Stoichiometry

The stoichiometric quantity of oxidizer is just that amount needed to

completely burn a quantity of fuel.

Fuel Lean = if more than a stoichiometric quantity of oxidizer is supplied

Fuel Rich = if less than a stoichiometric quantity of oxidizer is supplied

The stoichiometric oxidizer-fuel ratio (or air-fuel ratio) is determined by

writing simple atom balances, assuming that the fuel reacts to from an
ideal set of products.

For a hydrocarbon fuel given by CXHY, the stoichiometric relation:

C X H Y  a  O 2  3.76 N 2   xCO 2  ( y / 2) H 2 O  3.76 aN 2
Hence, a  x y/4
Stoichiometry

Assuming that the simplified composition for air is 21% O2

and 79% N2 (by volume), i.e., that for each mole of O2 in air,
there are 3.76 moles of N2.
 mair  4.76a MWair
( A / F ) stoic    
 m fuel  1 MW fuel
  stoic
Table below shows stoichiometric air-fuel ratios for methane,
hydrogen, and solid carbon at 298 K
Stoichiometry

The equivalence ratio , is commonly used to indicate

quantitatively whether a fuel-oxidizer mixture is rich, lean,or
stoichiometric. The equivalence ratio is defined as:
( A / F ) stoic ( F / A)
 
(A/ F) ( F / A) stoic

Fuel rich mixtures :  > 1

Fuel lean mixtures:  < 1
Stoichiometric mixtures:  = 1
Stoichiometry

Percent Stoichiometric air is a parameter which is

frequently used to define relative stoichiometry:
100%
% stoichiome tric air 


Percent excess air:

air
(1   )
% excess air  .100%

Stoichiometry

Example
A small, low emission,
stationary gas turbine
engine operates at full load
(3950 kW) at an
equivalence ratio of 0.286
with an air flowrate of 15,9
kg/s. The equivalent
composition of fuel (natural
gas) is C1.16H4.32. Determine
the fuel mass flowrate and
the operating air-fuel ratio
for the engine
Stoichiometry
Absolute (or Standardized) Enthalpy and Enthalpy of
Formation
In dealing with chemically reacting systems, the concept of absolute
enthalpies is very important.
Enthalpy of formation:
formation the net change in enthalpy associated with
breaking the chemical bonds of the standard state elements and forming
new bonds to create the compound of interest.
For any species, absolute (or standardized) enthalpy is the sum of an
enthalpy that takes into account the energy associated with chemical
bonds, the enthalpy of formation, hf ,and an enthaply that is associated
only with the temperature, the sensible enthalpy change, Δhs
Molar absolute enthalpy for species i:

hi (T )  h fo,i (Tref )  hs ,i (Tref )

Absolute ent halpy Enthalpyof format ion Sensible ent halpy
at t emperature T at st andardreference changein going from
o
stat e(Tref , P ) Tref to T
Where:
hs ,i  hi (T )  h fo,i (Tref )
Absolute (or Standardized) Enthalpy and Enthalpy of Formation

The standard reference state:

Tref = 25°C (298.15K) and Pref = P°=1 atm (101.325 Pa)

The enthalpies of formation are zero for the elements in their naturally
occuring state at the reference state temperature and pressure. E.g. at
25°C and 1 atm, oxygen exists as diatomic molecules; hence:
o
(h f ,O2 ) 298 0
To form oxygen atoms at the standard state requires the breaking of a
rather strong chemical bond. The bond dissociation energy for O2 at
298 K is 498390 kJ/kmolO2. Breaking this bond creates two O atoms;
thus, the enthalpy of formation for atomic oxygen is half the value of the
O2 bond dissociation energy, so that:
( h fo,O )  249195 kJ/kmol O
Absolute (or Standardized) Enthalpy and Enthalpy of Formation
Absolute (or Standardized) Enthalpy and Enthalpy of Formation

Example:
A gas stream at 1 atm contains a mixture of CO, CO2, and
N2 in which the CO mole fraction is 0.10 and the CO2 mole
fraction is 0.20. The gas-stream temperature is 1200 K.
Determine the absolute enthalpy of the mixture on both a
mole basis (kJ/kmol) and a mass basis (kJ/kg). Also
determine the mass fractions of the three component
gases.
Absolute (or Standardized) Enthalpy and Enthalpy of Formation
Absolute (or Standardized) Enthalpy and Enthalpy of Formation
Absolute (or Standardized) Enthalpy and Enthalpy of Formation
Enthalpy of Combustion and Heating Values

 First Law of Thermodynamics:

qcv  ho  hi  h prod  hreac
 Enthalpy of reaction = enthalpy of products – enthalpy of reactants

hR  qcv  h prod  hreac

Enthalpy of Combustion and Heating Values

Enthalpy of reaction (or enthalpy of combustion) in terms

of extensive properties

H R  H prod  H reac
Enthalpy of Combustion and Heating Values

Enthalpy of reaction (or enthalpy of combustion) in per-

mass-of-fuel basis:
 kJ 
hR    hR
 kg  MW
 fuel  fuel

This value can be converted to a per-unit-mass-of-

mixture basis:
 kJ   kJ  m fuel
hR    hR  
 kg  m
 kg mix   fuel  mix
m fuel m fuel 1
Where:  
mmix mair  m fuel ( A / F ) 1
Enthalpy of Combustion and Heating Values

Note that the enthalpy of combustion depends on the

temperature chosen for its evaluation since the enthalpies of
both reactants and products vary with temperature.

The heat of combustion, Δhc (known as heating value)

Δhc= - ΔhR

Higher heating value, HHV

all of the water in the products has condensed to liquid
Lower heating value, LHV
none of the water is assumed to condense
Enthalpy of Combustion and Heating Values

Example 2.4
A. Determine the upper and lower heating values at
298K of gaseous n-decane, C10H22, per kilomole of
fuel and per kilogram of fuel. The molecular weight of
n-decane is 142.284
B. If the enthalpy of vaporization of n-decane is 359
kJ/kgfuel at 298K, what are the upper and lower heating
values of liquid n-decane?
Example 2.4
Adiabatic Flame Temperature

 Two adiabatic temperatures are defined:

 For constant pressure combustion
 For constant volume combustion

Advantage: Simple.

Disadvantage: knowledge of the composition of the combustion

products is required while at typical flame temp, the products
dissociate and the mixture comprises many species.
 Adiabatic Flame Temperature

Constant pressure adiabatic

flame temperatures
The absolute enthalpy of the
reactants at the initial state (Ti, P)
equals the absolute enthalpy of
the products at the final state
(Tad, P)
H reac (Ti , P )  H prod (Tad , P)
or on a per-mass-of-mixture
basis: h (T , P )  h (T , P)
reac i prod ad Flame temperatures are
typically several thousand
Applications: Kelvin
Gas-turbine combustor and
furnace
Adiabatic Flame Temperature

Example 2.5
Estimate the constant-pressure adiabatic flame
temperature for the combustion of a stoichiometric
CH4 – air mixture. The pressure is 1 atm and the initial
reactant temperature is 298 K.
Hint: Use the following assumptions:
1.Complete combustion
2.The product mixture enthalpy is estimated using
constant specific heats evaluated at (≈0,5(Ti + Tad)
 Adiabatic Flame Temperature

Constant volume adiabatic flame temperatures

The first law of thermodynamics for a closed system
requires:
U reac (Ti , Pi )  U prod (Tad , Pf )
U is the absolute (or standardized) internal energy of
the mixture

Applications:
Ideal otto-cycle analysis
Adiabatic Flame Temperature

Since more compilations or calculations of

thermodynamic properties provides values of H rather
than U, we can rearrange the equation of constant
volume adiabatic flame temp becomes:
H reac  H prod  V ( Pi  Pf )  0
applying PV  nT
thus H  H
reac prod  ( nreacTi  n prod Tad )  0

or on a per-mass-of-mixture basis:
 Ti Tad 
hreac  h prod   0
 MW MW prod 
 reac 
Adiabatic Flame Temperature

Example 2.5
Estimate the constant-volume adiabatic flame
temperature for the combustion of a stoichiometric
CH4 – air mixture. The pressure is 1 atm and the initial
reactant temperature is 298 K.
Hint: Use the following assumptions:
1.Complete combustion
2.The product mixture enthalpy is estimated using
constant specific heats evaluated at (≈0,5(Ti + Tad)