# CE 3

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3. Chemical Kinetics of Combustion
Thermodynamics describes the potential of a reaction, but it does not give the rate at which the reaction precedes or tells how quickly the equilibrium is approached. Chemical kinetics along with thermodynamics is needed to predict the reaction rates of well-mixed components. In this chapter the rudimentary concepts of elementary rates of chemical reactions are considered. We want to ask if the reaction rates depend on the concentration of the reactants or the products? The key task of this consideration shows a characteristic way in which the rate laws can be expressed in terms of differential equations. The solutions of the differential equations are used to predict the concentration of species at any time after the start of the reaction. The first law of thermodynamics is best suited to show the variation of enthalpy h with temperature ϑ during a combustion reaction. First let us discuss an exothermic reaction of the form A + B → C + D as a function of the time t. The next figure shows that at the beginning of a combustion reaction only the reactants A and B exist. At a desired time a special amount of activation energy is added to the well-mixed components A and B and the energy level of the mixture becomes higher than the starting enthapy level h1. The time interval between the maximum enthalpy and the starting enthalpy is called time interval of start. It follows the time interval of reaction where the energy level of the mixture is decreasing continuously to the lowest energy level h2 at the end of the reaction, so that the enthalpy of reaction, which is Δh = (h2-h1), is transferred to the surroundings and can be used for technical purposes.

Enthalpy h During this time only the reactants A and B exist

Concentration [A(t)]

During this time the component A of the reactants is constant and equal to the initial concentration [A]o

[A(t)] [A]o
New coordinate system [A(t)] as a function of time t

h h1
Activation energy EA

Enthalpy of reaction = -Δh =h2-h1

h2

[A(t→∞)]
0 Time of reaction Start-time interval Time t Time t

Time t

Time of reaction Start-time interval

After this time only the components C and D exist

Exothermic reaction A+B →C+D. At the initial state of the reaction only the reactants A and B exist. In the final state there are only the products C and D.

After this time there is no concentration of the component A in the products

As the enthalpy at the end of the reaction h2 is lower than the enthalpy at the start h1, the combustion process is named an exothermic reaction.

3.1 Rate of Reactions
In the field of chemical reaction we will investigate the concentration of the component A during the time of reaction in a new time scale. The convention used throughout this script is that brackets around a chemical symbol or component, for example [A], signify the concentration of that species in moles or mass per cubic centimeter. Of course we are only interested in [A(t)] during the time interval where the combustion reaction takes place, so we can start with the investigation after the start time interval with a new coordinate system [A(t)] versus time t. The rate of reaction for each elementary reaction results from individual encounters between molecules and does not depend on the mixture environment. This fact allows, the application of elementary reaction rates under idealized laboratory conditions, such as low pressure and the presence of only reactant species, to complex situations where many other species may be present. Because of the considerations of molecular processes it is possible to identify three major types of elementary reactions:

1. Bimolecular atom exchange reactions of the form: 2. Trimolecular recombination reaction of the form: 3. Bimolecular decomposition reactions of the form:
Combustion Engineering, Prof. Dr.-Ing. R. Ruderich

Only molecules that possess energy greater than a certain amount of activation energy will react. R.-Ing. The rate constant k is positive if gas material is produced. however. The collision number is 4. Other reactions are dominated by a loose bond-breaking step. we may say that in each case the rate of reaction is proportional to the collision number (collision frequency). The reaction rate constant k is negative if a disappearance of the material A (reactants) takes place. Dr. Prof. Ruderich . In a similar fashion. which is proportional to the product of the reactant concentration. is proportional to the collision number NANB. Bimolecular atom exchange reactions: Combustion Engineering. The number of particles of the species A is NA and this is the amount of moles nA times Avogadro´s number NAvo. Glasmann S37 NB=2 molecules of the species B There are 4 possibilities for arranging a reaction. Three body collisions are much less likely than binary collisions and therefore such reactions are often relatively slow.CE 3- 2 The third body M is necessary to conserve the energy during the process of collision in the reaction of types 2 and 3. In the decomposition reaction the third body M provides the energy needed to split the molecule AB. NA=2 molecules of the species A NA=3 molecules of the species A Ruderich Comment: Ragland S 109 Ruderich Comment: besitzen. The amount of moles is proportional to the concentration and the volume of the species. while in the recombination reaction the third body M takes away the surplus energy. we have the same expression for the species B. and where α is the proportional constant. . The collision number is 12. the rates of reaction are respectively expressed as 1. which is d[A(t)]/dt. Most of these reactions come under the class of decomposition processes. nA = α [A(t)] V nB = α [B(t)] V Now the rate of reaction. From a simple viewpoint. where β is a new proportional constant. Substituting NA and NB into the last equation or . For the elementary reaction 1. In most chemical reactions the rate is dominated by collisions of two species that may have the capability to react. NB=4 molecules of the species B There are 12 possibilities for arranging a reaction. It follows that and . 2 and 3 above.

The factor Z has a very mild T1/2 temperature dependence that is generally ignored when plotting data. Rates of products are positive. Trimolecular recombination reactions: 3. thus the activation energy EA may be determined readily.3 for elementary reactions are exponential functions of temperature. The Arrhenius equation shows an increasing in k with T that permits a straight-line correlation of data on ln(k) versus the reciprocal temperature (1/T) plots. Prof. Data that correlate as a straight line in such a plot are said to follow Arrhenius kinetics. i=1.CE 3- 3 2. k2 and k3 are the reaction rate constants for the respective reactions. This fact is called Arrhenius equation. Bimolecular decomposition reactions: where the factors k1. R. Kinetic theory shows that the Boltzmann factor gives the fraction of all collisions that have an energy level greater than the activation energy EA. but according to the theory of Arrhenius and from experiments. where Z is the pre-exponential factor or the gas kinetic collision frequency and exp(-EA/RT) is the Boltzmann factor. Ruderich . Note that the rates (or the concentrations of reactants) above are negative for species that are being used up in the forward reaction. which occur in combustion. c and d are stoichiometric coefficients can be divided in rates of destruction of A and B and in rates of formation of the molecules (or atoms) C and D.-Ing. Both EA and Z have been determined from experiments for most elementary reactions. The slopes of lines on these plots are equal to (-EA/R). so that the backward reaction is For example.2. The rates of a stoichiometric equation of the form where a. Dr. the backward reaction of the concentration [A(t)] of the species A as a function of time is now Combustion Engineering. because there are formed by used up reactants. b. Rates of destruction: Rates of formation: Some elementary reactions are reversible. it is observed that the rate constants ki. The activation energy is the energy required to bring the reactants to a reactive state referred to as an activated complex. such that the chemical bonds can be rearranged to form products. These factors are not functions of time.

CE 3- 4 . Note that there is no time dependence of the concentrations. the rate of the species d[A(t)]/dt is zero. In a number of simple cases analytical solutions are easily obtained by using Maple commands on a computer. Combining the rates of the forward and the backward reactions. The practical importance of Kc. R. is that if one of the rate constant k or kback can be measured. It follows that the ratio of the forward and backward rate constants are related to the thermodynamic equilibrium constant Kc that is based on concentrations. then the reaction is written as A → Product and the rate is given by the differential equation . This is a unimolecular or first-order reaction of the species A where the rate of disappearance is proportional to the instantaneous concentration of that species. that is the time t1/2 when half of the original material or initial concentration has gone.-Ing. Ruderich . We turn our attention to the definition of elementary rate laws. Unimolecular Reaction or First-Order Reactions The determination of a rate law is simplified by the isolation method in which the concentrations of all reactants except one. At constant temperature and volume we may integrate this expression For example.2 Elementary Rate Laws and Order of Reactions An Elementary rate law involves the experimental determination and theoretical calculation of the rates of production or disappearance of chemical species during a combustion process and the effect of temperature and species concentration on these rates. If [A] is the concentration of interest. are in large excess. We have to integrate them if we want to find the concentrations as a function of time. Dr. Prof. the net reaction rate of the species A is affected by two rate constants k and kback . Rate laws are differential equations. The rate laws of the disappearance of A and B are: Combustion Engineering. At equilibrium. for example [A]. Bimolecular Reaction or Second-Order Reactions In a similar consideration a bimolecular reaction is a reaction where two species A and B undergo a reaction to form products like A + B → Products. the decay of a radioactive nucleus is a special case of a unimolecular reaction. Complex rate laws may be integrated numerically. The half-life. is independent of the initial concentration for a unimolecular reaction only. then the other one may be obtained if the equilibrium constant Kc is known. 3. and one finds that where the subscript eq designates the equilibrium concentrations. where the initial concentration at the beginning of the reaction is a known value [A(t=0)] = [A]o. The equation for Kc above relates the quantity of the concentrations of a stoichiometric equation to the equilibrium constants.

This equation is needed to find the dummy concentration [X(t)]. . Trimolecular Reaction or Third-Order Reactions A reaction of this type can be written as A + B + C → Products and the rates of the substances A. B and C are given by and and where the initial concentrations are [A(t=0)]=[A]o. where [X(t)] is a dummy concentration. Ruderich . Dr. Since the concentration of the material A and B is not necessarily equal. The simultaneous solution of the differential equations system is not easy. In general.[X(t)].[X(t)] [B(t)] = [B]o . If we take the two substitutions into account. [A(t)] ≠ [B(t)] ≠ [C(t)]. Reaction Order Many reaction are found to have rate laws of the form Combustion Engineering.-Ing.CE 3- 5 . the integration of the system of the differential equation for a constant temperature and a constant volume yields . but in the chemist’s notation each differential equation is a chemical reaction of the second order. R. These are two mathematical differential equations of first order. we can write or and the special solution is where the initial concentration of the material C is [C]o. In the case where they are equal. Prof. From [X(t)] we are able to calculate [A(t)] and [B(t)] by using the substitutions above. The solution of this equation needs two substitutions of the form Ruderich Comment: Stehlow S73 ff and [A(t)] = [A]o . [B(t=0)]=[B]o and [C(t=0)]=[C]o. we will find that .

CE 3- 6 where α and β are positive numbers. It shows that the concentration of A approaches zero more slowly than in a first-order reaction with the same initial rate. Ruderich . A consequence is that species that decay by second-order reaction. The half-life of a substance in a second-order reaction varies with the initial concentration [A]o. Even these more complex processes. involve separate steps that usually are simple two-body collisions. may persist in low concentrations for a long period because their half-lives are long when their concentrations are low. Some reactions obey a zero-order law. (product or reactant) is raised in a rate law of this kind is the order of the reaction with respect to that species. All reaction go faster at higher temperature. we are able to investigate a unimolecular reaction as a second-order reaction. by which NO2 and CO molecules collide and react. For example. and what we derive from bimolecular reactions can be applied to each of the individual steps of a complex process. The special solution is . however. The power to which the concentration of a species. From the Arrhenius equation the rate constant is represented by or Combustion Engineering. Prof. Arrhenius Plot and Activation Energy EA All reactions other than spontaneous decompositions of single particles involve collisions between atoms or molecules.2 kJ/mol The rate of the forward reaction.5[A]o. some reactions that look simple from their stoichiometric equations actually involve elaborate chain mechanisms. a reaction having the rate law d[A(t)]/dt = [A(t)]1/2 [B(t)] is half-order in A. As we have seen. A reaction with the rate law above is α-order in A and β-order in B. R. Can we also find some way to increase the rate constant k? From page 7-4 we know that the most obvious factor that affects k is the temperature. The solution of this differential equation of first-order (mathematics-order) gives the concentration [A(t)] of the substance A as a function of time. A reaction that does appear to proceed by a simply two-body collision is the following: (NO2)g + (CO)g ↔ (NO)g + (CO2)g EA= 132. because the molecules move faster according to the Brownian movement and collide more often and more effectively. Dr. The stoichiometric equation of such a rate law looks like A → Product and the rate law is where the initial concentration is [A(t=0)]=[A]o. can be written as Rate = k [NO2] [CO] We know that we can increase the rate of the forward reaction by increasing the concentrations of NO2 and CO. and it is not possible to predict the exact true mechanism just be looking at the equation for the chemical reaction. If we calculate the half-life of the species A that is used up in a second-order reaction we have to substitute t by t1/2 and [A(t)] by 0. and therefore have a rate that is independent of the concentration of the reactant or products. and the three-halves order overall.-Ing. The overall order of this rate law is the sum of the individual orders α+β. Unimolecular Reaction as Second-Order Reactions With the definition of the chemical order of a rate law. for example some environmentally harmful substances. first order in B. By this equation we can predict the concentration of the material A at any time after the start of the reaction.

4 kJ/mol (NO2)g + (CO)g ↔ (NO)g + (CO2)g Time t Activated complex or NO2 and CO NO and CO2 activated state Transition from reactant molecules to product molecules The activated complex during the reaction is 132. O. If product molecules are more stable than reactants (qEP<0). This kind of plot is named after the Swedisch chemist Svante August Arrhenius (1859 1927) who first developed the theory. h EA=132. ln(k) Slope = -EA/R 0 1/T 0. The relationships between energies of reactants. Ruderich .2 kJ/mol qEP = -226.002 Region where the temperature is low In the collision hypotheses of combustion reaction. sometimes called transition state.. Prof. Combustion Engineering. In the following reaction (NO2)g + (CO)g ↔ (NO)g + (CO2)g Transferring O this transition state. In order that the reverse reaction occurs.001 Region where the temperature is high Arrhenius Plot 0. nor completely acquired by CO . or activated complex. This is the barrier that both the forward and the reverse reaction must surmount for them to occur. The transition-state theory proposes that this activated state is an intermediate arrangement that the molecules go through.2+226.6 kJ/mol higher in energy than the reactant molecules.2 kJ/mol higher in enthalpy than the NO2 and CO reactants. called pre-exponential factor derived from the gas kinetic collision number. we obtain an Arrhenius plot like that shown below. and products are shown in the drawing below for the NO2+CO reaction for example in exhaust gas. The difference between these two activated state levels is the thermodynamic heat of reaction qEP. Dr.CE 3- 7 in which Z is a constant. which the molecules must reach before either the forward or the reverse reaction is possible is 132.-Ing. the same energy level for the reaction intermediates must be achieved by the collision of product molecules.4) higher in energy than the NO and CO2 products. would be one in which the oxygen atom O of the molecule (NO2)g to be transferred has not yet been completely lost by NO . This is the most direct method of obtaining the activation energy of a reaction. R. the activation energy is simply a barrier in the enthalpy-time diagram that the colliding molecules must surmount before they can react. The activated state. The next term exp(EA/RT) is the Boltzmann factor which shows the fraction of the colliding molecules which energy greater than the activation energy EA. O. then the energy of activation will be greater for the reverse reaction than for the forward reaction. which has a real physical existence although it cannot be isolated and studies at leisure. and +358. If we measure k at several temperature T and plot ln(k) against (1/T).. the activated state.6 kJ/mol (=132.