Chemical Engineering Principles - Second Year Dr.Ali.N.

Khalaf

1 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
1- Introduction:
The large changes in enthalpy and internal energy throughout a chemical reaction
require significant heat transfer (heating or cooling) from the reactor in order to
eventually maintain the reactor under optimum operating conditions. This chapter
demonstrates how to calculate the heat of reaction at a specific temperature and
illustrates how to estimate the heat of reaction from the heat of formation. The energy
balances for a reacting system using different methods are defined. Problems that
involve the application of combined material and energy balances are addressed.
Finally, a few applications, specifically, combustion, bioprocesses, and membrane
reactors, are discussed at length to practice the concepts further.

2-Heat of Reaction:
Heat of reaction (Enthalpy of reaction).The heat of reaction, ∆Hˆr(T, P), is the enthalpy
change for a process in which stoichiometric ratios of reactants at a given T and Pare
completely consumed and converted to products at the same T and P. Note that this
process starts with reactants and no products, and ends with all products (as all
reactants are consumed). An exothermic reaction is one for which ∆Hˆr(T, P)< 0; that
is, exothermic reactions carried out at constant T and P release heat. An endothermic
reaction is one for which ∆Hˆr(T, P)> 0; thus, heat must be input into the system in
order to sustain an endothermic reaction at constant T and P. The heat of reaction is
always reported per stoichiometric quantity of a reactant consumed or product
formed. The standard heat of reaction is the heat of reaction when both reactants and
products are at 1 atm and a specified reference temperature (almost always 25 oC).
Consider the following reaction:
aA+ bB→ cC+ dD

The standard heat of reaction ∆Hˆ0r(25)is calculated as the difference between the
product and reactant enthalpies when both reactants and products are at standard
conditions, that is, at 25°C and 1 atm. The symbol “o” denotes standard conditions.
Therefore,

…………………………………… (3.1)

Where ΔHof is the standard heat of formation. The reported ΔHRx applies to
stoichiometric quantities of each species. Consider the following example:

2 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
The enthalpy change for the given reaction is

If 150 mol/s of C was generated at 100°C and 1 atm, then

If ΔHRx(T) is negative, the reaction is exothermic; that is, energy must be removed
from the reactor to prevent the temperature from increasing. If ΔHRx(T) is positive,
the reaction is endothermic; that is, energy must be added to the reactor to prevent the
temperature from decreasing. The heat of reaction (ΔHRx (T, P)) is nearly
independent of pressure. The value of the heat of reaction depends on how the
stoichiometric equation is written and on the phase of the reactants and products.

3-Heats of Formation and Heat of Combustion:

The standard heat of reaction (𝛥𝐻𝑜 𝑟) can be calculated from the standard heat of
formation (ΔHof). The standard heat of formation is the enthalpy change associated
with the formation of 1 mol of the compound at 25°C and 1 atm. The values of ΔHof
for many compounds can be obtained from tabulated data (Table A.2). The standard
heat of reaction (𝛥𝐻𝑜 𝑟)from the heat of formation (∆Hif) of any reaction can be
calculated as:

Where
νiis the stoichiometric coefficient of reactant or product species i
ΔHof,iis the standard heat of formation of species i

The standard heats of formation of all elemental species are zero (H 2, O2, and N2).
The standard heat of reaction (𝛥𝐻𝑜 𝑟) of any reaction involving only oxygen and a
combustible species can be calculated as

This is the reverse of determining the heat of reaction from heats of formation, where
νiis the stoichiometric coefficient of reactant or product species i. (ΔHoc)i is the
standard heat of combustion of species i. If any reactants or products are combustion
products (i.e., CO2, H2O, SO2), their heats of combustion are equal to zero. For many

3 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
substances, it is much easier to measure the standard heat of combustion (ΔHoc) than
measuring the standard heat of formation (ΔHof). Consider the formation of pentane:

Carbon, hydrogen, and pentane can all be burned, and their standard heats of
combustion can be determined experimentally. Therefore,

The standard enthalpy of combustion is the enthalpy change when 1 mol of a reactant
completely burns in excess oxygen under standard thermodynamic conditions. The
standard heat of combustion of a species i. (ΔHoc)iis the enthalpy change associated
with the complete combustion of 1 mol of species i with oxygen at 25°C and 1 atm
such that all the carbon forms CO2 (g), all the hydrogen forms H2O (l), all the sulfur
forms SO2 (g), and all the nitrogen forms NO2 (g). The same value of standard heat of
reaction can be used to measure the standard heat of formation of pentane:

Since carbon and hydrogen are atoms, the magnitude of their standard heats of
formation is zero. Accordingly,

4- Extent of Reaction:
If nAr is the moles of A generated or consumed by a reaction at a temperature T and
pressure P, and vA is the stoichiometric coefficient of the reactant or product, the
associated enthalpy change is
…………………………………… (3.2)

Note that, as always, units must be consistent. Thus if units of ∆Hr (T, P)
areenergy/mole, x must be in units of moles; if instead ∆Hr. (T, P) is given in units of
Energy/mass, then ξ must be in units of mass.

The extent of reaction, ξ, is a measure of how far a reaction has proceeded:

…………………………………… (3.3)

Rearranging, the extent of reaction is expressed as

…………………………………….. (3.4)

4 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

The conversion of the reaction is defined is

(𝑛̇ 𝐴 )𝑖𝑛 − (𝑛̇ 𝐴 )𝑜𝑢𝑡

𝑥=
(𝑛̇ 𝐴 )𝑖𝑛
Then

−𝜉. 𝜈𝐴
𝑥= (𝑛̇ 𝐴 ) 𝑖𝑛
…………………………………………… (3.5)

Example 1:
The reaction stoichiometry and standard heat of the reaction on n-butane vapor is
shown here:

If 40 mol/s of CO2 is produced in this reaction and the reactants and products are all
at 25°C. The fresh feed to the reactor contains 20 mol/s of CO 2. Calculate the rate of
change in enthalpy ΔH (kJ/s).

The extent of reaction is calculated using the mole balance of CO 2:

Substitute the values of inlet and exit molar flow rates of carbon dioxide:

The extent of reaction is

The standard rate of change in enthalpy, ΔH, is

5- Calculation of Heats of Reaction from Hess's Law:

Statement: If the stoichiometric equation for a reaction can be derived from other
reaction equations (by multiplication by constants, addition and subtraction) then the
heat of reaction for the first reaction can be derived by performing the same algebraic
operations on the heats of reaction for the other reactions.
5 Chemical Engineering Department- University of Basrah
Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Example 2:
Calculate the heat of combustion for C2H6 from the following reactions:

The reaction for combustion of ethane is as follows:

- The first reaction minus the second reaction based on one mole reacted

The resulting reaction is added with the third one:

Accordingly, the heat of combustion of C2H6 is −1558.3 kJ

Example3:
Given

What is the heat of reaction for?

6 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

6- Energy Balances on Reactive Processes:

 Reactions in Closed Processes:
If the reaction is taking place in a closed system of constant volume, the change in the
internal energy of reaction, ΔUr, is given as

………………… (3.6)

The change in the number of moles is equivalent to the change in the number of
stoichiometric coefficients between the product and the reactant. Note: This last
relation assumes that the gases behave as ideal gases, and that the molar volumes of
the liquid or solid components are small.
If there are no gaseous species involved in the reaction,

Example 4:
Calculate the standard heat of the reaction of the following reaction

The internal energy of reaction at standard conditions (25°C, 1 atm) is ΔUr = −418
kJ/mol.

Substitute known quantities:

 Steady State Process:

For the usual case of a continuous process, the quantity of interest is ∆Hreactor, the rate
of enthalpy change due to the occurrence of the reaction. This rate is the difference
between the enthalpy out flow in the product stream at the outlet conditions from the
reactor and the enthalpy inflow with the reactants at the inlet conditions. The
approach to calculation of ∆Hreactor uses different paths for the heat of reaction and the
heat of formation method.

7 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
A- Heat of Reaction Method:
The heat of reaction method is ideal when there is a single reaction for which (𝛥𝐻𝑜 𝑟)
is known. This method requires calculation of the extent of reaction, ξ. The extent of
reaction can be obtained by performing material balance for any reactant or product
for which the feed and product flow rates are known. The reference state is such that
all reactant and product species are at 25°C and 1 atm in the states for which the heat
of reaction is known (Fig.9.1).

Fig.9.1 rate of change in enthalpy for a reactive process.

For a single reaction at a reference state of 25°C and 1 atm while reactant and product
are at different inlet and exit temperatures

………………… (3.7)

Where ℎ̅𝑖 J/mol is the specific molar enthalpy of a definite component. For multiple
reactions, where the reference state is 25°C and 1 atm and the inlet and exit streams
are at temperatures other than the reference states ,

………………… (3.8)

A reference temperature other than 25°C can be considered in this case, and the heat
of reaction should be calculated at the new reference state:

8 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
………………… (3.9)

The heat of reaction at any temperature (T)

………………… (3.10)

Example 5:
Hundred moles per minute of ammonia (NH 3) and 200 mol/min of oxygen (O2) at
25°C are fed into a continuous reactor in which ammonia is completely consumed.
The product gas emerges at 300°C. Calculate the rate at which heat must be
transferred to or from the reactor to maintain the reactor temperature at 300°C. The
standard heat of reaction for the gas phase oxidation of ammonia is

Solution:

Using the energy balance equation for an open system,

Since there is no shaft work in the process, no moving parts, no change in elevation
between inlet and exit stream, and no change in velocity of inlet and exit streams, the
general energy balance equation is reduced to

The heat of reaction method,

Material balance (Extent of reaction method)

9 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Because of complete conversion of ammonia (x= 1), no ammonia exits in the reactor
exit stream; 𝑛̇ NH3 = 0

Substituting the values of the extent of reaction in the material balance equation will
give the following molar flow rate of exit stream components:

𝑛̇ NH3 = 0.0 mol/min, 𝑛̇ O2 = 75 mol/min, 𝑛̇ NO = 100 mol/min, 𝑛̇ HO2 = 150 mol/min

Energy balance(Heat of reaction method)

Reference temperature: 25°C

Heat capacities of components involved in the process Cp (J/mol.C) are

Substitute known values:

10 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

The change in sensible heat is in the units of J/mol, so it should be divided by 1000 to
convert to the units of kJ/mol to be added to heat of reaction. Accordingly, the heat
transfer rate is

The heat released from the reaction process is −19,600 kJ/min (−326 kW).

B-Heat of Formation Method:

This method is usually followed when (𝛥𝐻𝑜 𝑟) is not given or when multiple
reactions occur simultaneously. The heats of reaction terms (𝛥𝐻𝑜 𝑟) are not required
as they are implicitly included when heats of formation of the reactants are subtracted
from the products. For single and multiple reactions

…………………………………… (3.11)

11 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Figure 9.2heat of formation or element balance method.

Where ℎ̅𝑖 accounts for the change in molar enthalpy with T and phase +ΔHof(Figure
9.2).In this case we find the enthalpy of all of the compounds relative to the elements
at 25°C. No heat of reaction needs to be calculated at all. We then plug these
enthalpies directly into the energy balance expression. In the absence of kinetic and
potential energy, the energy balance equation is

Where the specific molar enthalpy of component i in the inlet streams is

………………… (3.12)

Specific molar enthalpy of component i in the exit streams is

………………… (3.13)

Example 6:
Gas phase reaction is taking place in a continuous reactor. Stoichiometric proportions
of CO2 and H2 are fed to the reactor at 400°C. The reaction proceeds to 80%
completion. Given 1 mol of carbon dioxide, estimate the heat that must be provided
or removed, if the gas exit steams are to be kept at 500°C. Perform the energy
balance using the heat of formation method.

12 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Solution:

The standard heats of formation at 25°C, Components of heat capacity and heats of
formation are given below:

Component balance is calculated using the extent of reaction method as follows:

From the fractional conversion of CO2,

13 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
(𝑛̇ 𝐴 )𝑖𝑛 − (𝑛̇ 𝐴 )𝑜𝑢𝑡
𝑥=
(𝑛̇ 𝐴 )𝑖𝑛

Accordingly, the number of moles of carbon dioxide leaving the reactor is

nCO2=0.2mol. The extent of reaction, ξ, is calculated by substituting nCO2=0.2mol in
the CO2 mole balance equation: 0.2 = 1 − ξ.
Solving for the extent of reaction, ξ = 0.8.

To calculate moles of exit components, substitute values of the extent of reaction in

the mole component balance equations given earlier. The following results are
obtained:

nH2=0.8mol., nCH4=0.8mol., nHO2=1.6 mol

In this case, no heat of reaction needs to be calculated at all. We write the energy
balance as follows:

Next, we compute the enthalpy of each component in each stream relative to their
elements. The compound is formed from its elements at 25°C (this is the heat of
formation), and then we raise the temperature of the compound up to the temperature
of the stream.
The specific enthalpy of outlet compounds

14 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Thus, the sum of all of the outlet specific enthalpies is

The specific enthalpies of inlet compounds

Thus, the sum of all of the inlet enthalpies is

Finally, from the energy balance we obtain

15 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
We can solve the previous problem by different approach. In this approach, we use a
component energy balance and the path:

Reactants, 400oC ---->Reactants, 500oC ---->Products, 500oC

This requires that we know the heat of reaction at 500 oC

Reference temperature = 500°C

In this approach, we perform the energy balance using the heat of reaction method at
the reference temperature of 500°C: Tref = 500°C. This requires knowledge of the heat
of reaction at 500°C. The energy balance for this process includes the sensible heat to
change the temperature of everything in the inlet stream from 500°C to 400°C and the
heat of reaction at 500°C times the extent of reaction. Recall that the heat of
reactionwas expressed in kilojoules per mole, where the mole basis was per molar
extent of reaction:

Substituting the proper values,

The heat of reaction at 500°C is then

The ΔCp for the reaction is immediately obtained from the Δ row for use in
integration from one temperature to another:

16 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
The heat of reaction at 500°C is

Now the sensible heat term (first terms shown in the earlier equation) includes only
the moles of those compounds in the inlet stream. This gives

So finally, substitute estimated inlet, exit enthalpies and heat of reaction in the
general energy balance equation shown here:

The heat calculated using the two methods are equal.

7- Combustion Processes:
A substance that produces light and heat energy when burnt in excess air is called a
fuel. The main elements present in fuels are carbon and hydrogen. During the
combustion process of fuel, carbon gets converted into carbon dioxide and hydrogen
gets converted into water. The product of combustion fuels has less heat content than
the reactants. Therefore, fuels release heat energy during the combustion process.
Fuels are generally used for heating and producing energy. Fuels can be classified as:
1. Solid fuels
2. Liquid fuels and
3. Gaseous fuels.

17 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

 Solid Fuels
Solid fuels are classified into two types; primary solid fuels and secondary solid
fuels. The fuel which comes from the natural source is called primary fuel. The
examples of primary fuels are coal, wood, bagasse etc. The fuel which is derived
from the natural solid fuel is called secondary fuel. The examples of secondary solid
fuels are charcoal, coke, etc. Generally, the solid fuels contain carbon, hydrogen,
non-combustible ash, water and sulphur.
 Liquid Fuels
The liquid fuels are also classified into two types; primary liquid fuel and secondary
liquid fuel. The example of primary liquid fuel is petroleum and the examples of
secondary liquid fuels are Synthetic petrol, Diesel, Kerosene, Gasoline, etc.
Generally, the solid fuel contains Carbon, Hydrogen, Nitrogen, Oxygen and Sulphur.

 Gaseous Fuels
The gaseous fuels are classified into two types; Primary gaseous fuel and secondary
gaseous fuel. The example of a primary gaseous fuel is Natural gas and the examples
of secondary gaseous fuels are producer gas, water gas, LPG, coal gas and biogas.
The natural gas contains 80% to 90% methane and the rest is ethane and propane. It
also contains small amount of other gases like light hydrocarbon and acetylene.

A combustion process in which elements present in the fuel are completely get
converted into products is called complete combustion. For example, carbon reacts
with oxygen to form carbon dioxide is a complete combustion process.

Combustion or burning is an exothermic chemical reaction between a fuel and an

oxidant accompanied by the production of heat and conversion of chemical species.
For example, the complete combustion of methane is given by the following reaction:

The result is carbon dioxide and water vapor, with a standard enthalpy of reaction at
25°C and 1 atm being −242 kJ/mol; complete combustion is almost impossible to
achieve. As actual combustion reactions come to equilibrium, a wide variety of major
and minor species will be present, such as carbon monoxide. Total inlet oxygen is the
sum of the theoretical oxygen and excess oxygen. The equation for percent excess air
is as follows:

(moles of air) fed = (moles of air) theoretical (1 +% excess air) ………… (3.14)

Theoretical oxygen is the calculated amount of oxygen required to oxidize a

compound to its final oxidation products. In the methane oxidation reaction, 2 mol of
18 Chemical Engineering Department- University of Basrah
Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
oxygen is required to oxidize 1 mol of methane. For 100 mol of CH 4 the theoretical
oxygen is calculated as follows:

If the oxygen fed to the reactor is in excess amount than the theoretical oxygen, then
the percent excess oxygen is

(moles of O2) fed = (moles of O2) theoretical (1 +% excess O2)………… (3.15)

Calorific Value of Fuels:

It is defined as the total amount of heat released when a unit mass of fuel is
completely burnt in the presence of air. The calorific value is also known as heating
value or energy value. It is the characteristics of a combustible substance. The
calorific value of fuel is always positive. It is measured in units of energy per unit of
substance, usually in mass. The units may be expressed as kcal/kg or kJ/kg.
For examples, the calorific value of Methane = 50 MJ/kg, kerosene = 43 MJ/kg and
Coal = 20 MJ/kg. The calorific value of fuel is commonly determined by using Bomb
Calorimeter.
When a fuel is burnt, hydrogen present in the fuel reacts with oxygen supplied from
the air and results in the formation of water in the process. Because of this reason, the
latent heat of vaporization is lost.
Hence, this amount of heat is not available for any useful purpose. The latent heat of
vaporization of water can be made available for useful purpose if the water vapor in
the flue gas is removed completely by the process of condensation.

The net calorific value (NCV) is also known as low heating value (LHV). It is the
calorific value of the fuel which is determined in the presence of water. It is
expressed in kJ/kg.High heating value (HHV, is the calorific value of the fuel which
is determined in the absence of water vapor. It is expressed in unit of kJ/kg. The
relation between HHV and LHV may be expressed as:

19 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

…………………………….. (3.16)

If fuel contains a mixture of combustible substances, its heating value (lower or

higher) is

Where (HV)iis the heating value of the ith combustible substance. If the heating value
expressed in units of (energy/mass),then xi are the mass fractions of the fuel
components, while if the units of heating value are (energy/mol) then xi are the mole
fractions of the components.

20 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
Example 7: Combustion of Carbon Monoxide
Carbon monoxide (CO) at 10°C is completely burned at 1 atm pressure with 50%
excess air that is fed to a burner at a temperature of 540°C.The combustion products
leave the burner chamber at a temperature of425°C. Given 100 mol/h of carbon
monoxide, calculate the heat evolved from the burner.
Solution
Known quantities: CO and air inlet temperature and pressure, complete
combustion, 50% excess air.
Find: Heat evolved from the burner.
Analysis: Perform material balance and then energy balance.
Material balance
Basis: 100 mol/h of inlet CO

21 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

22 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

23 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Summary of the calculated enthalpies is shown in the following table:

24 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Example 8:
Methane and oxygen are fed in stoichiometric proportions to a continuous reactor at
25°C and 1 atm. The reaction proceeds to completion and the effluent stream is found
to be at 200°C. Calculate the heat transfer rate from the reactor. On the basis of 1 mol
of methane set up an energy balance using the elements balance approach. The
combustion reaction of methane is as follows:
CH4 + 2O2 → CO2 + 2H2O

Material balance:
Basis: 1 mol/s of methane and 2 mol/s of oxygen

25 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
Since the reaction goes to completion and the feed enters the reactor in stoichiometric
proportions, the exit molar flow rate of methane and oxygen are zero. Based on the
balance reaction stoichiometry for 1 mol of carbon dioxide reacted, 1 mol of carbon
dioxide and 2 mol of water areproduced. The schematic diagram of the combustion
process is shown below.

Energy balance:
The specific molar flow rate and molar enthalpies of inlet and exit components are
arranged in the following table:

From the following data

26 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
The general energy balance equation is

Specific molar enthalpy of inlet streams at T1 = 25°C is

Specific molar enthalpy of inlet oxygen at T2 = 25°C is

Specific molar enthalpies of the exit streams at T3 = 200°C are

Using the values calculated by the procedures shown earlier, we simply plug the
values of specific enthalpies into the general energy balance equation using the heat
of formation approach

27 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
Substitute the calculated values of specific enthalpies:

8- Adiabatic Flame Temperature:

When a fuel is burned, consider able amount of energy is released. Some of this
energy is transferred as heat through reactor walls, and the remainder raises the
temperature of reaction products; the less heat transferred, the higher the product
temperature. The highest achievable is reached if the reactor is adiabatic and all the
energy released by the combustion goes to raise the temperature of the combustion
products. This temperature is called the Adiabatic Flame Temperature, Tad.

When you calculate the adiabatic reaction temperatures for combustion reactions, you
assume complete combustion occurs, but equilibrium considerations may dictate less
than complete combustion in practice. For example, the adiabatic flame temperature
for the combustion of CH4 with theoretical air has been calculated to be 2010°C;
allowing for incomplete combustion at equilibrium, it would be 1920°C. The actual
temperature when measured is 1885°C.

The adiabatic reaction temperature tells you the temperature ceiling of a process. You
can do no better, but of course the actual temperature may be less. The adiabatic
reaction temperature helps you select the types of materials that must be specified for
the equipment in which the reaction is taking place. Chemical combustion with air
produces gases with a maximum temperature of roughly 2500 K,but the temperature
can be increased to 3000 K with the use of oxygen and more exotic oxidants, and
even this value can be exceeded, although handling and safety problems are severe.

Suppose 𝑛̇ 𝑓 (mol/sec) of a fuel with heat of combustion ∆𝐻𝑜 𝑐 is burned completely

with pure oxygen or air in continuous adiabatic reactor. If the reference state of the
feed and products are those used to determine ∆𝐻𝑜 𝑐 , the enthalpy change from inlet
to outlet is determined from

…………………….. (3.17)

28 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
Since the reactor is adiabatic 𝑄 =̇ 0 in the energy balance. If shaft work and kinetic
and potential energy change (𝑊̇ 𝑠 . ∆𝐸̇𝑘 . ∆𝐸̇𝑝 ) are negligible compared to each of the
first two terms, the energy balance simplifies to

This leads to

Example9:
Calculate the adiabatic flame temperature of liquid butane burned with 30% excess
air. Both the air and liquid butane enter at 25oC

Solution:
First we will perform the mass balance calculations so that we know the number of
moles of each component in the inlet and outlet streams.

Mass Balances
In: noO2 = (1 mol) (6.5) (1.3) = 8.45 mol note: 1.3 is the 30% excess O2
noN2 = (79/21) noO2 = 31.79 mol

Out: nO2 = 8.45 mol - (1 mol) (6.5) = 1.95 mol

nCO2 = (1 mol) (4) = 4 mol
nH2O = (1 mol) (5) = 5 mol
nN2 = noN2 = 31.79 mol

Energy Balances
Next we will set up the energy balance.

Q = Hout - Hin
We will calculate the change in enthalpy from the inlet to the outlet stream by using a
path of our choice. As was explained at the top of this page, the easiest path is to
react the materials at the inlet temperature and then heat everything in the outlet
stream up to the final temperature.
29 Chemical Engineering Department- University of Basrah
Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Where Q has been set to zero since we are finding the maximum or adiabatic flame
temperature.

The heat of reaction at 25oC is easily found from the heat of combustion of propane.
Note that it is not exactly the heat of combustion because the water formed by the
reaction is vapor whereas it must be in the liquid phase for the heat of combustion to
apply directly.
∆Hr = ∆Hc + 5∆Hvap, H2O (25oC) = -2855.6 kJ/mol + 5(44.01 kJ/mol) = -2635.5 kJ/mol

The sensible enthalpy term is evaluated from the heat capacities of everything in the
outlet stream. Don't forget to include the nitrogen in the air and the excess oxygen.
All of these will be in the product stream and will absorb some of the heat produced
by the combustion process, thereby affecting the final computed adiabatic flame
temperature. Combining the heat of reaction term with the heat capacity terms shown
in the energy balance gives,

The heat capacities will be a function of temperature. The final temperature, the
upper limit for the integrals, will therefore be the only remaining unknown. We can
therefore solve for the adiabatic flame temperature using an appropriate trial and
error method.

------------------------------------------------------------------------------------------------------

30 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf

Homework Problems:
1-Liquid methanol is to be burned with 100% excess air. The engineer designing the
furnace must calculate the highest temperature that the furnace walls will have to
withstand so that an appropriate material of construction can be chosen. Perform this
calculation, assuming that the methanol is fed at 25°C and the air enters at 100°C.
Assuming complete combustion.

Answer: (Tad=1257°C).

2-Methane at a molar flow rate of 55 mol/min is burned with dry air. A partial
analysis of the exit gas reveals that the mole fraction of nitrogen is 0.85 on a dry
basis, and the molar flow rate of the dry exit gas is 600 mol/min. The fractional
conversion of methane is 90%, and the molar ratio of CO2 to CO is 10. Based on the
given information, determine the percent excess air fed to the combustion chamber
and the mole fraction of water in the exit gas stream. Answer :( 23%)

3- Superheated steam at 40 bar and 350°C is produced from liquid water at 40 bar
and 50°C in a methane-fired boiler. To ensure complete combustion of the methane,
10% excess air is provided. Both methane and combustion air enter the boiler at
25°C. Determine the outlet temperature of the flue gas from the boiler, if 19.85
kg/min of superheated steam is produced from the combustion of 1.4 kg/min of
methane. Assume the boiler is perfectly insulated.
Answer :( 458°C)
4- Ammonia is synthesized through the reaction of nitrogen with hydrogen. The
reactor feed temperature is 400°C. The fresh feed consists of 1 mol% argon and
stoichiometric amount of nitrogen and hydrogen. The fractional conversion of N 2 to
NH3 in the reactor is 0.15. The converter is operated adiabatically and the heat of
reaction at 400°C is −53 kJ/mol. Given 100 mol of feed stream, estimate the
temperature of the effluent gases from the converter. The average heat capacities at
the pressure of the reactor for ammonia, hydrogen, nitrogen, and argon are 49.4, 29.5,
31.0, and 20.8 (J/mol °C), respectively.
Answer: (467.8°C)

5- Methane at 25°C is burned in a boiler furnace with 10.0% excess air. The air enters
the burner at a temperature of 100°C. Ninety percent of the methane fed is consumed;
the product gas is analyzed and found to contain 10.0 mol CO 2per 1 mol of CO. The

31 Chemical Engineering Department- University of Basrah

Chemical Engineering Principles - Second Year Dr.Ali.N.Khalaf
exhaust gases exit the furnace at 400°C.Calculate the rate of heat transferred from the
furnace, given that a molar flow rate of 100 mol/s CH 4is fed to the furnace.
Answer: (−58,626 kJ/s)
6- Propane (C3H8) enters a combustion chamber at 200°C at a rate of 100 mol/h. The
gas is mixed and burned with 50% excess air that enters the combustion chamber at
200oC. An analysis of the combustion gases reveals that 90% of the propane carbon
burns to CO2, with the remaining 10% forming CO, if the exit temperature of the
combustion gases is 200°C. The average specific heats of propane, oxygen, carbon
dioxide, carbon monoxide, and water vapor are 73.5, 29.4, 37.4, 28.6, and 34.7 J/mol
K, respectively. The standard heats of formation of propane, carbon dioxide, carbon
monoxide, and water vapor are −103.85, −393.51, −110.52, and −241.86 kJ/mol,
respectively. Determine the rate of heat transfer from the combustion chamber.
Answer :( −54 kW)
7- Liquid octane (C8H18) enters the combustion chamber of a gas turbine steadily at 1
atm and 25°C, and it is burned with air that enters the combustion chamber at the
same state. Determine the adiabatic flame temperature for a complete combustion at
400% theoretical air given 1 kmol octane. Assume constant heat capacities 45, 35, 30,
and 30 kJ/kmol K, for CO2, H2O, O2, and N2, respectively.
Answer: (977 K)

8- One mole of C8H14 and 14.0 mol of oxygen are placed into a lab scale batch
reactor. The reactor then is placed into a water bath at 25°C; the water bath contains
20.0 kg of water. The contents of the reactor are burned. The C8H14 combusts
completely to give H2O and CO2. At the end of the combustion, the water bath and
the reactor and its contents are at 90°C. Under these conditions, the water produced
during the combustion can be assumed to be completely in its liquid form. The top
surface of the batch reactor is insulated such that all heat lost from the reactor goes to
the water bath. What is the standard state heat of combustion of the C 8H14?
The following reaction took place:

Answer: (−5500 kJ/mol)

32 Chemical Engineering Department- University of Basrah