The exhaust gases emitted into the atmosphere are a combination of burned and unburned fuel. To understand the exhaust emission and its composition, we must review some basic chemistry.
When the air/fuel mixture is introduced into the engine, we are mixing air, composed of nitrogen (78 percent), oxygen (21 percent) and other gases (1 percent) with the fuel, which is 100 percent hydrocarbons (HC), in a semi-controlled ratio. As the combustion process is accomplished, power is produced to move the vehicle while the heat of combustion is transferred to the cooling system. The exhaust gases are then composed of nitrogen, a diatomic gas (N2), the same as was introduced in the engine, carbon dioxide (CO2), the same gas that is used in beverage carbonation, and water vapor (H2O). The nitrogen (N2), for the most part, passes through the engine unchanged, while the oxygen (O2) reacts (burns) with the hydrocarbons (HC) and produces the carbon dioxide (CO2) and the water vapors (H2O). If this chemical process would be the only process to take place, the exhaust emissions would be harmless. However, during the combustion process, other compounds are formed which are considered dangerous. These pollutants are hydrocarbons (HC), carbon monoxide (CO), oxides of nitrogen (NOx) oxides of sulfur (SOx) and engine particulates.
Hydrocarbons (HC) are essentially fuel which was not burned during the combustion process or which has escaped into the atmosphere through fuel evaporation. The main sources of incomplete combustion are rich air/fuel mixtures, low engine temperatures and improper spark timing. The main sources of hydrocarbon emission through fuel evaporation on most vehicles used to be the vehicle's fuel tank and carburetor float bowl.
To reduce combustion hydrocarbon emission, engine modifications were made to minimize dead space and surface area in the combustion chamber. In addition, the air/fuel mixture was made more lean through the improved control which feedback carburetion and fuel injection offers and by the addition of external controls to aid in further combustion of the hydrocarbons outside the engine. Two such methods were the addition of air injection systems, to inject fresh air into the exhaust manifolds and the installation of catalytic converters, units that are able to burn traces of hydrocarbons without affecting the internal combustion process or fuel economy.
To control hydrocarbon emissions through fuel evaporation, modifications were made to the fuel tank to allow storage of the fuel vapors during periods of engine shut-down. Modifications were also made to the air intake system so that at specific times during engine operation, these vapors may be purged and burned by blending them with the air/fuel mixture.
Carbon monoxide is formed when not enough oxygen is present during the combustion process to convert carbon (C) to carbon dioxide (CO2). An increase in the carbon monoxide (CO) emission is normally accompanied by an increase in the hydrocarbon (HC) emission because of the lack of oxygen to completely burn all of the fuel mixture.
Carbon monoxide (CO) also increases the rate at which the photo chemical smog is formed by speeding up the conversion of nitric oxide (NO) to nitrogen dioxide (NO2). To accomplish this, carbon monoxide (CO) combines with oxygen (O2) and nitric oxide (NO) to produce carbon dioxide (CO2) and nitrogen dioxide (NO2). (CO + O2+ NO = CO2+ NO2).
The dangers of carbon monoxide, which is an odorless and colorless toxic gas are many. When carbon monoxide is inhaled into the lungs and passed into the blood stream, oxygen is replaced by the carbon monoxide in the red blood cells, causing a reduction in the amount of oxygen supplied to the many parts of the body. This lack of oxygen causes headaches, lack of coordination, reduced mental alertness and, should the carbon monoxide concentration be high enough, death could result.
Normally, nitrogen is an inert gas. When heated to approximately 2500°F (1371°C) through the combustion process, this gas becomes active and causes an increase in the nitric oxide (NO) emission.
Oxides of nitrogen (NOx) are composed of approximately 97-98 percent nitric oxide (NO). Nitric oxide is a colorless gas but when it is passed into the atmosphere, it combines with oxygen and forms nitrogen dioxide (NO2). The nitrogen dioxide then combines with chemically active hydrocarbons (HC) and when in the presence of sunlight, causes the formation of photo-chemical smog.
To further complicate matters, some of the nitrogen dioxide (NO2) is broken apart by the sunlight to form nitric oxide and oxygen. (NO2+ sunlight = NO + O). This single atom of oxygen then combines with diatomic (meaning 2 atoms) oxygen (O2) to form ozone (O3). Ozone is one of the smells associated with smog. It has a pungent and offensive odor, irritates the eyes and lung tissues, affects the growth of plant life and causes rapid deterioration of rubber products. Ozone can be formed by sunlight as well as electrical discharge into the air.
The most common discharge area on the automobile engine is the secondary ignition electrical system, especially when inferior quality spark plug cables are used. As the surge of high voltage is routed through the secondary cable, the circuit builds up an electrical field around the wire, which acts upon the oxygen in the surrounding air to form the ozone. The faint glow along the cable with the engine running that may be visible on a dark night, is called the "corona discharge." It is the result of the electrical field passing from a high along the cable, to a low in the surrounding air, which forms the ozone gas. The combination of corona and ozone has been a major cause of cable deterioration. Recently, different and better quality insulating materials have lengthened the life of the electrical cables.
Although ozone at ground level can be harmful, ozone is beneficial to the earth's inhabitants. By having a concentrated ozone layer called the "ozonosphere," between 10 and 20 miles (16-32 km) up in the atmosphere, much of the ultra violet radiation from the sun's rays are absorbed and screened. If this ozone layer were not present, much of the earth's surface would be burned, dried and unfit for human life.
Oxides of sulfur (SOx) were initially ignored in the exhaust system emissions, since the sulfur content of gasoline as a fuel is less than 1⁄10 of 1 percent. Because of this small amount, it was felt that it contributed very little to the overall pollution problem. However, because of the difficulty in solving the sulfur emissions in industrial pollution's and the introduction of catalytic converter to the automobile exhaust systems, a change was mandated. The automobile exhaust system, when equipped with a catalytic converter, changes the sulfur dioxide (SO2) into sulfur trioxide (SO3).
When this combines with water vapors (H2O), a sulfuric acid mist (H2SO4) is formed and is a very difficult pollutant to handle since it is extremely corrosive. This sulfuric acid mist that is formed, is the same mist that rises from the vents of an automobile battery when an active chemical reaction takes place within the battery cells.
When a large concentration of vehicles equipped with catalytic converters are operating in an area, this acid mist may rise and be distributed over a large ground area causing land, plant, crop, paint and building damage.
A certain amount of particulate matter is present in the burning of any fuel, with carbon constituting the largest percentage of the particulates. In gasoline, the remaining particulates are the burned remains of the various other compounds used in its manufacture. When a gasoline engine is in good internal condition, the particulate emissions are low but as the engine wears internally, the particulate emissions increase. By visually inspecting the tail pipe emissions, a determination can be made as to where an engine defect may exist. An engine with light gray or blue smoke emitting from the tail pipe normally indicates an increase in the oil consumption through burning due to internal engine wear. Black smoke would indicate a defective fuel delivery system, causing the engine to operate in a rich mode. Regardless of the color of the smoke, the internal part of the engine or the fuel delivery system should be repaired to prevent excess particulate emissions.
Diesel and turbine engines emit a darkened plume of smoke from the exhaust system because of the type of fuel used. Emission control regulations are mandated for this type of emission and more stringent measures are being used to prevent excess emission of the particulate matter. Electronic components are being introduced to control the injection of the fuel at precisely the proper time of piston travel, to achieve the optimum in fuel ignition and fuel usage. Other particulate after-burning components are being tested to achieve a cleaner emission.
Good grades of engine lubricating oils should be used, which meet the manufacturers specification. Cut-rate oils can contribute to the particulate emission problem because of their low flash or ignition temperature point. Such oils burn prematurely during the combustion process causing emission of particulate matter.
The cooling system is an important factor in the reduction of particulate matter. The optimum combustion will occur, with the cooling system operating at a temperature specified by the manufacturer. The cooling system must be maintained in the same manner as the engine oiling system, as each system is required to perform properly in order for the engine to operate efficiently for a long time.