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7 Chemical Reaction
7 Chemical Reaction
Objectives:
Apply the conservation of mass to reacting systems to
determine balanced reaction equations.
Defined the parameters used in combustion analysis, such
as air-fuel ratio, percent theoretical air, and dew point
temperature.
Apply energy balance to reacting systems for both steadyflow control volumes and fixed mass systems.
Calculate enthalpy of reaction, enthalpy of combustion,
and the heating value of fuels.
Determine the adiabatic flame temperature for reacting
mixture.
Steam Generator
Rocket Engine
Jet Engine
Piston Engine
Fuels
Fossil Fuels: Coal, Petroleum, Natural Gases (LNG:
liquid natural gas, CNG: Compressed Natural Gas)
Petroleum: Gasoline, Kerosene, Diesel, Fuel Oil ,
Liquid Petroleum Gas (LPG)
Fuel
Approx. single Hydrocarbon
Gasoline ~ Octane (C8H18)
Diesel ~ Dodecane (C12H26)
Methanol ~ Methyl Alcohol (CH3 OH)
Natural gas~ Methane (CH4)
Combustion Air
Combustion is a chemical reaction during which a fuel is
oxidized and a large quantity of energy is released.
Oxidizer = Oxygen
Commonly AIR is used as oxidizer (free)
By volume: AIR = 21% O2 + 79% N2
Therefore, 1 mole of O2 N2 = 79/21 = 3.76 mole
1 kmol O2 + 3.76 kmol N2 = 4.76 kmol of Air
Assumption at normal combustion :
N2 absolutely inert (no reaction)
Water is also inert
Combustion
1 kmol C + 1 kmol O2 1 kmol of CO2
C + O2
Reactants
CO2
(15.2)
Products
(15.3)
Example 15.1
Balancing the combustion equation
One kmol of octane (C8H18) is burned with air that
contains 20 kmol of O2, Assuming the products
contain only CO2, H2O, O2, and N2, determine the
mole number of each gas in the products and the airfuel ratio for this combustion process.
Solution Chemical reaction equation:
C8H18 +20 (O2 + 3.76 N2) xCO2 + yH2O + zO2 + wN2
Balance of each element : @ ReactantS = @ ProductS
C:
8=x x =8
y=9
H:
18 = 2y
O:
(20x2) = 2x +y + 2z z = 7.5
N2:
20*3.76 = w
w = 75.2
Air Fuel Ratio, AF = mair/mfuel = (NM)air/(NM)fuel
= 24.2 kg air/kg fuel
1.2a = 2+ 3/2+0.2a
then
a = 3.5
Example 15.3
241,820 kJ
CO2
at 25oC, 1 atm
1 kmol O2
at 25oC, 1 atm
1 kmol H
at 25oC, 1 atm
H2O (g)
Combustion at 25oC, 1 atm
Chamber
1 kmol O2
at 25oC, 1 atm
and
Eproducts = -Ereactants
Enthalpy Change
Enthalpy is the system we use to measure that change
in energy of a closed system due to chemical bonds
being broken. Reaction enthalpies are real physical
quantities for which numeric values can be calculated or
measured. In order to put the calculation into algebraic
form, chemists use the defined equation:
H = Hf (products) - Hf (reactants)
The reaction enthalpy, which is the enthalpy change that
occurs in the reaction, is always calculated as the sum
of the enthalpies of the products minus the sum of the
enthalpies of the reactants.
H = Hf(products) - Hf(reactants)
Enthalpy of Combustion
The enthalpy of reaction in a combustion process is called
the enthalpy of combustion (symbolized by hc). The
calculation for an enthalpy of combustion is done for 1
kmol (1 kg) of fuel is burned completely at a specified
temperature and pressure and can be expressed:
hc = Hprod Hreact
Example 15.5
Evaluation of the Enthalpy of Combustion
Determine the enthalpy of combustion of liquid octane
(C8H18) at 25oC and 1 atm, using enthalpy-of-formation data
from table A-26. Assume the water in the products is in the
liquid form.
Solution
1. Write chemical reaction equation
based on 1 kmol of octane
a(O2 + 3.76 N2) 8 CO2 + 9H2O(l) + 3.76aN2
C8H18 +a
o
HR = N hf ,R = (Nhf)C8H18
o
_
_
_
o
HP = N hfo ,P = (Nhfo)CO2 + (Nhf)H2O
10
f ,C8H18
Enthalpy of combustion
Enthalpy of formation has 2 values : 1. for vapor vapor phase 2. for liquid vapor
phase -the different = laten heat of vaporization
11
Enthalpy of Formation
The enthalpy of formation is defined as the
enthalpy of a substance at a specified state due
to its chemical composition. This property makes
analyzing easier because it represents chemical
energy of an element or a compound at the
standard reference state.
The property values are obtained by first
assigning all of the elements in its chemically
stable form at the standard reference state a
value of zero (such N2, O2, N2, C).
Enthalpy of Formation
So we can use this concept to find the enthalpy of
formation of individual compounds by adding up the
enthalpy for each reaction it takes to react some of
the chemically stable elements to get the compound.
Consider the formation of CO2 (a compound) from
elements C and O2 at 25 oC, 1 atm. during SSSF
process
1st law: Qcv + Hi = He
Qcv = HP HR
Qcv = - 393,520 kJ
HR = 0 ; elements @ ref. state
Enthalpy of Formation of CO2
= - 393,520 kJ/kmol
12
13
o _
where h = h of + hT To
_
h = h of + (h h o )
(scrip o stand for reference state which is 25o C , 1 atm)
_
Qcv Wcv = N e h e - N i h i
= H Pr od H Ract
.........(15 - 11)
U = H PV
Then
U = N{h of + (h h o )} PV
or
U = N{h of + (h h o ) P v}...........(15....)
14
Example 15.6
First Law Analysis of Steady-Flow Combustion
Liquid propane (C3H8) enters a combustion chamber at 25oC
at a rate of 0.05 kg/min where it is mixed and burned with
50% excess air that enters the combustion chamber at 7oC,
as shown in the figure. An analysis of the combustion gases
reveals that all the hydrogen in the fuel burns to H2O but
only 90% of carbon burns to CO2, with the remaining 10%
forming CO. If the exit temperature of the combustion
gases is 1,500 K, determine (a) the mass flow rate of the air
and (b) the rate of heat transfer from the combustion
chamber.
Solution: Concepts
1. Write chemical reaction equation based on 1 kmol of propane
1.1 Theoretical Air-Fuel ratio (Stochiometic)
1.2 with 150% theoretical air
+ incomplete burned CO AF mass flow rate of air
2. Energy balance: SSSF Q = HP HR
- Stochiometic combustion equation based on 1 kmol of propane
C3H8 (l)+a
a(O2 + 3.76 N2) 3CO2 + 4H2O + 3.76aN2
15
Qcv + N i h i = Wcv + N e h e
(i = Reactants, and e = Products, Wcv = 0)
_
Qcv = N e h e N i h i
_
h = h of + (h h o ),
where
(h o = h 298K )
Assume air and combustion gases are ideal gases, get data from the property tables
_
h of
h 298K
h 280K
h1500K
Substance
C3 H 8 (l )
- 118,910
NA
NA
O2
8,682
8,150
49,292
N2
8,669
8,141
47,073
H 2O( g )
- 241,820
9,904
NA
CO2
- 393,520
9,364
NA
71,078
CO
- 110,530
8,669
NA
47,517
57,999
Remark : h of ( g ) = h of (l ) + h fg
Substitute, Qcv = 363,880 kJ/kmol fuel 8,270 kJ/kg fuel Qdot = mdotQ = 6.89 kW
Example 15.7
First Law Analysis of Combustion in a Bomb
Constant volume tank contains 1 kmol of methane (CH4) gas
and 3 kmol of O2 at 25oC and 1 atm. The contents of the
tank are ignited, and the methane gas burns completely. If
the final temperature is 1,000K, determine (a) the final
pressure in the tank and (b) the heat transfer during this
process.
Solution: Concepts
1. Write chemical reaction equation
Assume ideal gas for both reactants and
products: PV = NRuT P2
2. Energy balance: SSSF
Q = UP UR
= (Hp-PPV) - (HR-PRV)
16
First law :
Q12 = W12 + (U 2 U 1 )
W12 = 0 :
Q12 = (U Pr od U Re act )
_
from
or
U = H PV = N{h of + (h h o )} PV
_
U = N{h of + (h h o ) P v}
_
Ideal gas P v = Ru T
then
U=
_
_
_
o
N{h f + (h h o )
Ru T }
_
_
o
h f , ho
Answer
17
Qcv=0,Wcv=0 ,
,KE=
KE=PE=0 :
_
1st law
Qcv + N i h i = Wcv + N e h e
_
N i h i = N e h e
_
_
_
o
N R {h f + (h h o )}R
_
_
o
= N P {h f + (h h o )}P
Error
Tc
When/how to interporate
T2
b
-Ea
Inte
E2
Ta
Tb
-Ea
-Eb
0.0
T2
Tc
Tb
8
-Eb
ratio
rpo
T2
+Ec
T2 = 342 oC
Ta
E=0
mi =1.263 kg
+Ec
Error
18
Example 15.8
Adiabatic Flame Temperature in Steady Combustion
Liquid octane (C8H18) enters the combustion chamber of a
gas turbine steadily at 1 atm and 25oC, and it is burns with
air that enters the combustion chamber at the same state,
as shown in the figure. Determine the adiabatic flame
temperature for (a) complete combustion at 100%
theoretical air, (b) complete combustion at 400%
theoretical air and (c) incomplete combustion (some CO in
the products) with 90% theoretical air.
Asumptions:
1. SSSF process
2. Adiabatic
3. No work
4. KE=PE=0
5. Air and combustion gases are ideal gas
at TR = 298K
at TP = ?
HR = HP
2. Energy balance:
Qcv + N i h i = Wcv + N e h e
_
N i h i = N e h e
_
N R {h of + (h h o )}R = N P {h of + (h h o )}P
_
_
o
N R {h of }R = N P {h of + (h h o )}P
19
at TR = 298K
at TP = ?
by trial and error of TP
Adiabatic flame temperature = 962 K ..answer
at TR = 298K
at TP = ?
C and O balance a = 5.5 and b = 2.5
by trial and error of TP
Adiabatic flame temperature = 2,236K ..answer
Error
Tc
When/how to interporate
T2
b
-Ea
Inte
E2
Ta
Tb
-Ea
-Eb
0.0
T2
Tc
Tb
8
-Eb
ratio
rpo
T2
+Ec
T2 = 342 oC
Ta
E=0
mi =1.263 kg
+Ec
Error
20
Assume air and combustion gases are ideal gases, get data from the property tables
_
h of
h 298K
h xxxxK
h yyyyK
Substance
C8 H18 (l )
- 249,950
O2
N2
NA
NA
8,682
............
............
8,669
............
............
H 2O( g )
- 241,820
9,904
............
............
CO2
- 393,520
9,364
............
............
CO
- 110,530
8,669
.............
_
Remark : h of ( g )
............
_
_
h of (l ) + h fg
N R {h of }R = N P {h of + (h h o )}P
_
+ {47(0 + h 8,669)}N 2
2,395 K ..answer
21