Lecture6 .

THERMAL PROPERTIES OF BIOMASS-COMPLETE

COMBUSTION OF BIOMASS AND ENERGY RELEASE
WHAT IS A COMBUSTION REACTION?

A combustion reaction is a major class of chemical reactions, commonly referred to as

"burning". Combustion usually occurs when a hydrocarbon reacts with oxygen to
produce carbon dioxide and water. In the more general sense, combustion involves a
reaction between any combustible material and an oxidizer to form an oxidized product.
Combustion is an exothermic reaction, so it releases heat, but sometimes the reaction
proceeds so slowly that a temperature change is not noticeable.

Good signs that you are dealing with a combustion reaction include the presence of
oxygen as a reactant and carbon dioxide, water and heat as products. Inorganic
combustion reactions might not form all of the products, but are recognizable by the
reaction of oxygen.

Combustion doesn't not always result in fire, but when it does, a flame is a characteristic
indicator of the reaction. While the activation energy must be overcome to initiate
combustion (e.g., but using a lit match to light a fire), the heat from a flame may provide
enough energy to make the reaction self-sustaining.

GENERAL FORM OF A COMBUSTION REACTION

hydrocarbon + oxygen → carbon dioxide + water

EXAMPLES OF COMBUSTION REACTIONS

Here are several examples of balanced equations for combustion reactions. Remember,
the easiest way to recognize a combustion reaction is that the products always contain
carbon dioxide and water. In these examples, oxygen gas is present as a reactant, but
trickier examples of the reaction exist where the oxygen comes from another reactant.
 combustion of methane

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g)

 burning of naphthalene

C10H8 + 12 O2 → 10 CO2 + 4 H2O

 combustion of ethane

2 C2H6 + 7 O2 → 4 CO2 + 6 H2O

 combustion of butane (commonly found in lighters)

2C4H10(g) +13O2(g) → 8CO2(g) +10H2O(g)

 combustion of methanol (also known as wood alcohol)

2CH3OH(g) + 3O2(g) → 2CO2(g) + 4H2O(g)

 combustion of propane (used in gas grills and fireplaces)

 2C3H8(g) + 7O2(g) → 6CO2(g) + 8H2O(g)

COMPLETE VERSUS INCOMPLETE COMBUSTION

Combustion, like all chemical reactions, does not always proceed with 100% efficiency.
It is prone to limiting reactants that same as other processes. So, there are two types of
combustion you are likely to encounter:

 Complete Combustion - Also called "clean combustion", clean combustion is

oxidation of a hydrocarbon that produces only carbon dioxide and water. An
example of clean combustion is burning of candle wax, where the heat from the
wick vaporizes wax (a hydrocarbon), which reacts with oxygen in air to release
carbon dioxide and water. Ideally, all the wax burns so nothing remains once the
candle is consumed. The water vapor and carbon dioxide dissipate into air.
 Incomplete Combustion - Also called "dirty combustion", incomplete
combustion is hydrocarbon oxidation that produces carbon monoxide and/or
carbon (soot) in addition to carbon dioxide. An example of incomplete
combustion would be burning coal, where a lot of soot and carbon monoxide is
released. Many of the fossil fuels burning incompletely, releasing waste products.
COMBUSTION DEFINITION

Combustion is a chemical reaction that occurs between a fuel and an oxidizing agent
that produces energy, usually in the form of heat and light. Combustion is considered an
exergonic or exothermic chemical reaction. It is also known as burning. Combustion is
considered to be one of the first chemical reactions intentionally controlled by humans.

The reason combustion releases heat is because the double bond between oxygen
atoms in O2 are weaker than the single bonds or other double bonds.

So, although energy is absorbed in the reaction, it is released when the stronger bonds
are formed to make carbon dioxide (CO2) and water (H2O). While the fuel plays a role in
the energy of the reaction, it's minor in comparison because the chemical bonds in the
fuel are comparable to the energy of the bonds in the products.

HOW COMBUSTION WORKS

Combustion occurs when a fuel and an oxidant react to form oxidized products.
Typically, energy must be supplied to initiate the reaction. Once combustion starts, the
released heat can make combustion self-sustaining.

For example, consider a wood fire. Wood in the presence of oxygen in air does not
undergo spontaneous combustion. Energy must be supplied, as from a lit match or
exposure to heat. When the activation energy for the reaction is available, the cellulose
(a carbohydrate) in wood reacts with oxygen in air to produce heat, light, smoke, ash,
carbon dioxide, water, and other gases.

The heat from the fire allows the reaction to proceed until the fire becomes too cool or
the fuel or oxygen is exhausted.

EXAMPLE COMBUSTION REACTIONS

A simple example of a combustion reaction is the reaction between hydrogen gas and
oxygen gas to produce water vapor:
2H2(g) + O2(g) → 2H2O(g)

A more familiar type of combustion reaction is the combustion of methane (a

hydrocarbon) to produce carbon dioxide and water:

CH4 + 2O2 → CO2 + 2H2O

which leads to one general form of a combustion reaction:

hydrocarbon + oxygen → carbon dioxide and water

OXIDANTS FOR COMBUSTION BESIDES OXYGEN

The oxidation reaction may be thought of in terms of electron transfer rather than the
element oxygen. Chemists recognize several fuels capable of acting as oxidants for
combustion. These include pure oxygen and also chlorine, fluorine, nitrous oxide, nitric
acid, and chlorine trifluoride. For example, hydrogen gas burns, releasing heat and light,
when reacted with chlorine to produce hydrogen chloride.

CATALYSIS OF COMBUSTION

Combustion isn't usually a catalyzed reaction, but platinum or vanadium may act as
catalysts.

COMPLETE VERSUS INCOMPLETE COMBUSTION

Combustion is said to be "complete" when the reaction produces a minimal number of

products. For example, if methane reacts with oxygen and only produces carbon dioxide
and water, the process is complete combustion.

Incomplete combustion occurs when there is insufficient oxygen for the fuel to convert
completely to carbon dioxide and water. Incomplete oxidation of a fuel may also occur.
It also results when pyrolysis occurs prior to combustion, as is the case with most fuels.
In pyrolysis, organic matter undergoes thermal decomposition at high temperature
without reacting with oxygen. Incomplete combustion may yield many additional
products, including char, carbon monoxide, and acetaldehyde.
Chapter 11: Combustion

https://www.ohio.edu/mechanical/thermo/Applied/Chapt.7_11/Chapter11.html

(Thanks to David Bayless for his assistance in writing this section)

Introduction - Up to this point the heat Q in all problems and examples was either a
given value or was obtained from the First Law relation. However in various heat
engines, gas turbines, and steam power plants the heat is obtained from combustion
processes, using either solid fuel (e.g. coal or wood). liquid fuel (e.g. gasolene,
kerosine, or diesel fuel), or gaseous fuel (e.g. natural gas or propane).

In this chapter we introduce the chemistry and thermodynamics of combustion of

generic hydrocarbon fuels - (CxHy), in which the oxydizer is the oxygen contained in
atmospheric air. Note that we will not cover the combustion of solid fuels or the complex
blends and mixtures of the hydrocarbons which make up gasolene, kerosene, or diesel
fuels.

Atmospheric Air contains approximately 21% oxygen (O2) by volume. The other 79%
of "other gases" is mostly nitrogen (N2), so we will assume air to be composed of 21%
oxygen and 79% nitrogen by volume. Thus each mole of oxygen needed to oxidize the
hydrocarbon is accompanied by 79/21 = 3.76 moles of nitrogen. Using this combination
the molecular mass of air becomes 29 [kg/kmol]. Note that it is assumed that the
nitrogen will not normally undergo any chemical reaction.

The Combustion Process - The basic combustion process can be described by the
fuel (the hydrocarbon) plus oxydizer (air or oxygen) called the Reactants, which
undergo a chemical process while releasing heat to form the Products of combustion
such that mass is conserved. In the simplest combustion process, known
as Stoichiometric Combustion, all the carbon in the fuel forms carbon dioxide (CO 2)
and all the hydrogen forms water (H2O) in the products, thus we can write the chemical
reaction as follows:
where z is known as the stoichiometric coefficient for the oxidizer (air)

Note that this reaction yields five unknowns: z, a, b, c, d, thus we need five equations to
solve. Stoichiometric combustion assumes that no excess oxygen exists in the
products, thus d = 0. We obtain the other four equations from balancing the number of
atoms of each element in the reactants (carbon, hydrogen, oxygen and nitrogen) with
the number of atoms of those elements in the products. This means that no atoms are
destroyed or lost in a combustion reaction.

Amount in Reduced
Element = Amount in Products
reactants equation
Carbon (C) x a a=x
Hydrogen (H) y 2b b = y/2
Oxygen (O) 2z 2a+b z = a + b/2
Nitrogen (N) 2(3.76)z 2c c = 3.76z

Note that the water formed could be in the vapor or liquid phase, depending on the
temperature and pressure of the combustion products.

As an example consider the stoichiometric combustion of methane (CH4) in atmospheric

air. Equating the molar coefficients of the reactants and the products we obtain:
Theoretical Air and Air-Fuel Ratio -The minimum amount of air which will allow the
complete combustion of the fuel is called the Theoretical Air (also referred to
as Stoichiometric Air). In this case the products do not contain any oxygen. If we
supply less than theoretical air then the products could include carbon monoxide (CO),
thus it is normal practice to supply more than theoretical air to prevent this occurrence.
This Excess Air will result in oxygen appearing in the products.

The standard measure of the amount of air used in a combustion process is the Air-
Fuel Ratio (AF), defined as follows:

Thus considering only the reactants of the methane combustion with theoretical air
presented above, we obtain:

Solved Problem 11.1 - In this problem we wish to develop the combustion equation
and determine the air-fuel ratio for the complete combustion of n-Butane (C4H10) with a)
theoretical air, and b) 50% excess air.
Analysis of the Products of Combustion - Combustion always occurs at elevated
temperatures and we assume that all the products of combustion (including the water
vapor) behave as ideal gases. Since they have different gas constants, it is convenient
to use the ideal gas equation of state in terms of the universal gas constant as follows:
In the analysis of the products of combustion there are a number of items of interest:

 1) What is the percentage volume of specific products, in particular carbon

dioxide (CO2) and carbon monoxide (CO)?
 2) What is the dew point of the water vapor in the combustion products? This
requires evaluation of the partial pressure of the water vapor component of the
products.
 3) There are experimental methods of volumetric analysis of the products of
combustion, normally done on a Dry Basis, yielding the volume percentage of all
the components except the water vapor. This allows a simple method of
determining the actual air-fuel ratio and excess air used in a combustion process.

For ideal gases we find that the mole fraction yi of the i'th component in a mixture of
gases at a specific pressure P and temperature T is equal to the volume fraction of that
component.
Since from the molar ideal gas relation: P.V = N.Ru.T, we have:

Furthermore, since the sum of the component volumes Vi must equal the total volume
V, we have:
Using a similar approach we determine the partial pressure of a component using
Dalton's Law of Partial Pressures:

Solved Problem 11.2 - In this problem Propane (C3H8) is burned with 61% excess air,
which enters a combustion chamber at 25°C. Assuming complete combustion and a
total pressure of 1 atm (101.32 kPa), determine a) the air-fuel ratio [kg-air/kg-fuel], b)
the percentage of carbon dioxide by volume in the products, and c) the dew point
temperature of the products.
Solved Problem 11.3 - In this problem Ethane (C2H6) is burned with atmospheric air,
and the volumetric analysis of the dry products of combustion yields the following: 10%
CO2, 1% CO, 3% O2, and 86% N2. Develop the combustion equation, and determine a)
the percentage of excess air, b) the air-fuel ratio, and c) the dew point of the combustion
products.
The First Law Analysis of Combustion - The main purpose of combustion is to
produce heat through a change of enthalpy from the reactants to the products. From the
First Law equation in a control volume, ignoring kinetic and potential energy changes
and assuming no work is done, we have:

where the summations are taken over all the products (p) and the reactants (r). N refers
to the number of moles of each component and h [kJ/kmol] refers to the molar enthalpy
of each component.

Since there are a number of different substances involved we need to establish a

common reference state to evaluate the enthalpy, the common choice being 25°C and 1
atm which is normally denoted with a superscript o. Prof. S. Bhattacharjee of the San
Diego State University has developed a web based expert system at
<www.thermofluids.net> called TEST (The Expert System for Thermodynamics) in
which he has included a set of ideal gas property tables all based on the enthalpy ho =
0 at this common reference. We have adapted some of these tables specifically for this
section, and these can be found in the following link:

Combustion Molar Enthalpy Tables

As an example, consider again the complete combustion of Methane (CH 4) with

theoretical air:
Notice that in the reactants and the products of the above example we have basic
elements O2 and N2 as well as compounds CH4, CO2, and H2O. When the compound is
formed then the enthalpy change is called the Enthalpy of Formation, denoted hfo,
and for our example:

hfo
Substance Formula
[kJ/kmol]
Carbon dioxide CO2(g) -393,520
Water Vapor H2O(g) -241,820
Water H2O(l) -285,820
Methane CH4(g) -74,850

where (g) refers to gas and (l) refers to liquid.

The negative sign means that the process is Exothermic, i.e. heat is given off when the
compound is formed. Note that the enthalpy of formation of basic elements O 2 and N2 is
zero.

Consider first the case in which there is sufficient heat transfer such that both the
reactants and the products are at 25°C and 1 atm pressure, and that the water product
is liquid. Since there is no sensible enthalpy change the energy equation becomes:
This heat (Qcv) is called the Enthalpy of Combustion or the Heating Value of the fuel.
If the products contain liquid water then it is the Higher Heating Value (as in our
example), however if the product contains water vapor then it is the Lower Heating
Value of the fuel. The enthalpy of combustion is the largest amount of heat that can be
released by a given fuel.

Adiabatic Flame Temperature - The opposite extreme of the above example in which
we evaluated the enthalpy of combustion is the case of an adiabatic process in which
no heat is released. This results in a significant temperature increase in the products of
combustion (denoted the Adiabatic Flame Temperature) which can only be reduced
by an increase in the air-fuel ratio.

Solved Problem 11.4 - Determine the adiabatic flame temperature for the complete
combustion of Methane ( CH4) with 250% theoretical air in an adiabatic control volume.
This equation can only be solved by an iterative trial and error procedure using the
tables of Sensible Enthalpy vs Temperature for all four components of the products -
CO2, H2O, O2, and N2. A quick approximation to the adiabatic flame temperature can be
obtained by assuming that the products consist entirely of air. This approach was
introduced to us by Potter and Somerton in their Schaum's Outline of
Thermodynamics for Engineers, in which they assumed all the products to be N2. We
find it more convenient to use air assuming a representative value of the Specific Heat
Capacity of Air: Cp,1000K = 1.142 [kJ/kg.K].

Thus summing all the moles of the products we have:

Using the tables of Sensible Enthalpy vs Temperature we evaluated the enthalpy of
all four products at a temperature of 1280K. This resulted in a total enthalpy of 802,410
[kJ/kmol fuel], which is extremely close to the required value, thus justifying this
approach.

Problem 11.5 - - Determine the adiabatic flame temperature for the complete
combustion of Propane ( C3H8) with 250% theoretical air in an adiabatic control volume
[T = 1300K].

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