Combustion

From the Stone Age to modern times combustion remains one of the most
important phenomena known to the mankind. It is one of the most important
chemical reactions and may be acknowledged as an ultimate step in oxidation of
compounds. Combustion is a process in which heat is released by the reaction of
compounds with oxygen. It is a complex reaction process involving series of
exothermic reactions. The main products of combustion reaction are carbon
dioxide and water.[] www.britanica.com Initially it was considered to be the only
source of energy but sometimes combustion remains incomplete due to lack of
oxygen. This process of partial combustion leads to environmental pollution.

Basically five types of pollutants are emitted during combustion. They are Oxides
of Nitrogen (NOx) , Carbon Monoxide , unburnt Hydrocarbons( in case of
incomplete combustion) , Sulfur Oxide and Particulate Matter (aerosols).

In actuality the concentrations of various pollutants differ from their equilibrium

values. This emphasizes the requirement of knowledge of chemical kinetics in the
study of formation of pollutant.

Chemical reactions in Combustion

 Hydrogen combustion

Hydrogen fuel cells utilize the principle of chemical reaction of oxygen with
hydrogen to produce electricity, heat and water. The reaction mechanism for the
reactions between hydrogen and oxygen is very complex and involves exchange
of oxygen atoms and fragments. Studies have been conducted for the use of
hydrogen as a fuel in vehicles and the various characteristics have been
considered. It shows that hydrogen can be considered as a reliable fuel source
with no pollution threat. [] HYDROGEN-OXYGEN REACTION MECHANISM AND ITS
IMPLICATTON TO HYDROGEN ENGINE COMBUSTION L. M. DAS International Journal of
Hydrogen Energy Volume 21, Issue 8, August 1996, Pages 703-715
  Combustion of Carbon Monoxide

Pure mixtures of carbon monoxide and oxygen (or air) can be ignited only with
sparks of high energy or under high pressures and temperatures. There is still
some speculation going on the reaction mechanism of carbon monoxide
combustion since its oxidation occurs during the break down of hydrogen
compounds. [] Kinetics of carbon monoxide oxidation in postflame gases J.B.Howard G.C.
Williams D.H. Fine Symposium (International) on Combustion Volume 14, Issue 1, 1973, Pages
975-986

 Combustion of Hydrocarbons

The overall mechanism of hydrocarbon combustion is complicated due to

entanglement of array of molecules and radicals. Large n-alkanes are used as
fuels. Basically the reaction mechanism of n-alkanes can be categorized into two
classes: high temperature combustion in which the major alkyl radicals
decompose thermally into a smaller alkyl radical and an olefin species and low
temperature combustion in which there is addition of molecular oxygen to the
major alkyl radicals. []A comprehensive detailed chemical kinetic reaction mechanism for
combustion of n-alkane hydrocarbons from n-octane to n-hexadecane Charles K. Westbrook,
William J. Pitz, Olivier Herbinet, Henry J. Curran, Emma J. Silke, Combustion and Flame 156
(2009) 181–199

Fig 1: overall reaction mechanism of Hydrocarbons

Automotive emission

With the advent of 21st century, there is tremendous increase in diesel and
gasoline powered vehicles. These vehicles utilize energy produced by combustion
of air and fuel. The combustion reaction occurring in the engine not only produces
CO2 and H2O and some amount of H2, they also produce CO, NOx and
Hydrocarbons. These substances are major contributors of air pollution. Owing to
their rapid increase in number, these are the major contributors towards air
pollution.

Sources of Auto Emissions

There are basically two main sources of pollutants from automobiles:

 From Combustion

In an ideal situation all the hydrogen in fuel should be converted to water and
carbon to carbon dioxide by oxygen. The nitrogen in the air should remain
unaffected. But in reality this does not happen and the automobiles emit several
types of pollutants. [] Automobile Emissions: An Overview R Losses ACT SHEET OMS-5
August, 1994 U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF MOBILE SOURCES

 Evaporation of fuel

Majority of evaporative emissions contains hydrocarbons which escape from the

fuel. Evaporative emissions occur in several ways:

DIURNAL: Gasoline evaporation increases during the day due to increase in

temperature. This causes the fuel tank to heat up allowing gasoline vapors to
escape.
RUNNING LOSSES: gasoline can vaporize and vent out when the vehicle is still in
running mode.

HOT SOAK: gasoline can also escape when the vehicle is just stopped after
covering some distance since the exhaust system would be heated.

REFUELING: when the fuel tank is refilled, it pushes out the vapors of gasoline
already present in it.

Many other substances such as aldehydes, SO2 and particulate matter are also
produced alongside these pollutants. In the following Table 1, maximum
allowable concentration of various pollutants at workplace has been
summarized.[] Roth, L. and Daunderer, M. (1990). Sicherheitsdaten, MAK-Werte, Ecomed.
Landsberg

Pollutants Maximum Allowable Concentrations , mg/m3

Carbon Monoxide (CO) 33
Unburned Hydocarbons 9
Nitrogen Monoxide 9
Aldehydes 0.6
Lead 0.1
Sulfur Dioxide 2
Carbon Dioxide 9000

Table 1: pollutants and their max. allowable conc.

Composition of exhaust Gases

The interaction of motor vehicles and environment has become an increasingly

important consideration. It is very important to determine the composition of the
exhaust gases emitted from automobiles. Table 1 shows the various constituents
present in exhaust of the engine [4] Martin A. Elliott , George J. Nebel & Fred G. Rounds
(1955) The Composition of Exhaust Gases from Diesel, Gasoline and Propane Powered Motor
Coaches, Journal of the Air Pollution Control Association, 5:2, 103-108
 Table 2: constituents of exhaust emission

In order to reduce exhaust emissions it is important to get a clear and concise

data of exhaust constituents. The following Figure 2 shows the percentage of
various constituents emitted from an automobile powered by gasoline: [] Motor
Vehicle Exhaust Emission, Self Study Program Volkswagen

Figure 2: Composition of exhaust emission of petrol engines

Exhaust from petrol engine also contains some trace amount of Sulfur Dioxide
(SO2).

The composition of exhaust from diesel engine is different from that of petrol
engine. The following Figure 3 shows the composition of exhaust from diesel
engine: [] Motor Vehicle Exhaust Emission, Self Study Program Volkswagen
 Figure 3: Composition of exhaust emission of Diesel engines

Constituents of Exhaust

Automobile exhaust is a menace to the environment. Tail pipe exhaust emission is

major sources of automotive emissions. Engine exhaust contains carbon
monoxide, unburned HC, nitrogen oxide and lead compounds. These compounds
present in vapor phase are generally termed as VOCs (Volatile Organic
compounds). They cause direct and secondary (i.e. photochemical smog)
environmental effects.

Since Combustion occurs only within specific fuel:air ratios and is hard to control,
it often produces pollutants. The optimum air-fuel ratio is 14.64:1. Though the
mixture gives lowest levels of HC and CO but it produces very high levels of NOx.
[] catalytic converter theory operation and testing Kevin S. McCartney 1993

It is inefficient and energy recovery can be difficult. Sometimes due to incomplete

combustion unburnt hydrocarbons are produced which are emitted in
atmosphere in vapor form.
A description of various pollutants emitted from automobiles is given below:
 Carbon Dioxide
The increasing concentration of CO2 in the atmosphere is ringing alarms all over
the world. Majority of CO2 is emitted through vehicles. The main concern due to
rise in the levels of CO2 is Global warming. The data for the emission of CO2 from
diesel and gasoline powered engine is tabulated in the following Table 3: []
www.epa.gov

CO2 emission per Gallon of Gasoline 8,887 gm of CO2 / gallon

CO2 emission per Gallon of Diesel 10,180 gm of CO2 / gallon
Table 3: CO2 emission

 Carbon Monoxide
It is formed due to incomplete combustion of carbonaceous material present in
the fuel. The concentration of CO in the exhaust is lower than the concentration
in the combustion chamber. [] Kinetics of pollutant formation and destruction in
combustion, Craig T. Bowman ,Prog. Eneregy Combust.Sci.,1975, Vol. 1, pp. 33-45.

CO is converted to CO2 by the action of catalytic converter. When the

temperature drops, particularly during winters, the efficiency of catalytic
converters decreases because catalysts take more time to function. Also the air-
fuel ratio is low. Therefore combustion remains incomplete. Hence CO
concentration increases. [] The Ongoing Challenge of Managing Carbon Monoxide Pollution
in Fairbanks, Alaska (2002)

Effects of CO on human health show that CO not only decreases the O2-carrying
capacity of the blood, but also decreases the ability of the tissues to extract O2
from the blood during circulation.
CO emission by diesel vehicles is minimal.
 Nitrogen Oxides
NOx is a collective term used to refer to two Oxides of Nitrogen: Nitrogen Dioxide
(NO2) and Nitric Oxide (NO).
Nitrogen oxides are produced by two sources:
At very high temperature, Nitrogen and oxygen combine to form NOx known as
“Thermal Nox”
“Prompt NOx” formed by reaction of nitrogenous fuels with oxygen. [] CATALYTIC
COMBUSTION (REVIEW) D L Trimm Applied Catalysis, 1 (1983) 249-282

Other than the above mentioned sources, NOx are formed at high pressure and
excess amount of oxygen present in the engine during the combustion cycle. As
the air fuel ratio increases, Concentration of NOx also increases. []Kinetics of
pollutant formation and destruction in combustion, Craig T. Bowman ,Prog. Eneregy
Combust.Sci.,1975, Vol. 1, pp. 33-45.

The lowest concentration of Nox is observed when the engine is still cold and the
highest concentration at high loads.
Some N2O is also formed during catalytic reduction of NO at low temperatures. []
Nitric Oxide Catalysis in Automotive Exhaust Systems, Kathleen C. Taylor, CATAL. REV.-SCI. ENG.,
35(4). 457-481 (1993)

A series of complex reactions take place between HCs and NO2 which give rise to
photochemical smog.
 Hydrocarbons
HC from automobiles are emitted from two sources: evaporative emissions and
tailpipe exhaust emissions. The concentration of HC from both sources differs
from each other.
Since the air–fuel mixture is not homogeneous throughout, extremely high
excess-air ratios are present in certain zones during the combustion process. The
higher the air/fuel ratio, the lower is the local temperature. This means that
chemical reactions proceed fairly slowly or may even ‘freeze-up’, thus leading to
increased HC emissions. In general, HC concentrations of diesel engines are lower
than those of spark-ignition engines. [] ON THE EMISSIONS FROM INTERNAL-
COMBUSTION ENGINES: A Review INTERNATIONAL JOURNAL OF ENERGY RESEARCH Int.J
.Energy Res. ,22, 483–513 (1998)

Hydrocarbons mainly consist of Alkanes and olefins. Range of total HC

concentrations varied widely with the environmental conditions, resulting in
exposures from 8 to 3,000 ppmC; and Propane, butane, and pentane provide
more than 80 percent of total exposure. [2] Automotive Emissions JOHN H.JOHNSON
Michigan Technological University Air Pollution, the Automobile, and Public Health. Watson AY,
Bates RR, Kennedy D, editors. Washington (DC): National Academies Press (US); 1988.

The amount of olefins, mainly ethylene (11.2%), acetylene (8.7%) and propylene
(5.0%), amount to a total of 25 percent of total hydrocarbon produced. [5] The
hydrocarbon composition of exhaust emitted from gasoline fuelled vehicles P.F.Nelson
S.M.Quigley Atmospheric Environment (1967) Volume 18, Issue 1, 1984, Pages 79-87
Emission of HC depends upon the composition of gasoline. Market gasoline
contains 20-50% of aromatic HC. [ ] Passenger car hydrocarbon emissions speciation,
Frank Black, Larry High, EPA -600, May 1980

 Sulfur Dioxide
Emission of SOx is mainly due to the sulfur compounds present in the fuel. The
concentration of SO2 is more in diesel engine exhaust as in petrol engine exhaust.
Transportation sector contributes almost 5% emission of SO2 to the environment
pollution. This value reaches to 17% in some countries. [] TYPES AND AMOUNTS OF
VEHICULAR EMISSIONS HE Kebin, ZHANG Qiang and HUO Hong POINT SOURCES OF
POLLUTION: LOCAL EFFECTS AND IT’S CONTROL – Vol. I

 Particulate Matter
Particulate matter is produced from the exhaust from diesel engine. Particulate
matter can be classified as Primary or Secondary based on their origin. Primary
particulates occur directly in atmosphere whereas secondary is formed due to
reactions. Mostly secondary particulates are sulfates and nitrates formed in
reaction involving SO2 and NOx.
Volatile Organic Compounds
Volatile Organic Compounds is a term coined for those organic compounds of
Carbon excluding carbon monoxide, carbon dioxide, carbonic acid, metallic
carbides or carbonates, and ammonium carbonate. It is imperative to study these
VOCs because they pose a threat to the environment. They participate in
atmospheric photochemical reactions which are responsible for ozone formation.
[] www.epa.gov
The classification of VOCs as done by WHO based upon temperature is described
in the following Table 4: [] Volatile Organic Compounds (VOC s) Christophe Ponce,
Automotive Product Manager (Seating) Warwick, 16/05/07

Boiling point Term Examples

< 50 0 C Very Volatile Organic Formaldehyde (- 21 ºC)
Compounds (VVOC) Acetaldehyde (20 ºC)
> 50 ºC Benzene (80 ºC)
< 260 ºC Volatile Organic Compounds Toluene (110 ºC)
(VOC) Styrene (145 ºC)
 Dabco (175 ºC)
> 260 ºC Semi-volatile Organic BHT (265 ºC)
< 400 ºC Compounds (SVOC) Di-n-butyl phthalate (340 ºC)
Di-n-ethylhexyl phthalate
(390 ºC)
> 400 ºC Particulate Organic Matter PCB
(POM)

Table 4: Classification of VOCs

VOCs are measured in terms of their Carbon content. Their concentration can
range from ppm to few hundred ppbs.

Studies have been performed to estimate the emission of VOCs from vehicles
during different traffic density. The species that contribute the most to the total
VOCs (on a molar basis): ethene (10.6%), isopentane (7.6%), acetylene (7.3%),
toluene (5.9%), and butane (5.6%). [] Characterization of VOC Emissions from Light-Duty
Vehicles in Monterrey, Mexico: Tunnel Study Alejandro E. Araizaga, Yasmany Mancilla and
Alberto Mendoza ttnchie1 conference ei19

The emission of VOCs is greatly depended on temperature. As the temperature

increases VOC emission decreases. [] Effects of Temperature on Gasoline Exhaust VOC
speciation Anirban Roy, Darrell Sonntag, Charles Schenk, Joseph McDonald, Rich Cook,Catherine
Yanca ,David Hawkins ,Yunsoo Choi University of Houston USEPA, Ann Arbor USEPA’s Annual
Emissions Inventory Conference April 16th, San Diego

Studies show that as the speed of the vehicle decreases (10 km/hr) , the emission
of VOC increases. [] Exhaust emissions of volatile organic compounds of powered two-
wheelers: Effect of cold start and vehicle speed. Contribution to greenhouse effect and
tropospheric ozone formation M. Antonietta Costagliola, Fabio Murena ,M.VittoriaPrati Science
of the Total Environment 468–469 (2014) 1043 –1049
VOCs also cause hazy events and decreases light visibility. The main contributor is
aromatics (39.8%), followed by alkanes, hydrocarbons and alkenes. [] VOC
characteristics, emissions and contributions to SOA formation during hazy episodes Jie Sun,
Fangkun Wu, Bo Hu, Guiqian Tang, Junke Zhang, Yuesi Wang Atmospheric Environment 141
(2016) 560-570

The nature of VOC depends on the emission source. Alkanes, olefins,

alcohols, ketones, aldehydes, aromatics, halogenated hydrocarbons come under
the category of VOCs. [] R.M. Heck, R.J. Farrauto, Catalytic Pollution Control, second edition,
Wiley Interscience, New York, 2002.

Anthropogenic sources of VOC include mainly outdoor sources, such as chemical,

pharmaceutical and power plants, petroleum refineries, gas stations and dry
cleaners, food processors, textile manufacturers, etc.

VOCs can cause some serious health defects such as memory loss and irritation in
respiratory tracts. Some of the VOCs are also carcinogenic.

Control strategies for automotive emission

It is neither possible in the foreseeable future to curb the use of motor vehicle nor
desirable. Then, the challenge lies in the use of control technologies to minimize
the adverse effect.

Several clean-up technologies are well known and used today for treatment of gas
phase emissions from industrial plants. Thermal combustion and physical
reversible processes, coupled with organic compounds recovery, are profitable
when the concentration of the pollutants is relatively high [3]. I. Mazzarino and A.A.
Barresi CATALYTIC COMBUSTION OF VOC MIXTURES IN A MONOLITHIC REACTOR Catalysis
Today, 17 (1993) 335-348

Apart from these, there are several other methods used to control the vehicular
emission. These methods which are used to reduce emissions are all applied in
the combustion chamber.

Pre-Treatment of fuels

The composition of fuel and its properties influence the combustion process.
Thereby, help in reducing the exhaust emission. With the small amount of
addition of Hydrogen to the fuel, combustion process is amplified and exhaust
contains lower levels of pollutants. An oxygen enriched fuel also improves
thermal efficiency and helps in reducing CO and NOx emissions. [] A Before
Treatment Method for Reduction of Emissions in Diesel Engines ,Bade Shrestha, S., LeBlanc, G.,
Balan, G., and de Souza, M SAE Technical Paper 2000-01-2791, 2000
Air injection systems

It is the earliest method used for controlling exhaust emissions. They are used to
oxidize HC and CO forming H2O and CO2. Air is introduced into the exhaust ports
of the engine and it gets mixed with the exhaust.

Initially it was capable to meet the emission standards but with new regulations in
place, modifications in control strategies have been done. Also with the use of Air
Injection System there was increase in mass flow rates of exhaust since amount of
unburnt HC increased. The concentration of NOx also increased in the exhaust. []
The effect of air injection at the exhaust ports of a gasoline engine on the oxides of nitrogen
emissions Reid, Richard Stowell

Exhaust gas Recirculation

This is a control technique used for the reduction of NOx. It makes stable
combustion difficult to achieve because it causes some loss of efficiency due to
decrease in combustion rate. [] Using exhaust gas recirculation in internal combustion
engines: a review G.H.Abd-Alla, Energy Conversion and Management
Volume 43, Issue 8, May 2002, Pages 1027-1042

Though it reduces NOx but it increases Particulate Matter by lowering oxygen

concentration in case of diesel engines. []Diesel engine exhaust gas recirculation––a
review on advanced and novel concepts Ming Zheng Graham T. Reader J.Gary Hawley Energy
Conversion and Management Volume 45, Issue 6, April 2004, Pages 883-900

Despite having some limitations the above two control mediums are still in use.
Some modifications are done to make them according to modern needs.

Thermal converter

Thermal reactors were used in early days for the treatment of exhaust from
vehicles. They operate at high temperatures above 600-7000 C. They oxidize CO
and HC under oxygen rich condition. They operate under adiabatic conditions. In
this VOCs are heated to set point temperature and then oxidized to CO2 and H2O.
 Fig 4: Thermal Converters

Catalytic Converters

 Catalytic Combustion

Catalysis and combustion have long been linked. The introduction of a

heterogeneous catalyst allows better control of oxidation over wider fuel:air
ratios, produces less pollutants and, if the catalyst is carefully designed, improves
the efficiency of energy recovery.[] CATALYTIC COMBUSTION (REVIEW) D L Trimm Applied
Catalysis, 1 (1983) 249-282

Catalytic combustion seems to be the best way to eliminate vapor

phase organics at very low concentration, when the adiabatic temperature rise is
very low. Catalytic combustion is based on a very simple principle that when the
mixture of fuel and air are passed over a catalyst which is maintained at high
temperature, total oxidation occurs. Reaction is exothermic and products
released are oxidized. In case of organic fuels, these are carbon dioxide and
water, which may safely be discharged into the atmosphere.