Chemical Reactions

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 steady-
flow 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.

Combustion of fuel Æ Heat Æ Heat Engine Æ Work

Combustion of fuel Æ Chemical Reaction
How much fuel is needed? How about the air used?
How high the combustion flame temperature will be?

Steam Generator Rocket Engine

Jet Engine

Piston Engine

1
 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 Æ 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

2
 Combustion
1 kmol C + 1 kmol O2 Æ 1 kmol of CO2

C + O2 Æ CO2 (15.2)
Reactants Products

To have combustion reaction, it must:

• T > ignition temp
• Fuel : air ratio must proper

• To get good combustion Æ 3T

– Temperature (high)
– Turbulent (good mixing between fuel and air)
– Time (enough to reach complete combustion)

•Balancing of chemical reaction: Conservation of mass

principle
• Air fuel ratio, AF = mair/mfuel (15.3)

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 air-
fuel ratio for this combustion process.
Solution Chemical reaction equation:
C8H18 +20 (O2 + 3.76 N2) Æ xCO2 + yH2O + zO2 + wN2
Balance of each element : @ ReactantS = @ ProductS
C: 8=x Æ x =8
H: 18 = 2y Æy=9
O: (20x2) = 2x +y + 2z Æ z = 7.5
N2: 20*3.76 = w Æ w = 75.2
Air Fuel Ratio, AF = mair/mfuel = (NM)air/(NM)fuel
= 24.2 kg air/kg fuel

Theoretical and Actual Combustion

Processes
Complete combustion: 1) all C burns to CO2, and 2) all
HC burns to H2O
combustion Products contains Unburned
Incomplete combustion:
fuel or components สาเหตุหลัก: 1)Insufficient O2 2)
Insufficient mixing. 3) Dissociation
Stoichiometric Air or Theoretical Air:
Air
• = minimum amount of air needed for complete
combustion.
• Æ no unburned and no O2 left in products
• = Chemically correct amount of air or 100%
theoretical air

4
 Theoretical and Actual Combustion
Processes
Stoichiometric Combustion or Theoretical Combustion:
Combustion
• Complete combustion with 100% theoretical air ; ex
CH4 + 2(O2 + 3.76N2) Æ CO2 + 2H2O + 7.52N2
Actual combustion processes: need excess air to
complete combustion
% Excess air:
air = % more air needed than theoretical air
80% excess air = 180% theoretical air
Deficiency of air: = amount of air used < theoretical air
(10% deficiency of air = 90% theoretical air)

Theoretical and Actual Combustion

Processes
Equivalent Ratio = (AFactual)/(AFstoich)
การประเมิน/ตรวจสอบความสมบูรณของการการเผาไหม
Orsat Gas Analyzer = อุปกรณวิเคราะหองคประกอบของ combustion
gas (products) ปจจุบันไมคอยนิยมใชแลว – ใช gas analyzer

5
Example 15.2 dew point temperature of combustion products
Ethane (C2H6) is burned with 20% excess air during
combustion process. Assuming complete combustion
and a total pressure of 100 kPa, determine (a) the
air fuel ratio and (b) the dew point temperature of
the products.
Solution
(a) write the chemical reaction
equation at 120% theoretical air
C2H6 +1.2a (O2 + 3.76 N2)Æ2CO2 + 3H2O + 0.2aO2 +(1.2x3.76)aN2
From O2: 1.2a = 2+ 3/2+0.2a then a = 3.5
C2H6 +4.2(O2 + 3.76 N2) Æ 2CO2 + 3H2O + 0.7O2 + 15.79N2
Air Fuel Ratio, AF = mair/mfuel = (NM)air/(NM)fuel
= (4.2x4.76 kmol)(29 kg/kmol)/[(2kmolx12 kg/kmol)x(3 kmol x 2 kg/kmol)]
= 19.3 kg air/kg fuel

C2H6 +4.2(O2 + 3.76 N2) Æ 2CO2 + 3H2O + 0.7O2 + 15.79N2

(b) Tdp = Tsat @ Pv (H2O)

Ideal gas mixture Pi/Pm = Ni/Nm
Pv = (3 kmol/21.49 kmol)(100 kPa)
Pv = 13.96 kPa Æ Tdp = 52.3 oC

6
Example 15.3 combustion of gasous fuel with moist air
A certain natural gas has the following volumetric analysis:
72% CH4 , 9% H2 , 14%N2 , 2%O2 and 3%CO2. The gases is
now burn with stochiometic amount of air that enters
combustion chamber at 20oC, 1 atm, and 80%RH. Assume
complete combustion and a total pressure of 1 atm,
determine the dew point temperature of the products.
Solution

0.72CH4 +0.09H2+ 0.02O2 + 0.14N2 +0.03CO2

Æ ath(O2+3.76N2)+ xCO2 + yH2O+zN2

Example 15.3

1. write the chemical reaction equation

at 100% theoretical air (use dry air)
2. moles of air per kmol of fuel can be determined
3. then extra moles water vapor (20%RH at inlet conditions)
can be calculated
4. Rewrite the chemical reaction by adding the water vapor
into both side.
5. N of each component in products are known
6. Tdp = Tsat @ Pv (H2O) (Ideal gas mixture Pi/Pm = Ni/Nm)
Pv = 20.88 kPa Æ Tdp = 60.9 oC

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 Chemical Energy from Process
This session deal with the chemical energy within the
molecules of a closed system that involve a chemical
reaction. During a chemical reaction, some chemical
bonds that bind the atoms into molecules are broken
and new ones are formed. The chemical energy
associated with this process is usually different for the
reactants and products.

393,520 kJ 241,820 kJ
1 kmol C 1 kmol H
at 25oC, 1 atm CO2 at 25oC, 1 atm H2O (g)
Combustion at 25oC, 1 atm Combustion at 25oC, 1 atm
Chamber Chamber
1 kmol O2 1 kmol O2
at 25oC, 1 atm at 25oC, 1 atm

First Law of Thermodynamics

The first law of thermodynamics states that in any

closed system, energy is conserved. Which means that
energy cannot be created nor destroyed, but it can only
change forms. Meaning:

∆Esys = 0 and ∆Eproducts = -∆Ereactants

The molecules of a closed system possess energy in

various forms such as sensible and latent energy,
chemical energy, and nuclear energy. All of these forms
must balance out in the reactants and products to give
the system a net energy of zero.

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 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 = Σ∆Hf (products) - Σ∆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.

Standard Reference State

Since composition of a system at the end of a process is

no longer the same as that at the beginning of the
process, there’s a need to use a standard condition in
which to make the measurements from. This standard
condition is called the standard reference point, which
are 25oC and 1 atm.
atm.

The superscript “°” is used to indicate property values at

the standard state. The defined equation above, under
standard conditions, becomes:

∆H° = Σ∆H°f(products) - Σ∆H°f(reactants)

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 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) Æ 8 CO2 + 9H2O(l) + 3.76aN2
C8H18 +a
Balance of oxygen : get a = 12.5
2. Energy analysis hC = HP – HR
_ _
HR = ∑N hf ,R = (Nhf)C8H18
o o

_ _ _
HP = ∑N hfo ,P = (Nhfo)CO2 + (Nhf)H2O
o

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 Table A-
A-26 Enthalpy of Formation
_
hfo ,CO = -393,520 kJ/kmol
2
kJ/kmol
_
hfo,H2O = -285,830 kJ/kmol
kJ/kmol
_
ho = - 249,950 kJ/kmol
kJ/kmol
f ,C8H18

Enthalpy of combustion = - 5,471,100 kJ/kmol C8H18

= -47,891 kJ/kg C8H18

Disscussion: This is the HHV of liquid C8H18 in Table A-27

Enthalpy of formation has 2 values : 1. for vapor vapor phase 2. for liquid vapor
phase -the different = laten heat of vaporization

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 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 + ΣHi = ΣHe
Qcv = HP – HR
Qcv = - 393,520 kJ
HR = 0 ; elements @ ref. state
Enthalpy of Formation of CO2
= - 393,520 kJ/kmol

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 Heating Value of Fuel

= the amount of heat released when a fuel is burned completely in

SSSF process and the products returned to the state of the
reactants…..
= absolute value of the enthalpy of combustion of the fuel:
Heating value = |hC| kJ/kg fuel
Higher heating value, HHV,:
H2O in products is in LIQUID form
Lower heating value, LHV,:
H2O in products is in Vapor form
HHV = LHV + (mhfg)H2O (15.7)
m = mass fo water in the products per unit mass of fuel
hfg = the enthalpy of vaporization of water at the specified temp.

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15.4 First Law Analysis of Reacting System
SSSF Process: (see Chapter 4 the first law) Æ ∆KE~0, ∆PE~0
o o _ o o _
Qcv + Σ n i h i = Wcv + Σ n e h e ........(15 - 8) per rate of mole eqn.
_ _
Qcv + ΣN i h i = Wcv + ΣN e h e ...... (15 - 9) per unit mole eqn.
(i = Reactants, and e = Products)
_ _ _
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 = ΣN e h e - ΣN i h i
= H Pr od − H Ract .........(15 - 11)

Closed System Æ ∆KE~0, ∆PE~0

Q12 = W12 + (U 2 − U1 )
Q12 = W12 + (U Pr od − U Re act )........(15.....)
from U = H − PV
_ _ _
Then U = N{h of + (h− h o )} − PV
_ _ _ _
or U = N{h of + (h− h o ) − P v}...........(15....)
_
Q there is no u of Provided in tables

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 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 Æ AF Æ mass flow rate of air
2. Energy balance: SSSF Q = HP – HR

- Stochiometic combustion equation based on 1 kmol of propane

a(O2 + 3.76 N2) Æ 3CO2 + 4H2O + 3.76aN2
C3H8 (l)+a
Balance of oxygen : get a = 5
- 150% theoretical air combustion equation based on 1 kmol of propane
with 90%CÆCO2 + 10%CÆCO
(1.2*5)(O2 + 3.76 N2) Æ (0.9*3)CO
C3H8 (l)+(1.2*5) (0.9*3)CO2 + (0.1*3)CO + 2.65O2 + 4H2O + 28.2N2
(a) AF = mair/mfuel = (NM)air/(NM)fuel = ………………. = 25.53 kg air/kg fuel
mass flow rate of air, mdot,air = mdot,fuelAF
= (0.05 kg fuel/min)(25.53 kg air/kg fuel) = 1.18 kg air/min
Answer

15
 _ _
Qcv + ΣN i h i = Wcv + ΣN e h e
(i = Reactants, and e = Products, Wcv = 0)
_ _
Qcv = ΣN e h e − ΣN i h i
_ _ _ _ _ _
where h = h of + (h − h o ), (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 (kJ/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol)
C3 H 8 (l ) - 118,910 0 NA NA
O2 0 8,682 8,150 49,292
N2 0 8,669 8,141 47,073
H 2O( g ) - 241,820 9,904 NA 57,999
CO2 - 393,520 9,364 NA 71,078
CO - 110,530 8,669 NA 47,517
_ _ _
Remark : h of ( g ) = h of (l ) + h fg

Substitute, Qcv = 363,880 kJ/kmol fuel Æ 8,270 kJ/kg fuel Æ 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: Æ PV = NRuT Æ P2

2. Energy balance: SSSF

Q = UP – UR
= (Hp-PPV) - (HR-PRV)

16
(a) Combustion equation:
CH4 (g)+ 3O2 Æ CO2 + 2H2O + O2
Nreact = 1 + 3 = 4 kmol, Nreact = 1 + 2 + 1 = 4 kmol, Æ N1 = N2
Assume ideal gas for all gases:
State 1 (Reactants) P1V = N1RuT1 (1)
State 2 (Products) P2V = N2RuT2 (2)
eqn(2)/eqn(1) P2 = (T2 /T1)*P1 = (1,000K/298K)(1atm) = 3.36 atm
answer

First law : Q12 = W12 + (U 2 − U 1 )

W12 = 0 : Q12 = (U Pr od − U Re act )
_ _ _
from U = H − PV = N{h of + (h− h o )} − PV
_ _ _ _
or U = N{h of + (h− h o ) − P v}
_
Ideal gas P v = Ru T
_ _ _
then U= N{h f + (h− h o ) −
o
Ru T }
_ _ _
from property tables get valus of h f , ho
o
of each gas and h at each state
substitute in equation above - - >
Amount of heat transfer out = - Q12 = 717,590 kJ/kmol CH 4
or = 717,590/16 = 44,850 kJ/kg CH 4 Answer

17
 15.5 Adiabatic Flame Temperature
Adiabatic Flame Temperature = Maximum limit of combustion
gas temperature of each Air – Fuel mixture
(Adiabatic Flame Temperature = Combustion Temperature)
Æ Qcv=0,Wcv=0 ,∆
,∆KE=∆
KE=∆PE=0 : 1st law
_ _
Qcv + ΣN i h i = Wcv + ΣN e h e
_ _
ΣN i h i = ΣN e h e
_ _ _ _
_ _
ΣN R {h f + (h− h o )}R
o
= ΣN P {h f + (h− h o )}P
o

To Calculate the adiabatic flame temperature, TP

1. Write the combustion equation
2. Apply energy balance (1st law)
3. Solving by trial- and-error technique by assume a value of TP get values…
trial-and- values…and
substitute in (2) ….LHS = RHS ..if not try new TP …. (in good procedure we can
interporate the former value to get the right value of TP

Trail and error procedure

LHS - RHS = Error
• What is your first guess of T T
• What should be the 2nd trial.
• How about the 3rd, 4th ......
c T2 E2
• When/how to interporate Tc
ratio
n Ta -Ea
rpo
Inte
T2 Tb -Eb
T2 0.0
b Tb
Tc +Ec

a
8 Ta
T2 = 342 oC
mi =1.263 kg

-Ea -Eb E=0 +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

1. Combustion equation equation based on 1 kmol of octane

C8H18 +12.5(O2 + 3.76 N2) Æ 8 CO2 + 9H2O + 47N2
at TR = 298K at TP = ?

2. Energy balance: HR = HP
_ _
Qcv + ΣN i h i = Wcv + ΣN e h e
_ _
ΣN i h i = ΣN e h e
_ _ _ _ _ _
ΣN R {h of + (h − h o )}R = ΣN P {h of + (h − h o )}P
_ _
o
Q reactants are at reference state (h − h ) R = 0
_ _ _ _
ΣN R {h of }R = ΣN P {h of + (h− h o )}P

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 (b) 400% theoretical air : combustion equation:-.
Combustion equation equation based on 1 kmol of octane
C8H18 +4.0x12.5(O2 + 3.76 N2) Æ 8CO2 + 9H2O + (3.0x12.5)O2 + 4.0x47N2
at TR = 298K at TP = ?
by trial and error of TP
Adiabatic flame temperature = 962 K ……………………..answer

(C) 90% theoretical air : combustion equation:-.

Combustion equation equation based on 1 kmol of octane
C8H18 +0.9x12.5(O2 + 3.76 N2) Æ aCO2 +bCO + 9H2O + 0.9x47N2
at TR = 298K at TP = ?
C and O balance Æ a = 5.5 and b = 2.5
by trial and error of TP
Adiabatic flame temperature = 2,236K ……………………..answer

Trail and error procedure

LHS - RHS = Error
• What is your first guess of T T
• What should be the 2nd trial.
• How about the 3rd, 4th ......
c T2 E2
• When/how to interporate Tc
ratio
n Ta -Ea
rpo
Inte
T2 Tb -Eb
T2 0.0
b Tb
Tc +Ec

a
8 Ta
T2 = 342 oC
mi =1.263 kg

-Ea -Eb E=0 +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 (kJ/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol)
C8 H18 (l ) - 249,950 0 NA NA
O2 0 8,682 ............ ............
N2 0 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
_ _ _ _
ΣN R {h of }R = ΣN P {h of + (h− h o )}P
_ _ _ _ _ _ _ _ _ _
( Nh of ) C8 H18 = {N (h of + h − h o )}CO2 + {N (h of + h − h o )}H 2O + {N (h of + h − h o )}N 2
_ _
1x(−249,950) = {8(−393,520) + h − 9,364) CO2 + {9(−241,820) + h − 9,904)}H 2O
_ _
+ {47(0 + h − 8,669)}N 2

(a) Adiabatic flame temperature = 2,395 K ………………..answer

21