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Department of Mechanical Engineering

ME 322 Mechanical Engineering


Thermodynamics

Lecture 37
Heat of Reaction
1st Law Analysis of Combustion Systems

Combustion System Analysis


Consider the complete combustion of octane in 150%
theoretical air,
Q&

C8H18
PTA = 150%

Combustion
Chamber

Products (p)

In the previous lecture, we found the balanced reaction,


C8H18 + 18.75(O 2 + 3.76 N2 ) 8CO 2 + 9H2O + 6.25O 2 + 70.5N2

The First Law applied to the system identified above is,


Q& n&a ha n&f h f n&p hp
p

Combustion System Analysis


Q&
C8H18
PTA = 150%

Combustion
Chamber

Products (p)

C8H18 + 18.75(O2 + 3.76 N2 ) 8CO2 + 9H2O + 6.25O 2 + 70.5N2


Q& n&a ha n&f h f n&p hp
p

reactants combustion
(air and fuel) products

Potential issue: There are no h values (except for O2 and


N2). This has the potential to cause a datum state problem.
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Resolving the Datum State Problem


In combustion calculations, the enthalpy of all stable* elements
is defined as zero at the standard reference state (SRS),
25C 298.15 K at 0.1 MPa 1 atm

77F 536.67 R at 14.5 psia 1 atm

*Stable means chemically stable at the SRS. For example,


diatomic oxygen (O2) is stable at the SRS. Monatomic
oxygen (O) is not stable at the SRS.

Enthalpy of Formation
The enthalpy of a compound at the standard reference state
Heat released in an exothermic reaction (or absorbed
h f0 in an endothermic reaction) when a compound is
formed from its elements. (Elements and compound at the SRS)
Example Methane
Q&
25C
1 atm

2H2

CH4
25C
1 atm

Q& n&CH4 hCH4 n&C hC n&H 2 hH2


n&H 2
n&C
Q&
hCH4
hC
hH2
n&CH 4
n&CH 4
n&CH 4
Q&
hCH4 h f0,CH4
n&CH4

Enthalpy of Formation Values


Using EES*

*Unit setting = molar

Enthalpy of Formation Values


Results ...

Conclusion: EES uses the SRS as the datum state for enthalpy for
the ideal gases! Therefore, enthalpy of formation values can be
calculated from EES using the ideal gas substances (except AIR)
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Enthalpy Values in Combustion


What do we know so far?
1. The enthalpy of a stable element at the SRS is 0
2. The SRS is 25C, 0.1 MPa
3. The enthalpy of a compound at the SRS is the
enthalpy of formation (Table 15.1 or from EES)

Enthalpy Values at Other States


The enthalpy of a component at any temperature in a
combustion process can be evaluated by,
hi T h f0,i h i
Accounts for the
enthalpy difference
relative to the SRS

hi T h f0,i h i T h i TSRS

How is the enthalpy difference in brackets determined??

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Enthalpy Values at Other States


hi T h f0,i h i T hi TSRS

Three possibilities ...


1. If the heat capacity of the component can be assumed constant,

hi T h f0,i c p ,i T TSRS
2. If the constant heat capacity assumption is not accurate enough,
then use the ideal gas tables (Table C.16c). In this case the datum
state for the table does not have to match the enthalpy of
formation.
3. Use a set of property tables for all components that has all
enthalpy values referenced to the SRS. Does such a thing exist?

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Enthalpy Values at Other States


Exploring Option 3 from the previous slide ...
hi T h f0,i hi T hi TSRS

If a thermodynamically consistent set of tables exists, then


h f0,i hi TSRS

Therefore the enthalpy of the component could simply be


looked up in a table at the given temperature,
hi T hi T

If something like this were available ... combustion


calculations would be EESy!
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Enthalpy Values at Other States


ALL of the ideal gas enthalpy reference states (except for
the ideal gas AIR) in EES are referenced to the SRS!
This is from the EES Help Menu for the ideal gas CO2 ...

All other ideal gases in EES (except AIR) say the same thing!
Significance: Combustion calculations just became EESy!

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Heat of Reaction
Consider an aergonic combustion process as shown below
Q&
Fuel
Reactants (R)

Air

Combustion
Chamber

Products (P)

The First Law applied to this system results in,


Q& n&i hi n&i hi
P

Dividing by the molar flow rate of the fuel,


n&i

i
n&
Q&
q

hi
hi

&fuel
n&fuel
P n
R
n&fuel

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Heat of Reaction
n&i

i
n&
Q&
q

hi
hi

&fuel
n&fuel
P n
R
n&fuel

The molar flow rate ratios are the molar coefficients from the
balanced combustion reaction! Therefore,
Q&
q
i hi i hi
n&fuel
P
R

This is known as the molar heat of reaction.

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Heating Values of Fuels


Given: Gaseous octane (C8H18) is burned completely in
100% theoretical air. The reactants and the products are at
the SRS.
Q&

C8 H18
TR TSRS
PTA 100%

Combustion
Chamber

Products

TP TSRS

Find: The heat released during this combustion process per


mole of fuel for the following cases,
(a) the water in the products is all vapor
(b) the water in the products is all liquid
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Q&

Heating Values

C8 H18
TR TSRS

Combustion
Chamber

PTA 100%
The system boundary is drawn
around the combustion chamber. Applying the First Law
results in,

Products
TP TSRS

Q& n&i hi n&i hi


P

Dividing both sides of this equation by the molar flow rate of


the fuel,
n&i

i
n&
Q&

hi
hi

&
&
&
n fuel
P n fuel
R
n fuel

Number of moles of
reactant per mole of fuel

Number of moles of product


species per mole of fuel

How are these found?


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Q&

Heating Values

C8 H18
TR TSRS

Combustion
Chamber

Products
TP TSRS

The molar flow rate ratios on the PTA 100%


previous slide are the molar coefficients from the balanced
combustion reaction (for one mole of fuel)! Therefore,
n&i

i
n&
Q&

hi
hi

&
&
&
n fuel
P n fuel
R
n fuel

Observations ...

Q&
q
i hi i hi
&
n fuel
P
R
Notice: PTA = 100% means
stoichiometric combustion

1. The importance of being able to balance the


combustion reaction is evident!
2. As long as the combustion process is aergonic, the
First Law will be as written above, independent of the
conditions in and out of the combustion chamber!
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Q&

Heating Values

C8 H18
TR TSRS

Combustion
Chamber

Products
TP TSRS

For the complete combustion of PTA 100%


normal octane in 100% theoretical air, we previously found,
C8H18 + 12.5(O2 + 3.76 N2 ) 8CO2 + 9H2O + 47N2

Applying the First Law to the system,


Q&
q
i hi i hi
n&fuel
P
R
Q&
q
1h CO2 2 h H2O 4 h O2 5 h N 2 h C8H18 0 h O2 3.67h N 2

n&fuel

Q&
q
1h f ,CO2 2 h f ,H2O h f ,C8H18
n&fuel

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Q&

Heating Values

C8 H18
TR TSRS

PTA 100%

Combustion
Chamber

Products
TP TSRS

C8H18 + 12.5(O2 + 3.76 N2 ) 8CO 2 + 9H2O + 47N2

Q&
q
1h f ,CO2 2 h f ,H 2O h f ,C8H18
n&fuel

Now we have an interesting problem. Is the water liquid or gas (or both)?
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Q&

Heating Values

C8 H18
TR TSRS

PTA 100%

Combustion
Chamber

Lets consider both extremes


(1) the H2O is all vapor and (2) the H2O is all liquid.

Products
TP TSRS

C8H18 + 12.5(O2 + 3.76 N2 ) 8CO2 + 9H2O + 47N2


Q&
q
1h f ,CO2 2 h f ,H 2O h f ,C8H18
n&fuel

All vapor water ...


q

Q&
MJ
MJ
MJ


MJ
8 393.522
9 241.827
208.447
5,116.172

n&fuel
kmol
kmol
kmol
kmol

All liquid water ...


Q&
MJ
MJ
MJ


MJ
q
8 393.522

285.838

208.447

5,512.271

n&fuel
kmol
kmol
kmol
kmol

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Q&

Heating Values
All vapor water ...
Q&
MJ
q
5,116.172
n&fuel
kmol

C8 H18
TR TSRS

PTA 100%

Combustion
Chamber

Products
TP TSRS

Lower Heating Value (LHV)

All liquid water ...


Q&
MJ
q
5, 512.271
n&fuel
kmol

Higher Heating Value (HHV)

Observations ...
1. The reactants and products are at the SRS
2. The reaction occurs with PTA = 100% (i = i )
3. The difference between the HHV and the LHV is the
enthalpy of vaporization of water!
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Heating Values
q

1 mol fuel
TSRS, PSRS

TSRS
PSRS

Products

LHV

(vapor H2O)

H2O h fg ,H2O

Stoichiometric air
Products

HHV

(liquid H2O)

HHV LHV H2O h fg ,H2O

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Heating Values
The heating values represent the maximum possible heat
transfer that can occur per mole of fuel.
The reactants and products are at the SRS
The HHV represents fully condensed water vapor
The LHV represents all water vapor
These values provide a basis for the combustion efficiency,
comb

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Actual heat transferred per mole of fuel


HHV or LHV

Q&

Example

C8 H18
TR TSRS

Combustion
Chamber

PTA 100%
Back to our problem ... Is there
liquid water in the products at the SRS? If so, how much?

C8H18 + 12.5(O2 + 3.76 N2 ) 8CO2 + 9H2O + 47N2

Will water condense?


yw

9
0.1406
8 9 47

Pw yw P 0.1406 0.1 MPa 0.01406 MPa 14.06 kPa


Tdp 52.6C

Since TSRS < Tdp, water will condense

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Products
TP TSRS

Q&

Example

C8 H18
TR TSRS

Combustion
Chamber

How much water will condense? PTA 100%


At TSRS = 25C, the mole fraction of water vapor in the
products is,

Products
TP TSRS

C8H18 + 12.5(O2 + 3.76 N2 ) 8CO2 + 9H2O + 47N2


yv

nv
8 nv 47

The mole fraction of the water vapor at 25C can be found,


yw

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Pw 0.03142 bar

0.03101
P 1.01325 bar