ME301A: Energy Systems – I

Combustion Thermodynamics
Lecture 4-5
Instructor: Santanu De
NL – 302, Northern Lab
Ph: 6478, Email: sde@[Link]
Office hour: F 5:30 – 6:30 p.m. or by appointment

Course Website: [Link]

 EQUATION OF STATE
• An equation of state provides a relationship among P, T and V (or r) of a
substance
• Ideal gas behavior (neglect intermolecular forces and volume of molecules
themselves):
– P=rRT
– Pv=RT
– PV=mRT
– R=Runiversal/MW, Runiversal=8314 J/kmol K
• Assumption is appropriate for nearly all systems we will consider in this course
since high temperatures associated with combustion generally result in sufficiently
low densities for ideal gas behavior to be a reasonable approximation
Aside:
• Real gas laws try to predict true behavior of a gas better than ideal gas law by
putting in terms to describe attractions and repulsions between molecules
– These laws have been determined empirically or based on a conceptual model
of molecular interactions or from statistical mechanics
– Examples: van der Waals and Redlich-Kwong equations
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 Calorific Equation of State
Relation of internal energy (or enthalpy) to pressure or volume and temperature
u=u(T,v)
h=h(T,P)
The word ‘calorific’ relates to expressing energy in units of calories (now we use
joules in SI system).
General expressions for a differential change in u or h:
u u h h
du  ( )v dT  ( )T dv and dh  ( ) P dT  ( )T dP
T v T P
u h
For an ideal gas, ( )T = ( )T  0 . Also, the specific heats are
v P
u h
cv  (
)v and c p  ( ) P
T T
We obtain the following ideal-gas calorific equation of state:
T T
u (T )  uref   c dT
Tref
v and h(T )  href   c dT
Tref
p

cp and cv are generally function of temperature (for both ideal and real gases)
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 Calorific Equation of State

Three energy storage modes: (a) translational, (b) vibrational, and (c)
rotational.
As a consequence of the quantum theory, the vibrational and rotational modes
become increasingly active as temperature increases.

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Specific Heat as a Function of Temperature
Observations:
• Specific heat of H-atoms
(monoatomic) is almost constant
from 200 K to 5000 K.
• Triatomic species have higher
specific heats compared to the
diatomic species because of the
greater number of vibrational and
rotational modes available.
• Triatomic molecules also have a
greater temperature dependence
compared to the diatomic molecules
and monoatomic molecules.
• Enthalpy often approximated as
h(T)=CpT
• In combustion chemistry, enthalpy
must take into account variable
specific heats, h(T)=Cp(T)T
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 IDEAL-GAS MIXTURES: SOME USEFUL FORMULAS
• Mole fraction of species i, ci Ni Ni
ci  
• Sum of all constituent mole fraction is unity N1  N 2  ...N i  ... N total
c
i
i 1

mi m
• Mass fraction of species i, Yi Yi   i
m1  m2  ...mi  ... mtotal
• Sum of all constituent mass fractions is unity
Y
i
i 1

• Converting mole fraction to mass fraction

c i MWi
– MW = molecular weight Yi 
MWmixture
Yi MWmixture
• Converting mass fraction to mole fraction ci 
MWi
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 IDEAL-GAS MIXTURES: SOME USEFUL FORMULAS

• Molar Concentration of species i, Ci

Ni Pi
Ci (or [C ])  
V RT
( Pi / P) P P
Also, [C ]   Xi
RT RT
• Relationship between Mole Fraction and Partial pressure

Pi
Xi 
P

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HOW TO CALCULATE STOICHIOMETRIC FUEL/AIR RATIO
• General hydrocarbon, CnHm
• Complete oxidation, hydrocarbon goes to CO2 and water

 m m
Cn H m   n  O2  nCO2  H 2O
 4 2
• For air-breathing applications, hydrocarbon is burned in air
• Air modeled as 20.9 % O2 and 79.1 % N2 (neglect trace species)

 m m  m
Cn H m   n  O2  3.78 N 2   nCO2  H 2O  3.78 n   N 2
 4 2  4

• Stoichiometric Molar fuel/air ratio • Stoichiometric Mass fuel/air ratio

s 
1
s 
12n  m 
 m  m
4.78 n    n  32  3.78 * 28
 4  4

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HOW TO CALCULATE STOICHIOMETRIC FUEL/AIR RATIO
• Equivalence Ratio

( A / F )stoic ( F / A)stoic
 
(A/ F) ( F / A)

o For rich mixtures, >1

o For stoichiometric mixtures, =1
o For lean mixtures, <1
100
• % stoichiometric air =


(1   )
• % exces air = .100%


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HOW TO CALCULATE STOICHIOMETRIC FUEL/AIR RATIO
• Example: A small, low-emission stationary gas turbine engine operates at full load
(3950 kW) at an equivalenc ratio of 0.286 with an air flowrate of 15.9 kg/s. The
equivalent composition of the fuel (natural gas) is C1.16H4.32. Determine the fuel
mass flowrate and the operating air-fuel ratio for the engine.
Ans:
 A MWair
   4.76 a , where a=x+y/4=1.16+4.32/4 = 2.24.
 F stoic MWfuel

 A 28.85
Thus,    4.76(2.24)  16.82.
 F stoic 18.286
 A
 
 A   F stoic 16.82
   =58.8
F  0.286

m air 15.9
Thus, m fuel    0.27 kg/s
 58.8 WRONG A/F should be here

Note that even at full power, a large quantity of excess air is supplied to the
engine.
 ABSOLUTE (STANDARD) ENTHALPY, hi, AND ENTHALPY OF
FORMATION, hºf,i

• For chemically reacting systems concept of absolute enthalpy is very valuable

• Define:
– Absolute enthalpy = enthalpy that takes into account energy associated with
chemical bonds (or lack of bonds) + enthalpy associated only with T
– Absolute enthalpy, h = enthalpy of formation, hf + sensible enthalpy change,
Dhs
– In symbolic form:

hi T   h 
f ,i T   Dh T 
ref s ,i ref

– In words first equation says:

• Absolute enthalpy at T is equal to sum of enthalpy of formation at standard
reference state and sensible enthalpy change in going from Tref to T

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 ABSOLUTE (STANDARD) ENTHALPY, hi, AND ENTHALPY OF
FORMATION, hºf,i

hi T   h f ,i Tref   Dhs ,i Tref 

Absolute Enthalpy of Sensible
enthalpy reaction enthalpy
• To define enthalpy, you need a reference state at which enthalpy is zero (this state
is arbitrary as long as it is same for all species).
– Most common is to take standard state as Tref=298.15 K and Pº=1 atm
(Appendix A)
– Convention is that enthalpies of formation for elements in their naturally
occurring state at reference T and P are zero.
• Example, at Tref=25 ºC and Pº=1 atm, oxygen exists as a diatomic
molecule, so:
h f ,O2 Tref , P  h f ,O2  0
• Note: H is total enthalpy (kJ), h is enthalpy per kg (kJ/kg), whereas h is enthalpy
per mol (kJ/kmol).

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 GRAPHICAL EXAMPLE

Graphical interpretation of absolutely enthalpy, heat of formation and sensible enthalpy

• See Figure 2.6 and Appendix A.11 and A.12

• Physical interpretation of enthalpy of formation: net change in enthalpy associated
with breaking the chemical bonds of the standard state elements and forming news
bonds to create the compound of interest
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 COMMENTS ON TABLE 1: POTENTIAL ENERGY CHART
Consider two reactions:

H2+½O2 → H2O
• Heat of formation (gas): -241.83
kJ/mol
• Reaction is exothermic

More Endothermic
More Exothermic
½O2 → O
• Heat of formation (gas): 249.17
kJ/mol
• Reaction is endothermic

H2O → H2+½O2
• Reaction 1 going backwards
• Reaction is endothermic
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SELECTED PROPERTIES OF H2O

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SELECTED PROPERTIES OF CO2

sensible enthalpy

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 1st LAW OF THERMODYNAMICS

Fixed Mass
• In Words: Heat added to system in going from state 1 to state 2 (Q) minus
work done by system in going from state 1 to state 2 (W) equals change in total
system energy (E) in going from state 1 to state 2

Q12  W12  DE12 Units of Energy (J)

 1 2 
E  m u  V  gz 
 2 
q12  w12  De12  e2  e1 Unit mass
basis (J/kg)

  dE
Q12  W12  Units of Power (W)
dt
de

qw Unit mass basis
dt Representing an instant in time

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 1st LAW OF THERMODYNAMICS
Control Volume
• In Words: Rate of heat transferred across control surface from the
surroundings to control volume minus rate of all work done by control volume
(including shaft work, but excluding flow work) equals rate of energy flowing
out of control volume minus rate of energy flowing into control volume plus
net rate of work associated with pressure forces where fluid crosses the control
surface, called flow work

QCV  WCV  meo  mei  mPo vo  Pi vi 

 1
  
QCV  WCV  mho  hi   Vo2  Vi 2  g  zo  zi 
2
 
1
 
qcv  wcv  ho  hi  Vo2  Vi 2  g  zo  zi 
2

Assumptions:
• CV is fixed relative to coordinate system
• Properties of fluid at each point within CV, or on the CS, do not vary with time
• Fluid properties are uniform over inlet and outlet flow areas
• Only one inlet and outlet stream – keep this form simple, but can be easily
relaxed to allow for multiple inlet/outlet streams
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 ENTHALPY OF COMBUSTION AND HEATING VALUES

• The heat of combustion, also known as heating value or heat of reaction, is

numerically equal to enthalpy of reaction, but with opposite sign
– Heat of combustion (or heat of reaction) = - enthalpy of combustion (or = -
enthalpy of reaction)
• If heat of combustion (or heat of reaction) is positive → Exothermic
• If heat of combustion (or heat of reaction) is negative → Endothermic
• If enthalpy of combustion (or enthalpy of reaction) is positive →
Endothermic
• If enthalpy of combustion (or enthalpy of reaction) is negative →
Exothermic
• The upper or higher heating value, HHV, is the heat of combustion calculated
assuming that all of water in products has condensed to liquid.
– This scenario liberates most amount of energy, hence called ‘upper’

• The lower heat value, LHV, corresponds to case where none of water is assumed
to condense

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 ENTHALPY OF COMBUSTION AND HEATING VALUES

A steady flow reactor used to determine enthalpy of combustion

• The steady flow form of first law:

qcv  ho  hi  hprod  hreac

constant P and V

• Definition of enthalpy of reaction (or enthalpy of combustion)

DhR (per mass of mixture)  qcv  hprod  hreac
DH R  H prod  H reac (in terms of extensive property)
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 ENTHALPY OF COMBUSTION AND HEATING VALUES

A steady flow reactor used to determine enthalpy of combustion

• Sometimes, enthalpy of reaction is written per-mass-of-fuel basis:
kJ DH R
DhR ( )
kg fuel MWfuel
• For stoichiometric methane-air mixture, the enthalpy of the reactants is -74831 kJ. Enthalpy
of the combustion products have an absolute enthalpy of -877236 kJ. Thus,
kJ 802405
DH R  877236  (74831)  802405 kJ, DhR ( )  50016 kJ/kg fuel
kg fuel 16.043
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 ENTHALPY OF COMBUSTION AND HEATING VALUES

kJ kJ m fuel
VhR ( ) VhR ( )
kg mix kg fuel m mix

m fuel mfuel 1
 
m mix mfuel  m air (A/F)  1

For CH 4 -air mixture, A/F=17.11, hence

kJ 50016
VhR ( )  2761.8 kJ/kg fuel
kg mix 17.11  1

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 ENTHALPY OF COMBUSTION AND HEATING VALUES
• Example: Determine the upper and lower heating values at 298 K of gaseous n-decane,
C10H22.

C10H22 + 15.5(O2+3.76N2) --> 10CO2 + 11H2O + 15.5 (3.76)N2

Calculation for upper heating value

h f0, H 2O (l )  h f0, H 2O (g)  hfg  241847  44010  285857 kJ/kmol

DH C , H 2O (l )  1 h f0,C10 H 22  [10h f0, H 2O  11h f0, H 2O (l ) ]
 (1)( 249659)  [(10)(393546)  11( 285857)]  6830096 kJ
DH C 6830096 kJ
DhC    6830096 kJ/kmolC10 H22
N fuel 1 kmol
DH C 6830096
DhC    48003 kJ/kg C10 H22
MWfuel 142.284

Calculation for lower heating value (we have to use value of h f0, H 2O (g) )

DhC  6345986 kJ/kmolC10 H22 , DhC  44061 kJ/kg C10 H22

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 ENTHALPY OF COMBUSTION AND HEATING VALUES
• Example: Determine the upper and lower heating values at 298 K of gaseous n-decane,
C10H22.

C10H22 + 15.5(O2+3.76N2) --> 10CO2 + 11H2O + 15.5 (3.76)N2

When we use liquid n-decane

H reac  (1)( h f0,C10 H 22  hfg )
or Dhc (liquid fuel)  Dhc (gaseous fuel)-hfg
Higher heating value: DhC  48003 - 359 = 47644 kJ/kg C10 H 22
Lower heating value: DhC  44601 - 359 = 44242 kJ/kg C10 H 22

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 ENTHALPY OF COMBUSTION AND HEATING VALUES
• Example: Determine the upper and lower heating values at 298 K of gaseous n-decane,
C10H22.

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 LATENT HEAT OF VAPORIZATION, hfg
• In many combustion systems a liquid ↔ vapor phase change may occur
– Example 1: A liquid fuel droplet must first vaporize before it can burn
– Example 2: If cooled sufficiently, water vapor can condense from combustion products

• Latent Heat of Vaporization (also called enthalpy of valorization), hfg: Heat required in a constant P
process to completely vaporize a unit mass of liquid at a given T
– hfg(T,P) ≡ hvapor(T,P)-hliquid(T,P)
– T and P correspond to saturation conditions

• Latent heat of vaporization is frequently used with Clausius-Clapeyron equation to estimate Psat
variation with T
dPsat h fg dTsat

– Assumptions:
Psat R Tsat2
• Specific volume of liquid phase is negligible compared to vapor
• Vapor behaves as an ideal gas
– If hfg is constant integrate to find Psat,2 if Tsat,1 Tsat,2, and Psat,1 are known

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SELECTED PROPERTIES OF HYDROCARBON FUELS

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 ADIABATIC FLAME TEMPERATURE
• For an adiabatic combustion process, with no change in KE or PE, temperature of products
is called Adiabatic Flame Temperature
– Maximum temperature that can be achieved for given concentrations of reactants
– Incomplete combustion or heat transfer from reactants act to lower temperature

• Adiabatic flame temperature is generally a good estimate of actual temperature achieved in

a flame, since chemical time scales are often shorter than those associated with transfer of
heat and work

• Most common is constant-pressure adiabatic flame temperature

H reac Ti , P   H prod Tad , P 

hreac Ti , P   h prod Tad , P 
• Conceptually simple, but in practice difficult to evaluate because requires detailed
knowledge of product composition, which is function of temperature

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 ADIABATIC FLAME TEMPERATURE
• Constant-pressure adiabatic flame temperature

H reac Ti , P   H prod Tad , P 

hreac Ti , P   h prod Tad , P 

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 ADIABATIC FLAME TEMPERATURE
Example: 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.
Assumptions:
1. We assume complete
combustion
2. The product mixture
enthalpy is estimated
using constant specific
heats evaluated at 1200
K; we guessed the flame
temperature to be about
2100 K
Observations
1. Tad,eq=2226 K

2. For a better estimate:

T
hi  h f0,i  c
298
p ,i dT
We obtain, Tad=2328 K
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 CONSTANT VOLUME ADIABATIC FLAME TEMPERATURE
• Constant-volume adiabatic flame temperature

U reac Tinit , Pinit   U prod Tad , Pf 

H reac  H prod  V  Pinit  Pf   0

• Using ideal gas Equation of State:

H reac  H prod  Ru  N reacTinit  N prod Tad   0

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CONSTANT VOLUME ADIABATIC FLAME TEMPERATURE

Final Pressure:
Tad
Pf  Pinit ( )  9.69 atm
Tinit

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