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“Effects of Combustion on our Environment”
1. Combustion:
Combustion or burning is the sequence of exothermic chemical reactions between a fuel and
an oxidant accompanied by the production of heat and conversion of
chemical species. The release of heat can result in the production
of light in the form of either glowing or a flame. Fuels of interest often
include organic compounds (especially hydrocarbons) in the gas,
liquid or solid phase.
a) Complete combustion:
In a complete combustion reaction, a compound reacts
with an oxidizing element, such as oxygen or fluorine, and
the products are compounds of each element in the fuel
with the oxidizing element. For example:
A simple example can be seen in the combustion of hydrogen and oxygen, which is a commonly
used reaction in rocket engines:
2 H2 + O2 → 2 H2O(g) + heat
The result is water vapor. Complete combustion is almost impossible to achieve. In reality, as actual
combustion reactions come to equilibrium, a wide variety of major and minor species will be
present such as carbon monoxide and pure carbon (soot or ash). Additionally, any combustion
in atmospheric air, which is 78% nitrogen, will also create several forms of oxides. In complete
combustion, the reactant burns in oxygen, producing a limited number of products.
b) Incomplete combustion:
Incomplete combustion will only occur when there isn't enough oxygen to allow the fuel to
react completely to produce carbon dioxide and water. It also happens when the combustion is
quenched by a heat sink such as a solid surface or flame trap.
For most fuels, such as diesel oil, coal or wood, pyrolysis occurs before combustion. In incomplete
combustion, products of pyrolysis remain unburnt and contaminate the smoke with noxious
particulate matter and gases. Partially oxidized compounds are also a concern; partial oxidation of
ethanol can produce harmful acetaldehyde, and carbon can produce toxic carbon monoxide.
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c) Smoldering:
Smoldering is the slow, low-temperature, flameless form of combustion, sustained by the
heat evolved when oxygen directly attacks the surface of a condensed-phase fuel. It is a typically
incomplete combustion reaction.
d) Rapid combustion:
Rapid combustion is a form of combustion, otherwise known as a fire, in which large
amounts of heat and light energy are released, which often results in a flame. This is used in a form
of machinery such as internal combustion engines and in thermobaric weapons. Sometimes, a large
volume of gas is liberated in combustion besides the production of heat and light. The sudden
evolution of large quantities of gas creates excessive pressure that produces a loud noise. Such a
combustion is known as an explosion.
e) Turbulent combustion:
Combustion resulting in a turbulent flame is the most used for industrial application (e.g.
gas turbines, gasoline engines, etc.) because the turbulence helps the mixing process between the
fuel and oxidizer.
Besides damage caused by the combustion process itself, there is also damage associated to the
management of fuels (and oxidisers, if special). Coal handling produces respiratory hazards, and crude-
oil derivatives are carcinogenic. Liquefied petroleum gases, LPG, and particularly cryogenic fluids like
LNG, may cause severe frostbite and structural damage (carbon- and low-alloy steels show a marked
ductile to brittle transition at freezing temperatures).
Physical hazards: mechanical (explosion), thermal (excessive heat, out-range temperatures), radiation
(blinding flare).
Chemical hazards: oxygen depletion, gas poison, aerosols, liquid poisons, solid poisons.
Only a descriptive view of the subject is here presented (some theoretical insight can be found on
Combustion Kinetics). Thermal effects on materials in general, which may be originated from a combustion
process, are presented aside. We have tried to follow a top-down approach in the analysis of the
environmental effects of combustion, i.e. from
deadly explosions to inconvenient
electromagnetic interferences.
3. Pollutant Emission:
Life is a polluting process, because life must
live at the expense of the environment. The
problem is that the amount and concentration
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of pollutants emitted by human activities has gone too far and seriously menace life, both locally and
globally.
The first and traditional approach to fight pollution is to go away or throw it away, e.g. to make a
chimney for venting the fireplace, to have out-side-air sealed combustion boilers, to build power
stations aside, etc.
The effects on the environment are usually identified with pollutant emission through the tail-pipe of
combustors, but handling of fuels, fuel losses at the inlet, and product losses from the combustor shell,
are other sources (up to 20% of the hydrocarbon emissions in a car do not go out along the tail-pipe).
Mass losses and energy losses may be a danger to humans, animals, plants and goods: explosion
danger (in confined places), open flame danger, toxicity from CO (and other toxic gases in chemical
fires), suffocation or anoxia from CO2, hyperthermia by heat, respiratory and visual irritation by smoke
and noxious gases, etc. Mechanical pollution (noise) and electromagnetic pollution (interferences,
EMI), are dealt apart.
Main contaminants, besides the unavoidable CO2 in carbon-containing fuels that contribute to the
greenhouse warming (the legacy left by these emissions would be felt mainly by our offspring), are:
VOCs (Volatile Organic Compounds), CO, NOx, SOx, and particulate matter (PM, or PM10 to explicitly
restrict to sizes <10 m). Soot is formed in non-premixed flames and on premixed flames for
equivalence ratios >1.5. Diesel engines produce more pollutants in the stated order (more PM and less
VOC), whereas Otto engines do just in the reverse order. Some 40% of man-produced VOCs come from
transport (not only through the tail-pipe but from reservoirs and at the stations). Sometimes, instead of
VOC, the term HC (hydrocarbons) is used, even splitting between methane and NMHC (non-methane
hydrocarbons).
a) CO2 :
Carbon dioxide (CO2) is an unavoidable emission in the combustion of carbon-containing
fuels. There is little concern with local contamination by CO2 emissions, being an inert gas like nitrogen.
Like nitrogen, it may cause local suffocation; a 10%CO2 is fatal to a person after a few minutes, by
anoxia, and a 5% already produces troubles after 1 hour. The main concern of CO2 emissions is at
global scale, with the positive correlation found between anthropogenic CO2 generation and the
increase of CO2 fraction in air (e.g. from 310 ppm molar in 1950, to 380 ppm molar in 2007), and the
foreseeable consequences on climate change due to the associated increase in the global greenhouse
effect, which is feared to be highly non-linear, with a small global warming but larger regional changes
(desertification, floods, hurricanes, and so on.
b) CO:
Carbon monoxide (CO) is found in exhaust emissions due to a poor combustion process
(i.e. too rich a mixture, unburnt fuel pyrolises at crevices, or not enough residence time for
equilibrium), particularly in the Otto engine at cold starts, idle, and full power conditions. Unburnt
pyrolysed fuel would be in negligible amounts if sufficient time for equilibrium at the low exit
temperatures were allowed, as in large combustion chambers and large marine engines, where the
residence time is near one second (combustion is similar to eating; it takes time for a good digestion,
starting by proper food preparation, chewing and so on).
CO is a deadly poison that reduces the ability of the blood to absorb oxygen and, as a result, lowers
the blood oxygen content by producing carboxyhemoglobin. Even as low a proportion as 0.5 percent by
volume of CO in the air can prove fatal within 1 hour (>50% carboxyhemoglobin in blood), 0.05%
produces headache after 10 hours (10% carboxyhemoglobin in blood). In uncontrolled fires, like in a
hotel room, typical concentrations of up to 5% are achieved after the fire runs away of control.
Measured in the blood. For clean air standard EU sets a limit of 10 mgCO/m3 in a 8 hours average.
c) NOx:
NOx stands for all nitrogen oxides, mainly NO and NO2, but also N2O, N2O2, N2O3, N2O4
and N2O5, and all appear from atmospheric nitrogen during combustion with air (coals and heavy fuel-
oils have some intrinsic nitrogen also, up to a few percent by weight). All nitrogen oxides are unstable
at ambient conditions when pure, i.e. they dissociate, but their decomposition may be very slow. They
are formed at very high temperatures in the presence of air (there is a high peak in the range =1..1.1),
and two approaches are followed to avoid their emission: avoidance of high temperature formation (by
using very lean mixtures, exhaust gas recirculation, porous burners, catalytic burners, water injection), 5
and catalytic reduction at the exhaust. Notice that the peak in NOx production practically coincides
with the range of maximum combustion efficiency (minimum entropy production), so that it might be
said the NOx emission is a sign of good combustion, contrary to unburnt emissions.
The most polluting of NOx-components is nitrogen dioxide, NO2, a brown gas at normal conditions (but
readily condensable, Tb=11 ºC). When heating an ampoule containing NO 2 from above, some
dinitrogen tetroxide N2O4 (2NO2=N2O4(g)+57 kJ/mol) is exothermically formed; N2O4 is a colourless
heavier gas that appears at the bottom (because of buoyancy), although the reaction would be more
displaced to the left in equilibrium at high temperature (but kinetics dominates). A third gas appears
when heating at 600 ºC, nitrogen oxide, NO (N2O4=2NO+O2, also transparent. Nitrogen oxide, NO, is a
colourless gas that in the presence of atmospheric oxygen, rapidly converts to yellow NO 2; NO
concentration can be measured by chemiluminescence with ozone: NO+O 3=NO2+O2+h. NO2 smells
pungently and causes pronounced irritation of the respiratory system if > 10 ppm, and is fatal if >100
ppm after minutes; due to the fact that it destroys the lung tissue, for clean air standard EU sets a limit
of 40 gNO2/m3. When NO2 or N2O4 are cooled, a blue liquid condensate first develops (a strong
mixture of N2O4 in NO2), and after further cooling, a blue solid appears, mainly consisting of N 2O3. N2O
is a powerful greenhouse gas. Atmospheric ozone, O3, is another pollutant (contrary to stratospheric
ozone), and, although not directly emitted in combustors, it is formed by reaction with air of NOx
emissions. Nitrogen oxides also combine with water vapour to form acid mists (pH<5.6 at 288 K) that
give way to acid rain, damaging forest, lakes and rivers ecosystems, one of the key reactions being
NO(g) + (3/4)O2(g) +(1/2)H2O = H+(aq) + NO3-(aq).
VOC (and CO) emissions should be very low for premixed combustion with excess air (even with
stoichiometric air), but Otto engines are the major source of them because of the small residence time
(some milliseconds for combustion, against near one second in premixed industrial burners), and the
associated small size of the combustion chamber (limited to say half a litre per cylinder for this fact).
The most pollutant are the small two-stroke Otto engines used in motorcycles and gardening, because
the fresh mixture is directly thrown to the exhaust to sweep the burnt gases in the cylinder. By the way,
for reciprocating engines, VOC are not only due to the fuel but to the lubrication oil that seep through
the segments and gets burnt (in the small two-stroke engines oil is add directly to the fuel).
e) Particulate matter:
Particulate matter (PM, or PM10 to explicitly restrict to sizes <10 m) is harmful to the respiratory
system for sizes smaller than say 10 m (larger particles do not follow the air stream and get stuck at
the nose and trachea), but the worst are sizes <2 m. Particulate matter consists of soot from all kind of
hydrocarbon combustion (mainly in non-premixed flames), and fly ash from coal and waste combustion
and incineration. Premixed combustion starts
producing soot for air-to-fuel relative ratios <0.5
or 0.6, depending on the fuel.
Finer particles, of sizes smaller than 2.5 m (named PM2.5), are even worse than PM10; they are issued
from combustor exhaust, but also form by atmospheric reactions of NOx and SO2 emissions (forming
nitrates and sulphates).
f) SO2:
Sulfur dioxide (SO2) emissions mainly depends on type of fuel and not on combustion details, and the
trend has been to get off the market sulfur-containing fuels (by desulfurising those that need it), or
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implementing desulfurising agents in fluidised-bed combustion (e.g. adding lime for
CaO+SO2+2H2=CaSO3·2H2O, or limestone), or in the exhaust (deSOx dry or wet scrubbers). Nowadays
only very large marine engines and large power stations still burn sulfur-containing fuels (residual fuel
oil and coal, respectively), causing severe local and global pollution (acid rain); even in 2005 the IMO-
MARPOL limit on marine fuel is 4.5% in sulfur (down to 1.5% in special areas like in EU seas).
a) Combustion process:
The combustion process is the process in which all the burning of gasoline or diesel fuel
takes place. This procedure actually powers vehicles causing it to move. Also, during this process,
pollution takes into effect. It causes a
vehicle to exhaust by-products and
evaporate fuel.
Diesel fuel and gasoline are composed
of mixtures of compounds of carbon
and hydrogen known as
hydrocarbons. The oxygen in the air
combined with the hydrogen and
carbon in the fuel, in a "perfect"
engine, will form compounds of water
and carbon dioxide. The remaining gas
in the air, nitrogen, will not suffer any
change. These explanations can be
easily expressed in the following
chemical equations:
As you can see, the previous equations also portray how a "perfect" engine, in comparison with the
typical engine, is less hazardous to the environment.
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6) Evaporative Emissions:
All the emissions of pollutants are not only due to the exhausting of
a vehicle. Some percentage of this perilous process is owing to the evaporation of fuel. The
evaporation of fuel causes hydrocarbon toxins escape into the air. These kind of emissions are
reprehensible for the majority of the amount of hydrocarbons that are being exposed to open air
and for the increase in the ozone level.
Evaporative expulsions of a vehicle can take place in various ways. During the day, when
the temperature rises, the amount of the evaporation of fuel also increases. The vehicle's fuel tank
begins to receive heat from the sun and gasoline vapors emerge. This kind of emission is called
diurnal. Another kind of evaporative emissions are running losses. This occurs when a car is running
and its engine, which possesses much heat, continues to vaporize gasoline. Even when a car is in
cessation if it had been running for a long period of time it gasoline will continue to vaporize. This is
known as hot soak. Another evaporative expulsion possibility is refueling. At some point a car is
going to need refueling. Since there will always be gasoline vapors present in the fuel tank, they will
escape when it is refueled. The liquid fuel will replace the gas in the tank.
9) Global Warming:
Global warming is the increase in the average temperature of Earth's near-
surface air and oceans since the mid-20th century and its projected continuation. Most of the observed
temperature increase since the middle of the 20th century has
been caused by increasing concentrations of greenhouse gases,
which result from human activities such as the burning of fossil
fuel and deforestation. An increase in global temperature will
cause sea levels to rise and will change the amount and pattern
of precipitation, probably including expansion
of subtropical deserts. Other likely effects of the warming
include more frequent occurrence ofextreme weather events
including heat waves, droughts and heavy rainfall
events, species extinctions due to shifting temperature regimes,
and changes in agricultural yields.
Ecological systems:
In terrestrial ecosystems, the earlier timing of spring events, and poleward and
upward shifts in plant and animal ranges, have been linked with high confidence to recent
warming. Future climate change is expected to particularly affect certain ecosystems, including tundra,
mangroves, and coral reefs. It is expected that most ecosystems will be affected by higher atmospheric
CO2 levels, combined with higher global temperatures Overall, it is expected that climate change will
result in the extinction of many species and reduced diversity of ecosystems.
Natural systems:
Global warming has been
detected in a number of systems. Some of these
changes, e.g., based on the instrumental
temperature record, have been described in the
section on temperature changes. Rising sea
levels and observed decreases in snow and ice
extent are consistent with warming. Most of the
increase in global average temperature since the
mid-20th century is, with high
probability, attributable to human-induced changes in greenhouse gas concentrations.
Even with current policies to reduce emissions, global emissions are still expected to continue to grow
over the coming decades. Over the course of the 21st century, increases in emissions at or above their
current rate would very likely induce changes in the climate system larger than those observed in the
20th century. 11
10) Greenhouse effect:
The greenhouse effect is a process by which thermal radiation from a
planetary surface is absorbed by atmospheric greenhouse gases, and is re-radiated in all directions.
Since part of this re-radiation is back towards the surface, energy is transferred to the surface and the
lower atmosphere. As a result, the temperature there is higher than it would be if direct heating by
solar radiation were the only warming mechanism.
Greenhouse gases:
By their percentage
contribution to the greenhouse effect on Earth the
four major gases are:
water vapor, 36–70%
carbon dioxide, 9–26%
methane, 4–9%
ozone, 3–7%
The major non-gas contributor to the Earth's
greenhouse effect, clouds, also absorb and emit
infrared radiation and thus have an effect on
radiative properties of the atmosphere.
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