Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

CHAPTER 4

SOME IMPORTANT CHEMICAL MECHANISMS

A reaction mechanism refers to a set of elementary reactions that describe the chemical steps
converting the reactant to the product.

Understanding reaction mechanisms will help to explain experimental observations, and to build
predictive models for combustion phenomena. This is one of the most researched topics in
combustion field at present.

Reaction mechanisms for combustion are typically complex. Depending on the fuel burned, they may
involve hundreds of species and thousands of reactions. Knowledge about many of the reactions is
unknown and difficult to measure experimentally.

Discussed here are some best understood reaction mechanisms, including H2 oxidation, CO oxidation,
and NO formation in combustion, which are building blocks for large combustion mechanisms. Major
features of the combustion mechanisms of larger hydrocarbons (C>3) are also presented. Methane
(C1) and ethane (C2) have quite different oxidation mechanisms than larger hydrocarbons. We will
not discuss them here (methane mechanism can be found in the Chap.5 of Turns’s book).

As will be seen, almost all elementary reactions in combustion are free radical reaction, and all types
of chain reactions, i.e., initiation, propagation and termination, are involved.

1. The H2-O2 System

1.1. Reaction mechanism

Hydrogen oxidation with oxygen is one of the best understood combustion mechanisms, which in
general consists of 20 reactions (40 if considering reversible reactions) and 8 species, including H2,
O2, H, O, OH, HO2, H2O2, and H2O. This is shown on the next page. Some of these reactions have
been seen in Chapter 3.

Some principles for understanding these reactions.

1) H2 splitting into two H is more likely than O2 splitting into two O, because the H-H (single) bond is
weaker than O=O (double) bond. For this reason, the initiation reactions are unlikely to include
H2 + O2 → H2O + O
2) Due to high bond energy of O=O, O radical is very reactive. This is why the H.3 reaction is not
only the single most important reaction for H2 high temperature (>1500 K) combustion, but also
generally one of the most important reactions for hydrocarbons combustion.
3) HO2 is also a radical but much less reactive than H or O atoms. Forming HO2 requires less
activation energy than H and O, so the H.2 reaction is more important at low temperature
conditions.
4) H2O2 is meta-stable at temperature < 1100 K. Above that, H2O2 decomposes into two OH radicals
(chain branching) and dramatically accelerates the overall reaction rate. The H2O2 decomposition
reaction (H.20) can be considered the most important combustion reaction at low temperatures.

The initiation reactions are

H2 + M → H + H + M (high activation energy) (H.1)
H2 + O2 → HO2 + H (low activation energy) (H.2)

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The propagation reactions are

H + O2 → O + OH (H.3)
O + H2 → H + OH (H.4)
H2 + OH → H2O + H (H.5)
O + H2O → OH + OH (H.6)
Chain termination reactions are
H + H + M → H2 + M (H.7)
O + O + M → O2 + M (H.8)
H + O + M → OH + M (H.9)
H + OH + M → H2O + M (H.10)
At certain conditions, HO2 radical is formed via
H + O2 + M → HO2 + M (H.11)
and becomes important for the overall reaction rate. Its reactions are
HO2 + H → OH + OH (H.12)
HO2 + H → H2O + O (H.13)
HO2 + O → OH + O2 (H.14)
and
HO2 + HO2 → H2O2 + O2 (H.15)
HO2 + H2 → H2O2 + H (H.16)
The reactions of H2O2 are
H2O2 + OH → H2O + HO2 (H.17)
H2O2 + H → H2O + OH (H.18)
H2O2 + H → HO2 + H2 (H.19)
H2O2 + M → OH + OH + M (H.20)

1.2 Explosion characteristics of H2-O2 system

The H2-O2 system has interesting explosion characteristics that can be explained using the above
mechanism.

In a closed homogeneous reactor where H2 and O2 are mixed in the stoichiometric composition (φ = 1),
there are three distinctive limits to define whether explosion will occur, as shown in the figure below,
depending on the temperature and pressure.

Below the first limit, the pressure is so low that nearly all radicals formed by reactions H.2 – H.6 are
destroyed by collision to the wall. This is not a gas-phase reaction and thus generally not included in
the mechanism.

Above the first limit and below the second limit, the pressure is high enough so that the radicals from
reactions H.2 – H.6 can survive the wall collision and find chance to hit each other and further react to
cause explosion.

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Second limit

From I. Glassman, Combustion (2008) (similar plot also in Turns’s book)

Above the second limit, the higher pressure makes it possible for reaction H.11 to occur, which
converts a reactive H radical to a less reactive HO2 radical. This effectively terminates the chain
sequence because the HO2 radicals can diffuse to the wall and get destroyed there.

Finally at the third limit, with the higher pressure, H2O2 accumulated from HO2 reactions (H.15 – H.16)
reaches the critical concentration and then decomposes to triggers the chain branching (H.20) and
explosion.

2. Carbon Monoxide Oxidation

Carbon monoxide oxidation is extremely important to the oxidation of hydrocarbons. This is because
simply speaking, hydrocarbon combustion can be considered as a two-step process: the first step is
to convert all the fuel and derived species into carbon monoxide, and the second step is to oxidize
carbon monoxide to carbon dioxide. In other words, carbon monoxide is the last species being
oxidized in hydrocarbon combustion, and its oxidation accounts for significant portion of heat release
from burning these compounds.

The reaction rate for CO oxidation is known to be slow, unless there are hydrogen-containing species
present: small quantities of H2O or H2 can have a tremendous effect on CO oxidation rate. This is
because the CO reacts much faster with hydroxyl radical, OH, than with O radical.

CO oxidation mechanism involving water can be written

CO + O2 → CO2 + O (CO.1)
O + H2O → OH + OH (CO.2)
CO + OH → CO2 + H (CO.3)
H + O2 → OH + O (CO.4)
The CO.1 reaction is slow, again because the strong O=O double bond, and does not contribute
much to the formation of CO2. But it serves as the initiator of the whole chain sequence. The CO.3 is
the key reaction in the overall scheme, which is the main channel for CO2 formation. Note that CO.3 is
a chain propagation reaction in which a reactive H radical is formed, which then participates in the

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important chain branching reaction CO.4 (the same reaction as H.3). CO.3 also releases a large
amount of heat which accelerates the overall reaction rate.

The CO oxidation involving hydrogen requires all 20 (or 40 forward and reverse) hydrogen reactions
to be included. And a new CO2 formation reaction opens up with the presence of HO2:
CO + HO2 → CO2 + OH (CO.5)
which is not as important as the CO.3 reaction though.

CO oxidation with the presence of H2 has important applications in the emerging energy technologies.
Synthesis gas, or syn-gas, produced from gasification of coal, biomass, or natural gas contains mainly
CO and H2, and is being increasingly used for electricity generation via combustion in gas turbines.

3. Oxides of Nitrogen Formation

Nitric oxide, or NO, is an important minor species in combustion because of its contribution to air
pollution, e.g. producing smog. NO is primarily produced from the oxidation of N2 from air, but can
also be produced from nitrogen-containing species in the fuel.

In the combustion where the fuel contains no nitrogen, NO is formed by four chemical mechanisms
that involves nitrogen from air.

3,1 Thermal or Zeldovich mechanism

This is the most important NO formation pathway for combustion applications involving flames, i.e.
high temperature combustion.

The extended Zeldovich mechanism consists of three reactions

O + N2  NO + N (N.1)
N + O2  NO + O (N.2)
N + OH  NO + H (N.3)
This mechanism is generally coupled to the fuel combustion mechanism through O2, O, and OH
species; however, in processes where the fuel combustion is complete before NO formation becomes
significant, the two processes can be decoupled.

Nitrogen molecule has very strong N≡N triple bond. Therefore the N.1 reaction requires high
activation energy to start and becomes increasingly important at high temperatures. As a rule of
thumb, the thermal mechanism is usually unimportant at temperature below 1800 K. Compared with
the time scales of fuel oxidation processes, NO is formed rather slowly by the Zeldovich mechanism.
Thus, thermal NO is generally considered to be formed in the post-flame gases.

3,2 N2O-intermediate mechanism

The N2O-intermediate mechanism is important in fuel-lean (φ < 0.8) conditions. The three steps
of this mechanism are
O + N2 + M  N2O + M (N.4)
H + N2O  NO + NH (N.5)
O + N2O  NO + NO (N.6)
This mechanism becomes important in NO control strategies that involve lean premixed combustion,
such as in gas turbines and in natural gas fueled spark-ignition engines.

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3.3 Prompt or Fenimore mechanism

The prompt mechanism is intimately linked to the combustion chemistry of hydrocarbons. Fenimore
discovered that some NO was rapidly produced in the flame zone of laminar premixed flames long
before there would be time to form NO by the thermal mechanism, and he called the rapid formed NO
prompt NO.

The prompt mechanism is important at fuel rich φ > 1 conditions, but becomes less important
above φ ~ 1.2. The sequence is primarily initiated by CH radicals attacking N2
CH + N2  HCN + N (N.7)
followed by the formation and conversion of HCN to NO:
HCN + O  NCO + H (N.8)
NCO + H  NH + CO (N.9)
NH + H  N + H2 (N.10)
N + OH  NO + H (N.11)

3.4 NNH mechanism

The mechanism is recently discovered and involves key two steps
N2 + H → NNH (N.12)
NNH + O → NO + NH (N.14)
which has been shown to be particularly important in the combustion of hydrogen and for
hydrocarbon fuels which produce large concentrations of H radicals during combustion.

NO emitted from combustion eventually oxidizes to nitrogen dioxide, NO2, which is important to
production of acid rain and photochemical smog. NO2 can also directly be formed during combustion
and the mixture of NO and NO2 is collectively called NOx.

4. Oxidation of Higher Alkanes

Higher alkanes (paraffins), with carbon number ≥ 5, are major constituents for transportation fuels, e.g.
gasoline, diesel and jet fuels. Combustion mechanisms of these compounds are much more complex
than the species discussed above, mainly due to two reasons:
1) With larger hydrocarbon molecule, the number of reactions that can possibly happen increases
exponentially. For example, oxidation of the simplest alkane, CH4, requires more than 200
reactions to describe the process. For higher alkanes it is not uncommon that a detailed
combustion mechanism could contain hundreds of species and thousand of reactions.
2) Oxidation chemistry of these hydrocarbons often differs as reaction conditions (in particular,
temperature) change. For example, for most alkanes, their low-temperature combustion chemistry
(T < 1100 K), which produces cool flame and negative temperature coefficient (NTC) behavior as
introduced in Chap. 1, is essentially different from the high temperature combustion chemistry
(T > 1500 K) that typically occurs in hot flames.

Given the complex nature, we will not attempt to explore or list the many elementary reactions
involved; rather, we will present an overview of the process and discuss some general principles
involved.

4.1 Classification of combustion regimes

Different combustion regimes can be classified according to oxidation temperature and pressure, as
shown in the figure below. It indicates that in each regime alkane oxidation is controlled by different
combustion mechanisms and dominated by different species. The lines delineate the main kinetic
chain-branching processes. The upper line connects points where the overall H + O2 reaction is
neutral: above the line it is net branching; below it is net terminating. The lower lines are where the

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alkyl peroxy chemistry is neutral: above these lines there is net termination and below net branching.
The regime between the two lines is the region of negative temperature coefficient. The “low”-,
“intermediate”-, and“high”-temperature regimes are broadly characterized by the types of chemistry
indicated.

Source: Low Temperature Combustion and Autoignition, M. J. Pilling (1997).

4.2 High-temperature combustion

High-temperature combustion typically occurs at the presence of flames. The reaction temperature is
so high (>2000 K, as we calculated) that the fuel molecules rapidly break into small alkyl species and
hydrogen radicals. Hydrogen radicals then react with oxygen via the important chain-branching
reaction that we discussed in the H2-O2 system.
H + O2 → OH + O (HC.1)
This reaction is essential to build a pool of radicals which further attack fuel molecules as well as
small species and convert nearly all carbon-containing intermediates into CO. During this process, H2
is formed and converted into H2O. The final stage is CO oxidation to CO2 which releases a majority of
heat for the combustion.

Compared to other combustion regimes, high-temperature combustion kinetics is less dependant on

the fuel used. This is because the high temperature makes the fuel molecule, no matter what the
structure is, rapidly decompose into similar small species that resemble little of the parent molecules.
The overall reaction rate is largely controlled by the oxidation of the small hydrocarbon species rather
than the original fuel molecules. For this reason, constructing combustion mechanisms of higher
alkanes can be done in a hierarchical manner, as shown in the figure below, which starts from the
simplest H2 combustion and then progressively incorporates new species and reactions till the original
fuel molecule is included.

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H2 CO HCHO C2 Species CnC2n+2 (n>2)

oxidation Oxidation Oxidation Oxidation Oxidation

4.3 Low-temperature and intermediate-temperature combustion

Oxidation at low temperature (typically < 900 K) and intermediate temperature (typically 900 -1100 K)
is closely related, and in many occasions they are collectively called low-temperature combustion,
simply to differentiate from the high-temperature combustion. Combustion chemistries in these two
regimes are closely coupled, which together cause the cool flame and negative temperature
coefficient behavior we saw in Chap. 1.

Chemical kinetics at low-temperature combustion is dominated by alkyl peroxy radicals. A peroxy

radical is formed by an alkyl radical, R, and an oxygen molecule,
R + O2 → ROO (HC.2)
Alkyl radical generally refers to any radicals derived from hydrocarbon molecules, for example, CH3,
CH2, C2H5, C2H3, n-C7h17, etc.
However, the major difference of low-temperature combustion from high-temperature combustion is
that fuel molecules are much unlikely to break down at low temperatures. This is because
decomposition reactions require high activation energy, and are unlikely to happen at low
temperatures (collisions do not have enough energy to overcome the energy barrier). The overall
reaction is thus much slower than at high temperature due to lack of or slow build-up of the radical
pool.

Therefore, the radicals involved in reaction HC.2 are typically fuel radicals (fuel molecule lost one
hydrogen) or other alkyl radicals of similar size. Unlike H or OH radicals, peroxy radicals, ROO, are
not very reactive. They have several paths to further react. One is to undertake several unimolecular
reactions – reaction involves only one molecule (itself) – and lead to low-temperature chain branching.
Cool flame is resulted from low temperature chain branching which produces CO, instead of CO2, as
the major end product, and only increases the reaction temperature moderately, < 200 K.

As temperature increases, however, ROO becomes less stable and its decomposition becomes
dominant:
ROO → R + O2 (HC.3)
Since the temperature is not high enough yet to break down alkyl radicals, these alkyl radicals
undertake several other reactions, such as
R + O2 → olefin + HO2 (HC.4)
This reaction essentially terminates the chain reaction because of the low reactivity of olefins and HO2
radical at the given temperature. As a result, the overall reaction rate of low-temperature combustion
appears to decrease despite the temperature rise resulted from the cool flame. This is the chemistry
behind the negative temperature coefficient behavior and the reason why a cool flame does not lead
to hot flame. Further, as reaction rate decreases, the mixture temperature drops. At some point, the
temperature is low enough so that ROO formation (HC.2) picks up again and restarts the low-

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temperature chain branching. This explains the oscillating cool flames observed in a flow reactor, as
seen in Chap. 1.

In some cases the temperature past cool flame can continue rising due to external factors, such as,
piston compression in engines. In this case, the reaction then enters the intermediate temperature
regime. In this regime, reactions of hydrogen perxoy radical, HO2, becomes important. Similar to H2
oxidation, the following reaction
HO2 + HO2 → H2O2 + O2 (HC.5)
occurs to accumulate H2O2 while the overall reaction rate remains slow. As the temperature increases
to the critical point for H2O2 to decompose, the resultant OH radicals then greatly accelerate the
reaction rate and trigger the hot ignition.
H2O2 + M → OH + OH + M (HC.6)

Unlike high temperature chemistry where radical concentrations are high and collisions between
species are frequent, in low temperature regime the most important reactions are unimolecular, where
the reacting species gains energy from collisions with a third body, M, and then proceeds with
intramolecular reactions. Therefore fuel molecular structure has paramount importance for the low-
temperature combustion kinetics.

Low temperature combustion is central to the combustion process in internal combustion (IC) engines,
i.e. spark ignition (gasoline) engines and compression-ignition (diesel) engines. The process
controlled by low-temperature combustion chemistry (incl. both low-temperature regime and
intermediate-temperature regime) is called autoignition, which is the process that fuel and air are
compressed to a point to self-ignite. Autoignition is unwanted in gasoline engines but is required in
diesel engines. Because of this difference, molecular structures are essentially different for the major
compounds in gasoline and diesel fuels.