UNIVERSITA’ DEGLI STUDI DI PADOVA

Dipartimento di Ingegneria Industriale DII

Master’s degree in Energy Engineering

Combustion

Notes

Academic Year 2022/2023

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PART I ........................................................................................................................................................................ 4

INTRODUCTION ......................................................................................................................................................... 4
BASIC CONCEPTS................................................................................................................................................................. 5
PART II ....................................................................................................................................................................... 5
STOICHIOMETRY ........................................................................................................................................................ 5
PART III .................................................................................................................................................................... 19
REACTIONS .............................................................................................................................................................. 19
PART IV ................................................................................................................................................................... 25
COMBUSTION REACTION ......................................................................................................................................... 25
STOICHIOMETRY OF COMBUSTION ........................................................................................................................................ 25
Lambda ................................................................................................................................................................... 27
EXERCISE......................................................................................................................................................................... 31
PART V .................................................................................................................................................................... 34

DEGREE OF PROGRESS – STOICHIOMETRIC COEFF. ................................................................................................... 34

EXERCISE......................................................................................................................................................................... 35
MULTIPLE REACTIONS ........................................................................................................................................................ 37
PART VI ................................................................................................................................................................... 39

Δ𝑯𝑹 ........................................................................................................................................................................ 39
PART VII .................................................................................................................................................................. 45
CHEMICAL EQUILIBRIUM ......................................................................................................................................... 45
CRITERIA FOR THE CALCULATION OF THE EQUILIBRIUM .............................................................................................................. 45
Minimization of Gibbs free energy .......................................................................................................................... 45
Equilibrium constant ............................................................................................................................................... 45
TEMPERATURE EFFECT ....................................................................................................................................................... 46
PRESSURE EFFECT ............................................................................................................................................................. 47
ACTUAL CALCULATION OF THE EQUILIBRIUM ........................................................................................................................... 49
PART VIII ................................................................................................................................................................. 50
ENERGY BALANCES .................................................................................................................................................. 50
SIMPLIFIED DESCRIPTIONS OF ENERGY BALANCES ..................................................................................................................... 51
Open system............................................................................................................................................................ 51
Closed system.......................................................................................................................................................... 52
PART IX.................................................................................................................................................................... 53

INTERNAL ENERGY AND RATE OF REACTION ............................................................................................................ 53

KINETICS ......................................................................................................................................................................... 54
RATE OF REACTION............................................................................................................................................................ 56
PART X..................................................................................................................................................................... 58
KINETICS .................................................................................................................................................................. 58
GLOBAL VS ELEMENTARY REACTION ...................................................................................................................................... 58
Radicals ................................................................................................................................................................... 59

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PART XI.................................................................................................................................................................... 61

MATERIAL BALANCES .............................................................................................................................................. 61

ENERGY BALANCES ............................................................................................................................................................ 62
PART X..................................................................................................................................................................... 64
LOCAL BALANCES ..................................................................................................................................................... 64
Diffusion coefficient ................................................................................................................................................ 64
ENERGY BALANCE ............................................................................................................................................................. 66
PART XI.................................................................................................................................................................... 68
COMBUSTION OF SOLIDS ......................................................................................................................................... 68
BIOMASS ........................................................................................................................................................................ 68
Proximate analysis .................................................................................................................................................. 68
Elemental analysis .................................................................................................................................................. 68
DEVOLATILISATION ............................................................................................................................................................ 70
Rate of consumption of the solid ............................................................................................................................ 70
DAE MODEL (DISTRIBUTED ACTIVATION ENERGY)................................................................................................................... 72

PART XII................................................................................................................................................................... 74
HOMOGENEOUS & HETEROGENEOUS REACTIONS ................................................................................................... 74

MATERIAL BALANCE .......................................................................................................................................................... 74

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 Part I
Introduction
The combustion is an oxidation reaction in which a fuel reacts with an oxidizer, typically air since it
is the cheapest source of oxygen. Oxygen for this reason is usually the most used oxidizer.

𝐹𝑢𝑒𝑙 + 𝑂𝑥𝑖𝑑𝑖𝑧𝑒𝑟 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡

In case of a total combustion (total oxidation), the only products are CO2 and H2O. In case of
partial oxidation also other substances are present in the products. We may want to limit the
oxidation to a point in which we can save some useful products. For example this is the case of the
production of syngas, useful in many applications.

The chemical energy of the fuel is used in the following way:

Increase the temperature → Decrease the density → Increase of volume → Mechanical power
produced

The combustion reaction is very fast: it is a chemical process mostly controlled by physical
processes such as transport of mass and heat from one place to another, and if the rate of these
processes and the amount of the reactants are not enough the reaction will not proceed. The reaction
rate can be increased in several ways, such as:

- Increasing surface area (pulverized/spray fuels)

- Increase T

Combustion can be classifieds by:

- Whether the mixture is homogeneous or heterogeneous, depending on if the oxidizer

(typically air) and the fuel are premixed or they meet only at the point of reaction.
- Whether the fluid flow conditions are laminar or turbulent
- Whether the fuel is gaseous, liquid or solid

The conversion of a chemical into sensible energy takes place in the thin flame zone and causes the
flame temperature to be high. Additionally, heat transfer and mixing with the surrounding air cause
the temperature to rapidly decrease as the products move away from the flame.

The nature of the combustion also depends on whether the fuel is gaseous, liquid or solid. Gaseous
fuels such as natural gas are easy to feed and mix and are relatively clean burning. Liquid fuels are
typically broken into small droplets by being sprayed through a nozzle at high pressures. When
heated, liquid fuels vaporize and burn as a gaseous diffusion flame. Many solid fuels are pulverized
or ground before being fed into a burner or combustion chamber. Larger sized solid fuels combust
in a fuel bed with air flowing through it. When heated, solid fuels such as wood or coal release
gaseous volatiles with the remainder being solid char, that is mostly porous carbon and ash and
burns out as a surface reaction, while the volatiles burn as a diffusion flame. Vaporization of liquid

4
fuels and devolatilization of solid fuels occurs much more slowly than gas phase chemical
reactions, char burnout occurs even more slowly than devolatilization.

Basic concepts

1. Momentum, heat and mass transport mechanism: we must be familiar with the

Part II
Stoichiometry
The stoichiometric quantity of oxidizer is just that amount needed to completely burn a quantity of
fuel. If the quantity of oxidizer is more than stoichiometric, the mixture is lean, if it is less the
mixture is rich.

In this course, we will consider hydrocarbures as fuels, that have the common structure HC. C has 4
bonds, that can be single or multiple bonds. Multiple bonds can be included in the chains.

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IUPAC nomenclature describes all the different kinds of hydrocarbures.

𝑀𝑊! is the molecular weight of the species X.

𝐴𝑊! is the atomic weight of the element X.

Extensive property → Its numerical value depends on the amount (mass or number of moles) of
the substance considered. Extensive properties are usually denoted with capital letters (V, U, H..)

Intensive property → It is expresses per unit mass (or mole) and its numerical value is
independent on the amount of substance present. Mass based intensive properties are indicated with
lower-case letters, molar based intensive properties are denoted with an overbar.

For example, density can be expressed as follows:

and the correlation between the two is:

A “phase” is a region of space having similar properties. Different phases are separated in the H - T
or p - v diagram by a saturation line.

Combustion is not a phase transformation, it is a reaction producing products on another phase.

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 𝐺 = 𝐻 − 𝑇𝑆

𝐺 " (𝑝, 𝑇) = 𝐺# (𝑝, 𝑇)

The relationship is expressed by the Clapeyron equation:

The Clapeyron equation estimates saturation pressure variation with temperature. In the equation
molar entropy and molar volume of the considered phase appear. The change of phase is a liquid-
gas change, where α is a liquid and β is a gas. The evaluation of entropy in a phase change is
connected to the variation of enthalpy. The molar volume of the liquid phase is considered as
negligible compared to the molar volume of the gas, cause it is a 0.1 % of it. So the equation can be
replaced by the Clausius/Clapeyron equation:

The integrated form of that is

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If I want to know the evaporation temperature of a species at 20 bar, I can use the evaporation
temperature at 1 bar and calculate the result with the variation of enthalpy.

For an empirical gas:

𝐵
lnA𝑝(𝑡)B = 𝐴 +
𝑇+𝐶

where A,B,C are unique constants for each species.

Energy and thermal behavior are strictly connected. We want to be able to predict the enthalpy of a
species based on temperature, pressure, amount, and internal energy. This allows us to evaluate the
energy content of a species at a precise temperature. We refer to specific properties, in order to deal
with intensive properties and not with the physical amount of species, which is an extensive
property. The thermal equation can be simplified as just dependent on temperature: enthalpy of an
ideal gas can be considered NOT affected by pressure. The approximation isn’t valid for real gases.

For example considering water:

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In the following chart, the slope is the local value of the heat capacity in that specific phase. We
observe that for a gas the sensitivity is much higher.

Moving from pure species to mixtures, we put different species and phases together. A mixture has
a number of components (species) (substances having a different chemical nature) larger than 1.

As we did for pure species, the goal is to be able to measure:

• Amount
• Volume
• Transition of phase
• Thermal behavior

Another important value is the relative amount:

If the substance is a mixture, the relative amount of a component is always lower than 1. The same
%
applies to the mass fraction 𝑦$ and to the molar fraction 𝑥$ = &'(! % . Two species is a mixture. A
" "

mixture is in general when the number of species is higher than one.

We want to investigate the measurement of:

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 • Amount
• Volumetric effect
• Phase transfer
• Thermal properties

1) Amount

Molar fraction is the most common unit of relative amount, but since masses are more intuitive, it is
possible to convert molar fraction to mass fraction and viceversa through the molar weight. So the
mass fraction can be expressed as a function of the molar fraction:

Mass and molar concentration are conceptually the same as mass and molar density. It is supposed
to give information about the amount contained in a volume.

2) Volumetric effect

When two substances mix, they can remain as two different phases or they can mix perfectly. For
example wine and water mix perfectly: the two volumes cannot be defined, but the volumes before
and after the mixing can be compared. For example, alcool and water will give a total volume
smaller than the sum of the two volumes.

The volume of the mixture is the sum of the number of moles of the single species, multiplied by
the molar volume (volume per unit mole) of each single species plus a variation due to the type of
mixing. It can be expressed equally in terms of mass.. The concept of ideal mixture is the extension
of the concept of an ideal gas. An ideal mixture is made of species that behave together as they do
alone.

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Biofuels are likely to form mixtures where volume changes. Gases ae quite unlikely to form real
mixtures. In a gas, molecules are quite far apart, so for gases the difference is close to zero. The
same applies for similar liquids. In this course, the volume of a mixture is the scalar product
between the vector of unit mass for the vector of molar volumes.

In addition, specific volumes are always the inverse of densities, so the volume of the mixture per
unit mass is the inverse of density of the mixture, and this can be evaluated as the scalar vector of
the mole fraction times the molar volume or fraction times the specific volume:

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The density of the mixture is the inverse of the sum of the mass fraction of single species divided by
the density of single species:

Volume of the single species are given by pure species’ equation of state.

Mixtures of solids are not that easy.

4) Thermal properties
The generic property of a mixture is a combination of properties of a single species for ideal
mixture plus the effect of mixing (variation).

So the same story we have seen on volume applies on most of the properties, such as U, H, c_p, G
(gibbs energy), S. In ideal mixtures:

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So EVEN ideal mixtures have an effect on entropy through mixing. It makes sense because mixing
is irreversible process, and entropy measures irreversibilities. Mixing causes ALWAYS a gain on
mixing. The same goes for G, since it has an entropy part (G = H - ST).

It means that the internal energy of a mixture is the sum of mass fraction multiplied by the internal
energy of pure species.

Intensive enthalpy:

As far as mixtures are ideal, the property of the mixture, just requires the knowledge of pure species
and the relative amount.

3) Phase behaviour of mixtures

Mixture a encounters with mixture b. Let’s consider the example of gasoline.

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Some of the gasoline species can migrate to air (in fact we perceive the smell of gasoline, it means
that some of its molecules are in the air).

Temperature, pressure and composition determine the chemical potential of the phase.

Equilibrium of forces and temperature between the two phases:

We assume to have a gas phase and a liquid phase, with different compositions. Is there a
connection betweeen the two? Giving the composition of one of those, may i predict the
composition in the other phase if I know the composition of the other phase? No, but i will be able
to predict the equilibrium, next to the interphase. The equilibrium is ruled by thermodynamics. At
the end of the story, the mole fraction in the gas phase multiplied the pressure.

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The saturation curve is determined by the Antoine equation: by mastering it we can predict whether
a single species at a given temperature and pressure is a gas or a liquid but also to predict the
composition of that species in another case. This is called the Raoult equation.

The Raoult equation requires a few assuptions:

• It applies to gas and liquids

• Gas must be an ideal mixture
• Liquid must be an ideal liquid
• The species i at temperature and pressure at the equilibrium is subcritical

Subcritical is where the end of the line that divides gas and liquid. It’s easy to say if a species is a
gas or a liquid.

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Liquid → Takes the form of the vessel

Gas → Will fly away

Steam → Condition at very low density, large volume per unit mass

Liquid is condensed

So moving from gas to liquid and liquid gas is clear, but above the critical poin there not a
distinction of those, you can shrink and shrink and density will keep increasing, without the
collapse.

There’s no Antoine condition for oxygen at ambient condition. Oxygen and hydrogen are
supercritical. CO_2 is in the range of ambient temperature, normal eptane is a lot higher. At
ambient condition they have discontinuity at ambient condition. The saturation temperature is a
function of pressure. Roault is useful to predict the composition of subcritical species at ambient T.

Upper flammability limity → Above this amount there’s too much fuel.

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Let’s consider the case of nC_6

Reactions

Reactions are defined as processes where chemical bonds are rearranged. Bonds are connections
between atoms

A pure species cannot react and become the same pure species, this cannot happen. It has no sense.

Why do reactions happen? → Gain of energy and of stability. The product must be more stable than
the reactants. This means that the gain in stability corresponds to some release of energy. This is the
standard condition, where the release of energy has the form of heat. We want to stimulate some
species to react and release energy that was contained in the chemical bonds. Reaction is a
conversion of chemical energy into thermal energy. You can think of reactions as:

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We can sketch an energy scale: there are different forms of energy. Gibbs free energy is the scale.
Gibbs free energy has entropy and enthalpy, where enthalpy contains internal energy. Energy
exchanges can be of enthalpy or entropy. In this course we’ll focus on the gain of enthalpy, which
means release of energy.

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 Part III
Reactions
Combustion is an oxidation reaction, meaning a reaction in which oxygen is involved, that has
oxides as products. It is a process that releases the energy that was stored in the bound of the atoms.

A reaction is spontaneous if there is a gain in energy: the specific energy that rules the
transformation is Gibbs free energy, that is defined as a combination of entropy and enthalpy. There
are 2 reasons for a reaction to take place:

1. The internal energy decreases

2. The entropy is increasing

The dominant contribution is that connected with the enthalpy, so with the internal energy, that is
the energy of the bonds.

Through the rules of thermodynamics we can determine the final configuration of the species,
which is called equilibrium.The equilibrium is defined as the theroretical condition reached after
enough time has passed (centuries or milliseconds): that is ruled by the rate of reaction, that
measures the velocity to reach the final state.

In chemical reactions we change the connections of the species but not their mass: the number of
moles multiplied by the molecular weight is constant.

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We must set one of the unknown, for example we can set a = 10. Now we can solve the equation
balance and find the other parameters:

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We think at this reaction as 2 MOLES of CO and 1 MOLE of oxygen. We cannot deal with
molecules, they are too small, we deal instead with moles.

The following is the total oxidation

The total oxidation is the final state of the reaction, for which the maximum amount of energy is
released. A partial oxidation is instead an oxidation that didn’t reach the total state.

The volume of an ideal gas is calculated to the usual gas state equation:

For example:

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Some oxygen is already in the fuel, so you need less oxygen in the air, based on the provided
equation.

Stoichiometry of partial oxidation:

Air-to-fuel ratio can be defined on a molar base or on a mass base:

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Let’s consider the following example:

The molar fraction of methane in a stoichiometric mixture is the number of moles of methane
divided by the total number of moles. This can be expressed as:

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Flammability limit

Expressing the air-to-fuel ratio on a mass basis is:

Equivalent ratio

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We can write the following table

If Φ < 1, it means that the air-to-fuel effective is larger than the stoichiometric one. We are in
excess of air condition and the mixture is called lean (from the fuel side).

If Φ = 1, the air is exatly the amount needed for total oxidation.

If Φ > 1, it’s the reverse condition, the mixture is rich (from the side of the fuel), there’s less air
than needed.

Part IV
Combustion Reaction
Stoichiometry of combustion

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We need x molecules of CO2 to account for each atom of hydrocarbure. The coefficient of steam is
y/2, cause its carrying twice hydrogen. If we introduce y atoms we need y/2 molecules of steam. “a”
is the amount of molecules of oxygen per each molecule of fuel.

Oxygen is seldom used as pure, it is costly separating it from the air. So we use the air. We define
the AF ratio that expresses the amount of air for each amount of fuel. We need to specify how the
amount is calculated. Assuming they behave as ideal gases, they could be volume of air per volume
of fuel. A typical tricky oral question would be:

→ “Asking about AF ratio for a fuel that is a liquid”. The AF is not the volume ratio if the
fluid is a liquid. A fuel in the liquid phase is not an ideal gas.

The equivalent ratio expresses how far I am from the stoichiometric conditions.

Fi < 1 ⇒ Fuel lean = Air rich

Fi > 1 ⇒ Fuel rich = Air lean

However the adjective is usually referred to fuel

“Even if the AF ratio can be molar (volumetric or all ideal gases), or masses, we may expect
that the equivalent ratio could be different in the two cases. So is there a molar AF ratio and a
different mass AF ratio?”

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No, its a ratio between two consistent values. The result is always the same. There is no difference
between the two.

Lambda

It measures how effective was the combustion in the engine. It measures the oxygen. It can
determine if you are feeding the engine with the appropriate amount of fuel. It measures if there is
more or less oxygen from the expected value in a total perfect combustion.

Car producers prefer to talk about lambda, but it is just the reverse of the equivalence ratio (just as
the case of resistances and conductivities).

In terms of mass there are no big differences between hydrocarbures, while there are in molar cases.
In the case of the H2 there is a very large gap in MW between air which is 29 and H2 as a molecule
which is 2, so it is a factor of 15. Very big difference for hydrogen, less difference for the others.

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For simple HC the AF ratio is approximately linear with the number of C atoms.

For HC that have oxygen in the molecule, the AF ratio is much lower, so you need less oxygen
because some is already available from the fuel itself.

We have used some “stoichiometric numbers”

We introduce the real stoichiometric number. The stoichiometric number is the coefficient in the
reaction plus a sign that is fundamental. The stoichiometric coefficient of methane total oxidation
are -1, -2, 1, 2:

A reaction can be written as a sum of stoichiometric coefficients for their speicies.

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Using the stoichiometric coefficient, we can carry out all the quantitative calculations of the
variation of species of a reaction. We may obtain this following simple equation:

It says that any variation of amount of single species, if divided by the stoichiometric coefficient is
equal to a constant, which is the degree of progress of the reaction.

Using the example of the total oxidation of methane, we can write:

We expect that the given amount of methane will change. Through the “ignition delay” nothing
changes from the point of view of the methane, up to a point where its starts reacting and very fast it
has completely changed. Delta changes during the process.

Delta = after - before.

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The variation of methane produces a variation of hydrogen that is twice that amount. So the
progress f the reactionof a total oxidation means that methane will produce negative variation, while
CO2 will produce positive variations. Some species are increasing and some are decreasing, but the
ratios are not 1:1. If methane is decreasing by 5, you need to decrease oxygen by 10.

The equation that connects all species variations to a single coordinate that is a coordinate of the
reaction that tells if the reaction is progressing more or less, means that by knowing the variation of
one species I can know the variation of another species:

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Exercise

Partial oxidation → Starting from a mixture gradually oxidizing species but not to final point.

Incomplete oxidation → Assuming everythig gone to CO2 and steam, but not all the product
converted in that, and not even in intermediates.

We are on the light blue curve.

The variation of the vector of amount is equal to the scalar product of the vector of the
stoichiometric coefficient times the degree of progress of the reaction.

The amount of oxygen in the end minus the amount of oxygen at the beginning is equal to the
stoichiometric coefficient of oxygen (-2) multiplied by the unknown degree of progress.

In the final mixture the amount of oxygen compared to the total moles at the end is equal to 3 %.

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The molar density of an ideal gas is the inverse of the molar volume, that is constant (in normal
conditions) as 22,4 nL/mol (normal litres per moles).

You can try to explicit the exercise.

We have 1.5 moles that become just 1 mole of CO2. There is a decrease on the total number of
moles.
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Let’s consider for example C6H14:

Considering instead methane:

The number of moles may increase or decrease, or stay the same, depending on the stoichiometry of
the reaction. Increase the number of moles means generate volume, decrease it means reducing it.

In the three cases, to sum up:

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 Part V
Degree of progress – Stoichiometric coeff.
In the previous exercise, the 3 % of oxygen is left: it means that the number of moles of oxygen is
the 3 % of the total number of moles in the end.

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The degree of progress connects every species with the reaction:

The sum of all the stoichiometric coefficients tells the variation of the number of moles. In the case
of 𝐶𝐻) combustion, the sum is 0 because there is not any increase in the number of moles. There
can be an increase if there is an increase of temperature, but in that case it is just a thermal effect,
not a stoichiometric one.

Exercise

In this exercise we know the volume of methane at t = 0 s. By multiplying the molar volume of
methane by its molar density, we can obtain the number of moles of methane. From this value it is
then possible to determine the number the number of moles of the other species, based on the
stoichiometric reaction:

𝐶𝐻) + 2𝑂* → 𝐶𝑂* + 2𝐻* 𝑂

35
where 469.6 moles is the total number of moles of the reaction. Considering that 3 % is the number
of moles of oxygen relative to the total number, it is possible to calculate this number in absolute
terms as follows, and then finally determine the degree of progress of the reaction.

The degree of progress is used to determine the final number of moles of each species:

The relative amount of 𝐶𝑂* is calculated by dividing its number of moles at the end for the total
number of moles at the end of the reaction:

𝑁+,# 30
𝑋+,# = |/01 = ≈ 6 %
𝑁-.- 469

The fact that not all the oxygen is converted means that the final amount of 𝐶𝑂* is less than the
maximum. The maximum degree of progress is achieved when the limiting reactant disappears,

36
making the conditions to go further not satisfied anymore. In a stoichiometric mixture the maximum
is reached instead when both reactants disappear.

In this exercise, the initial amount of methane was of 44.64 moles and the maximum degree of
progress corresponds to the point where methane is completely burnt, meaning that it is exactly
equal to 44.64 moles. The calculated one was 30, so there was still space for the reaction to develop.

The main limits of a reaction and of its degree of progress are:

- Limiting reactant
- Thermodynamics

About the second one in fact, products will push to re-form reactants, making the equilibrium of the
reaction at a value of the degree of progress lower than the maximum one. This equilibrium is
decided by the thermodynamics. As it is shown below, this equilibrium can be very close to the the
maximum but also very close to the beginning in some cases.

Multiple reactions

Methane can react with oxygen in different ways:

37
If there is more than one reaction, there will be also multiple degrees of progress (one for each
reaction). It is necessary to account for all the possible reactions that may increase or decrease that
species, meaning that the sum of the stoichiometric coefficients is needed over all the reactions:

If the bonding energy of a compound is known, it is possible to calculate the required energy to
break the molecules of that compound. If the amount of energy calculated at the output is higher
that the needed in the input, some net energy is realeased by the reaction: this is the case of the
reaction:

2𝐶𝑂 + 𝑂* → 2𝐶𝑂*

where the input required energy is 635 and the output energy is 768.

Considering instead the case of methane combustion, the input required energy is of 634 kcal/mol,
while the output is 828 kcal/mol. The released heat is therefore:

𝑘𝑐𝑎𝑙
𝛥 = 𝑂𝑈𝑇 − 𝐼𝑁 = 194
𝑚𝑜𝑙
This result is called heating value of the reaction, and it is evidence of the microscopic level of the
reaction. There are some limitations on the predictability of the heating value:

1. Bond energy is affected by neighboring atoms

2. The chemical structure of the molecule is needed (single, double bonds). For complex
species it is a problem.

38
Therefore, the dH of reaction can be evaluated with bonds for simple species but without knowing
the structure alternative methods are needed to estimate the variation of the enthalpy of reaction.

The enthalpy of a mixture can be expressed as the relative amount of each species multiplied by the
molar enthalpy of pure species

By knowing the temperature and in the case of an ideal gas not dependent on pressure, it is possible
to evaluate enthalpy as its function:

Reference enthalpy is not needed when the species is not reacting. The absolute scale of the
enthalpies is defined with H = 0 for elements in stable and standard form (when composition,
pressure and aggregation state are specified).

Part VI
Δ𝑯𝑹
39
The energy content of different components depends on the bonds. In a reaction, from the
stoichiometric mixture to the maximum there will be just products and the reactants will disappear
completely (in ideal case). So the enthalpy of the products compared to that of the reactants can be
lower or higher. In the first case (red) the dH is negative, so there is a release of energy (heat).
Products are more stable than reactants. In the second case the dH is positive, and products are less
stable than reactants: energy must be given to make the reaction happen.

Exothermic reactions are usually spontaneous, meaning that they can happen without an external
input, apart from the activation energy that can still be needed. Let’s consider for example oxidation
of CO to CO2:

From tables we can take the values of the enthalpy of formation and do the calculations. The result
show that the 𝛥𝐻2 of the single mole of CO oxidized to 𝐶𝑂* is 283 kJ: this corresponds to the
energy that is released when the oxidation happens. Since this reaction is extremely exothermic,
there are two reasons to complete the oxidation of C:

1. Large amount of energy is lost

2. Environmental reasons (CO is toxic)

The same calculations can be done based on bond energies, obtaining a comparable result of 278
kJ/mol. The following table shows the heat of formation of different compounds at 298 K:

40
The table shows that going from top to bottom is spontaneous, while the inverse requires energy.
We can consider now the case of methane:

𝐶𝐻) + 2𝑂* → 𝐶𝑂* + 2𝐻* 𝑂

𝜈 = [−1 − 2 + 1 + 2]

The resulting 𝛥𝐻2 is 802,5 kJ/mol of 𝐶𝐻) . With bond energy the result is again comparable.
Clearly also this reaction is exothermic. In terms of mass it can be expressed as:

41
This result expresses the heat released from the combustion of 1 kg of methane. Let’s consider now
the evaporation of 1 kg of water:

As shown it requires 2000 kJ. Compared to the combustion of methane, that releases 50000 kJ, it is
a lot lower. By considering instead sensible heat, meaning a certain increase of temperature without
phase transition, they are again much lower compared to the released heat from methane
combustion:

The same example can be repeated with the following molecules:

These two molecules are less stable than the elements, but they remain in that state because
activation energy represents an obstacle. This depends on the kinetics of the reaction, not on the
thermodynamics.

42
The temperature of the reaction cannot be determined a priori, an energy balance is needed.

The reaction stops at the equilibrium before reaching the maximum; two hypotheses are made:

1. Stoichiometric reactants are assumed and no products at time 0

2. The maximum corresponds to no product present

In the ideal case of reached maximum:

While in the real case:

The composition of the mixture must be estimated: for this purpose the equilibrium must be studied.
It is possible to distinguish between:

- Thermal equilibrium à It is reached when the temperature is uniform, meaning that in all
the phases it is the same (𝑇 " = 𝑇# = ⋯ )
- Mechanical equilibrium à It is reached when there is the equilibrium of the forces, that is
described by the pressures (𝑝" = 𝑝# = ⋯ )

In general chemical equilibrium requires the uniformity of the potential, and a general criteria
requires that, for an isolated system (with constant volume and internal energy), the entropy is
maximum. Gibbs free energy is minimum at the equilibrium:

43
 Gibbs free energy

44
 Part VII
Chemical equilibrium
The maximum point is never reached: the reaction always goes back and reactants are formed again
starting from products, stopping the reaction at an equilibrium point, that can be very close to the
maximum or very far from it. The goal is to be able to determine its position. In this study open
systems are considered.

Figure – Equilibrium of reaction

Criteria for the calculation of the equilibrium

Minimization of Gibbs free energy

Considering constant temperature and pressure, the total Gibbs free energy depends on the amount
of the single species and on the number of components: when they are more than two it becomes
challenging to plot the function. This criteria is based on the minimization of this function, that
depends on the amount of these species, and it is the criteria on which are based all the professional
softwares. The process tries to figure out the possible products and to evaluate the combination of
type of species and relative amount that produce the minimum of the function. We act by changing
the amount of some species and the process tells the combination that brings the function to the
minimum. It is better to suggest the largest possible number of species: it is less intuitive because
species are specified before without knowing which ones form another.

Equilibrium constant

This second method is more intuitive, but it is less used professionally since from the computational
point of view the Gibbs free energy criteria is more robust. This equilibrium constant method
requires to write the reactions and it is solved with numerical calculations.

If 𝛥𝐺 3 < 0 à The reaction is very close to the maximum

If 𝛥𝐺 3 > 0 à The reaction is far from the product

45
The equilibrium constant is defined as the product of the activity of single species raised to the
correspondent stoichiometric coefficient in that specific reaction.

𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 ≠ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

The activity means the amount of species and if that species has a chemical activity and propension
to change more than other species. Concentration tells instead just the amount of the species. The
activity of the species 𝑖 in the gas phase can be expressed as the partial pressure of 𝑖 divided by the
reference pressure.

Temperature effect

Increasing the temperature makes some reactions move to the right and some to the left. In
particular, increasing the temperature benefits endothermic reactions, while it worsens the behavior
of exothermic reactions, that tend to regress and move the equilibrium to the left. However the
benefits of endothermic reactions, that normally don’t go very far, are usually higher than the losses
of exothermic reactions, for the increase of temperature.

Figure – Temperature effect

46
This behavior is ruled by Van’t Hoff equation.

Partial oxidation of HC

Pyrolisis à Heating without oxygen.

In the following table, different cases of partial oxidation and pyrolysis of HC are compared based
on their 𝛥𝐻4 :

HC P.O Pyrolisis

𝑪𝑯𝟒 -74 74

𝑪 𝟔 𝑯𝟔 -712 -47

𝑪𝟏𝟐 𝑯𝟐𝟔 -978 348

For example, for benzene the T should never be increased, which sounds strange since pyrolysis
needs a temperature increase. However the reaction will not go far if T is too high. The goal is to
find the right compromise. In addition, temperature can change role depending on the species, even
in the same category of reactions.

Pressure effect

If in a reaction there is an increase in the number of moles, you should expect an increase of volume
too.

47
 𝑅𝑇𝑛
𝑣=
𝑝

An increase in the number of moles is not uncommon: ν summarizes this since it is the sum of the
stoichiometric coefficients:

- ν > 0 à Moles of the products > Moles of the reactants

- ν < 0 à Moles of the products < Moles of the reactants
- ν = 0 à Constant number of moles

If we consider the total oxidation of an hydrocarbure:

𝑦 𝑦
𝐶9 𝐻: + f𝑥 + g 𝑂* → 𝑥𝐶𝑂* + 𝐻* 𝑂
4 2
𝑦 𝑦 𝑦
𝜈= − f1 + g = − 1
2 4 4
:
It can be seen that the number of C is not relevant and that the total variation of n depends on ) − 1,
where y is the amount of H. For example:

HC ν volume P

𝑪𝑯𝟒 1 constant No effect of p

−1=0
4
𝑪 𝟑 𝑯𝟖 8 expanding Lower is better
−1=1
4
𝑪𝟖 𝑯𝟏𝟖 18 expanding Lower is better
− 1 = 4, …
4

- For CH4 the number of moles doesn’t change: this means no variation of volume and
therefore no effect on pressure and on the total number of moles
- For C3H8 (propane) there is a net increase on the number of moles
- For C3H18 (octane) there is an increase too.

Apart from methane, the total oxidation of an HC always increases the number of moles and that is
one of the effects of the internal engines; the volume in cylinders increases for two reasons:

- Combustion increases T
- The reaction increases the number of moles

So we can conclude that:

- If ν > 0 it is not useful to increase the pressure, since it works against the expansion. At
lower pressures the equilibrium gets closer to the maximum
- If ν < 0 it is useful to increase the pressure

48
Adding an inert is useful if the reaction expands (ν > 0) and it is not useful if the reaction is
contracting (ν < 0).

The conclusions can be taken also for partial oxidation:

𝑥 𝑦
𝐶9 𝐻: + f g 𝑂* → 𝑥𝐶𝑂 + 𝐻*
2 2
𝑦 𝑥 𝑥+𝑦
𝜈=𝑥+ − f1 + g = −1
2 2 2
For example:

HC ν volume P

𝑪𝑯𝟒 1+4 expanding Lower is better

− 1 = 1.5
2
𝑪 𝟑 𝑯𝟖 3+8 expanding Lower is better
− 1 = 4.5
2
𝑪𝟖 𝑯𝟏𝟖 8 + 18 expanding Lower is better
− 1 = 12
2

Actual calculation of the equilibrium

This evaluation requires a tool, for example EES or ASPEN. The evaluation requires the following
three steps:

1. Initial configuration of species

2. Set T and p
3. Evaluate the configuration at the equilibrium of all the species

49
 Part VIII
Energy Balances
It measures the energy transfer from one form to another, it tells how a flux of energy can increase
or decrease the energy of a system.

𝑑𝐸
= 𝐸̇=% − 𝐸̇,>?
𝑑𝑡
Energy can be expressed in two different forms:

The terms without the dot tell the total amount of energy within a system, the terms with the dot tell
instead the flow of energy across the system. Energy variations can be convective or non-
convective, depending on if there is or not a mass exchange (for example it is non convective when
there is a shaft or heat transfer, etc.).

Specific energy is composed by two different contributions: internal energy, potential energy and
kinetic energy.

𝐸m = 𝑈
n + 𝐸m@ + 𝐸mA

However, in combustion applications, internal energy is by far more important than kinetic and
potential energy, that can therefore be neglected:

𝐸mB.(C'&-$.0 ≅ 𝑈
n

Inlet energy can have a convective part and a non-convective one. This can be heat (𝑄̇), work at the
shaft (𝑊̇D )or mechanical work as a shrinking of the system causing a variation of its volume,
1E
positive if the system expands, negative if it contracts q𝑝 f− 1- gr. The variation of internal energy
can therefore be expressed as:

50
And can be simplified in:

This is the general equation of energy conservation, applying to non-dimensional systems, that
can be obtained using a single value for properties (?????), for example, speaking of system’s
temperature, there are no temperature differences anywhere (perfectly mixed uniform condition).

Simplified descriptions of energy balances

Open system

There is a mass flow in and out, typically associated with the assumption of steady state condition.
1
In particular, 1- = 0 for any variable of the system. Therefore, the energy balance is:

𝛥𝐻̇ = 𝑄̇

In case of the system being also adiabatic, 𝑄̇ = 0, therefore:

̇ F=!
𝛥𝐻̇ = 0 → 𝐻̇=% = 𝐻̇,>? → 𝐻̇=% = 𝑚̇𝐻

The number of moles at the inlet and outlet are connected by:

𝑛,>? = 𝑛=% + 𝜈𝜀

There are different possibilities:

51
Some time is needed to reach the equilibrium, during which the combustion reaction must be
sustained, and after which two different equilibriums can be reached, depending on if the same
enthalpy is maintained or if heat is given too.

Closed system

In this system there is no mass flow across the system, meaning that there is no convective term in
the energy balance equation.

𝑑𝐻 𝑑𝑉
=0−0−𝑝 + 𝑄̇
𝑑𝑡 𝑑𝑡
The energy balance can be reformulated in terms of enthalpy at constant pressure.

1E
In particular, in a rigid vessel, 1-
= 0, therefore:

1'
If the vessel is adiabatic, | = 0. The adiabatic temperature hp is different from the adiabatic
1- G
temperature uv: it depends on the constraints of the systemand on the progress of the reaction and
on whether the mixture expands or contracts.
I '
𝑇H1 ≠ 𝑇H1

52
The cp of a 3 atoms molecule is higher than that of a 2 atoms one, therefore in general, the more
complicated is the molecule, the higher is the heat capacity, because it is a macroscopic property
that tells how the external energy can be included in groups of atoms: the more bonds the molecule
has, the more possibilities there are to accumulate the energy as heat.

Considering the equivalence scale, on the rich side there are more biatomic species, while in the
lean case there are much more triatomic species. If the cp is higher, the same amount of energy
leads to a lower adiabatic temperature, and viceversa.

For this reason, since closer to the lean side the cp is lower, the adiabatic temperature has a
maximum shifted to that side. The adiabatic temperature curve is usually non symmetrical, being
higher on the rich side as shown in the picture below:

Part IX
Internal energy and rate of reaction
Since combustion is an exothermic process, the final temperature is higher than the starting one. If
some pressure is spent to allow the mixture to expand by going against the external pressure, the
53
final temperature is expected to be lower than that of the case in which pressure is all spent inside
the vessel.

By calculating the equilibrium point and conducting the energy balance, it is possible to identify the
composition and the temperature of the mixture. However, the thermodynamics just give
information about starting and final state, without any mention about the time needed, that can be of
one second or one millennium.

Kinetics

The kinetics describe the process from the start to the equilibrium. Kinetics means describing rates,
of physical processes, heat and mass transfer. Increasing the temperature means releasing energy. If
there is no dissipation, the process is adiabatic. The higher the dissipation, the more far you are
from the adiabatic condition.

Temperature can be defined as an indicator of the progress of the reaction. The energy balance
alone is independent from the equilibrium: for example in the case of a closed, rigid region it says
that the internal energy can change only because there are heat transfers with the outside. If the
system is also insulated, the internal energy remains constant.

𝑑𝑈($9
= 𝑄̇
𝑑𝑡
This means that

𝑊̇& = 0

𝑑𝑣
𝑝 =0
𝑑𝑡
The internal energy of a mixture depends on temperature, not really on pressure since for ideal
gases, solid condensed phases the effect of pressure is always negligible. The internal energy
depends also on how many species are present in the mixture, on their amount and on what type
they are. The internal energy is an extensive property and it is measured in [J]. In an ideal mixture,
the internal energy of the mixture is the sum extended to all the species of the number of moles of
each species, multiplied by the internal energy per unit mole of each single species, as shown in the
following:

[𝐽] = 𝑢($9 = 𝑢($9 (𝑇, 𝑝, 𝑁)

%

= v 𝑁$ 𝑢w$ (𝑇)
$

where 𝑢w$ is a property of every pure species, and it is expressed as:

?
4/J
𝑢w$ = 𝑢$ +x 𝑐̃G,$ 𝑑𝑇
? $%&

54
where cv is the constant volume specific heat, meaning the partial derivative of the internal energy
with respect to temperature at constant volume.

The energy balance is equal to the derivative of the sum of the number of moles times the internal
energy, and this derivative can be developed as follows:
%
𝑑𝑢($9 𝑑 ∑ 𝑁$ 𝑢w$ 𝑑𝑢w$ 𝑑𝑁$
𝑄̇ = = = v {𝑁$ + 𝑢w$ |
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
$

where:
L!
1' 1?
1-
= 𝑐̃G,$ 1-

1%!
1-
= 𝑟̃$ à Rate of production of species i

The seen equation can be developed as:

𝑑𝑇
𝑄̇ = qv 𝑁$ 𝑐̃G,$ r + v 𝑢w$ 𝑟̃$
$ 𝑑𝑡 $

that finally corresponds to

𝑑𝑇
𝑄̇ = 𝐶G,($9 + v 𝑢w$ 𝑟̃$
𝑑𝑡 $

That expression shows that if there is an external flow of heat we can expect a change in
temperature but also a change in the composition. In particular the interest is in how the change of
composition will modify the change of temperature. For example, considering the total combustion
of 𝐶𝐻) :

𝐶𝐻) + 2𝑂* → 𝐶𝑂* + 2𝐻* 𝑂

The rate of production of 𝐶𝑂* is equal to the rate of reaction. If the reaction shifts to the product,
the production of water will be twice as much. The rate of reaction is negative for a reactant and
positive for a product, if the reaction is going towards the products.

55
Thermal inertia à It is the heat capacity, the higher it is, the lower the increase of temperatuere
with the same amount of heat supplied.

Heating rate à It decreases if the heat capacity is higher. It depends on mass and specific heat of
the species. More complex molecules with more atoms and many degrees of freedom means higher
heat capacity.

If we consider a closed system with constant pressure, with the possibility of expanding/contracting
the volume, the energy balance is:

𝑑𝑢($9 𝑑𝑣
= 𝑄̇ − 𝑝
𝑑𝑡 𝑑𝑡
𝑑𝐻
| = 𝑄̇
𝑑𝑡 M

Rate of reaction

A comparison can be made with systems different from the chemical one. For example, the velocity
can be expressd as the rate of change of position, the acceleration is the rate of change of velocity,
and similarly the kinetics expresses the rate of chemical reactions.

Considering for example the complete combustion of methane

𝐶𝐻) + 2𝑂* → 𝐶𝑂* + 2𝐻* 𝑂

methane is not bouncing into oxygen to generate products, there are instead two very simple
elementary steps, as shown in the following:

𝐶𝐻) →. 𝐶𝐻N +. 𝐻

𝐻. +𝑂* → 𝑂𝐻. +𝑂.

The rate of reaction is defined based on the elementary steps. In addition, generally in an
exothermic reaction there is the activation energy, that acts as an obstacle to obtain the products.

The equilibrium point is reached in a reaction when the net rate, meaning the difference between
forward and reverse reaction, becomes zero. In the reverse path a different activation energy is
needed, and it can be found by knowing the activation energy of the direct reaction and its dH. The
net rate is a function of the kinetic constant. Arrhenius describes the effect of the temperature on the
kinetic constant and on the rate of reaction as:

𝐸HB-
𝑘 = 𝐴𝑒𝑥𝑝 q− r
???
Now we wanna see the effect of composition on the rate of reaction. Each species pushes based on
its amount: if the amount is larger, the rate of reaction due to that species is larger. If the reactant
increases the rate decreases, being proportional to species concentration.

56
Collecting everything:

In general, since there are different species, there are different rates. There can be exothermic and
also endothermic steps in each reaction, and since the rate of reaction depends on temperature, the
energy balance must be coupled.

57
 Part X
Kinetics
Kinetics are useful to determine the rate of change of the species. The rate of reaction is the rate of
chemical reaction, also called rate of combustion. It can be defined as based on the displacement of
one reaction.

1 𝑑𝜀
𝑅(𝑇, 𝑆) = 𝑅 ≡
𝜈 𝑑𝑡
The rate in a reaction is always the net difference between direct and reverse reaction rates:

𝑅0/- = 𝑅•⃗ − 𝑅⃖•

•⃗𝜋$ 𝑐 "!
= 𝐾 $

where 𝛼$ is the partial reaction order, while in the case of an elementary reaction, defined as the
reactions that describe molecular events, the partial reaction order 𝛼$ is the same as the
•⃗ can be expressed as:
stoichiometric coefficient 𝜈$ , therefore 𝛼$ = |𝜈$ |. The coefficient 𝐾

𝐸H--
•⃗ = 𝐴𝑒𝑥𝑝 q−
𝐾 r
𝑅𝑇

Global vs elementary reaction

Elementary à It describes simple chemical events, such as the breaking or building of a bond

Global à Stoichiometric equations: the reaction globally describes the process, that is made of
multiple elementary steps where radicals are formed: there is not a direct reaction from reactants to
form products. Radicals are like homogeneous catalysts, and from the first elementary step, the
formed radical can react with an element, for example a fuel, in a subsequent step. Alternatively, 2
radicals can react to form a product. A fuel producing a radical produces actually 2 radicals, one
reacting with oxygen to generate a product.

Figure – Fuel producing radicals

58
A higher number of radicals means a higher rate of reaction: this can be obtained:

1. Increasing the temperature, to increase the crackings

2. Brenching

à Combustion reactions accelerate exponentially.

Radicals

Radicals are the engine of all combustion reactions, but they are extremely reacting species. Let’s
consider the case of a gas combustion: it is a chain reaction, meaning that radicals are involved in it.
Having a higher amount of radicals means having a faster combustion, and this also means releasing
the energy at a faster rate.

Discussing about the rates of reaction means discussing about how fast the energy can be obtained.

Gas phase is the most common reaction regarding combustion, but for carbon and renewables also
solid phase is considered. The most simple case of combustion is 𝐻* combustion:

𝐻* + 𝑂*

The number of obtainable species is limited, being:

𝐻* 𝑂 𝐻* 𝑂* 𝐻. 𝑂. 𝑂𝐻. . 𝐻𝑂*

The simplicity of this reaction is due to the fact that there is no carbon, that when present can form a
lot of different species, making the reaction very complicated.

In this reaction there are approximately 21 steps, and the initiation can occur in two different ways.
Hydrogen molecule is broken into 2 H. radicals: this reaction requires a third body, a molecule to
accommodate some of the extra energy involved in the process of breaking stable molecules. This
in particular is more frequent at higher T, meaning that the activation energy is larger.

The other initiation happens at a lower T, and it is an unlikely collision between H and O molecules
that produces the hydroxide and hydrogen radical, this happens at around 500 °C.

The following chart shows that, at different T and p, the ignition takes place in different regions:

59
Decreasing the pressure means causing molecules to be more distant, having lower density and
concentration. Radicals, even if generated, react more difficultly: statistically we can say that below
0.5 torr there is no ignition. At a constant T of 500 °C, there are different regions of no combustion,
ignition,…, depending by the pressure. This behavior depends on the interaction between radicals.
The line in the chart is called explosion limit, and it is different from the flammability limit.

Explosion limit à Ranges of T and p at given initial concentration for the chemical reaction to
start and propagate: it is a chemical feature. Because of the complex mechanism, is not obv that if
p++ you get to ignition without changes in the mechanism. The shape of the curve says there are
changes of behaviour if we increase pressure. On the other hand, a temperature increase will always
move to an easier ignition. Pressure increase instead introduces an obstacle to propagation.

Flammability limit à Equivalence ratio for the stability of the flame, that contains the chemical
reaction, but it is also a physical process. A flame is a reaction is space that produces heat. That is
functional to support the raction. A flame is a mix of chemistry and heat/mass transfer.

The explosion is a property of the chemistry. Flammability is a property of chemistry and physics.
If the flame is stable and propagates rapidly, the flame is in the flammability limit.

60
 Part XI
Material balances
The purpose of a material balance is that of predicting the evolution of the composition from the
initial to the final state. The x-axis is time, the y-axis can be anything: in the following we consider
it to be T.

Figure – Material balances

In a combustion reaction, the final (equilibrium) temperature is usually much higher than the initial
room temperature. The shape is normally the one displayed above: there is a starting delay and a
final one, up to the maximum value. In some cases, the temperature increase can be very sharp.

Figure – Very sharp increase

In the above case, the delay is very big: that is the ignition time.
61
The ignition point is instead the one where there is the change of slope: for example it can be
identified where there is at least a 5 % T increase in a small quantity of time.

The goal of the material balance is that of characterizing this curve, to see also how the amount of
species changes through time. The amount of each species can be measured in different terms:

𝑚$ (𝑡) 𝑁$ (𝑡) 𝑥$ (𝑡) 𝑦$ (𝑡) 𝑐$ (𝑡)

These are all different ways to express the same thing, that is how the amount of species changes
over time. A typical trend is presented in the following:

Figure – Characteristic curve of the amount

Energy balances

0-dimensional system → Base system. Well mixed uniform system. Temperature is a single one
for the whole system.

1-dimensional system → Increased complexity. Typical of a vessel that has a direction that is
much larger than the other. That is typical of a pipe or a river. You can describe everything as
“distance from the origin”.

Figure – 1-dimensional system

2-3-dimensional system → If u increase firmly the dimension, you end up in a system in which
any property varies with x,y,z. That is the case of combustion.

𝑇(𝑥, 𝑦, 𝑧) → ∇𝑇 ≠ 0

62
We may measure material in terms of total mass, mass of single species, number of moles of single
species. In the case of total mass we know that generation will be 0, cause mass is just rearranged.

Generation à Rate of production of species i. Production has a + sign. We expect an increase in

the system. It is defined as moles of i produced divided by unit time. But is also specific based on
the volume. The rate of production is not consistent with the other terms. There’s a volume that
must be fixed. If the system is closed, we end up with the following simple expression. The amount
of single species will change based on reaction multiplied by the volume:

The rate of production is ruled by temperature and concentration:

63
 Part X
Local balances
A local balance locally describes the following characteristics of a single species:

- mass
- temperature
- density
- pressure
- velocity

We can express the local density as

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖
𝜌‡$ = = 𝜌‡$ (𝑥, 𝑦, 𝑧, 𝑡)
𝑣𝑜𝑙𝑢𝑚𝑒
Its variation is described through the gradient of fluxes as follows

𝛿𝜌‡$
= −∇𝑚̇ O PP + 𝑟̂$
𝛿𝑡
where the dot indicated that it is a value per unit of time, the double quotes indicate that the amount
is considered per unit section and finally the arrow indicates that it is a vector. The goal of the local
balance is to describe how the single molecule of i will move locally: the movement is the result of
many mechanisms, such as convective, diffusive and others. The driving force for convection is
velocity, but there are other driving forces. The contribution of convection to the total flux is the
local velocity multiplied by the concentration.

Diffusion coefficient

It can be defined for two species or we can define the binary diffusion coefficient, that is the
diffusion coefficient of one into the other.

64
For more than two species we need to account foer all the combinations of the diffusion coefficients
of single species, that is function of the composition. We talk about concentrated species when all
the species are present in a significant amount (more than 10 – 20 %). Therefore, for concentrated
species it depends only on t and p, like in the binary case.

As for diluted species, these are identified when their concentration is less than 5 %. In this case,
Fick law can be applied:

𝑚
••⃗$,1$JJ = −𝜌($9 𝐷$,($9 ∇𝑦$

where 𝜌($9 is the density of the mixture, 𝐷$,($9 is the diffusion coefficient of i in the mixture and
∇𝑦$ is the gradient of mass fraction of i. Fick law is the analogous of the mass transfer of Fourier’s
law for heat transfer: driving force for heat is temperature difference, while driving force for mass
transfer is concentration difference.

We can define also an analogous for momentum transport: momentum can be transported by
convection or by diffusion (viscous transport of momentum), proportionally to the gradient of
velocity and viscosity. Mass transport of i can also be thermal diffusion: if there is a significant
gradient of T, single species will move proportionally according to a thermal diffusion coefficient.
This is specific of combustion: locally the temperature gradient could be of thousands of degrees
per mm! The local mass balance of the species i will look like this:

65
To solve the equation we need the distribution of temperature and velocity.

Energy balance

The accumulation of the internal energy is equal to – the gradient of flux.

𝛿𝜌‡($9 𝑢‡($9
= −∇𝑓𝑙𝑢𝑥 = 𝑞̇ B.0G + 𝑞̇ 1$JJ + ⋯
𝛿𝑡
The dot shows that values are expressed per unit of time, the lower case specifies it is a flux and not
a flow rate. Heat flow changes from point to point, the heat flux depends by the mechanism. The
diffusion can be quite important in combustion because of radiation, that is quite important at high
temperatures reached during the reaction.

𝑞̇ 1$JJ = −𝜆($9 ∇𝑇

The assumptions are those of steady state, no change in time. The normally used energy balance in
combustion reactions is the following one:

where the terms appearing are the gradient of convective flux, the gradient of diffusive flux and the
sum of all the species multiplied for their enthalpy per unit mass.

The thermal diffusion coefficient is defined as the ratio between thermal conductivity and density
and heat capacity. This coefficient has the same role of the diffusion coefficient. If these two
coefficients are similar, we expect the nondimenonal to be similar, meaning they have the same
shape.

Lewis number → It compares the rate of thermal diffusion with rate of mass diffusion

- By increasing the temperature, species diffuse faster

- By increasing the pressure, species diffuse less easily

In the case of a real gas, we use Fuller equation.

To conclude, the coefficient of diffusion of oxygen at a general T in air is the one at 300 K
multiplied by the ratio new T/old T elevated at 1,75.

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The same can be seen for H2 and CH3OH as follows

The full set of balances includes also the complicated equations of momentum balance, total mass
balance and continuity equation.

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 Part XI
Combustion of Solids
Biomass

To define the composition of a biomass there are two methods.

Proximate analysis

Ashes are easy to define, they are inorganic components containing calcium, silicon, potassium,
sodium and so on.

It allows to obtain the composition by gradually increasing the temperature. While we gradually
increase the T we plot the weight of the sample, comparing it to the initial weight. At some point
there will be a small loss of weight in the region of 100 °C (moisture will evaporate). By increasing
further the T, up for example to 200 °C, there will be a much sharper loss of weight, because of the
release of the volatiles (onset of release of volatiles).

Moisture is identified as the species releasing gas at a temperature above 100° C. At higher
temperature, depending on the inert the stop point will be identified: if it is air we will remain with
only ashes, because of the presence of oxygen that will lead to combustion. If the gas is a pure inert,
there will be no combustion, but just pyrolysis: heat causes degradation of the molecule but not
combination with other molecules.

Elemental analysis

TGA à Thermal Gravimetric Analysis

Tar à Molecules that at high temperature (300 °C) are vapours but may condense at around 150
°C

With the elemental analysis we do not identify the behavior of the biomass on the combustion, we
go into more detail. Considering for example wood, it is not an isotropic material: the properties in
one direction are different from those on another direction.

Homogeneous combustion

It is the slowest part of the combustion and therefore controls the whole process; it is also the part
generating most of the energy.

Considering instead the case of carbon, the reaction will take place on the external surface, that is
not homogeneous, leaving much surface for the reaction to develop. The contact area expands, and
that is extremely important for the combustion, however the internal surface is much larger than the

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external one. The same happens for sand: its density is of a few square meters per gram, it is very
low, inf act sand is very porous, its internal surface is very high.

The dH of reaction of the combustion of carbon is very high, it is 3 – 4 MJ/kg, and it is completely
released with the complete combustion to CO2, a lot less with only partial combustion.

The homogeneous combustion is the slowest part but also the one generating the biggest amount of
energy.

Cooling towers → Cool a gas by means of evaporation: air must disengage from liquid, we don’t
want the air to be taken outside. Some devices are needed to switch the direction of velocity. By
inertia the particle will continue and collapse on the stable surface.

During a combustion reaction of carbon, the mass of the particle is expected to decrease: we can
determine the carbon consumption in terms of mass, moles, size. The variation of mass can be
expressed as minus the rate of surface reaction multiplied by the surface of the particle.

The rate of surface reaction is expressed as the kinetic constant multiplied concentr. of carbonatum
on the surface and oxygen concentration on the surface. The concentration of carbonatum of the
surface is a constant.

that can also be written as:

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 &'4JHB/
𝑅PP = 𝐾𝐶,*

For the mass transfer we define an analogous of the ht coefficient: the driving force is the
concentration difference between the bulk and surface concentration. The ht transfer coefficient is
evaluated with experimental correlations; the nondimensional number is the Sherwood number,
depending on mass transfer coefficient, a characteristic length and a property of mass transfer
without convection. The Sherwood number varies from species to species.

Solid fuels are distinguished by the number of volatiles they release.

A reaction is heterogeneous when it happens between a solid and a gas, for example when a solid
fuel reacts with air, it is a two phase reaction.

Devolatilisation

Some product is released from the solid to the gas phase, this is some HC that is only partially
oxidized and can still be burnt: they are tars, oil, etc. Some H2O and CO2 may be present too, but
they are completely oxidized and thus won’t react anymore.

Rate of consumption of the solid

Two intermediates are produced: volatiles and char. The rate of burning depends on the
concentration close to the solid particle of char. Volatiles will instead burn instantly, the rate of
burning is that of products production. V is the amount of volatiles, and its derivative in time is the
rate of volatilization.

The rate of volatile increase is equal to the rate of loss of mass of the solid.

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The final amount of solid will be ashes that cannot be burnt, therefore the simplified rate of
volatilization is:

and it is proportional to the mass of solid that is left: if more solid is available, more volatiles will
be released, and faster. It represents the blue chart, however the real model is more complex, it
doesn’t consider the saturation:

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The degree of devolatilization measures the extent of production of volatiles in non-dimensional
form: 0 means no volatiles, 1 means maximum amount of volatiles. Its standard representation is:

With the kinetic constant that can be expressed as:

DAE model (Distributed Activation Energy)

We try to use a simplified equation to describe a complex model. Based on this model, activation
energy is not a single number but a whole distribution. It is the energy barrier for the reaction to
take place: if it is small it means that the reaction is easy, if it is large the reaction is difficult.

Volatiles will become energy, heat flow:

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Volatiles are produced with energy used to break the molecules of a solid: it is very similar to
pyrolysis, it happens when there is a lack of oxygen, there is no combustion so the energy used is
lost. With the use of energy there is a linear increase of temperature, its slope is the heating rate.
Increasing the heating rate increases the amount of volatiles, it is in the order of 10^3 degrees per
m.

Fluidized bed à Feeding air from the bottom at a velocity sufficient to make the sand move. At
the beginning there is just a bed, but with increasing velocity some bubbles create and incorporate
in the sand and their rise will mix the sand. If the velocity goes up too much, the waves could make
the solid go out of the chamber. This can be useful to improve the efficiency of wood combustion
and reduce the releases to the environment.

last lines in notion, see if they are useful

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 Part XII
Homogeneous & heterogeneous reactions
Material balance

Assuming no porosity to simplify, the material balance of carbon is expressed as the rate of
production on a mass basis of carbon on the surface multiplied by the surface of the carbon:

The rate of carbon consumption is ruled by a kinetic constant that conveys the effect of temperature:
the higher T, the higher K and the higher the rate of burning of the atoms. The material balance of
oxygen at the surface is:

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Similarity between mass transfer and heat transfer coefficient

The structure of the correlation is similar: the flow of a fluid against a solid is standard in heat
transfer, and the solid can have many different forms (pipe, sphere, plate…).

The sherwood number is a tool to obtain a value of the mass transfer coefficient: it is equal to the
diffusion coefficient divided by the radius of the particle. The diffusion coefficient depends on the
type of molecule, even in the same mixture. The mass transfer coefficient depends on the type of
particle that is moving.

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