Theory of Combustion

3/4/2010

Stoichiometry & Heat of formation HW #1 Due 3/9

Stoichiometry: example (1/2)

Stoichiometric CxHyOz - air

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Stoichiometry: example (2/2)

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Equivalence ratio
Equivalence ratio : Quantitatively indicate that if a fuel-oxidizer mixture is rich, lean, or stoichiometric

F /O = F / Ost

=1 <1 >1
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Other ways for defining stoichiometry

Percent of stoichiometric air % stoichiometric air = 100 % / Percent excess air % excess air = 100% * (1 )/

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Global reaction for 1

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Approaches for > 1

More complicated if fuel left over is allowed Simple approach: No left-over O2 Fuel breaks down into CO and H2

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Extensive and intensive properties

The numerical value of an extensive property depends on the amount (mass or number of moles) of the substance considered.

usu. Denoted with CAPITAL letters. e.g. V (m3) for volume, U (J) for internal energy, H (J) (=U+PV) for enthalpy

The numerical value of an intensive property is independent of the amount of substance present.

Mass-based intensive properties are generally denoted with lower-case letters. e.g., v (m3/kg) for specific volume, u (J/kg) for specific internal energy, h (J/kg) (=u+Pv) for specific enthalpy.

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Equation of State
An equation of state provides the relationship among the pressure, P, temperature, T, and volume V (or specific volume v) of substance. For ideal gas (single component)

Ideal gas: a model treat molecules as point particles exchanging momentum in elastic collisions, neglecting both molecular size and intermolecular attractions,.

Low density (pressure) High temperatures

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Other forms of equation of state

For ideal gas, mole fraction is equivalent to volume fraction.

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Calorific equations of state (1/2)

For pure substance at thermodynamic equilibrium, independent intensive properties define the state.

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Calorific equations of state (2/2)

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Mixtures
Consider a system of i = 1, 2, Nsp chemical species occupying a volume V

Mass fractions Yi

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Mole fractions
Mole fractions xi

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Ideal-gas mixtures
Molar concentration

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Ideal-gas mixtures (2/2)

Partial pressure Pi

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Latent heat of vaporization

Latent heat of vaporization (also known as the enthalpy of vaporization, denoted as hfg): the heat required in a constant-pressure process to completely vaporize a unit mass of liquid at a given temperature hfg(T,P)=hvapor(T,P)-hliquid(T,P) where T and P are the corresponding saturation temperature and pressure, respectively. Clausius-Clapeyron equation can be used with the latent heat of vaporization to estimate saturation pressure variation with temperature:

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First law of thermodynamics

First law fixed mass

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First law of thermodynamics

First law control volume

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Enthalpy
For any species i Absolute enthalpy at temperature T = Enthalpy of formation at Tref, P0 + Sensible enthalpy change in going from Tref to T

Enthalpy of formation (hf): an enthalpy that takes into account the energy associated with chemical bonds. Sensible enthalpy (hs): An enthalpy that is associated only with temperature.

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Enthalpy at Reference State

At Pref and Tref, enthalpy of elements in their natural state is zero. Reference state

Pref=P0= T
Elements in natural state

Oxygen Hydrogen Carbon Nitrogen

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Enthalpy of formation
To form oxygen atoms at the standard state requires the breaking of the covalent bond of oxygen The dissociation energy for O2 at 298 K is 498390 kJ/kmolO2 Thus, the enthalpy of formation for atomic oxygen is

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Enthalpy of formation
Consider the formation of H2O at Pref, Tref

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Enthalpy of formation

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Enthalpy of formation
The enthalpy of formation chart from high to low Similar to a potential energy chart As species at the top react to form species at the bottom, heat is , and an system exists
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Relationship between bond energies and heat of formation

The bond energy for dissociation D0(R-X), is also know as the strength of a chemical bond between R and X of the molecule RX The energy required to break the R-X bond at 298.15 K, RX->R+X, is related to the enthalpy of formation D0298(R-X)=h0f,R+h0f,X-h0f,RX (per mole) Bond and resonance energies can be used to estimate heats of formation for some molecules and heats of combustion for certain reactions. Ex: Bond energies (kcal/mol) H-H 104.20 C-H 80.88+- 0.29 H-O 102.20 C-O >= 141.97 C=O 173 NN 225.94+-0.14 O=O 119.11 C=C 145.08 +- 5.02
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Example 1 (1/4)
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.
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Example 1 (2/4)

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Example 1 (3/4)

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Example 1 (4/4)

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Enthalpy of reaction
Heat released by complete combustion of a specific fuel at specified P and T

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Enthalpy of reaction
Stoichiometric CH4/air

Per mass of fuel

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