4.1 Thermochemistry 143 (1) Equations (2-55) and (4-1) are used to find the air-fuel ratio: AF = ma/my = NyMy/N/My = ((15)(476)(29)) = 18:16 (2) Equation (256) is used to find the fuel-air ratio FA = my/m, = 1/AF = 1/1816 = 0055 @) Fuel-air ratio of stoichiometric combustion is (FA) aon = ((1)(114)]/[125)(4.76)(29)] = 0.066 Equivalence ratio is obtained using Eq, (4-2): (FA)sa/(FA) os = (0.085)/(0.066) = 0.833, Even when the flow of air and fuel into an engine is controlled exactly at stoi chiometric conditions, combustion will not be “perfect,” and components other than CO;, H;0, and N; are found in the exhaust products. One major reason for this is the extremely short time available for each engine cycle, which often means that less than complete mixing of the air and fuel is obtained. Some fuel molecules do not find an oxygen molecule to react with, and small quantities of both fuel and oxygen end up in the exhaust. Chapter 7 goes into more detail on this and other reasons that ideal com- bustion is not obtained. SI engines have a combustion efficiency in the range of 95% to 98% for lean mixtures and lower values for rich mixtures, where there is not enough air to react with all the fuel (sce Fig. 4-1). CI engines operate lean overall and typically have combustion efficiencies of about 98%. Chemical Equilibrium Ifa general chemical reaction is represented by 4A + vgB—> eC + ypD (43) where A and B represent all reactant species, whether one or two or more, and C and D represent all products, regardless of number, then v4, ¥p, ¥c, and vp represent the stoichiometric coefficients of A, B, C, and D. Equilibrium composition for this reaction can be found if one knows the chemical equilibrium constant Ky = [NEN GP) /(NGANg) P/N) (4-4) where 1c + YD — 14 — Up number of moles of component i at equilibrium jotal number of moles at equilibrium ‘otal absolute pressure in units of atmospheres144 Chapter 4 Thermochemistry and Fuels 109, - - - z 0 06 os 15 12 14 Fuel Equivalence Ratio, & FIGURE 4-1 ‘Combustion efficiency a a function of fel equivalence rato. Efficiency for engines operating lean is generally on the order of 98%. When an engine operates fuel rch, there isnot enough oxygen to react witha the fuel and combustion efficiency decreases Cl engines operate lean and typically have high combustion effin. Adapted from [58]. Equilibrium constants for many reactions can be found in thermodynamic text- books or chemical handbooks, tabulated in logarithmic form (In or logo). An abbrevi- ated table can be found in the Appendix of this book (Table A-3). K, is very dependent on temperature, changing many orders of magnitude over the temperature range experienced in an IC engine. As K, gets larger, equilibrium is more towards the right (products). This is the maximizing of entropy. For hydrocarbon fuels reacting with oxygen (air) at high engine temperatures, the equilibrium constant is very large, meaning that there are very few reactants (fuel and air) left at final equi- librium. However, at these high temperatures another chemical phenomenon takes place that affects the overall combustion process in the engine and what ends up in the engine exhaust Examination of the equilibrium constants in Table A-3 shows that dissociation of, normally stable components will occur at these high engine temperatures. CO; dissoci- ates to CO and O, O2 dissociates to monatomic O, Np dissociates to monatomic N, ete. ‘This not only affects chemical combustion, but is a cause of one of the major emission problems of IC engines. Nitrogen as diatomic N; does not react with other substances, but when it dissociates to monatomic nitrogen at high temperature it readily reacts with oxygen to avoid gem mobile en also lower Example | One major peratures. in the aird cylinders mation off tion: No Inth there is nos The T = 35008 Eq. (4-4) or extent a This} for predicg time-temp the order ber for the of NOxemt engines, Exhaust4.1 Thermochemistry 145 ‘oxygen to form nitrogen oxides, NO and NO», a major pollutant from automobiles. To avoid generating large amounts of nitrogen oxides, combustion temperatures in auto- mobile engines are lowered, which reduces the dissociation of Nz. Unfortunately, this also lowers the thermal efficiency of the engine. Example Problem 4-2 One major reason for nitrogen oxides NOx in automobile engine exhaust is that a the high tem peratures experienced in the engine a small amount of the normally stable diatomic nitrogen ¥; in the air dissociates to monatomic nitrogen N, which is very reactive, Near the end of comb tion in a modern diesel engine operating on a Dual cycle the temperature and pressure in the cylinders are 3500 K and 10,500 kPa, Use Equation (4-4) to get an order-of-magnitude approx mation of the percent of diatomic nitrogen that dissociates to monatomic nitrogen inthe reac tion: Ny —>2N In the reaction there is only one reactant (N;), 50 this will be component A in Ea, (4-4) there isno component B. Component C represents the only product (N)thereis no component D. The total pressure in atmosphere units is P= (10,500 kPa)/(101 kPa/atm) = 104 atm The actual dissociation reaction for I mole of Ny is Ni72kN + (1-2) Np where x = extent of reaction ‘The chemical equilibrium constant K, is obtained from Table A-3 in the Appendix at T = 350K: login Ke = -7346 — K, = 4508 x 10° Eq. (4-4) is then K, = 4508 x 10 = [(2x)3/(1 — x)J[(104)/(2x + (1 — x) or extent of reaction x = 0,00001041 = 0,001041% ‘This number should be considered only as a crude order-of-magnitude approximation for predicting the formation of NO and NOs in the engine cylinders. Chemical kineties and the time-temperature-pressure relationship in the cylinders must be considered, time being on the order of milliseconds and chemical equilibrium never being obtained. This very low num: ber for the production of N and the consequent formation of NOx underlines the seriousness ‘of NOx emissions, which is considered one of the major air pollutants generated in automobile Exhaust Dew Point Temperature When exhaust gases of an IC engine are cooled below their dew point temperature, water vapor in the exhaust starts to condense to liquid. It is common to see water droplets come out of an automobile exhaust pipe when the engine is first started and the pipe is cold. Very quickly the pipe is heated above the dew point temperature, and condensing water is then seen only as vapor when the hot exhaust is cooled by the sur- rounding air, much more noticeable in the cold wintertime,