HHV, LHV, and Closed Systems.

Enthalpy of Reaction and Enthalpy of Combustion
When the products and reactants are at the same temperature, the enthalpy of
reaction hR, is the difference in their enthalpies. When the combustion is assumed to
be complete with theoretical air supplied the enthalpy of reaction is called the
enthalpy of combustion hC. The enthalpy of combustion can be calculated at any
value of the temperature, but it is usually determined at 25oC or 298 K.
hC  H P  H R when TP  TR  25o C  298 K

o o
  e fe
N h
Products
 i fi
N h
Reactants
Heating Value
The heating value, HV, of a fuel is the absolute value of the enthalpy of combustion
or just the negative of the enthalpy of combustion.
HV  hC
The lower heating value, LHV, is the heating value when water appears as a gas in
the products.
LHV  hC   hC with H2 Ogas in products 38

The lower heating value is often used as the amount of energy per kmol of fuel
supplied to the gas turbine engine.
The higher heating value, HHV, is the heating value when water appears as a
liquid in the products.
HHV  hC   hC with H2 Oliquid in products

The higher heating value is often used as the amount of energy per kmol of fuel
supplied to the steam power cycle.
See Table A-27 (Cengel’s book) for the heating values of fuels at 25oC. Note that
the heating values are listed with units of kJ/kg of fuel. We multiply the listed
heating value by the molar mass of the fuel to determine the heating value in units
of kJ/kmol of fuel.
The higher and lower heating values are related by the amount of water formed
during the combustion process and the enthalpy of vaporization of water at the
temperature.
HHV  LHV  N H2 O h fg H2 O 39
Example 9
The enthalpy of combustion of gaseous octane C8H18 at 25oC with liquid water in the
products is -5,512,180 kJ/kmol. Find the lower heating value of liquid octane.
LHVC8 H18 gas  HHVC8 H18 gas  N H 2O h fg H 2O

kJ kmol H 2O kJ
 5,500,842
5,512,180 9 (44, 010)
44,000
kmol C8 H18 kmol C8 H18 kmol H 2O
kJ
 5,104, 752
5,116,180
kmol C8 H18
LHVC8 H18 liq  LHVC8 H18 gas  h fg C8 H18

kJ
5,116,180 41,382)
 (5,104752
kmol C8 H18
kJ
5,074,978
 5, 063,370
kmol C8 H18 liq
Can you explain why LHVliq< LHVgas? 40

Closed System Analysis
Example 10
A mixture of 1 kmol C8H18 gas and 200 percent excess air at 25oC, 1 atm, is burned
completely in a closed system (a bomb) and is cooled to 1200 K. Find the heat
transfer from the system and the system final pressure.
Apply the first law closed system:
41
Assume that the reactants and products are ideal gases; then
PV  NRu T
The balanced combustion equation for 200 percent excess (300 percent theoretical)
air is
C8 H18  ( 3)(12.5) ( O2  3.76 N 2 ) 

8 CO2  25 O2  9 H 2 O  141 N 2
42
Qnet  8( 393,520  53,848  9364  8.314(1200)) CO2
 9( 241,820  44,380  9904  8.314(1200)) H2 O
 25(0  38,447  8682  8.314(1200)) O2
 141(0  36,777  8669  8.314(1200)) N 2
 1( 208,450  h298 K  h o  8.314(298)) C8 H18
 37.5(0  8682  8682  8.314( 298)) O2
 141( 0  8669  8669  8.314(298)) N 2
6 kJ
 112
.  10
kmol C8 H18
To find the final pressure, we assume that the reactants and the products are ideal-
gas mixtures.
PV
1 1  N 1 Ru T1
PV
2 2  N 2 Ru T2
43
where state 1 is the state of the mixture of the reactants before the combustion
process and state 2 is the state of the mixture of the products after the combustion
process takes place. Note that the total moles of reactants are not equal to the total
moles of products.
PV
2 2 N 2 Ru T2

PV
1 1 N 1 Ru T1
but V2 = V1.
44
A mixture of 1 kmol C2H6 (Ethane) gas and 300 percent excess air at 25oC, 1 atm , is
burned completely in a closed container. The mixture is now ignited, and the product
gases are observed to be at 1000 K at the end of the combustion process. Assuming
complete combustion, and treating both the reactants and the products as ideal
gases, determine the heat transfer from the combustion chamber during this process
and the system final pressure
45

HHV, LHV, and Closed Systems.

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Enthalpy of Reaction and Enthalpy of Combustion

hC  H P  H R when TP  TR  25o C  298 K

LHV  hC   hC with H2 Ogas in products 38

HHV  hC   hC with H2 Oliquid in products

LHVC8 H18 gas  HHVC8 H18 gas  N H 2O h fg H 2O

LHVC8 H18 liq  LHVC8 H18 gas  h fg C8 H18

Can you explain why LHVliq< LHVgas? 40

Apply the first law closed system:

C8 H18  ( 3)(12.5) ( O2  3.76 N 2 ) 

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