Part IV Chemical Kinetics of Combustion and Pollutants Formation

2103555 Engine Emissions and Control

Combustion Theory
Why study combustion? combustion of fossil fuels is currently, and should remain for the foreseeable future, the main source of the worlds energy. It is therefore a fundamental driver of almost all human activity. it is also now generally accepted that the combustion of fossil fuels is the major cause of global warming via the release of carbon dioxide CO2 into the atmosphere. Given that fossil fuel combustion is currently essential to the world economy, the more benign use of this resource is of increasing concern.

Combustion Theory
Basic definitions combustion reactions are one form of chemical reaction 1. combustion is defined as the oxidation of a fuel, with large amounts of released energy 2. the oxidiser is in most cases air (or more specifically, O2 in air) because of its abundance. 3. a fuel is any material that can be burned to release energy. Hydrocarbon fuels of the form CxHy are the most common.

Combustion Theory
Basic definitions many hydrocarbon fuels are mixtures of many different hydrocarbons although they mainly consist of the following:

gasoline ~ octane, C8H18 diesel ~ dodecane, C12H26 methanol = methyl alcohol, CH3OH LNG (liquefied natural gas) ~ methane, CH4 LPG (liquefied petroleum gas) ~ propane, C3H8

Combustion Theory
Composition of air on a molar (or volume) basis, dry air is composed of:
20.9% oxygen O2 78.1% nitrogen N2 0.9% CO2, Ar, He, Ne, H2, and others

a good approximation of this by molar or volume is: 21% oxygen, 79% nitrogen thus, each mole of oxygen is accompanied 0.79/0.21 = 3.76 moles of nitrogen.

Combustion Theory
Composition of air at ordinary combustion temperatures, N2 is inert, but nonetheless greatly affects the combustion process because its abundance, and hence its enthalpy change, plays a large part in determining the reaction temperatures.
1. this, in turn, affects the combustion chemistry, as we shall see later. 2. also, at higher temperatures, N2 does react, forming species such as oxides of nitrogen (NOx), which are a significant pollutant.

Combustion Theory
Stoichiometry and air/fuel ratios the amounts of fuel and air taking part in a combustion process are often expressed as the air to fuel ratio:

where: mfuel, mair = mass of fuel or air (kg), equivalent, and widely used, terms to the AFR are the fuel/air ratio FAR, the equivalence ratio, , and the lambda ratio :

m air AFR = m fuel

FAR = = FAR stoich

Combustion Theory
Thermodynamics of Combustion When molecules undergo chemical reaction, the reactant atoms are rearranged to form new combinations. The chemical reaction can be presented by reaction equations. However, reaction equations represent initial and final results and do not indicate the actual path of the reaction, which may involve many intermediate steps and intermediate species. This approach is similar to thermodynamics system analysis, where only end states and not path mechanism are used. The dissociation of the products into species with a higher enthalpy of formation occurs in many combustion reactions of practical importance. In such cases, the temperature of the products is lower than the undissociated temperature, because some of the energy released by the original combustion reaction is absorbed by endothermic, dissociative reactions.

Combustion Theory
Thermodynamics of Combustion The concept of chemical equilibrium must be introduced in order to quantify the degree of dissociation. Chemical equilibrium occurs when the Gibbs free energy of a chemical mixture is at a minimum i.e. there has been sufficient time for all reactions to reach completion. This latter condition may seem rather restrictive in many combustion reactions of practical importance, such as those involving the transient flow of fuel and air through an internal combustion engine. However, combustion reactions are generally very fast, and equilibrium or near equilibrium is achieved in many cases.

Chemical Equilibrium
To obtain thermodynamic equilibrium, it is necessary to have complete equilibrium between the molecular internal degrees of freedom, complete chemical equilibrium, and complete spatial equilibrium. Internal molecular energies are the way that molecules store energy. The major form of energy for polyatomic molecules are translational, vibrational, and rotational energy, electronic energy excitation, and nuclear spin. For most engineering combustion application it is safe to assume equilibrium among the internal degree of freedom.

Chemical Equilibrium
One case where it is not safe to assume equilibrium is in shock waves. The times for relaxation of the various internal degrees are typically: translation 10-13 s, rotation 10-8s, and vibration 10-4 s. Thus, for a very sudden change in temperature the rotational energy will not reach equilibrium until about 10-8s and the vibrational until about 10-4 s. Therefore, the translational energy will briefly overshoot the equilibrium value, and one cannot strictly assume internal equilibrium until 0.1 ms has elapsed.

Chemical Equilibrium
Chemical equilibrium is achieved for constant temperature and pressure systems when the rate of change of concentration go to zero for all species. In a complex reaction some species may come to equilibrium rapidly due to fast reaction rates or a very small change in concentration, while others approach equilibrium more slowly. For example, consider the flow of high-temperature hydrogen in a nozzle. Suppose that at the stagnation temperature the hydrogen is all dissociated to H atoms. If the expansion is very slow, the reaction 2H ---> H2 will follow the dropping temperature rapidly enough to give a series of equilibrium values (called shifting equilibrium). If the expansion is very rapid, hardly any reaction can occur and the result will be an essentially constant concentration of H atoms (frozen equilibrium).

Chemical Equilibrium
Between these two extremes the concentration will be determined by the rate of reaction and is said to be kinetically limited. This is important because chemical equilibrium does not exist in the flame zone. In the flame zone, temperature gradient are very steep and many short lived species are found there. In the postflame zone, many of combustion products are in chemical equilibrium or possibly shifting equilibrium. An example of practical interest is nitrogen oxide production. The major species may follow an essentially equilibrium path while the NO reacts too slowly to stay in equilibrium as the temperature is lowered by heat transfer or expansion.

Chemical Equilibrium
Chemical Equilibrium Criterion Thermodynamics alone cannot determine what species may be in the product mixture. However, given an assumed set of constituents, thermodynamics can determine the proportion of each species which exist in the equilibrium mixture. Once the composition is determined, the thermodynamics properties of the mixture, such as u,h,etc., may be calculated.

Chemical Equilibrium
Chemical Equilibrium Criterion For a system of J species in chemical equilibrium, the pressure and temperature do not change, equilibrium criterion may be specified by stating that the Gibbs free energy of the system (G=H-TS) does not change. (dG ) = 0 (1) T ,p Where J G = j =1 N j g j (2) j And where g j = h j = Ts . Since p j = s j o R ln j s p (3) T o c o = p dt sj and (4)
To

Chemical Equilibrium
Chemical Equilibrium Criterion

the Gibbs free energy for species j can be written as

Chemical Equilibrium
Chemical Equilibrium Criterion

Chemical Equilibrium
Chemical Equilibrium Criterion

Chemical Equilibrium
Chemical Equilibrium Criterion

Chemical Equilibrium
Chemical Equilibrium Criterion

The equilibrium constant at constant pressure Kp is not a function of the total pressure, but only a function of temperature. When solving for equilibrium products using Eq. 13, the reactions to be considered are identified, and the equilibrium constants are evaluated at the specified temperature. Then the atom balance constraints are specified for the system and an equilibrium equation is written for each of the specified reactions using the form of Eq. 12. This set of equations is solved simultaneously to obtain the species mole fractional and other thermodynamic properties of the system.

Chemical Equilibrium
Chemical Equilibrium Criterion

For combustion products, important gas phase equilibrium reactions include:

Reactions (i), (ii), (v), (vi), and (vii) are dissociation reactions. Reaction (iii) is the so called water-gas shift reaction. Reaction (iv) accounts for equilibrium OH formation, which is an important species in chemical kinetics reactions. Reaction (viii) accounts for equilibrium NO, an important air pollutant.

Chemical Equilibrium
Chemical Equilibrium Criterion An example of the thermodynamic equilibrium products from kerosene-air combustion is shown in Figures 1 and 2. Major products of lean combustion are H2O, CO2, O2, and N2; and for rich combustion the major products are H2O, CO2, CO, H2, and N2. At stoichiometric conditions at the flame temperature O2, CO, and H2 are present, whereas for the assumption of complete combustion, i.e., no dissociation, these three species are zero. Minor species equilibrium of combustion products at the flame temperature includes O, H, OH, and NO. Carbon monoxide is a minor species in lean products, while O2 is a minor species in rich products.

Chemical Equilibrium
Chemical Equilibrium Criterion

Figure 1 Equilibrium composition and temperature for adiabatic combustion of kerosene (CH1.8) as a function of equivalence ratio.

Chemical Equilibrium
Chemical Equilibrium Criterion

Figure 2 Variation of equilibrium composition with temperature for stoichiometric combustion of kerosene, CH1.8

Chemical Equilibrium
Chemical Equilibrium Criterion Several thermodynamic equilibrium calculations can also be done with a calculator rather than with a computer as shown in an example given below. The equilibrium constant method is used because it is conceptually and computationally straightforward when only one equilibrium reaction is involved. An example on using the method of minimizing G is also given.

Properties of Combustion Products

Properties of Combustion Products

The effect of dissociation is not large except at high temperatures. This is illustrated in Figure 3, where enthalpy is plotted versus temperature for a product of a stoichiometric methane and air reaction. The line of constant pressure coincides at lower temperature where dissociation is small. At higher temperature the changing composition due to dissociation cause the lines of separate. For a fixed temperature, dissociation is largest at low pressure and becomes quite small at very high pressures. In general, Le Chateliers rule states that if the moles of products exceed the moles of reactants, then an increase in pressure decreases the dissociation as shown by Eq. 12.

Properties of Combustion Products

Figure 3 Absolute enthalpy of products from stoichiometric methane-air reaction.

Properties of Combustion Products

Figure 3 can be used illustrate the effects of dissociation on a simple adiabatic throttling process. Neglecting changes kinetic energy, h1 = h2. If enthalpy is a function of T only, then T1 = T2. This is true for the ideal gas mixture of Figure 3 in the nondissociated region. However, at the higher temperatures the moles fraction of the ideal gas constituents vary with both T and p, so that h is a function of both T and p. Throttling cause a drop in pressure resulting in some energy being used to break molecular bonds and lowering the downstream temperature. For example, throttling the products in Figure 3 from 3000 K and 150 atm to 1 atm gives a downstream temperature of 2700 K. Note that this energy is recovered by a constant pressure cooling process to a nondissociated state provided that we assume shifting equilibrium. The processes do however cause a loss in available energy. Because the throttled gas may go from state 1 to state 2 in a very short time the assumption of shifting equilibrium may not hold for all species.