Combustion & Thermochemistry

Dr. V. Mahendra Reddy

Assistant Professor
Mechanical Engineering Department
Indian Institute of Technology, Kharagpur
Kharagpur, India
Mob: +91 7573855876
[email protected]; [email protected]
 Combustion and Prerequisites

Thermodynamics Chemistry
(Heat Transfer) • Stoichiometry
• Energy Balance • Equilibrium
• Flame Temperature Combustion • Kinetics
Technology • Emissions and Pollutants

Fluid Mechanics • Rapid oxidation generating heat

• Flame Propagation • Slow oxidation accompanied by
• Laminar/Turbulent relatively little heat and no light
• Premixed/Diffusion
• Atomization • Combustion transforms energy
• Combustor Aerodynamics stored in chemical bonds to heat
that can be utilized in a variety of
ways
 Combustion modes and flame types
• Combustion can occur in flame mode
– Premixed flames
– Diffusion (non-premixed) flames
• Combustion can occur in non-flame mode

• What is a flame?
– A flame is a self-sustaining propagation of a localized combustion zone
at subsonic velocities
• Flame must be localized: flame occupies only a small portion of combustible
mixture
• A discrete combustion wave that travels subsonically is called a deflagration
• Combustion waves may be also travel at supersonic velocities, which are
called detonations
• Fundamental propagation mechanisms are different in deflagrations and
detonations
 Laminar premixed flames
• Fuel and oxidizer mixed at molecular level prior to occurrence
of any significant chemical reaction

Flame color gives indication of temperature

Not quite red: T~500-550 ºC
Dark red: T~650-750 ºC
Bright red: T~850-950 ºC
Yellowish red: T~1050-1150 ºC
Not quite white: T~1250-1350 ºC
White: T > 1450 ºC
4. LAMINAR PREMIXED FLAMES
 Premixed flames
• Fuel and oxidizer mixed at molecular level prior to occurrence of any
significant chemical reaction

spark-ignition (SI) engines

 Diffusion flames
• Reactants are initially separated, and reaction occurs only at interface
between fuel and oxidizer (mixing and reaction taking place)
• Diffusion applies strictly to molecular diffusion of chemical species
• In turbulent diffusion flames, turbulent convection mixes fuel and air
macroscopically, then molecular mixing completes process so that
chemical reactions can take place
Diffusion Flames: Earth vs. Space
 Detonation
• Pure Explosion vs. Detonation (not same)
– Explosion requires rapid energy release
• An explosion does not necessarily require passage of a combustion
wave through exploding medium
– Both deflagrations and detonations require rapid energy
release and presence of a waveform
• To have either a deflagration or a detonation, an explosive gas
mixture must exist

• Recall:
• Deflagration: a subsonic wave sustained by a chemical reaction
• Detonation: a supersonic wave sustained by a chemical reaction
 Emissions and pollutants
• Major pollutants produced by combustion are:
– Unburned and partially burned hydrocarbons, C nHm
– Nitrogen oxides (NOx, NO and NO2)
– Carbon monoxide (CO)
– Sulfur oxides (SOx, SO2 and SO3)
• Subjected to legislated controls (smog, acid rain, global warming, ozone
depletion, health hazards, etc.)
 Major combustor components

Fuel
d u ct s
ro
u sti on P
Comb

Turbine
Compressor

A ir

• Key Questions:
– Why is combustor configured this way?
– What sets overall length, volume and geometry of device?
 COMBUSTOR REQUIREMENTS

• Complete combustion
• Low pressure loss
• Reliable and stable ignition
• Wide stability limits
– Flame stays lit over wide range of operating conditions
• Freedom from combustion instabilities
• Tailored temperature distribution into turbine with no hot spots
• Low emissions
– Smoke (soot), unburnt hydrocarbons, NOx, SOx, CO
• Effective cooling of surfaces
• Low stressed structures, durability
• Small size and weight
• Design for minimum cost and maintenance
 Ideal Gas Mixtures
• Mole fraction of species i:

• Mass fraction of species i:

• The sum of all the mole (and mass) fractions must be

unity:

• Relations between χ and Y ?

 Ideal Gas Mixtures
• Mixture molecular weight (mass):

• Enthalpy of ideal gas mixtures:

Neither pure species nor mixture properties depend on partial

pressure
• Mixture entropies:

Specie entropy depends on its partial pressure

 Reactant and Product Mixtures
• Stoichiometry:
The stoichiometric quantity of oxidizer is just the amount needed
to completely burn a quantity of fuel.
Stoichiometric reltion of a hydrocarbon fuel, (CxHy):
CxHy + a(O2 + 3.76N2) → xCO2 + (y/2)H2O+3.76aN2
For 1 mole of fuel a moles of oxidizer is required
a = x+y/4

The stoichiometric air-fuel ratio:

 Equivalence Ratio
Comparison of actual fuel-to-air and stoichiometric ratio is called equivalence ratio
For most modern aircraft f ~ 0.3

Equivalence ratio: (A/F) stoic

Fuel MWfuel x y a mair/kg of fuel
CH4 16 1 4 2 17.255
C3H8 44 3 8 5 15.68636
C12H26 170 12 26 18.5 15.022
C12H23 167 12 23 17.75 14.67192
• Φ > 1: Fuel-rich mixtures.
• Φ < 1: Fuel-lean mixtures.
• Φ = 1: Stoichiometric mixtures.
 Design Steps of a combustor
• What id the thermal input (Qin, kW)
• What is the thermal intensity (, MW/m3)
• What is the fuel CV
• What is the range of operating A/F ratios (or φ)
• Calculate the residence time (τ) =
• Find the τign for the entire range of φ
• Run the simulations
• Check whether complete reaction in the combustor ?
• Check the emissions (CO, NOx, UHC)
• If not redesign…………. By reducing the
 Absolute Enthalpy and Enthalpy of Formation:
• For any species, we can define an absolute enthalpy that is the
sum of an enthalpy of formation and sensible enthalpy change

• Standard reference state: Tref = 298.15K (25 oC);

Pref = Po = 1atm (101.325 kPa)
 Absolute Enthalpy and Enthalpy of Formation:
• Enthalpies of formation are zero for the elements in their
naturally occuring state at the reference temperature and
pressure.
• 25 oC and 1 atm, oxygen exists as diatomic molecules; then
(hof,O2)298 = 0
• To form oxygen atoms at the standard state requires breaking of
a chemical bond.
• The bond dissociation energy of O2 at standard state is 498, 390
kJ/kmol.
• Breaking of the bond creates two O atoms; therefore the
enthalpy of formation of atomic oxygen is (hof,O)298 = 249, 195
kJ/kmol
 Enthalpy of Combustion and Heating Values

• Reactants: stoichiometric mixture at standard state conditions.

• Products: complete combustion, and products are at standard
state conditions.
• For products to exit at the same T as the reactants, heat must be
removed.
• The amount of heat removed can be related to the reactant and
product absolute enthalpies
 Enthalpy of Combustion and Heating Values
• The enthalpy of reaction, or the enthalpy of combustion, ΔhR:

• In terms of extensive properties:

• Per mass of the fuel:

• For a per-unit-mass-of-mixture basis:

 Enthalpy of Combustion and Heating Values
• Enthalpy of combustion depends on temperature chosen for its
evaluation since enthalpies of reactants and products are
temperature dependent.
• The heat of combustion, Δhc (known also as the heating value or
calorific value), is numerically equal to the enthalpy of
combustion, but with opposite sign.
• HHV: higher heating value (H2O→ liquid)
• LHV: lower heating value (H2O→ vapor)
 Adiabatic Flame Temperatures

• Two adiabatic flame temperatures:

– Constant-pressure combustion
– Constant-volume combustion
• Constant-Pressure: Fuel-air mixture burns adiabatically at
constant pressure.
• Absolute enthalpy of reactants at the initial state (say, T 1 = 298
K, P = 1 atm) equals absolute enthalpy of the products at final
state (T = Tad, P = 1 atm).

• When dealing with constant-pressure combustion systems,

such as gas turbine combustors and rocket engines, the
appropriate approach would involve constant-pressure Tad.
Constant-volume analysis is
used for closed systems
 Adiabatic Flame Temperatures
• Constant Volume Tad

H = U + PV
 Adiabatic Flame Temperatures

• When dealing with constant-volume combustion

systems, such as enclosed explosions or Otto-cycle
(idealized thermodynamic cycle for gasoline engine
combustion) analysis, the appropriate approach
would involve constant-volume Tad.
 Chemical Equilibrium
• Ideal combustion products for a hydrocarbon fuel:

• Real combustion products of a hydrocarbon fuel include

CO2, H2O, N2, O2, H2, OH, CO, H, O, N, NO, ....
• Major species, CO2, H2O, N2, O2, H2, CO, dissociate into minor
species H, N, O, OH, NO.
• How to calculate mass or mole fraction of all product
species ??
Second-Law Considerations
 Second-Law Considerations
• Second-Law of Thermodynamics → Concept of chemical
equilibrium.
• Consider a constant volume adiabatic reaction vessel in which
a fixed mass of reactants form products.
• As reaction proceeds, T and P rise until a final equilibrium
condition is reached.
• This final state is not governed solely by first-law
considerations, but requires invoking the second law.
• Consider the case of CO-CO2 combustion reaction
 Second-Law Considerations
• If the final T is high enough, CO2 will dissociate. Assuming
products are CO2, CO, and O2

• α = fraction of CO2 dissociated.

• It is possible to calculate the adiabatic flame temperature as a
function of α.
• α = 1: no heat release; T, P, and χi remain unchanged.
• α = 0: maximum possible heat release; P and T would be the
highest possible allowed by the first-law.
• Hence, the temperature varies with α
 Second-Law Considerations
• Entropy of the mixture:

• The mixture entropy versus α

shows that entropy reaches
maximum at about α = 0.5
• Second law requires that entropy
change internal to the system is

• χi will shift toward the point of maximum entropy when

approaching from both sides.
• Once maximum entropy is reached, no change in χ i is allowed.
• The condition for equilibrium is