ENTHALPY OF FORMATION

The “Enthalpy of Formation of a compound is the enthalpy at the Arbitrary

Reference State (t = 25°C and P = 1 Atm).

1 mole C
25°C, 1 atm
Combustion 1 mole CO2
Chamber
25°C, 1 atm
1 mole O2
25°C, 1 atm

Let;
HR – total enthalpy of Reactants
HP – total enthalpy of products

From 1st Law

Q  HR  HP
or
Q   ni hi   ni hi
R P

but the enthalpy of all the reactantsis Zero (for they are all elements)
Q  HP  -393,757 KJ
therefore
KJ
(h° f )CO2  393,757  Enthalpy of formation of CO2
kgm
Note : Negative sign is due to the reaction's being " Exothermic"

FIRST LAW ANALYSIS FOR STEADY STATE REACTING SYSTEM

W

1 mole C
25°C, 1 atm
Combustion 1 mole CO2
Chamber
25°C, 1 atm
1 mole O2
25°C, 1 atm

By energy balance

Q   ni hi  W   ni hi
R P
 In most cases, neither the reactants nor the products are at the reference
state (t = 25°C and P = 1 Atm). In these case we must account for the property
change between the reference state and the actual state. The change in
enthalpy between the reference state and the actual state is

(h°  h° 298 )
where
°  denotes that the pressureis 1 Atmosphere

General Equation for a Steady State, Steady flow reaction process

  
Q   ni h° f  (h°  h°298 ) i W   nj h° f  (h°  h°298 )
R P
 j

ADIABATIC FLAME TEMPERATURE

1 mole C
25°C, 1 atm
Combustion 1 mole CO2
Chamber
25°C, 1 atm
1 mole O2
25°C, 1 atm

If Q = 0 ; W = 0 ; KE = 0 and PE = 0, all the thermal energy would go into raising the
temperature of the products of combustion. When the combustion is complete, the
maximum amount of chemical energy has been converted into thermal energy and the
temperature of the product is at its maximum. This maximum temperature is called the
“ Adiabatic Flame Temperature” (AFT)

HR  H P
ENTHALPY OF COMBUSTION OR HEATING VALUE

It is the difference between the enthalpies of the products and the reactants at the
same temperature T and Pressure P.

KJ
hRP  HP  HR
kgm ol

  
hRP   n j h ° f  (h°  h° 298 )  ni h ° f  (h°  h° 298 )
R P
 i
KJ
kgm ol
(HP  HR ) KJ
hRP 
M kg
where
M - molecular weight

HEATING VALUE

Heating Value - is the energy released by fuel when it is completely burned

and the products of combustion are cooled to the original fuel temperature.
Higher Heating Value (HHV) - is the heating value obtained when the water
in the products is liquid.
Lower Heating Value (LHV) - is the heating value obtained when the water
in the products is vapor.

For Solid Fuels

 O2  KJ
HHV  33,820c  144,212 H2    9,304S
 8  kg

where: C, H2, O2, and S are in decimals from the ultimate analysis

For Coal and Oils with the absence of Ultimate Analysis

 A HHV
   kg of air/kg of fuel
 F  t 3,041

HHV = 31,405C + 141 647H KJ/kg

For Liquid Fuels

HHV = 43,385 + 93(Be - 10) KJ/kg

Be - degrees Baume

For Gasoline

HHV = 41,160 + 93 (°API) KJ/kg

LHV = 38,639 + 93 (°API) KJ/kg

For Kerosene

HHV = 41,943 + 93 (°API) KJ/kg

LHV = 39,035 + 93 (°API) KJKkg

For Fuel Oils

HHV = 41,130 + 139.6(°API) KJ/kg

LHV = 38,105 + 139.6(°API) KJ/kg

API - American Petroleum Institute

For Fuel Oils (From Bureau of Standard Formula)

HHV = 51,716 - 8793.8 (S)2 KJ/kg

LHV = HHV - QL KJ/kg
QL = 2,442.7(9H2) KJ/kg
H2 = 0.26 - 0.15(S) kg of H2/ kg of fuel
141.5
S
131.5  ° API
140
S
130  °Be
Where:

S @ t = S - 0.0007(t-15.56)
S - specific gravity of fuel oil at 15.56 °C
H2 - hydrogen content of fuel oil, Kg H/Kg fuel
QL - heat required to evaporate and superheat the water vapor formed by the combustion
of hydrogen in the fuel,KJ/kg
S @ t - specific gravity of fuel oil at any temperature t
Oxygen Bomb Calorimeter - instrument used in measuring heating value of solid and
liquid fuels.
Gas Calorimeter - instrument used for measuring heating value of gaseous fuels.

SAMPLE PROBLEM NO. 1

A small gas engine uses C8H18 (liquid) for fuel and 400% theoretical air. The air and fuel
enters at 25°C and the products of combustion leave at 900 K. The output of the engine
and the fuel consumption are measured and it is found that the specific fuel consumption
is 0.25 kg/sec of fuel per Megawatt output. Determine the heat transfer from the engine
per kgmol of fuel. Assume complete combustion.

Combustion with 100% theoretical air

C8H18  12.5O 2  47N2  8CO2  9H2 O  47N2

Combustion with 400% theoretical air or e = 300%

C8H18  50O2  188N2  8CO2  9H2O  37.5O2  188N2

From Table
KJ
h ° f C8H18 (liq )  250,102
kgm
KJ
h° f (CO2)  393,757
kgm
KJ
h° f (H2O)  241,971
kgm
h ° f (O2 )  0
h ° f ( N2 )  0
at 900 K
h CO 2  28,041
h H2 O  21,924
h O2  19,246
h N2  18,221
    
Q   ni h° f  (h°  h° 298 ) i  W   n j h° f  (h°  h° 298 )
R P
j

1000  kg  KJ
W  114   456,000
0.25  kgm  kgm
Q  HR  456,000  HP
KJ
Q  52,776
kg mFuel

SAMPLE PROBLEM NO. 2

A diesel engine used gaseous Dodecane (C12H26) as fuel. The air and fuel enters the
engine at 25°C and 100% excess air is required for combustion. The products of
combustion leaves at 600 K and the heat loss from the engine is 232,000 KJ/kgm fuel.
Determine the work for a fuel rate of 1 kgmfuel/hr.
Air and Fuel Products

Engine W

Q = -232,000 KJ/kgmol
Combustion with 100% theoretical air

C12H26  18.5O2  69.56N2  12CO2  13H2O  69.56N2

Combustion with 400% theoretical air or e = 300%

  
Q   ni h° f  (h°  h°298 ) i W   nj h° f  (h°  h°298 )
R P
 j

C12H26  37O 2  139.12N2  12CO2  13H2O  18.5O 2  139.12N2

Q  HR  W  HP
W  Q  (HP  HR )
W  232,000  ( 5,365,265.1)
KJ
W  5,133,265
kg mol Fuel
 1 
W  5,133,265   1426 KW
 3600 

SAMPLE PROBLEM NO. 3

An internal combustion engine producing 600 KW of power uses Gasoline fuel (C8H18)
at 25°C and 400% theoretical air is used. Air and fuel enters the engine at 400 K and the
products of combustion leaves the engine at 700 K. The heat loss from the engine is
146.5 KW. Determine the fuel consumption of the engine in kg/hr.

Combustion with 100% theoretical air

C8H18  12.5O2  47N2  8CO2  9H2O  47N2

Combustion with 400% theoretical air or e = 300%

C8H18  50O2  188N2  8CO2  9H2O  37.5O2  188N2

  
 ni h° f  (h°  h° 298 ) i  (250,000)  50(3,029)  188(2,971)
R

KJ
HR  459,896.0
kgm fuel
 
 n j h° f  (h°  h° 298 ) j  8(-393,757  17,761)  9(-241,971 14,184) 
P

37.5(12,502)  188(11,937)
KJ
HP  -2,345,070.0
kgm fuel
By EnergyBalance
Q  n f (HR )  600  n f (HP )
- 146.5  n f (459,896)  600  n f (-2,345,070)
600  146.5 kg
nf   0.00027 m fuel
(459,896  2,345,070) sec

mFuel  0.0002712(8)  1(18)(3600)  109.2

kg
of Fuel
hr

SAMPLE PROBLEM No. 4

A fuel oil represented by C10H22 is burned with 25% excess air in a laboratory to
determine its heating value. Air and fuel enters at 25°C and the products of combustion
leaves the apparatus at 500 K. Determine the higher heating value of the fuel
considering;(assume h°f(C H ) =-289,402 KJ/kgmol Fuel )
10 22

A. Complete combustion with no CO in the products

B. Incomplete combustion with 5% of the carbon atoms oxidizes to CO

Complete Combustion no CO in the products

 Combustion with 100% theoretical air

C10H22  15.5O2  58.28N2  10CO2  11H2O  58.28N2

Combustion with 125% theoretical air or e = 25%

C10H22  19.375O2  72.85N2  10CO2  11H2O  3.875O2  72.85N2
 6,180,735.8 KJ
HHV   54,217
114 kg Fuel

B. Combustion with 125% theoretical air and CO in the products

C.
C10H22  19.063O2  71.675N2  9.5CO2  0.5CO  11H2O  3.813O2  71.675N2

5,989,412.4 KJ
HHV   42,179
114 kg Fuel

Instructor: Engr. Yuri G. Melliza

August 05, 2017