CHAPTER 9

ENERGY BALANCES
ON
REACTIVE PROCESSES

1
 Introduction
• The importance of energy balance on reactor:
To tell the process engineer how much heating
or cooling requires in order to operate at the
desired conditions.
• Consequences of unstable heat on a reactor:
Failure of the reactor temperature control
system which can lead to
 rapid overheating
 possibly an explosion.

2
Exothermic vs. Endothermic Reaction
Exothermic Reaction Endothermic Reaction

More energy is released when the More energy is required/ adsorbed to

product bonds form than it took to break the reactant bonds than it took
break the reactant bonds. to form the product bonds.

Energy (heat or work) must be Energy (heat or work) must be added

transferred away from the reactor to to the reactor to keep the reactor
keep the temperature below a value temperature (and hence the reaction
that leads to safety and product rate) from decreasing; unprofitable.
quality problems.

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 Heat of Reaction
• Definition:

The heat of reaction (enthalphy of reaction),

(T,P), is the enthalphy change for a process in
which stoichiometric quantities of reactants at
temperature, T and pressure, P react completely
in a single reaction to form products at the same
temperature and pressure.

4
 Heat of Reaction (cont’d)
Consider a reaction:

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 Heat of Reaction (cont’d)

• One O-O bond and two H-H bonds broken.

System absorbs energy, Usystem and Hsystem
increase from reactants to transition state.

• 4 O-H bonds are formed. System releases

energy, Usystem and Hsystem decrease from
transition state to products.

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 Heat of Reaction (cont’d)
Suppose stoichiometric quantities of the reactants
(2 mol H2 + 1 mol O2) react completely, with the
reactants starting at specified T and P and the
products (2 mol H2O) ending at the same T and P.

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 Heat of Reaction (cont’d)
The change in enthalpy from reactants to products,

is the heat of reaction.

For stoichiometric quantities of H2 and O2 reacting

completely at T=25ºC and P =1 atm,

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 Heat of Reaction (cont’d)
Negative
more energy released by product bond formation
than absorbed when reactant bonds break. The
reaction is therefore exothermic.

For example:

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 Heat of Reaction (cont’d)
If 5 mol H2/s consumed in which the reactants
and products are at 25°C, then the energy
balance is

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 Standard Heat of Reaction

• is the heat of reaction when

reactants are reacting completely to form
products at a specified reference temperature
and pressure, usually at 25°C and 1 atm.

• (The “standard” part, which refers to the

specified temperature and pressure, is denoted
by the superscript°.)

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 Heat of Reaction (cont’d)
If A is a reactant or product, vA is its stoichiometric
coefficient (negative for reactant, positive for product), and
nA,r is mol of A are consumed or generated at 25°C and 1
atm, then the enthalpy change is

where ξ is the extent of reaction.

For an open system, dots would go above the ∆H, nA,r, and
ξ.
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 Heat of Reaction (cont’d)
• Properties of the heat of reaction (p. 443)
 exothermic reaction if negative,
 endothermic reaction if positive;
 ΔĤr (T, P) nearly independent of pressure at low
and moderate pressures;
 the value of heats of reaction depends on how the
stoichiometric equation is written (e.g.,standard
heat of the reaction 2A→2B is twice that of A→B)
 the value of heat of reaction depends on the
states of aggregation (g, l, s) of the reactants and
products.
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Class Discussion

• EXAMPLE 9.1-1

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 Internal Energy of Reaction
• If a reaction take place in a closed reactor at constant
volume, the heat released/absorbed is determined by the
change in internal energy between reactants and
products, not enthalpy.
• The internal energy of reaction, ΔÛr(T) is the difference
Uproducts – Ureactants if stoichiometric quantities of
reactants react completely at temperature T.
• Suppose a reaction occurs by assuming ideal gas
behavior and neglecting specific volume where υi is the
stoichiometric coefficient of species i, thus the internal
energy of reaction is related to the heat of reaction
(closed system) is given by

15
Internal Energy of Reaction (cont’d)

• For example, for the reaction

• The internal energy of reaction is

∆Ûr (T) =

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Class Discussion

• EXAMPLE 9.1-2

17
 Hess’s Law
General statement of Hess’s Law:
If the stoichiometric equation for reaction 1 can be
obtained by algebraic operations (multiplication by
constants, addition, and substraction) on stoichiometric
equations for reaction 2, 3,…, then the heat of reaction
ΔĤr1 can be obtained by performing the same operations
on the heat of reactions ΔĤr2, ΔĤr3,…

In the other words:

Hess’s law states that if you can obtain a stoichiometric
equation as a linear combination of the stoichiometric
equations for other reactions, you can determine its
heat of reaction by performing the same operations on
the heats of the other reactions.
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• For example, suppose we experimentally determine
the following two standard heats of reaction:

• We want to determine the heat of the reaction A →

B + 2D but can’t carry out that reaction
experimentally. We observe, however, that we can
obtain that stoichiometric reaction as [1] + 2x[2]:

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Class Discussion

• EXAMPLE 9.2-1

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 Formation Reactions and
Heats of Formation
Formation reaction:
A reaction in which a compound is formed from its elemental
constituents as they occur in nature [e.g., O2(g), and not O].
Standard heat of formation :
The enthalpy change associated with the formation of 1 mole
of the compound at a reference pressure and temperature
(25˚C, 1 atm). Standard heats of formation of many species
are given in Table B.1. For example, liquid benzene:

The standard heat of formation of an elemental species [C(s),

H2(g), O2(g),...] is zero. 21
 Formation Reactions and
Heats of Formation (cont’d)
We can use Hess’s law to show that for any
reaction a hypothetical process path can be
drawn from reactants to elements to products:

22
 Formation Reactions and
Heats of Formation (cont’d)
It may be shown using Hess’s Law that:
if vi is the stoichiometric coefficient of the ith species
participating in a reaction (+ for products, - for
reactants) and is the standard heat of formation
of this species

and since enthalpy is a state function,

23
Class Discussion

• EXAMPLE 9.3-1

24
 Heat of Combustion
Standard Heat of Combustion :
Heat of the combustion of any substance with oxygen to
yield specified products [e.g., CO2 (g), H2O (l), SO2 (g)
and N2 (g)], with both reactants and products at 25°C
and 1 atm.

The standard heats of combustion can be found in

Table B-1. For example, for acetone:

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 Heat of Combustion (cont’d)
If a reaction only involves combustible reactants and
products, then we can calculate the standard heat of the
reaction from tabulated standard heats of combustion.
The formula is:

where vi is the stoichiometric coefficient of the ith

reactant or product species and is the standard heat
of combustion of that species. The formula looks like the
one involving heats of formation, except that
summations are reversed (reactants - products).

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 Heat of Combustion (cont’d)
This formula is derived from Hess’s law in the
same way that the heat of formation formula was
derived:

27
Class Discussion

• EXAMPLE 9.4-1

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Energy Balances on Reactive
Processes
To perform energy balance calculation on a reactive
system, you must include the following aspects:
1. Draw and label flowchart
2. Use material balances and phase equilibrium
relationship to determine the amount of stream
component and flow rates
3. Choose reference states for specific
enthalpy/internal energy
4. Prepare and fill the inlet-outlet enthalpy table
5. Calculate
6. Calculate
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Energy Balances on Reactive
Processes
Two methods are commonly used to choose
reference states for enthalpy calculations:
1. Heat of Reaction Method
- Generally preferable when there is a single
reaction for which is known.
2. Heat of Formation Method
- Generally preferable for multiple reactions
and single reactions for which is not
readily available.
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Energy Balances for Heat of Reaction Method

Energy balance equation for heat of reaction

method:

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Energy Balances for Heat of Reaction Method
(cont’d)
The process path that leads to this expression for
(recalling that the reference states are the reactants and
products at 25˚C and 1 atm) is

Writing and substituting for each of the

three enthalpy changes on the right leads to the given
expression for
32
Energy Balances for Heat of Formation Method

Energy balance equation for heat of formation

method:

33
Energy Balances for Heat of Formation Method
(cont’d)

The process path for (recalling that the reference

states are the elemental species at 25°C and 1 atm) is

Writing and substituting for each of the

two enthalpy changes on the right leads to the given
expression for
34
Class Discussion

• EXAMPLE 9.5-1
• EXAMPLE 9.5-2
• EXAMPLE 9.5-3
• EXAMPLE 9.5-4

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THANK YOU….

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