CHE-422

Fuels & Combustion

Lecture 5
Part-II : Combustion
Thermodynamics of Combustion

Instructor
Dr. Taqi Mehran
• Textbook
• An Introduction to Combustion Concepts and
Applications, 3rd ed., Turns
• http://
[Link]/mhhe/viewProductDetai
[Link]?isbn=0073380199
• [Link]/turns3e
Combustion is a source of:
• Useful Energy for • Pollution
• Light • Un- and partially-burned hydrocarbon
• Space Heating fuel (CXHY)
• Material Processing • Oxides of nitrogen (NO, NO2)
• Boilers, refineries, smelters, dryers • Particulates (carbon soot)
• Incinerators (waste “disposal”) • Smog
• Heat engines • Acid rain
• Electric Power Generation
• Transportation
• Intellectual Challenges
• Integrates thermal science, chemistry,
• Safety hazards computational methods
• Building and Forest Fires
• Heat and toxic fumes
• Nuclear Waste Transport
 Combustion Types
• Flaming Combustion
• Rapid Oxidation of fuel, generating heat and light
• Converts chemical bond to sensible energy
• Non-flame combustion modes
• Detonation
• Supersonic, volumetric,
• engine knock, explosives
• Smoldering
• Coal mine
Types of Flaming Combustion
• Diffusion Flames
• Pre-mixed Flames Fuel Vapor Oxidizer
• Oxidizer and fuel mixed at
Products
molecular level before reaction
takes place
• Combustion takes place where
Products Fuel + Oxidizer oxidizer/fuel “ratio” is favorable
• Candle, campfire, pool fire
• Auto engine, kitchen stove • Orange/yellow flame (soot)
• Blue flame
Products
Fuel +
Oxidizer
 General Combustion Reaction
•  Fuel + Oxidizer + small activation energy  Products + Energy
• Fuels (Hydrocarbons)
• General hydrocarbon fuel, CxHy (or CxHyOz if oxygenated)
• Air (the most common oxidizer)
• Mostly Nitrogen N2 and Oxygen O2 (plus traces of other gases, H2O, CO2,…)
• Mole Fractions: , (ignoring trace gases)
• Molecules of N2 per O2 molecule:
• For Ideal Combustion (with no dissociation to CO, H, HO, NO, NO2, O)
• All products are CO2, H2O, N2, O2
• All C atoms  CO2
• All H atoms  H2O
• All N atoms  N2 (do not participate)
 Ideal Gas Equation of State
•  •  Avogadro's Number
• Universal Gas Constant

• Inside book front cover

• Number of molecules in 12 kg of C12
• kJ = kN*m= kPa*m3
• Calorific Equations of State
• Specific Gas Constant
• R=

For ideal gases

 o x
Ideal Gas Mixtures x
x
x xx
x
x
o o o x
•  number of moles of species in
system •  Mixture Molar Weight
•
• Mole Fraction of species i
• Conversion between and
• Total Mass

• Mass Fraction of species i

• Useful fact:
• ; but
 Partial Pressure of a specie in a mixture of pressure

•  Each specie acts as if it was the only

component at the given V and T
• Specie :
• Mixture:
• Ratio:
Extensive and Intensive System Properties
• Extensive thermodynamic properties •  Intensive Properties
depend on System Size (extent) • Independent of system size
• Examples • Examples
• Per unit mass (lower case)
• Volume V [m ]3
• v = V/m [m3/kg]
• Internal Energy E [kJ] • u = U/m [kJ/kg]
• Enthalpy H = E + PV [kJ] • h = H/m [kJ/kg]
• Molar Basis (use bar )
• V = vm =
• U = um =
• H = hm =
• N number of moles in the system
• Useful because chemical equations deal
with the number of moles, not mass
Calorific Equations of State for a pure substance
•  •  Specific Heat [kJ/kg C]
• Energy input to increase temperature of
one kg of a substance by 1°C at constant
For ideal gases volume or pressure
• Differentials (small changes) • How are and measured?
𝑐  𝑝 T [K] Q [joules]
𝑐
  𝑣
w
• For ideal gas Q m, T Q m, T
• = 0;

V = constant P = wg/A = constant

• For ideal gas

• = 0; • Calculate
• =; =
Internal Energy and Enthalpy
•  Once cp(T) and cv(T) are known, internal energy change can be
calculated by integration

• Appendix A (pp. 687-699, bookmark)

• Note =
• =
Mixture Properties • Use these relations to calculate
•  Enthalpy mixture enthalpy and internal
energies (per mass or mole) as
functions of the properties of
the individual components and
their mass or molar fractions.
• u and h depend on temperature,
but not pressure
• Internal Energy • Individual gas properties are on
pp. 687-699 as functions of gas
and T
Ideal Stoichiometric
air
Hydrocarbon Combustion
•  CxHy + a(O2+3.76N2)  (x)CO2 + (y/2) H2O + 3.76a N2
• a = number of oxygen molecules per fuel molecule,
• Number of air molecules per fuel molecule is a(1+3.76)
• If a = aST = x + y/4, then the reaction is Stoichiometric
• No O2 or Fuel in products
• This mixture produces nearly the hottest flame temperature
• If a < x + y/4, then reaction is fuel-rich (oxygen-lean, “fuel” left over)
• If a > x + y/4, then reaction is fuel-lean (oxygen-rich, O2 left over)
Air to fuel mass ratio [kg air/kg fuel] of reactants
• 

• For a stoichiometric mixture

Stoichiometric Air/Fuel Mass Ratio

•  For Hydrocarbon fuel CxHy

• aSt = x + y/4

• For ,
 Equivalence Ratio
• 
• Stiochiometric

• Fuel Lean
•;
• CxHy + a(O2+3.76N2)
• % Stoichiometric Air (%SA)
• % Excess Oxygen (%EO) = (%SA)-100%
Example
Standardized Enthalpy and Enthalpy of
Formation
• 
Needed to find and for chemically-reacting masses because energy is required to
form and break chemical bonds

• Standard Enthalpy at Temperature T =

• Enthalpy of formation from “normally occurring elemental compounds,” at standard
reference state: = 298 K and P° = 1 atm
• Sensible enthalpy change in going from Tref to T =
• Normally-Occurring Elemental Compounds
• Examples: O2, N2, C, He, H2
• Their enthalpy of formation at are defined to be = 0
• Use these Normally-Occurring compounds as bases to tabulate the energy to form other
compounds
Standard Enthalpy of O atoms

298K

•  Experiments show that to form 2O atoms from one O2 molecule requires 498,390
kJ/kmol of energy input to break O-O bond (initial and final T= 298K and P= 1atm)
• At 298K: (1 mole) O2 + 498,390 kJ  (2 mole) O
•
• energy input to form 1 mole O from 0.5 mole O2 (normally-occurring form of O)
• for other compounds are in Appendices A and B, pp 687-702
• To find enthalpy of O at other temperatures use
• (Appendix A)
Enthalpy of Combustion
Reactants Products of Ideal Complete Combustion
298.15 K, P = 1 atm Assume all CCO2 and HH2O
Stoichiometric 298.15 K, 1 atm
 
𝑊
˙ 𝑂𝑈𝑇 =0
 
• How
  much energy is released from a reaction if
the product and reactant temperatures and
pressures are the same?
• 1st Law, Steady Flow Reactor

• and Enthalpy of Reaction (Into system)

• Dependent on T and P of reaction
• Heat of Combustion
• Out of system; standardized enthalpies
 Adiabatic () Flame Temperature
Stoichiometric Complete Combustion Products
Reactants CCO2 HH2O
TR PR PP = PR, T = TAd
  𝑄
˙ 𝐼𝑁 =0 𝑊
˙ 𝑂𝑈𝑇 =0
 

•  1st Law, Steady Flow Reactor

• All chemical energy goes into heating the

products
• To find adiabatic flame temperature use
• PP = PR and
 
Assuming
• 

• (heat of combustion > 0)

• Molecular constant pressure heat of combustion

• , where
Constant Volume Adiabatic Flame Temperature
𝑄=0
   𝑊 =0
V, m

• 
• so
• But standard internal energy is not tabulated
• So use definition:

• Idea gas: ; ,

• Only and are unknown

 
Assuming
• 

•;
To calculate adiabatic flame temperatures
•  Assuming , need heat of combustion:

• Constant Pressure

• Constant Volume
Chemical Equilibrium
𝑄=0
 
𝑊 =0
 
V, m
𝑄
˙ 𝐼𝑁 =0
  𝑊
˙ 𝑂𝑈𝑇 =0
 

• “Ideal”
  combustion assumes CCO2 HH2O

• Specifies product mole fractions in the products

• To find Tad (1st law)
• Constant Volume:
• Constant Pressure:
• In real high temperature combustion the product species may dissociate (break apart) yielding: H 2,
OH, CO, H, O, N, NO, ….
• How to find actual final molar fractions of each component for different temperatures and
pressures?
• Chemical Equilibrium (2nd Law)
Constant Volume Reaction Constraints
 
V, m
•  Conservation of atoms (C, H, O, N)
• For Constant Volume and no interaction with surroundings
• Q=W=0
• Time-dependent Ideal Gas Equation of State: P(t)V = N(t)RuT(t)
• Initially: T1 P1 and (initial mole fraction of each specie)
• Find: T2 P2 and
• Before we specified final mole fractions
• Now we find them.
• Chemical Equilibrium
• 1st and 2nd laws of Thermodynamics
• Reaction stops when entropy reaches a maximum
Example: Carbon Dioxide Formation/Dissociation
•  (carbon monoxide combustion)
• At high temperature a fraction () of the will
dissociate back to
• (net change)

• Were is the fraction of that dissociates

• How do we find ?
• First step: Find [as a function of ]
• Find and 1− 𝛼
 
• Use 1st Law () to find
• Use ideal gas law to find
• How much dissociation will actually take
place?
Find Entropy of Product Mixture
•  Entropy is a function of composition, temperature, and pressure
• Product Mixture

• Extensive Property

• Where partial pressure of species is:

• =
• =
• How does vary with ? Need
Gibb’s 2nd equation
• 
•
• For Ideal Gases: ;

• Standard entropy

• Appendix A, pp 687-699
Equilibrium

•  Plot versus
• Maximum at
• For Q = W = 0 (constant volume) and constant mass, 2nd law requires
• Once a system gets to it can no longer change spontaneously (on its own)
• At equilibrium for given U, V and m:
 𝑊=∫ 𝑃𝑑𝑉
 
Now, find equilibrium composition
(reactants and products) for a given G
Temperature, Pressure & Mass Q
T, P
•  aA + bB + …  eE + fF + … a

• Use Q and boundary work to achieve P and T

• Introduce Gibbs Function

• ; = partial pressure of
• is Gibbs function at P = Po = 1 atm
• For a constant temperature, pressure, and mass, and only boundary work (PdV)
• It can be shown (take my word for it) that second Law requires for spontaneous changes
(no outside influence) It can be shown…
For a small (dk) change of a General
Reaction
•  aA + bB + …  eE + fF + …
• Reactants: dNA = -a(dk), dNB = -b(dk)
• Products: dNE = +e(dk), dNF = +f(dk)

• … do these steps at home for extract credit…

•
Partial Pressures Temperature
(Mole Fractions)
Solution Method
• 
• Equilibrium Constant

• Note: = 1 atm;
• Standard State Gibbs Function Change

• In terms of Gibbs functions of formation (tabulated in App. A and B)

• Products (numerator) are “favored” as increases, which happens when
decreases
• reactant increases compared to products
• Exothermic reaction
 Example 2.7
•  Consider the dissociation of CO2 as a function of temperature and pressure: .
• Find the composition of the mixture, i.e. the mole fractions of , and , that results
from subjecting the originally pure to various temperatures, and pressures
• T = 1500, 2000, 2500 and 3000K
• P = 0.1, 1, 20 and 100 atm

• Find final values of: , ,

• Initially ___?
Solution
•  Last time: CO2 as a function of temperature and pressure:
• ; three unknowns: , ,
•;

• MathCAD solution
• [Link]
Pressure and Temperature
Dependence

•  For this reaction

• > 0 ( > 0 exothermic) and Nproducts > Nreactants

• (product) increases as T increases and P decreases
Pressure and Temperature
Dependence

•  ;
• Products are “favored” as KP increases and decreases
• Standard State Gibbs Function Change
Equilibrium Products of Hydrocarbon
Combustion
••  Combine Chemical Equilibrium (2nd law) & Adiabatic Flame
Temperature (1st law)
• For Example: Propane and air combustion
• Ideal

• Four products for a range of air/fuel ratios:

• Now consider seven more possible dissociation products:

• What actually happens as air/fuel (equivalence) ratio changes

 Data: Flame temp and major mole-fractions vs
•  Equivalence Ratio
Tad[K]
• At
• O2, CO, H2 all present
• Not present in “ideal” combustion
• at .15
 
%
“Old”
• at .05

• and decrease for

“New” • For decreases faster
• For decreases faster

Fuel Lean Fuel Rich

O2 Get CO, H2
Minor-Specie Mole Fractions: NO, OH, H, O
1%
 

•  Not considered in Ideal combustion

• For all
• < 4000 ppm = 0.4%
• Peak near
 
ppm
 Simple Product Calculation method
• 
• Add
• Neglect “minor” species: NO, OH, H, O
•

• Assume and are known

• What is a good assumption
• for lean or stoichiometric mixtures ?
•
• c = e = 0 (no CO or H2), but now include
• 3 unknowns (b, d, f), 3 atom balances (C, H, O)
  Atomic Balance for Lean combustion
• 
• C: so
• H: so
• O: so
•
• A check: if

• Mole Fractions
• ; ; ; MathCAD Solution
• [Link]
 
Comparison
0.2
0.155
45
41.667

40 0.15
Xco2( Phi)
H2O
Xh2o( Phi)
Ntot( Phi) 35
Xo2( Phi) 0.1
Xn2( Phi)
CO2
30 10
N2/10
25.8 0.05
25
0.6 0.7 0.8 0.9 O2
0.6 Phi 1
0
0
0.6 0.7 0.8 0.9
0.6 Phi 1

•  Total number of modes decreases as increases

• Does not include CO or H2 at
• Not bad for a simple model for