Fuelling Theory
Let's start with the theory then. We are concerned with spark ignition gasoline engines here. I'm only going to cover gasoline, since Diesel is for trucks and diggers, and alcohol is for drinking and drag racing.
Chemistry
Now you might think that petrol is petrol right? Not exactly. You will probably have heard the term "hydrocarbons" before, perhaps as part of the MOT emissions check. Hydrocarbons are raw fuel. They are a chemical compound of hydrogen and carbon. Without getting into too much of the chemistry, there are different fuels, the simplest of which in structure (the alkanes) consist of chains of carbon molecules, each linked with the next carbon molecule and with two hydrogen molecules. The end carbons then have an extra hydrogen. This leads to a family of fuels with the chemical formulae CH4, C2H6, C3H8 etc. These three examples are more commonly known as methane, ethane and propane.
Now because of the weird and wonderful way in which chemistry works, you can also get different arrangements of atoms, where the structures vary according to which H is bonded to what C, and how strong the bond is. Take for example C7H16. For the same number of C's and H's, it can be arranged in four different ways. Why is this important? Because the structure defines their properties as a fuel, and how they are broken down when they burn.
We're all familiar with the RON value of petrol right? (If not don't worry, I'll come to it in a bit). A higher RON means the fuel is more resistant to knocking (self igniting). Well for our example C7H16, n-heptane has RON of 0, i-heptane (2,4-dimethylpentane) has a RON of 83, i-heptane (2,2-dimethylpentane) has a RON of 93 and good old i-heptane (2,2,3-trimethylbutane) has a RON of 112.
Overall a typical gasoline is predominantly a mixture of paraffins (alkanes), naphthenes (cycloalkanes), aromatics and olefins (alkenes). The exact ratios depend on the oil refinery that makes the gasoline, but with ever stricter requirements from manufacturers and government, gasolines from different companies are generally very similar in composition.
As you can imagine, there is a whole lot more to fuels than this, and that is why fuel companies spend a lot of money on research, playing with new blends of fuels and various additives (anyone remember lead) to improve certain desirable qualities. Here are a couple of interesting links to start you off.
http://www.atsdr.cdc.gov/toxprofiles/tp72-c3.pdfChevron Products: Ask Mr. Gasoline
If you need to know more about fuels, then find yourself a good book on the subject like I did. The information in this section "Chemistry" is taken from Chapter 3 of "Introduction to Internal Combustion Engines" by Richard Stone. Don't act so surprised that I didn't have all this info in my head. Hey I'm an engineer, not a chemist!
Combustion
So that's the fuel itself, but how do we get any useful work out of it. Firstly we need to unite the fuel with oxygen (which comes in air as O2). We mix the fuel and air together so that we get a good chance of O2's being near to CxH's, and if we have done a good job of mixing it (so that the fuel is spread out evenly through the air) the mixtures is called "homogeneous", and this is the condition in which we will get the best combustion. Once we have ignited the mixture with a spark, a chemical reaction occurs where the C's, H's and O's all swap around and end up as CO, CO2 and H2O, plus some extra heat. The heat makes these gases (combustion products) expand, and that drives the piston down the cylinder and voila, we have power!
Complete combustion occurs when just the right number of O2's are available to react exactly with the number of CxH's we have so that all the C's H's and O's get converted. We express this "stoichiometric" mixture as the ratio of mass of air (since we actually ingest air, not pure oxygen) to mass of fuel. This is the air fuel ratio (AFR), and this turns out to 14.7:1 for air:gasoline.
Another way to express the AFR is as the excess air factor. Or to put it another way, the actual AFR/stoichimetric AFR. This value is called lambda. Lambda=1 equals AFR=14.7:1 for gasoline.
Lambda Efficiency
In just the same way that the engine can still run with different spark advance, it can also run at different air fuel ratios. There are some pretty complex interactions occurring here.
As the fuelling increases, the incoming aircharge is cooled (as it loses its heat to the fuel), increasing the charge density, which as we know is a good thing.
The highest flame speed has been found by research to occur at a lambda of about 0.82. High flame speed is good because it increases thermal efficiency by reducing the time available for heat to be transferred to the cylinder walls, meaning the gasses expand more, and hence make more power.
Theoretically, the highest combustion temperature occurs at the stoichiometric AFR, but in reality the highest temperature is reached at the lambda of around 0.88. This is due to thermal decomposition and that's about all I know about it. High combustion temperature is good because the more heat we get (assuming the engine can cope), the more expansion we get, and hence more power.
Lastly, the highest exhaust gas temperature is found at around lambda = 1.
If we combine those effects, and if we consider the engine torque produced at stoichiometric to be 100%, then we can plot a lambda efficiency curve, just as we did with ignition timing.