

A new function called “Gibbs function” can be defined as

g  h  Ts kJ / kg

And g  h T s kJ / kmol

Then the reversible work can be written as:

W rev   ni g i  ne g e  G
R P
This final relation is used for calculating the reversible work in chemical
reactions and the Gibbs function is calculated and tabulated as a function of
temperature for the basic chemical reactions that used in combustion processes.

232
Example:

Solution:

233
The reversible work is equal to the decrease in Gibbs function
Since each component is at the standard-state pressure Po then G=Go.

N2 is canceled from both sides as it enters and exits at standard conditions

234
 G o  H o  To S o kJ / kmol

This reversible work means that, the heat released from the combustion chamber is
received by reversible engine having the cold reservoir of 298 K and produces Wrev

235
Example:

(3) Calculate the irreversibility

Solution:

236
Then the increase in entropy is:

237
Calculating the availability of products:

For the same combustion process, the reversible work is calculated in the previous
example:
W rev
 46851 kJ / kg
So, if we have an engine working with the adiabatic flame temperature, its maximum
efficiency equals:
p 23517
 engine    50%
W rev 46851 238
 Calculating the irreversibility:

This means that about 50% of the chemical energy of the combustion process is
consumed in the entropy change and the remain 50% is available as a work.

239
Example:

Solution:

The combustion equation:

240
 T P
S *  S o  C p ln
 R ln
To Po
Where: T is the component temperature which is (298 K in this problem)
and To is 298 K, So, the entropy change equation can be written as:

241
Calculating the entropy under the partial pressure for each component

242
The value of reversible work is essentially the same when using each component
separately at 100 kPa
243
 Evaluation of actual combustion efficiency
If we have ideal combustion , products temperature will be the adiabatic flame
temperature.
For actual combustion, some energy is lost due to incomplete combustion and heat
transfer.
To reach the same temperature value we need to burn more fuel, hence:
The combustion efficiency
=mass of fuel in ideal combustion/mass of fuel in actual combustion

This means:

For internal combustion engines

244
Example:

Solution:

245
246
247
Then:

mass of fuel 1* M fuel 1*114.23

FAideal   
mass of air no 2  nN 2  * M air 45.53  3.76 * 45.53 * 28.96

248
Example:

Solution:

249