Energy Balance on

Reactive Processes
 Content
Introduction
Heat of Reaction or Enthalpy of Reaction
Relationship Between Enthalpy Change and Heat of
Reaction
Properties of Heat of Reaction
Hesss Law
Heats of Formation
Heats of Combustion
Energy Balance on Reactive Processes
 Introduction

In any reaction:
Energy is required to break the reactant chemical bond
Energy is released when product chemical bond is formed
Exothermic reaction
If energy required to break the reactant chemical bond is less
than energy released when product chemical bond is formed
the product molecules have lower internal energies than the
reactants at the same T and P (i.e H=-ve)
Heat of reaction must be released as heat or work to maintain
the operation temperature
Endothermic reaction
If energy required to break the reactant chemical bond is
larger than energy released when product chemical bond is
formed
the product molecules have higher internal energies than the
reactants at the same T and P (i.e H=+ve)
Energy is need by the process to maintain the operation
temperature
 Heat of Reaction or Enthalpy of Reaction: r (T,P)

Heat of reaction or enthalpy of reaction

- Enthalpy change for a process in which stoichiometric
quantities of reactant at T & P reacted completely in single
reaction to form a products at the same T & P.
- Stoichiometric quantities of reactant means molar amount of
the reactant numerically equal to their stoichiometric
coefficient.

In simple word;
Reactants and products: stoichiometric quantities
Complete Reaction
Reactants are fed at T,P
Products are emerging at T,P

H r (T , P) H products H reactants
 Heat of Reaction : Per mole of what ?
2A + B 3C r (100C, 1 atm) =-50 kJ/mol

Meaning that:

50kJ 50kJ 50kJ

H r
2 mol A reacted 1 mol B reacted 3 mol C produced

If 150 mol C/s is generated, enthalpy change is

-50 kJ 150 mol C generated =

H= -2500 kJ/s
3 mol C generated s
 Relationship Between Enthalpy Change
and Heat of Reaction
Although the Heat of Reaction is defined so, the actual enthalpy
change of the reaction depends on how many moles of reactant
has been consumed (Extent of reaction). Therefore:
Where:
vA - stoichiometric coefficient
- extent of reaction
nA,r - moles of A consumed or generated

H r (T , P) (n A,out nA,in ) nA , r
H nA , r
vA vA vA

H H r (T , P)
 Properties of Heat of Reaction
1. Standard heat of reaction (r) - heat of reaction when both
reactants and products are at reference conditions (usually 25 C
and 1 atm)
2. At low and moderate pressure, r is nearly independent of
pressure
3. Exothermic (r= -ve) and Endothermic (r= +ve)
4. r depends on how the stoichiometric equation is written
CH4 (g) + 2O2(g) CO2(g) + 2H2O(l)
r1 (25C)= -890.3 kJ/mol for 1 CH4
2CH4 (g) + 4O2(g) 2CO2(g) + 4H2O(l)
r2 (25C)= -1780.6 kJ/mol for 2 CH4

5. r depends on the states of aggregation (gas, liquid, or solid)

CH4 (g) + 2O2(g) CO2(g) + 2H2O(l)
r1 (25C)= -890.3 kJ/mol
CH4 (g) + 2O2(g) CO2(g) + 2H2O(g)
r2 (25C)= -802.3 kJ/mol
 Internal Energy of Reaction
For a reaction takes place in a closed reactor or constant volume

U r (T) U products U reactant

U r (T ) H r (T ) RT vi vi


gaseous gaseous
products reactants
Example for the reaction
C6H14 (l) + 19/2 O2 (g) 6 CO (g) + 7 H2O (v)

U r (T ) H r (T ) RT (6 7 19 / 2)
H (T ) 7 / 2 RT
r
 Hesss Law (Caltion of Reaction Heat
Normal procedure using calorimeter, however has a limitation
If the stoichiometric equation for reaction 1 can be obtained by
algebraic operations (multiplication by constant, addition, and
subtraction) on stoichiometric equation for reaction 2,3.., then
the heat of reaction r1 can be obtained by performing the same
operations on the heats of reactions r2 , r3 .

C + 1/2O2(g) CO (incomplete combustion)

Alternative method
C + O2 CO2 Hr1 = -393.51 kJ/mol
CO + O2 CO2 Hr2 = -282.99 kJ/mol

C + O2 (+ O2) CO (+ O2)
H 0 r 3 H 0 r1 (H 0 r 2 )
H 0
r3
H H 0 r1 393.51 282.99
H H 0 r 2
110.52kJ / mol
CO2
 Class Discussion

Example 9.1-1
Example 9.1-2
Example 9.2-1
 Heats of Formation
Formation reaction
reaction in which the compound is formed from its elemental
constituents as they normally occur in nature (e.g. O2 rather
than O)
standard heat of formation (f )
- Enthalpy change associated with the formation of 1 mole of
compound at a reference temperature (25C) and pressure
(1 atm)
Standard heat of formation are listed in Table B.1.
Standard heat of formation for elemental species (e.g O2) is zero
Relationship between standard heat of formation and heat
of reaction based on Hesss Law

H r vi H fi i fi
v H i fi
v H
i products reac tan t
 Example 9.3-1
Determine the standard heat of reaction for the combustion of
liquid n-pentane assuming H2O (l) is a combustion product.
 Heats of Combustion
Standard heat of combustion,
heat of combustion of that substance with oxygen to yield
specified products (e.g. CO2, H2O) with both reactant and
products at 25C and 1 atm.
Several value are listed in Table B.1
Relationship between heat of reaction and heat of combustion

H r vi H ci i ci
v H i ci
v H
i reac tan ts products
 Example 9.4-1
Calculate the standard heat of reaction for the dehydrogenation of
ethane
C2 H6 C2 H4 + H2
 Energy Balance on Reactive Processes
Method 1: Heat of Reaction Method
preferable when there is a single reaction for which
r is known

Reactants
H Products
Tin Tout

H1 H2

Reactants Hro Products

T=25 oC T=25 oC
 Method 1: Heat of Reaction Method
1. Complete the material balance
2. Choose reference states for specific enthalpy changes
- reactant and products species at 25C and 1 atm for which r is known
- For nonreacting species at any convenient temperature, such as reactor inlet
or outlet
3. For a single reaction in a continuous process, calculate the extent of reaction
-choose as species A any reactant or product for which the feed and product
flow rates are known
(n A,out n A,in )

vA
4. Prepare inlet-outlet enthalpy table
5. Calculate each unknown stream component enthalpy
6. Calculate H for the reactor ; use following eq.

H H ro nout H out nin H in (single reaction)

H H n
reaction
j
o
rj out H out nin H in (multiple reactions)

7. Substitute calculated value H in the energy balance equation and complete

the required calculations.
 Energy Balance on Reactive Processes
Method 2: Heat of Formation Method
preferable when there is a multiple reaction and single reaction for
which r is unknown

Reactants
H Products
Tin Tout

H1 H2

Elements
25 oC
 Method 2: Heat of Formation Method

1. Complete the material balance

2. Choose reference states for specific enthalpy changes
- elemental species that constitute the reactants and products in the
states in which the elements are found at 25C and 1 atm
- For nonreacting species at any convenient temperature
3. Prepare inlet-outlet enthalpy table
4. Calculate each unknown stream component enthalpy
5. Calculate H for the reactor for single or multiple reaction. Note that
heat of reaction terms are not required if the element are chosen as
references ; use following eq.

H nout H out nin H in

6. Substitute calculated H value in the energy balance equation and

complete the required calculations.
 Example 9.5-1
The standard heat of reaction for the oxidation of ammonia is
given below:

4 NH3 (g) + 5 O2 (g) 4 NO (g) + 6 H2O (v)

r=-904.7 kJ/mol

100 mol NH3/s and 200 mol O2/s at 25C are fed into a reactor in
which the ammonia is completely consumed. The products gas
emerges at 300C. Calculate the rate at which heat must be
transferred to or from the reactor, assuming operation at
approximately 1 atm.
 Class Discussion

Example 9.5-2
Example 9.5.3
Example 9.5.4
GOOD LUCK
FOR YOUR
FINAL EXAM