Adiabatic flame temperature

In the study of combustion, there are two types of adiabatic flame temperature depending on how the process is completed, constant volume and constant pressure, describing the temperature the combustion products theoretically reach if no energy is lost to the outside environment. The constant volume adiabatic flame temperature is the temperature that results from a complete combustion process that occurs without any work, heat transfer or changes in kinetic or potential energy. The constant pressure adiabatic flame temperature is the temperature that results from a complete combustion process that occurs without any heat transfer or changes in kinetic or potential energy. Its temperature is lower than the constant volume process because some of the energy is utilized to change the volume of the system (i.e., generate work).

Common flames

Propane

Octane, a major constituent of gasoline

In daily life, the vast majority of flames one encounters are those of organic compounds including wood, wa , fat, common plastics, propane, and gasoline. The constant!pressure adiabatic flame temperature of such substances in air is in a relatively narrow range around "#$% &'. This is because, in terms of stoichiometry, the combustion of an organic compound with n carbons involves breaking roughly (n ')* bonds, n ')' bonds, and ".$n +( bonds to form roughly n '+( molecules and n *(+ molecules. ,ecause most combustion processes that happen naturally occur in the open air, there is nothing that confines the gas to a particular volume like the cylinder in an engine. -s a result, these substances will burn at a constant pressure allowing the gas to e pand during the process. Common flame temperatures -ssuming initial atmospheric conditions (" bar and (% &'), the following table list the adiabatic flame temperature for various gases under constant pressure conditions. The temperatures mentioned here are for a stoichiometric fuel!o idizer mi ture (i.e. e.uivalence ratio ).

/ote these are theoretical, not actual, flame temperatures produced by a flame that loses no heat. The closest will be the hottest part of a flame, where the combustion reaction is most efficient. This also assumes complete combustion (e.g. perfectly balanced, non!smokey, usually bluish flame)
Adiabatic flame temperature (constant pressure) of common gases/Materials

Fuel -cetylene ('(*() -cetylene ('(*() ,utane ('0*"%) 'yanogen ('(/() 5icyanoacetylene ('0/() 6thane ('(*3) *ydrogen (*() *ydrogen (*() 9ethane ('*0) /atural gas :ropane ('1*2) :ropane ('1*2) 9-:: gas 9ethylacetylene ('1*0) 9-:: gas 9ethylacetylene ('1*0) ;ood <erosene =ight fuel oil 9edium fuel oil *eavy fuel oil ,ituminous 'oal -nthracite -nthracite

Oxidizer air + ygen air + ygen + ygen air air + ygen air air air + ygen air + ygen air air air air air air air + ygen

(C) ($%% 102% "#4% 0$($ 0##% "#$$ (("% 1(%% "#$% "#3% "#2% ($(3 (%"% (#(4 "#2% (%#1 718 ("%0 718 ("%" 718 ("%( 718 ("4( 718 ("2% 718 >(#%% 7see "8

(F) 0$1( 3(#3 1$42 2"44 #%"% 1$$" 0%"% $4#( 7"8 1$0( 1$3( 7(8 1$#3 0$4# 13$% $1%" 1$#3 12%" 12(% 12"$ 12"4 1#01 1#$4 >$($$

^ The temperature equal to 3200 K corresponds to 50 % of chemical dissociation for CO2 at pressure 1 atm. The latter one stays in ariant for adia!atic flame and the car!on dio"ide constitutes #$ % of total %as output in the case of anthracite !urnin% in o"y%en. &i%her temperatures 'ill occure for reaction output 'hile it %oin% under hi%her pressure (up to 3)00 K and a!o e

Thermodynamics

?irst law of thermodynamics for a closed reacting system ?rom the first law of thermodynamics for a closed reacting system we have,

where, and are the heat and work transferred during the process respectively, and and the internal energy of the reactants and products respectively. In the constant volume adiabatic flame temperature case, the volume of the system is held constant hence there is no work occurring,

are

and there is no heat transfer because the process is defined to be adiabatic@ . -s a result, the internal energy of the products is e.ual to the internal energy of the reactants@ . ,ecause this is a closed system, the mass of the products and reactants is constant and the first law can be written on a mass basis, .

Internal energy versus temperature diagram illustrating closed system calculation

6nthalpy versus temperature diagram illustrating closed system calculation In the constant pressure adiabatic flame temperature case, the pressure of the system is held constant which results in the following e.uation for the work,

-gain there is no heat transfer occurring because the process is defined to be adiabatic@ the first law, we find that,

. ?rom

Aecalling the definition of enthalpy we recover@ . ,ecause this is a closed system, the mass of the products and reactants is constant and the first law can be written on a mass basis, . ;e see that the adiabatic flame temperature of the constant pressure process is lower than that of the constant volume process. This is because some of the energy released during combustion goes into changing the volume of the control system. +ne analogy that is commonly made between the two processes is through combustion in an internal combustion engine. ?or the constant volume adiabatic process, combustion is thought to occur instantaneously when the piston reaches the top of its ape (+tto cycle or constant volume cycle). ?or the constant pressure adiabatic process, while combustion is occurring the piston is moving in order to keep the pressure constant (5iesel cycle or constant pressure cycle).

-diabatic flame temperatures and pressures as a function of stoichiometry (relative ratio of fuel and air)

'onstant volume flame temperature of a number of fuels If we make the assumption that combustion goes to completion (i.e. and ), we can calculate the adiabatic flame temperature by hand either at stoichiometric conditions or lean of stoichiometry (e cess air). This is because there are enough variables and molar e.uations to balance the left and right hand sides,

Aich of stoichiometry there are not enough variables because combustion cannot go to completion with at least and needed for the molar balance (these are the most common incomplete products of combustion),

*owever, if we include the ;ater gas shift reaction,

and use the e.uilibrium constant for this reaction, we will have enough variables to complete the calculation. 5ifferent fuels with different levels of energy and molar constituents will have different adiabatic flame temperatures.

'onstant pressure flame temperature of a number of fuels

/itromethane versus isooctane flame temperature and pressure ;e can see by the following figure why nitromethane is often used as a power boost for cars. Bince it contains two moles of o ygen in its molecular makeup, it can burn much hotter because it provides its own o idant along with fuel. This in turn allows it to build!up more pressure during a constant volume process. The higher the pressure, the more force upon the piston creating more work and more power in the engine. It is interesting to note that it stays relatively hot rich of stoichiometry because it contains its own o idant. *owever, continual running of an engine on nitromethane will eventually melt the piston andCor cylinder because of this higher temperature.

6ffects of dissociation on adiabatic flame temperature In real world applications, complete combustion does not typically occur. 'hemistry dictates that dissociation and kinetics will change the relative constituents of the products. There are a number of programs available that can calculate the adiabatic flame temperature taking into account dissociation through e.uilibrium constants (Btanjan, /-B- '6-, -?T:). The following figure illustrates that the effects of dissociation tend to lower the adiabatic flame temperature. This result can be e plained through =e 'hatelierDs principle.