ANTIKNOCK

AGENTS USED IN FUEL AND THEIR ENVIRONMENTAL CONSEQUENCES AND REMEDIES

Aditya Khokhar, P2009ME1086 Indian Institute of Technology, Ropar

INTRODUCTION
The phenomenon of knocking in engines is universal and it is no wonder universally undesirable due to its harmful and catastrophic effects. Since long researchers are trying to find new and effective ways to reduce knocking and one of the most common method is to use antiknock agents in our fuels. These substances have been thoroughly checked for their efficiency and are used all over the world. But as everything has its pros and cons; environmental problems regarding their use creeps in here also. Therefore it is necessary to use those substances which are eco-friendly because if unchecked these chemicals can cause severe damage to our environment.

KNOCKING
Knocking (also called knock, detonation, spark knock, pinging or pinking) in sparkignition internal combustion engines occurs when combustion of the air/fuel mixture in the cylinder starts off correctly in response to ignition by the spark plug, but one or more pockets of air/fuel mixture explode outside the envelope of the normal combustion front. In other words, we know that in normal engine operation, the fuel/air mixture is ignited by the spark plug and the flame spreads through the combustion chamber. Although the flame moves very quickly (passing through the cylinder in just a few milliseconds) it is nonetheless a relatively smooth process with a correspondingly smooth release of heat energy. However, during this process, the "end gas" at the edges of the combustion chamber experiences a rise in pressure and temperature due to the spreading flame. In some cases this is enough to cause the remaining fuel/air mixture to self-ignite before the flame arrives, pretty much instantaneously. This causes a sudden very rapid release of heat energy causing an equally sudden rise in pressure and temperature - an "explosion" rather than a "smooth burn". This explosive release of energy is what causes the characteristic "knocking", "pinging" sound from which the phenomenon gets its name. Unfortunately it is not just an unpleasant sound; the sudden rise in pressure and temperature can cause

catastrophic damage to pistons and head gaskets, among other engine components, and so it is vital to avoid anything other than very light, occasional knock.

The end gas is shown pictorially below:

Normal combustion takes place as follows:

And, abnormal combustion resulting in knocking takes place as follows:

So summing up the main causes of knocking in engines can be seen as follows:

The main driver for knock is ignition timing. As the ignition is advanced - the spark is fired earlier in the engine operating cycle - the pressure and temperature during the combustion event become higher, thus making knock more likely. Happens when fuel burn ignites irregularly and prematurely Usage of fuel with low octane rating Poor design of engine and due to their own structural problem

EFFECTS OF KNOCKING
Knocking in engines has many desirable effects like: If the shockwaves created due to knocking have enough intensity and/or over a long enough periods of time, these shockwaves and excessive pressure and temperature can cause engine damage including (going from minimal to destructive). Erosion and pitting of the piston and/or cylinder liners, resulting in small wear particles which may enter the engine lubrication/oil system, plug the catalysts, and/or possibly block valves from closing completely. The wear may not be unlike water pump cavitations' damage. Actual holes punched or burned in the pistons

REDUCTION OF KNOCKING
The knocking in engines can be reduced by following means: Reducing air and coolant temperatures is always good for suppressing knock (colder air is also denser, allowing the engine to take in a greater mass of air.) The strategy for reducing knock - and so allowing more ignition advance (and hence more torque) - is to use a fuel with a higher octane rating. Higher octane fuels contain more components such as benzene that are resistant to self-ignition, and less of components such as n- heptane that self-ignite relatively easily. There are two ways to meet the demand of modern high-performance engines for fuels of high octane numbers. 1. The first one is to produce artificial petrol that is rich in branched-chain alkanes. 2. Another method is to add an anti-knock agent to petrol. The most commonly added compound is tetraethyl lead [(CH3CH2)4Pb]. When burned, this lead compound produces small particles of lead oxide which tend to combine with the free radicals produced in the chain reaction of combustion. This slows down the reaction and makes it smoother.

OCTANE RATING
Octane rating of a spark ignition engine fuel is a measure of the resistance to detonation or knocking compared to a mixture of iso -octane (2,2,4-tri methyl pentane, an isomer of octane) and n- heptane. It is a numerical representation of the antiknock properties of motor fuel, compared with a standard reference fuel, such as isooctane, which has an octane number of 100. Octane rating does not relate to the energy content of the fuel .It is only a measure of the fuel's tendency to burn in a controlled manner, rather than exploding in an uncontrolled manner.

ANTIKNOCK AGENTS
An antiknock agent is a gasoline additive used to reduce engine knocking and increase the fuel's octane rating. Fuels have a tendency to ignite before the flames reach which results in high abrupt energy release leading to damaging effects like knocking or detonating. As we know that the octane rating of a fuel tells us about its tendency to ignite before time. Higher the octane rating lesser are the chances of the fuel to burn before time. So, these antiknock agents try to increase the octane rating of our fuels. The typical antiknock agents in use are: Tetra-ethyl lead Methylcyclopentadienyl manganese tricarbonyl (MMT) Ferrocene Iron pentacarbonyl Tetra-ethyl lead: Tetraethyllead (common name tetraethyl lead), abbreviated TEL, is an organolead compound with the formula (CH3CH2)4Pb. Its mixing with gasoline (petrol) as an inexpensive additive beginning in the 1920s allowed octane ratings and thus engine compression to be boosted significantly, increasing power and fuel economy.

TEL chemical structure

The advantages of leaded gasoline its higher energy content and storage quality eventually led to a universal switch to leaded fuel. One of the greatest advantages of TEL over other antiknock agents or the use of high-octane blend stocks is the very low concentrations needed. Typical formulations called for 1 part of prepared TEL to 1260 parts untreated gasoline.

Though TEL was a very effective antiknock agent but it was banned in most parts of the world due to high toxicity due to lead content present in it. Leaded gasoline posed severe harm to soil and air pollution and lead is a strong neurotoxin. Lead poisoning leads to lower IQ in children and anti-social behaviour because the nervous system was attacked. Methylcyclopentadienyl manganese tricarbonyl (MMT): Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (CH3C5H4)Mn(CO)3. Marketed initially in 1958 as a supplement to the gasoline additive tetraethyl lead to increase the fuel's octane rating, MMT was later used in unleaded gasoline.

Though MMT is less toxic than TEL but still it has its own environmental issues. The health considerations associated with MMT are divided into two areas; (1) MMT in its original chemical form and (2) the manganese combustion products emitted from vehicles operating on gasoline containing MMT as an octane improver. MMT in its raw form prior to its addition to gasoline is highly toxic and thus its not accessible by general public. Immediate symptoms of MMT exposure are mild skin and eye irritation. Short-term symptoms resulting from MMT poisoning by high exposures include giddiness, headache, nausea, and difficulties in breathing. Animal studies have shown that chronic exposure to MMT can result in damage to the liver and kidneys. Chronic exposure to high levels of manganese, typically in certain occupational activities, has also been known to cause manganism, a disease with symptoms similar to those of Parkinson's disease. Ferrocene: Ferrocene is an organometallic compound with the formula Fe(C5H5)2. It is the prototypical metallocene, a type of organometallic chemical compound consisting of two cyclopentadienyl rings bound on opposite sides of a central metal atom.

Although of not much practical use as an antiknock agent, it is used in some specialised applications in petrol fuels. Iron pentacarbonyl: Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5.

Fe(CO)5 is toxic, which is of concern because of its volatility (vapour pressure: 21 mmHg at 20 C). If inhaled, iron pentacarbonyl may cause lung irritation, toxic pneumonitis, or pulmonary edema.

REMEDIES
Gasoline mixtures that are rich in straight-chain alkanes such as heptanes ignite very readily and explode rapidly. This causes 'knocking' and inefficient combustion. But combustion of branch-chain alkanes like 2,2,4-trimethylpentane (iso -octane) is much smoother and more controlled. Hence, gasoline mixtures rich in branch-chain alkanes are more efficient in burning and less likely to cause knocking. Also their usage will do away with the usage of lead-the prime polluter, and other metals.

Other method to prevent pollution caused by antiknock agents is the use of alternative fuels; green fuels. The fuels that are likely to serve our purpose are:

(1) Electric (3) Natural gas (5) Fuel cells (7) Biodiesel (B100)

(2) Hybrid (4) Hydrogen (6) clean diesel (low sulfur) (8) Ethanol

ELECTRIC
The main advantage of using electric fuel is PLUG IN AND GO. Being that they are operated purely on battery, they give out no emissions or other toxins usually associated with modes of transportation. As far as being green and the lesser evil of most fuels, electric is the least damaging fuel to the environment. But there are also disadvantages of using electric fuel. Some of the main disadvantages can be summed up below: Unlike a gas engine, it takes a lot longer to charge an electric car and it can be a hassle when making long road trips. For numerous reasons such as, not every gas station is equipped with compatible equipment to fuel electric cars, if your car stalls from a low battery it is harder to transport electric, than a gallon of gas. In addition, the price of electric fueled vehicles is quite expensive and the price to convert your mobile can range from $5,000-$10,000. Not to mention your electric bill.

HYBRID
A hybrid is a Vehicle that uses two sources of fuel, some use gas combined with electric, solar or water. The main advantages of hybrid are: Since it is also using other sources of fuel it gives got lesser emissions than an engine solely using gasoline. In addition, some hybrid cars you can get up to 50 per gallon. This means on long drives or road trips you could drive well over 500 miles before you would need to stop and get gas. Hybrid cars are also very affordable where some are priced brand new from just $12,000 and up. The main disadvantages are: When a hybrid battery is drained or just stop working, it can cost around $5,000 to replace In addition, hybrids have a lighter body weight to compensate for its heavy engine where in case of accident it can be extremely dangerous for the driver

NATURAL GAS
The use of natural gas is desirable because it burns clean as well as releases 70% less carbon dioxide than fossil fuel, making it a lot cleaner than traditional fuel. Natural gas has a higher heating value as well as is less expensive than traditional fuels. But, it cannot be recycled; the world can only produce so much which in time natural resources can run out. In addition, the price to recover remaining natural gas due to flow, access etc, is expensive.

HYDROGEN
Hydrogen or water powered vehicles, even though they are not yet on the market, or even close to being completely developed as far as the other fuels mentioned in this report, hypothetically there would be many advantages. Emissions would be close to none, which is beneficial to our environment. Everyone would be able to afford to fuel their vehicle. But the main disadvantage of using hydrogen as a fuel is that till now it has not been developed for mass production. In addition, unemployment would sky rocket due to no need for gas stations, or any other gas related occupations. As well as we can only assume that, the purchase price of purely watered power vehicles would be very pricey.

FUEL CELLS
A fuel cell is like a battery in a sense, but instead it combines hydrogen and oxygen to produce electricity. Although it is a chemical process, it does not involve heat. It has an advantage that it does not involve any moving parts, so traditional mechanical complications are minimal. Fuel cell emissions only emit water and it is very quite during operation. But sadly it has some disadvantages also; like: It is expensive to make as it relies on the use of platinum. Platinum even though already in use throughout the market is a natural resource and is bound to run out eventually, especially if we increase our dependency on using this rare metal. In addition, with changing technology mechanics will slowly find themselves out of a job as well as other vehicle maintenance services.

CLEAN DIESEL
Clean Diesel is diesel fuel put through a process where pressure is used to remove the majority of its sulfur content. It is also called as Ultra Low Sulfur Diesel (ULSD). It has following advantages: It reduces 90% of emissions content, compared to traditional diesel energy. This promotes cleaner air as well as complies with EPA (Environmental Protection Agency) quality standards and regulations. This type of fuel is also compatible with all diesel-fueled engines.

It has following disadvantages: The potential purchase price is more expensive as well as current availability is limited. In addition, this type of fuel is susceptible to eating through engine seals as well as during cold weather its liability decreases.

BIO DIESEL
Biodiesel Fuel is diesel fuel consisting of oils derived from animal fat and recycled cooking grease. The main advantage of using bio diesel is that it can be made from home. Most diesel engines can utilize biodiesel fuel as well as it emits less air pollutants and greenhouse gas. In addition, it is also biodegradable, non-toxic as well as is a lot safer to handle compared to traditional diesel. But the use of bio diesel is not favoured in cold weather.

ETHANOL
The usage of ethanol has following advantages: Ethanol emits less air pollutants than traditional gasoline, also it is resistant to engine fuel mixture detonation or in laymen, engine knock. Ethanol is also not as expensive compared to gasoline. The main disadvantages are: Only certain cars can run this fuel, such as flex-fuel cars, trucks, SUVs. In addition, not every gas station carries E85, as well as your vehicle will have lower gas mileage and as of now producing, the mixture is costly.

CONCLUSION
Concluding my report here I would like to say that in todays time when the hunger for fuel is growing at a very rapid phase; it is necessary to use alternative fuels in place of metallic antiknock agents. These metallic compounds pose a very severe threat to our environment and to humans itself. Therefore it is high time that the usage of green fuels should be taken seriously; not only their use will help preserve our environment but also they are more economical than traditional fuels.

REFERENCES
Wikipedia.com Biodiesel. (2008), from Fuel Economy. Gov Website: www.fueleconomy.gov E85. (2008),from Fueleconomy.gov Website: http://www.fueleconomy.gov/feg/ethanol.shtml Explore Fuel Cells. (2007), from New Mexico Solar Energy Association Website: www.nmsea.org Freedom, O. (2009, March). Water Powered Car: The Benefits and Disadvantages from CarPoweredWater.Blogspot.com Wisler, A. J. (2009). Advantages of Electric Cars. from LoveToKnow: GreenLiving Website: http://greenliving.lovetoknow.com/Advantages_of_the_Electric_Car