AUTOMOTIVE EMISSIONS:

Emissions come principally from three automotive sources: the exhaust, the fuel system (evaporative),
and crankcase ventilation gases. Regulations require exhaust emission measurements during the
operation of the vehicle (or engine) on a dynamometer during a driving cycle that simulates vehicle road
operation.

TYPES OF EMISSIONS:

Emissions of many air pollutants have been shown to have variety of negative effects on public health and
the natural environment. Emissions that are principal pollutants of concern include:

 Hydrocarbons (HC) - A class of burned or partially burned fuel, hydrocarbons are toxins.
Hydrocarbons are a major contributor to smog, which can be a major problem in urban areas. Prolonged
exposure to hydrocarbons contributes to asthma, liver disease, lung disease, and cancer. Regulations
governing hydrocarbons vary according to type of engine and jurisdiction; in some cases, "non-
methane hydrocarbons" are regulated, while in other cases, "total hydrocarbons" are regulated.
Technology for one application (to meet a non-methane hydrocarbon standard) may not be suitable for
use in an application that has to meet a total hydrocarbon standard. Methane is not directly toxic, but is
more difficult to break down in fuel vent lines and a charcoal canister is meant to collect and contain
fuel vapors and route them either back to the fuel tank or, after the engine is started and warmed up, into
the air intake to be burned in the engine.
 Carbon monoxide (CO) - A product of incomplete combustion, inhaled carbon monoxide reduces the
blood's ability to carry oxygen; overexposure (carbon monoxide poisoning) may be fatal. (Carbon
monoxide persistently binds to hemoglobin, the oxygen-carrying chemical in red blood cells, where
oxygen (O2) would temporarily bind. The bonding of CO excludes O 2 and also reduces the ability of the
hemoglobin to release already-bound oxygen, on both counts rendering the red blood cells ineffective.
Recovery is by the slow release of bound CO and the body's production of new hemoglobin—a healing
process—so full recovery from moderate to severe [but nonfatal] CO poisoning takes hours or days.
Removing a person from a CO-poisoned atmosphere to fresh air stops the injury but does not yield
prompt recovery, unlike the case where a person is removed from an asphyxiating atmosphere [i.e. one
deficient in oxygen]. Toxic effects delayed by days are also common.)
 NOx - Generated when nitrogen in the air reacts with oxygen at the high temperature and pressure inside
the engine. NOx is a precursor to smog and acid rain. NOx is the sum of NO and NO2.[1] NO2 is
extremely reactive. NOx production is increased when an engine runs at its most efficient (i.e. hottest)
operating point, so there tends to be a natural tradeoff between efficiency and control of NO x emissions. 
 Particulate matter – Soot or smoke made up of particles in the micrometre size range: Particulate
matter causes negative health effects, including but not limited to respiratory disease and cancer. Very
fine particulate matter has been linked to cardiovascular disease.
 Sulfur oxide (SOx) - A general term for oxides of sulfur, which are emitted from motor vehicles burning
fuel containing sulfur. Reducing the level of fuel sulfur reduces the level of Sulfur oxide emitted from
the tailpipe.
 Volatile organic compounds (VOCs) - Organic compounds which typically have a boiling point less
than or equal to 250 °C; for example chlorofluorocarbons (CFCs) and formaldehyde. Volatile organic
compounds are a subsection of Hydrocarbons that are mentioned separately because of their dangers to
public health. 

ROLE IN AIR POLLUTION

Pollutants from cars contribute to various types of air pollution. When hydrocarbons and NO x combine in
sunlight, they produce ozone. High in the atmosphere, ozone protects us from the sun’s ultraviolet rays.
When holes in the atmosphere's ozone layer allows ozone to come closer to Earth, it contributes to smog and
causes respiratory problems.

Air pollutants emitted from cars are believed to cause cancer and contribute to such problems as asthma,
heart disease, birth defects and eye irritation.

Emissions from cars increase the levels of carbon dioxide and other greenhouse gases in the atmosphere. At
normal levels, greenhouse gases keep some of the sun’s heat in the atmosphere and help warm Earth. That
said, many scientists believe that burning fossil fuels such as gasoline causes greenhouse gas levels to spike,
leading to global warming.

Scientists use sophisticated instruments to measure concentrations of harmful substances in the air, but it’s
tough to say exactly what percentage of air pollution comes from cars. This makes sense, because many
other human activities contribute to air pollution as well. In fact, the production of electricity by coal-
fired power plants and other sources can cause more pollution than most cars. If that wasn't enough, we
pollute the air when we heat our homes and public buildings with fuels other than electricity -- just as we do
when we drive our cars. Even people who don’t drive add to pollution when they buy goods and services
that involve fuel when they're made or delivered.

Although the U.S. Environmental Protection Agency (EPA) declared cars "mobile sources" of pollution,
they aren’t the only culprits. Big trucks, bulldozers, ships and boats, and trains pollute the air.

According to the EPA, motor vehicles collectively cause 75 percent of carbon monoxide pollution in the
U.S. The Environmental Defense Fund (EDF) estimates that on-road vehicles cause one-third of the air
pollution that produces smog in the U.S., and transportation causes 27 percent of greenhouse gas
emissions. The U.S. has 30 percent of the world's automobiles, yet it contributes about half of the world's
emissions from cars.

The United States was long considered the world’s biggest polluter in terms of carbon dioxide and other
greenhouses gases, but by 2008, the United Nations had reported that China had moved into the top spot.

The percentage of air pollution caused by cars is higher in urban areas and higher still near major highways.
REMEDIES:
DO’s DON’Ts
Walk to work, or ride a bicycle. Don't use extensively your private vehicles, try to
use public transportation whenever possible.
Carpool. Two - or four - can ride as cheaply as Avoid congested road and rush hours.
one.
Get a valid pollution under control certificate from Don’t idle away energy. Beyond one minute, it is
authorized testing centre. more fuel - efficient to restart your car.
Keep automobiles fuel filters clean and save the Don't forget to Keep your vehicle tuned up. When a
fuel. vehicle is running well, it uses nine per cent less
fuel and thus emits fewer toxic and noxious fumes.
Clean the air filter and oil filter regularly. Don't try to replicate mechanical works and
experiment with your car.
Clean the carbon deposit from silencer. Don't forget to replace your old battery with new
battery when it required.
Maintain recommended tyre pressure. Don't use clutch pedal as footrest.

GREEN ENGINE

The Green engine is a six phase, internal combustion engine with much higher expansion ratio. The term
"phase" is used instead of "stroke" because stroke is actually associated to the movement of the piston.
The traveling of the piston from bottom dead centre to the top dead centre or vice versa is termed a
stroke. But, in this engine pistons are absent and hence, the term "phase" is used. The six phases are:
intake, compression, mixing, combustion, power and exhaust.

Construction & Working

The engine comprises a set of vanes, a pair of rotors which houses a number of small pot-like containers. It
is here, in these small containers that compression, mixing, combustion are carried out. The engine also
contains two air intake ports, and a pair of fuel injectors and spark plugs. The spark plugs are connected in
such a system so as to deactivate them, when a fuel which does not need sparks for ignition is used. The
rotor is made of high heat resistance and low expansion rate material such as ceramic. Whereas, the metal
used is an alloy of steel, aluminium and chromium.
Even though the engine is of symmetric shape, the vanes traverse an unsymmetrical or uneven boundary.
This shape cannot be compromised as this a result of the path taken by the intake and exhaust air. This
uneven boundary is covered by the vanes in a very unique fashion. The vanes are made in such a way that it
comprises of two parts: one going inside a hollow one. At the bottom of the hollow vane is a compressive
spring. On top of this spring is mounted the other part of the vane. Now, let us come to the working of the
engine.
The air arrives to the engine through the direct air intake port in the absence of an air inlet pipe, throttle and
inlet valves on the air intake system. A duct is provided on the sides of the vane and rotor. The duct is so
shaped that when the air moves through, strong swirls generate when it gets compressed in the chamber. The
air pushes the vane blades which in turn impart a proportionate rotation in the small rotor which houses the
chambers. The inlet air duct ends with a very narrow opening to the chamber.
The Green engine's prototypes have been recently developed, and also because of the unique design,
limitations have not been determined to any extent. But even in the face of limitations if any, the Green
engine is sure to serve the purpose to a large extent.

The advantages of this innovative model of Green engine over the contemporary piston engines are
many

 Small Size and Light Weight

 Limited Parts
 High Efficiency
 Multi-fuels
 Near-zero Emissions
 Smooth Operation
 Fast Accelerating Response
 Quietness and Low Exhaust Temperature
 PHOTOCHEMICAL SMOG
Photochemical smog is a mixture of pollutants that are formed when nitrogen oxides and volatile
organic compounds (VOCs) react to sunlight, creating a brown haze above cities. It tends to occur
more often in summer, because that is when we have the most sunlight.
Primary pollutants
The two major primary pollutants, nitrogen oxides and VOCs, combine to change in sunlight in a
series of chemical reactions, outlined below, to create what are known as secondary pollutants.
Secondary pollutants
The secondary pollutant that causes the most concern is the ozone that forms at ground level.
While ozone is produced naturally in the upper atmosphere, it is a dangerous substance when
found at ground level. Many other hazardous substances are also formed, such as peroxyacetyl
nitrate (PAN).
While nitrogen oxides and VOCs are produced biogenically (in nature), there are also major
anthropogenic (man-made) emissions of both. Natural emissions tend to be spread over large
areas, reducing their effects, but man-made emissions tend to be concentrated close to their source,
such as a city.
Biogenic sources
In nature, bushfires, lightning and the microbial processes that occur in soil generate nitrogen
oxides. VOCs are produced from the evaporation of naturally-occurring compounds, such as
terpenes, which are the hydrocarbons in oils that make them burn. Eucalypts have also been found
to release significant amounts of these compounds.
Anthropogenic sources
Nitrogen oxides are produced mainly from the combustion of fossil fuels, particularly in power
stations and motor vehicles. VOCs are formed from the incomplete combustion of fossil fuels,
from the evaporation of solvents and fuels, and from burning plant matter—such as backyard
burning and wood-burning stoves.

Composition of Photochemical Smog

The following substances are identified in photochemical smog:
Nitrogen dioxide (NO2) from vehicle exhaust, is photolyzed by
ultraviolet (UV) radiation (hμ) from the sun and decomposes into Nitrogen Oxide
NO2+hμ→NO+O
The oxygen radical then reacts with an atmospheric oxygen molecule to create ozone, O3
O+O2→O3
Under normal conditions, O3 reacts with no, to produce NO2 and an oxygen molecule
O3+NO→O2+NO2
This is a continual cycle that leads only to a temporary increase in net ozone production. To create
photochemical smog on the scale observed in Los Angeles, the process must include Volatile
organic compounds
VOC's react with hydroxide in the atmosphere to create water and a reactive VOC molecule
RH+OH→R+H2O
The reactive VOC can then bind with an oxygen molecule to create an oxidized VOC
R+O2→RO2
The oxidized VOC can now bond with the nitrogen oxide produced in the earlier set of equations
to form nitrogen dioxide and a reactive VOC molecule
RO2+NO→RO+NO2
Effects of photochemical smog

Health Effects

Photochemical smog is capable of inflicting irreversible damage on the lungs and heart.
Even short-term exposure to photochemical smog tends to have ill effects on both the
young and the elderly. It causes painful irritation of the respiratory system, reduced lung
function and difficulty breathing; this is more evident while exercising or working
outdoors. High levels of smog also trigger asthma attacks because the smog causes
increased sensitivity to allergens, which are triggers for asthma.

Effects on Environment

Photochemical smog has devastating effects on the environment. The collection of

chemicals found in photochemical smog causes problems for plants and animal life. Some
plants such as tobacco, tomato and spinach are highly responsive to ozone, so
photochemical smog can decimate these sensitive crops, trees and other vegetation. Ozone
causes necrotic (dead) patterns on the upper surfaces of the leaves of trees. Ground-level
ozone also can interfere with the growth and productivity of trees. The effects of smog on
animals are also similar to its effect on humans; it decreases lung capacity and lung
elasticity.

How can we reduce the occurrence of photochemical smog?

The most effective way of reducing the amount of secondary pollutants created in the air is
to reduce emissions of both primary pollutants.
Reduction of nitrogen oxide
The main method of lowering the levels of nitrogen oxides is by a process called ‘catalytic
reduction’, which is used in industry and in motor vehicles. For example, a catalytic
converter fitted to a car’s exhaust system will convert much of the nitric oxide from the
engine exhaust gases to nitrogen and oxygen. In Australia, all motor vehicles built after 1985
must be fitted with catalytic converters. Nitrogen is not in the actual fuels used in motor
vehicles or power stations; it is introduced from the air when combustion occurs. Using less
air in combustion can reduce emissions of nitrogen oxides. Temperature also has an effect on
emissions—the lower the temperature of combustion, the lower the production of nitrogen
oxides. Temperatures can be lowered by using processes such as two stage combustion and
flue gas recirculation, water injection, or by modifying the design of the burner.
Reduction of VOCs
There are various ways to reduce VOC emissions from motor vehicles. These include the use
of liquefied petroleum gas (LPG) or compressed natural gas (CNG) rather than petrol,
decreasing distances vehicles travel by using other modes of transport, such as buses and
bikes, and implementing various engine and emission controls now being developed by
manufacturers.
The other major contributor to VOC emissions, however, is not as simple to police because
solvent evaporation occurs in many different places, from large factories to backyard sheds.
Control strategies to reduce these emissions must be widely varied.
What is Smog?

Smog is a common form of air

pollution found mainly in urban
areas and in large human centers.
The term refers to any type of
atmospheric pollution - no matter
where it comes from, how it is
constructed, or how concentrated it
is - that produces significant
damage to the atmosphere. Smog
encompasses a wide range of air pollution generated by a number of processes directly
related to the atmospheric conditions of the constructed region. In the early 1900's, London
was hit by a plume of smoke that came from a mixture of mist and coal from a coal fire. In
modern times, the Los Angeles Basin is often associated with heavy chemical smoke, which
is produced by a combination of car exhaust and sunlight. These are two of the plethora of
examples of pollutants that are classified as smog, but they have nothing to do with
chemicals. Smog refers to numerous categories of air pollution containing variegated
chemicals; however, all forms of smoke create a visible blurry haze that reduces the visibility
of the atmosphere.

Photochemical Smog : Formation and Causes

Photochemical smog is a type of

smog produced when ultraviolet
light from the sun reacts with
nitrogen oxides in the atmosphere.
It is visible as a brown haze, and is
most prominent during the
morning and afternoon, especially
in densely populated, warm cities
Photochemical smog is produced when sunlight reacts with nitrogen oxides and at least one
volatile organic compound (VOC) in the atmosphere. Nitrogen oxides come from car
exhaust, coal power plants, and factory emissions. VOCs are released from gasoline, paints,
and many cleaning solvents. When sunlight hits these chemicals, they form airborne particles
and ground-level ozone—or smog.

Photochemical Smog : Reactions and Composition

Nitrogen dioxide (NO2) can be broken down by sunlight to form nitric oxide (NO) and an
oxygen radical (O):
1) NO2 + sunlight □ NO + O

Oxygen radicals can then react with atmospheric oxygen (O2) to form ozone (O3):
2) O + O2 □ O3
Ozone is consumed by nitric oxide to produce nitrogen dioxide and oxygen:
3) O3 + NO □ NO2 + O2

Harmful products, such as PAN, are produced by reactions of nitrogen dioxide with various
hydrocarbons (R), which are compounds made from carbon, hydrogen and other substances:
4) NO2 + R □ products such as PAN

The main source of these hydrocarbons is the volatile organic compounds or VOCs.
Similarly, oxygenated organic and inorganic compounds (ROx) react with nitric oxide to
produce more nitrogen oxides:
5) NO + ROx □ NO2 + other products

The importance of the presence of VOCs in these two approaches is very important. Ozone is
commonly used by nitric oxide, as seen in reaction 3. However, when VOCs are present,
nitric oxide and nitrogen dioxide are consumed as in reaction of 4 and 5, allowing the
formation of ozone ground level.
Adverse Effects of Smog

Smog is a major problem in many cities and continues to damage human health. Low levels
of ozone, sulfur dioxide, nitrogen dioxide and carbon monoxide are particularly dangerous in
the elderly, children, and people with heart and lung conditions such as emphysema,
bronchitis and asthma. It can irritate the respiratory tract, reduce lung function, cause
shortness of breath, pain when inhaling deeply, breathing and coughing. It can cause irritation
of the eyes and nose and dry up the protective lining of the nose and throat and impair the
body's ability to fight infections, making it easier to get sick. Hospital admissions and
respiratory deaths often increase at times when ozone levels are high.

How to Reduce Smog Formation

● Keep your car serviced regularly and tires filled using the manufacturer clarification.
This will ensure that the car is running smoothly and does not emit pollutants.
● If you are trading in your old car, replace it with a smaller, fuel-efficient car.
● Instead of using a car, try cycling or walking, and use buses, trams or trains whenever
you can.
● Use energy-saving devices. Check the Energy Star logo when you buy a computer,
printer, air conditioner, clothes dryer, dishwasher, dishwasher, refrigerator or freezer
you buy.
● When renovating or building, use energy-efficient designs and materials.
● Turn off unnecessary electrical appliances when possible.
 ● Make it your goal to buy 'green energy' - energy produced by clean, renewable energy
sources.
● Use your green energy - investigate Government Discount Solar Hot Water, Photo-
voltaic discount and Remote Renewable Power Generation grants.
● Schools can join Airwatch, a primary and secondary school system there students can
become pollinators in their local environments.

Smog in Delhi, India

A few years ago, cities in northern India were shrouded in smoke during the winter. The
situation has worsened at National Capital, Delhi. The smoke is caused by the accumulation
of Particulate Matter (a type of dust and toxic gases) in the air due to the constant movement
of air during the winter.

Delhi is the most polluted city in the world and according to some estimates, air pollution
causes the deaths of an estimated 10,500 people in Delhi every year. During 2013-14, the
high levels of fine particulate matter (PM) in Delhi increased by about 44%, mainly due to
high car and industrial emissions, construction work and burning of crops in the combined
areas. Delhi has a very high level of carbon dioxide. , PM2.5 is considered to be the most
dangerous to health, at 153 micrograms. The increase in air pollution levels has significantly
increased lung-related diseases (especially asthma and lung cancer) among children and
women in Delhi. Heavy smoke in Delhi during the winter causes severe disruptions to air
trains and trains every year. According to Indian meteorologists, temperatures in central
Delhi during the winter have dropped significantly since 1998 due to rising temperatures.
HOMOGENOUS AND HETROGENOUS
Homogeneous simply means suppose if we put a pinch of salt in water it takes time to be
dissolved completely once it is dissolved it is called homogeneous mixture but in the case of
water and iron nail it is not dissoluble so it is a heterogeneous mixture.

Similarly in the case of diesel engine combustion process there is air which is compressed 40
to 50 bar is highly dense and diesel which is atomized and thrown with 100 to 200 bar into
cylinder gets not mixed properly and meanwhile, combustion takes place.

And in the case of petrol engine, there is air and petrol previously mixed in carburettor which
made it homogeneous and thrown into a cylinder with high pressure and combustion takes
place when the piston moves from BDC to TDC.

What is combustion
Combustion is a chemical process or a reaction between Fuel (Hydrocarbon) and Oxygen.
When fuel and oxygen react, it releases the heat and light energy. Heat and light energy then
result in the flame. So, the formula for Combustion reaction is Hydrocarbons + Oxygen = Heat
energy

The Fire Triangle

Three things are required in proper combination before ignition and combustion can take place-
--Heat, Oxygen and Fuel.

1. There must be Fuel to burn.

2. There must be Air to supply oxygen.
3. There must be Heat (ignition temperature) to start and continue the combustion
process.

Combustible mixture

Homogenous- fuel and oxygen molecules are uniformly distributed.

Heterogenous- combustion in porous media, is a type of combustion in which a solid and gas
phase interact to promote the complete transfer of reactants to their lower energy potential
products.

HOMOGENEOUS COMBUSTION

Our understanding of the phenomenon of combustion dates from the second half of the
Eighteenth century, when Antoine-Laurent Lavoisier demonstrated that the process was not
due to the release of phlogiston, then considered to be one of the constituent parts of matter,
but instead to the combining of one component of the air, oxygen, with particular gaseous,
liquid or solid combustible materials. Its special characteristic is the manifest emission of light
and heat which often takes on the typical aspect of flames. In reality, combustion processes
have been the main source of energy for mankind ever since prehistoric times, and even today
they play a central role in our economy, supplying about 90% of the energy we consume. In
spite of the relentless and, in certain respects, challenging search for alternative sources of
energy, this pre-eminent position is bound to remain unchallenged for a long time to come. The
fuels commonly used as sources of energy are natural gas, which is principally made up of
methane; petroleum products, which are composed of mixtures of hydrocarbons; and coal.
When these combine with oxygen (the carburant substance) carbon dioxide and water are
formed through a series of chemical reactions that, as a rule, are very complex because they
take place in various stages and involve, as will be explained further on, many intermediate
species. Leaving aside these details, it is nevertheless easy to formulate the global reactions
through which combustion products are formed from the fuels mentioned. These can be
expressed as follows:
[1] CH4_2O2 2H2O_CO2 for methane
[2] CnHm n_1_O2 nCO2_1H2O
for a generic hydrocarbon
[3] C_O2 CO2 for coal
These reactions release significant quantities of heat energy whose values can be calculated
from the enthalpies of formation of the various species involved (see below). Alongside the
preceding combustion reactions, there is also, for example, the combination of oxygen with
hydrogen to form water, and the combination of hydrogen with chlorine and bromine to form
the corresponding hydrochloric and hydrobromic acids. In short, the category of combustion
processes includes all reactions that are very rapid and strongly exothermic. The peculiar nature
of combustion processes stems from the interaction of an ensemble of physical and chemical
phenomena which give rise to particular and diversified situations. The simplest is that of a
gaseous mixture containing a fuel, methane, for example, oxygen and any inert gases such as
nitrogen which may be present, in which a very rapid exothermic reaction is triggered that
produces a strong heating effect with consequent sharp variations of the temperature and
concentrations of the reagents in time and space. The geometrical configuration and the
physical conditions of the mixture, in particular the temperature, of the mixture create the right
conditions for its ignition to take place. If the fluids are in motion, changes in components and
operating conditions cause different identifiable situations to arise, each of which is
characterized by specific problems for the description and handling of combustion processes.
The case of a gaseous mixture formed by a fuel and a carburant (combustion-support) that
moves with laminar flow in a given direction at constant rate will be considered
first. If a combustion reaction is triggered at a particular position in the direction of the flow, a
flame is generated which causes a sharp increase in the temperature of the mixture. The reactive
event takes place in a thin layer in which, besides the temperature increase, an abrupt decrease
in the concentration of the reagents also occurs, while the concentration of the reaction products
increases at an equivalent speed and attains its corresponding value in the
final mixture. In substance, one can identify a reaction front that moves at a given rate of direct
propagation in the direction opposite to that of the gaseous flow. If the numerical values of the
two velocities are identical, the position of the flame front remains unchanged in time and the
flame is said to be stationary. This description identifies the behavior of what are known as
premixed one-dimensional flames. A different situation occurs in the case of diffusion flames,
in which the two gaseous reagents flow into two separate zones and then converge in a third
zone where the combustion takes place.
Emission Formation :
The enormous increase in environmental pollution caused by combustion processes makes it essential that
solutions are found for their reduction. Soon after World War II it was recognized that a major portion of
this problem is caused by the exhaust emission from the internal-combustion engines (Taylor, 1985). The
causes and the control of this problem have been the objective of an enormous amount of research and
development, which is still continuing. The reactions that occur in the engine combustion process not only
produce substances such as CO2 , H2 O and H2 , but also various pollutants which are found in the engine
exhaust. The three main pollutants which are subject to exhaust emission legislation are carbon monoxide
(CO), unburned hydrocarbons (HC) and nitrogen oxides (NOx ). These emissions are worse from the spark-
ignition engine than from the compression ignition engine. Other important pollutants contained in exhaust
emissions are aldehydes (H—C—O compounds), lead components produced by use of leaded fuels,
Sulphur dioxide (SO2 ), and particulates (including soot), especially with diesel engines. A typical exhaust
composition (ECE test) is shown in Figure 1. Emissions of pollutants vary between different engines and
are dependent on such variables as ignition timing, load, speed, and in particular, fuel/air ratio. Figure 2
(Stone, 1991) shows typical variations of pollutant concentrations with the fuel/air ratio for a spark-ignition
engine.

Figure 1 Mean exhaust composition without catalytic converter in

ECE test (medium-size vehicle) Figure 2 Spark ignition engine emissions for
different fuel/air ratios

The share of toxicity that may be attributed to the ICE pollutants is well realized, an outline of which is
given in the following section along with the maximum workplace (MAK) concentrations.

Carbon monoxide (CO): Due to its strong adherence to haemoglobin, even low concentrations may
therefore be sufficient to cause suffocation. The MAK value is 33 mgm~3.

Unburned hydrocarbons (HC): They generally cause irritation to mucous membranes in humans.

Nitrogen dioxide (NO2 ): Even low concentrations cause lung irritation, tissue damage and irritation of
mucous membranes. A risk of acid formation is present. The MAK value is 9 mgm~3.

Nitrogen monoxide (NO): It modifies the function of the lungs and irritates mucous membranes in
humans. There is a risk of nitric acid formation. The MAK value is 9 mg m~3.

Aldehydes (H—C—O compounds): They have a narcotic effect. Some of these compounds are believed
to cause cancer, the MAK value (for example, of formaldehyde) is 0)6 mg m~3.
Lead: Reduces oxygen absorption of the blood. The MAK value is 0)1 mgm~3.

Sulphur dioxide (SO2 ): Causes irritation of mucous membranes. It is the main cause of producing
sulphuric acid in the atmosphere. The MAK value is 2 mgm~3.

Particulates: Part of the particulates can enter the lungs, which results in health hazard. Particulates also
contain soot (as pure carbon or with deposited hydrocarbons). Soot is believed to have a carcinogenic effect.

Carbon dioxide (CO2 ): Excessive concentrations may lead to suffocation. It generally contributes to the
long-term environmental damage caused by atmospheric changes (global warming or greenhouse effect).
The MAK value of carbon dioxide is 9000 mgm~3.

The following two sections will give a short account on the causes of emissions from internal combustion
engines for both spark-ignition engines and compression-ignition engines.

Causes of emissions in spark-ignition engines CO:

Emissions of CO are influenced primarily by the air/fuel ratio.
Figure 3 shows the CO levels in the exhaust of a conventional
spark-ignition engine for several fuel compositions differing in
the H/C ratio (Novak and Blumberg, 1978). For a specific air/fuel
ratio, CO concentrations vary with the composition of the used
fuel; the higher the H/C ratio the lower the concentrations will
be. For a given fuel composition, for fuel-rich mixtures, CO
concentrations increase steadily with decreasing air/fuel ratio.
For fuel-lean mixtures, CO concentrations vary little with air/fuel
ratio. SI engines often operate on nearly fuel rich composition at
full load, which means significant emissions of CO. Even for
fuel-lean mixtures, some CO will be generated because of poor
mixing, local rich regions, incomplete combustion and also
because there is not enough time to reach equilibrium of
Figure 3 Variation of SI engine CO emissions with
fuels of different H/C ratio with air/fuel ratio oxidation of CO to CO2 .

Unburned HC: Emissions of HC are primarily due to incomplete combustion of hydrocarbon fuel. Essential
components of unburned hydrocarbons are aromatics (benzene, toluene, ethyl benzene), olefins (e.g.
propane, ethylene), acetylene and paraffines (e.g. methane). Unburned hydrocarbons will remain only in
those areas where the flame does not propagate such as gaps close to the cylinder head gasket, piston top
land, piston rings and spark plugs. HC emissions are also formed due to the quench effect, misfire as well
as due to the detachment of lubricating film.
NOx : Figure 2 shows that the nitrogen oxides reach a maximum at a slight excess of air. Generation of
these components is enhanced by high, local peak temperatures and a corresponding excess of air. The
high-temperatures encourage splitting of N2 and O2 into their atomic constituents. Excess air ensures that
sufficient oxygen is present. All engine-related parameters (e.g. load, air/fuel ratio, ignition angle,
compression ratio) influence NOx emissions. NO emissions account for approx. 90—98% of all NOx
emissions during engine operation.
Aldehydes: Aldehydes are hydrocarbons with additional embedded oxygen atoms. These O—H—C
compounds are produced mainly during the combustion of fuels with high oxygen contents, e.g. alcohols.
One major representative of this pollutant group is formaldehyde (HCHO) which is already subject to
regulations in places like California.
Lead compounds: Lead emissions of spark-ignition engines are caused exclusively by lead additives
contained in gasoline. Lead is usually found in anti-knock additives based on chlorine and bromium
compounds that are used to reduce the high boiling temperature of lead. The use of lead additives is
decreasing rapidly as they contaminate the catalytic converters used today. A qualitative illustration of the
formation mechanisms of HC, CO and NO in a spark-ignition engine is given in Figure 4 (Heywood, 1988).

Figure 4 Summary of HC, CO, and NO pollutant formation mechanisms in spark ignition engine

Causes of emissions in compression-ignition engines:

CO : The mean air/fuel ratio present in the combustion chamber per cycle is far higher in the diesel engine
than in the SI engine. Due to a lack of homogeneity of the mixture built up by stratification, however,
extremely ‘rich’ local zones are present. This produces high CO concentrations that are reduced to a greater
or lesser extent by post-oxidation. When the excess-air ratio increases, dropping temperatures cause the
post-oxidation rate to be reduced (the reactions ‘freeze-up’). The CO concentrations of diesel engines
therefore are far lower than in SI engines. The basic principles of CO formation, however, are the same.
Unburned HC: Since the air—fuel mixture is not homogeneous throughout, extremely high excess-air ratios
are present in certain zones during the diesel 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.
NOx : NOx concentrations are lower than in spark-ignition engines; the share of NO in the NOx emissions
is slightly higher. The type of combustion process has a significant effect on nitrogen oxide formation. In
engines with a divided combustion chamber, combustion initially occurs in the pre-combustion or swirl
chamber under conditions of extreme oxygen deficiency. This generates high temperatures, and NOx levels
are low due to a lack of air and, hence, oxygen. This process is reversed in the main combustion chamber.
Extreme excess air ratios and, hence, low temperatures also result in low NOx formation. The direct-
injection diesel engine does not have the above features that keep NOx emissions low. As a result, NOx
formation is approximately twice as high as in an engine with divided combustion chamber.
Sulphur compounds: Sulphur compounds are caused exclusively by the sulphur content of the fuel. When
combined with the water produced during the combustion process, SO2 produces sulphuric acid. Sulphur
compounds cause problems with regard to acid rain and particulate formation via sulphates.
Particulates: Basically, soot emissions are part of particulate emissions. Soot formation occurs at extreme
air deficiency. This air or oxygen deficiency is present locally inside diesel engines. It increases as the
air/fuel ratio decreases. Soot is produced by oxygen deficient thermal cracking of long-chain molecules. A
separation of hydrogen leads to C-structures showing an increasing lack of hydrogen. Acetylene and other
polymerization processes lead to formation of molecules rich in carbon that form soot particulates
(Homann, 1985). Once soot has formed, it can be oxidized only to a limited extent. Soot formation produces
molecules with an increasingly low hydrogen content and higher weight that will finally agglomerate to
form soot particulates. Particulates consist of solid (organically insoluble) and liquid (organically soluble)
phases. The solid phase consists of amorphous carbon, ash, oil additives, corrosion products and abrasion
products. The liquid phase consists of fuel and lubricant contents which are, in most cases, combined with
soot. The hydrocarbons contained in the hot exhaust are still largely gaseous and are converted into a liquid,
organically soluble phase (particulates) after cooling by turbulent intermixing with air. Particulate
composition is largely dependent on the operating point and the combustion process. Figure 5 shows a
typical particulate composition of diesel engine exhaust. Figure 6 illustrates how various parts of the fuel
jet and the flame affect the formation of NO, unburned HC and soot during the pre-mixed and mixing-
controlled phases of diesel combustion in a direct-injection engine with swirl (Heywood, 1988).

Figure 5 Particulate composition of diesel engine exhaust

 Incomplete Combustion
Internal combustion engines (ICE) are the most common form of heat engines, as they are used
in vehicles, boats, ships, airplanes, and trains. They are named as such because the fuel is ignited
in order to do work inside the engine. Carbon monoxide is the product of incomplete combustion
in IC engine. But when there is not enough oxygen for the combustion process Carbon
monoxide (CO) forms, that is incomplete combustion. Complete combustion needs ample
amounts of oxygen

Incomplete combustion

The urban air pollution is a very complicated problem. The exhaust emissions from internal-
combustion engines account for a major portion of this problem. It is realized that the content
and concentrations of the exhaust emissions depend on various parameters. These parameters
include engine design parameters, operational parameters, exhaust gas aftertreatment, fuel types,
fuel additives and lubricants.

Incomplete combustion occurs when the supply of air or oxygen is poor. Water is still produced,
but carbon monoxide and carbon are produced instead of carbon dioxide.

In general for incomplete combustion:

hydrocarbon + oxygen → carbon monoxide + carbon + water

The carbon is released as soot. Carbon monoxide is a poisonous gas, which is one reason why
complete combustion is preferred to incomplete combustion. Gas fires and boilers must be
serviced regularly to ensure they do not produce carbon monoxide.

Carbon monoxide is absorbed in the lungs and binds with the haemoglobin in our red blood cells.
This reduces the capacity of the blood to carry oxygen.
Carbon monoxide(CO): Due to its strong adherence to haemoglobin, even low concentrations
may therefore be sufficient to cause suffocation. The MAK value is 33 mg m~3 .

Unburned hydrocarbons(HC): They generally cause irritation to mucous membranes in

humans.

Nitrogen dioxide(NO2): Even low concentrations cause lung irritation, tissue damage and
irritation ofmucous membranes. A risk of acid formation is present. The MAK value is 9 mg
m~3.

Nitrogen monoxide(NO): It modifies the function of the lungs and irritates mucous membranes
in humans.There is a risk of nitric acid formation. The MAK value is 9 mg m~3.

Aldehydes(H–C–O compounds): They have a narcotic e§ect. Some of these compounds are
believed tocause cancer, the MAK value (for example, of formaldehyde) is 0)6mgm~3.

lead: Reduces oxygen absorption of the blood. The MAK value is 0)1mgm~3.

Sulphur dioxide(SO2): Causes irritation of mucous membranes. It is the main cause of

producing sulphuricacid in the atmosphere. The MAK value is 2 mg m~3.

Particulates: Part of the particulates can enter the lungs, which results in health hazard.
Particulates alsocontain soot (as pure carbon or with deposited hydrocarbons). Soot is believed to
have a carcinogenic e§ect.

Carbon dioxide(CO2): Excessive concentrations may lead to su§ocation. It generally

contributes to thelong-term environmental damage caused by atmospheric changes (global
warming or greenhouse e§ect). TheMAK value of carbon dioxide is 9000 mg m~3.
Precautions to be taken to prevent incomplete combustion are :-

Proper air to fuel ratio: For complete combustion of the fuel each droplet should be surrounded
by air which is equal or greater to the air-fuel ratio.

Proper atomisation of fuel: Fuel should be sprayed in the form of mist so that it can mix with
air for proper combustion.

Heat: Heat required for combustion of different fuels are also different. Petrol or Gasoline need
very less heat to ignite as it vaporises but not the diesel fuel. It needs much higher heat than the
gasoline counterparts. Proper heat should be provided for complete combustion.

Engine timing: Engine timing is very crucial for complete combustion as early spark can lead to
a flame travelling into the intake valve and also it can lead to knocking.
After-burning: Prevent afterburning by introduction of multiple spark plugs so that the entire
charge ignites simultaneously because there are chances that fuel exits the chamber unburnt. So
make sure all the parts in the combustion chamber gets equal heat.
 Hydrocarbon:
A hydrocarbon is an organic compound consisting entirely of hydrogen and carbon.

[1] 620 Hydrocarbons are examples of group 14 hydrides. Hydrocarbons from which one
hydrogen atom has been removed are functional groups called hydrocarbyls.
[2] Hydrocarbons are generally colorless and hydrophobic with only weak odors.
Hydrocarbons can be gases (e.g. methane and propane), liquids (e.g. hexane and benzene),
waxes or low melting solids (e.g. paraffin wax and naphthalene) or polymers (e.g.
polyethylene, polypropylene and polystyrene).

The vast majority of hydrocarbons found on Earth occur in petroleum, coal, and natural gas.
Petroleum (literally "rock oil" – petrol for short) and coal are generally thought to be
products of decomposition of organic matter. In contrast to petroleum, is coal, which is
richer in carbon and poorer in hydrogen. Natural gas is the product of methanogenesis.

Combustion of hydrocarbon fuels

Hydrocarbon fuels can undergo complete combustion or incomplete combustion, depending
on the amount of oxygen available.
Complete combustion
- Complete combustion happens when there is a good supply of air. Carbon and
hydrogen atoms in the hydrocarbon fuel react with oxygen in an exothermic reaction:
- carbon dioxide and water are produced energy is given out
Carbon dioxide is an atmospheric pollutant. Incomplete combustion produces other
pollutants.
Incomplete combustion
- Incomplete combustion happens when the supply of air or oxygen is poor.
- Water is still produced, but carbon monoxide and carbon are produced. Less energy is
released than during complete combustion.
For example, here is one possible equation for the incomplete combustion of propane:
propane + oxygen → carbon + carbon monoxide + water
C3H8 + 3O2 → C + 2CO + 4H2O
Soot
The carbon is released as fine black particles. We see this in smoky flames, and it is deposited
as soot. Soot can cause breathing problems and it blackens buildings. It may block boilers and
other appliances, or cause a fire.
 Fig: Incomplete combustion produces smoke and invisible carbon monoxide
Carbon monoxide
Carbon monoxide is a toxic gas. It is absorbed in the lungs and binds with the haemoglobin in
the red blood cells. This reduces the capacity of the blood to carry oxygen. Carbon monoxide
causes drowsiness, and affected people may fall unconscious or even die.

Hydrocarbon Combustion and Fossil Fuels

Note that CO2 is always produced in hydrocarbon combustion; it doesn't matter what type of
hydrocarbon molecule. Producing CO2 and H2O is actually how useful energy is obtained from
fossil fuels. For this reason, it is important to distinguish between carbon dioxide and other
"waste" products that arise from impurities in the fuel such as sulfur and nitrogen
compounds. Wastes that arise from impurities can be eliminated with the right technology;
CO2 cannot be eliminated unless the fossil fuels are not burned (used) in the first place.
Not all fossil fuels have the same composition. Natural gas is composed of over 90% methane
(CH4) which is the smallest hydrocarbon molecule. Oil tends to be composed of medium sized
molecules, although composition varies greatly from one grade of crude to the next. In
general, the denser the oil, the longer the carbon chains in the molecules. Finally coal
contains the largest and most complex hydrocarbon molecules.
Since different hydrocarbons have different ratios of hydrogen to carbon, they produce
different ratios of water to carbon dioxide. In general, the longer and more complex the
molecule, the greater the ratio of carbon to hydrogen. For this reason, combustion of equal
amounts of different hydrocarbons will yield different quantities of carbon dioxide,
depending on the ratio of carbon to hydrogen in molecules of each.
Since coal contains the longest and most complex hydrocarbon molecules, burning coal
releases more CO2 than burning the same mass of oil or natural gas. This also changes the
energy density of each of these fuels.
Incomplete combustion is generally due to poor mixing of the air and fuel, insufficient
residence time, insufficient temperature and low total excess air.
 CARBON MONOXIDE EMISSION IN I.C. ENGINES
CARBON MONOXIDE GAS

Carbon monoxide is a colorless, odorless gas that is very stable and has a life of 2–4 months in
the atmosphere. It is a component of motor vehicle exhaust, which contributes about 53% of all
CO emissions nationwide. (including CO from wildfires), and 74% of all CO emissions
excluding wildfires. High concentrations of CO occur in areas with heavy traffic congestion
where as much as 95% of all CO emissions may come from automobile exhaust.

FORMATION OF CARBON MONOXIDE IN IC ENGINES

Carbon monoxide is the product of incomplete combustion in IC engine. It is produced by the

partial oxidation of carbon containing compounds. Generally in combustion process carbon
dioxide(CO2) is formed after combustion. But when there is not enough oxygen for the
combustion process Carbon monoxide (CO) forms, that is incomplete combustion.

HARMFUL EFFECTS OF CARBON MONOXIDE

High concentrations of CO can cause physiological and pathological changes and ultimately
death. Carbon monoxide enters the bloodstream through the lungs and reduces oxygen delivery
to the body's organs and tissues. The health threat from lower levels of CO is most serious for
those who suffer from cardiovascular diseases, such as angina pectoris. At much higher levels of
exposure, CO can be poisonous, and even healthy individuals can be affected. Visual
impairment, reduced work capacity, reduced manual dexterity, poor learning ability, and
difficulty in performing complex tasks are all associated with exposure to elevated CO levels.
Carbon monoxide appears to have no detrimental effects on material surfaces. At ambient
concentrations, experiments have not shown CO to produce any harmful effects on plant life.
Carbon monoxide has been found to be a minor participant in photochemical reactions, leading
to ozone formation.

CARBON MONOXIDE MITIGATION TECHNIQUES

The catalytic converter is used in internal combustion engines fueled by petrol or diesel used in
automobiles to reduce the emission of carbon monoxide into the atmospheric air. Shifting BS4
vehicles to BS6 vehicles and moving from diesel or petrol vehicles to electric vehicles.
OXIDES OF NITROGEN DURING EMISSION IN I.C ENGINES

Exhaust gases of an engine can have upto 2000ppm of oxides of nitrogen. Most of this will be
nitrogen oxide , with a small amount of nitrogen dioxide . NOx is very undesirable . Released NOx
reacts in the atmosphere to form ozone & is one of the major cause of photochemical smog. .
At low temperatures , atmosphere nitrogen exists as a stable diatomic molecule. Therefore , only
very small trace amounts of oxides of nitrogen are found. However at very high temperatures that
occur in the combustion chamber of an engine , some diatomic nitrogen breaks down to
monoatomic nitrogen which is reactive.

The higher the combustion reaction temperature , the more diatomic nitrogen will dissociate to
monoatomic nitrogen & the more NOx is formed. Although the maximum flame temperature will
occur at a stoichiometric air fuel ratio ( ɸ=1) . The maximum NOx is formed at a slightly lean
equivalence ratio of about ɸ=0.95.At this condition flame temperature is still very high & in
addition there is an excess of oxygen that can combine with the nitrogen to form various oxides.

In addition to temperature the formation of NOx depends on the pressure & air fuel ration .
Combustion duration plays a significant role in NOx formation within the cylinders . NOx vs time
relationship & supports the fact that NOx is reduced in modern engines with fast burn combustion
chambers .The amount of NOx generated also depends on the location of the spark plug within
the combustion chamber. If the spark is advanced , the cylinder temperatures will be increased &
amount of NOx created will increase . Because CI engines have a high compression ratio & higher
temperature & pressure they with divided combustion chambers & indirect injection IDI tend to
generate higher level of NO x .

Exhaust gas recirculation is an emission control technology allowing significant NOx emission
reduction from most types of diesel engines : from light duty engines through medium & heavy
duty applications right up to low speed , two stroke marine engines.
Introduction

An aldehyde is a hydrocarbon group that chemically comprises a carbon atom that is doubly-
bonded to an oxygen atom. It is commonly represented as the R-CHO group in organic chemistry
and is known as the carbonyl group.Aldehydes are common in organic chemistry, and many
fragrances contain aldehydes.

Fig 1: Different forms of aldehydes

Formation

Aldehydes do not freely occur in nature. The most common method of synthesizing aldehydes is
through the oxidation of an alcohol. This is precisely what happens in Internal combustion
engines as well.

To earn savings on fuel prices, adding ethanol and other alcohol derivatives to gasoline has been
a common practice since the 1980s. Brazil was the first country to adopt this policy. Due to an
abundance of sugarcane, there is a vast supply of resources for the production of ethanol from
sugarcane. Once this was synthesized, it was added to the fuel to improve fuel economy. Today,
the United States has more than 98% of its gasoline containing ethanol additives.
Ethanol additives result in fuel blends with a lower fuel calorific value as compared to standard
gasoline. Further, the Internal combustion engines would need to be specifically modified to
allow the use of these ethanol-based fuels.

The advantage of using ethanol-based additives is that while they result in lower fuel economies,
they are naturally synthesized. This results in lower dependence on fossil fuels and other
conventional sources. In the big picture, this is actually a much more economical method. Also,
if synthesized sustainably it can result in a very low carbon footprint.

Furthermore, Acetaldehyde is also formed during the incomplete combustion of hydrocarbon-

based fuels. In both gasoline as well as diesel fueled vehicles, acetaldehyde is a primary pollutant
in tailpipe emissions.

Fig 2: An ethanol-based fuel petrol station in Brazil

Emission

Unfortunately, ethanol additives result in the formation of Aldehyde emissions. These emissions
are harmful for humans. It is well documented that Aldehydes such as Acetaldehyde and
Formaldehyde are known carcinogens. In addition to being directly harmful to humans, they also
cause various environmental degradations. Formaldehyde is a major precursor to photochemical
smog. This reacts with other chemicals to ultimately result in the formation of ozone. Exposure
to aldehyde emissions is known to cause acute as well as long term respiratory distress in
humans. It can cause severe headaches, nausea and nosebleeds. Long term exposure to aldehydes
is known to considerably increase the chances of humans developing lung cancer.

Formaldehyde, acetaldehyde and other aldehydes are produced when alcohols are oxidised.
When only a 10 per cent mixture of ethanol is added to gasoline (as is common in American E10
gasohol and elsewhere), aldehyde emissions increase 40 per cent. Some study results are
conflicting on this fact however, and lowering the sulphur content of biofuel mixes lowers the
acetaldehyde levels. Burning biodiesel also emits aldehydes and other potentially hazardous
aromatic compounds which are not regulated in emissions laws.

Aldehyde emissions through various fuel engines

In alcohol run engines there is an increased emission of carbonyls (aldehydes and ketones),
compared with pure gasoline on conventional engines. Aldehyde emissions (both formaldehyde
and acetaldehyde), major exhaust pollutants formed as intermediate compounds due to
incomplete combustion of the fuel, cause many human health disorders.

Aldehyde and alcohol emissions are the primary concerns for emission control for vehicles
fueled with methanol and ethanol. Both emissions contribute to the formation of ozone. Also,
aldehydes are considered to be toxic materials. However, gasoline engines emit less aldehydes
than alcohol engines and have higher exhaust gas temperatures which promote the catalytic
destruction of emitted aldehydes.

Control of Aldehyde Emissions

The primary means of removing gaseous hydrocarbons from exhaust emissions is via complete
oxidation to carbon dioxide. The ease of oxidation increases in the order:

methane < paraffins < aromatics < olefins < oxygenates

In general, when operating near stoichiometry, palladium catalysts are superior to platinum
catalysts for the oxidation of methane and unsaturated hydrocarbons, while platinum catalysts
are better for the oxidation of paraffins. Rhodium is an excellent catalyst for steam reforming
under rich conditions, and in addition it improves the durability of platinum and palladium
catalysts and has high activity for the reduction of nitrogen oxides. Therefore, the catalyst
formulation can greatly influence the hydrocarbon reactivity in automotive exhaust and allows
emission control catalysts to be tailored for specific fuel-vehicle-catalyst systems.
The aldehydes (formaldehyde and acetaldehyde) in the exhaust were estimated by wet chemical
technique with high-performance liquid chromatography (HPLC). Aldehyde emissions increased
with an increase in alcohol induction. The low heat rejection (LHR) engine showed a decrease in
aldehyde emissions when compared to a conventional engine. However, the variation of injection
pressure showed a marginal effect in reducing aldehydes, while advancing the injection timing
reduced aldehyde emissions. LHR engine marginally reduced aldehyde emissions at the peak
load operation with pure diesel.Advanced injection timings reduced aldehyde emissions in the
LHR engine, while increased the same in conventional engine. Aldehyde emission decreased
marginally with the increase of injection pressure in both versions of the engine.

Formaldehyde emissions were higher with methanol induction, while acetaldehyde emissions
were observed to be higher with the ethanol induction in both versions of the engine. Control of
aldehyde emission from alcohol fueled vehicles is needed to meet emission control requirements.
“Five-Way” catalysts placed close to the engine manifold to make use of higher exhaust gas
temperatures are effective for suppressing aldehyde and alcohol emissions from flexible fuelled
vehicles.

References

1. https://www.britannica.com/science/aldehyde
2. https://afdc.energy.gov/fuels/ethanol.html
3. https://www.sciencedirect.com/topics/engineering/aldehyde-emission
4. https://www.researchgate.net/publication/5932203_Control_of_aldehyde_emissions_in_th
e_diesel_engines_with_alcoholic_fuels
5. https://www.technology.matthey.com/article/36/4/185-195/
6. https://lh3.googleusercontent.com/proxy/f3l6KYqcmL2P-
4hhHwbQ3LV2z37NXelDFsNDqtiufCH7q1lyOIX_s2oyH-
zLrgHUs5tK50W9sjkJZZmcqYgWGiA9JzIsq2R6Xoom0SqDDw