+

BKF2343
MATERIAL AND ENERGY
BALANCE

Sem II 2016/2017 Energy

Balance

Chapter 5:
Energy Balance on
Reactive System
1
+ 2

Topic Outcomes
 Apply the concept of exothermic and endothermic reactions and
solve for standard heats of reaction, heat of formation and heat of
combustion.

 Construct an enthalpy table and perform energy balance of reactive

processes using heat of reaction method and heat of formation
method.
+ CHEMICAL REACTION 3

 In any chemical reaction:

 Energy is required to break the reactant chemical bond
 Energy is released when product chemical bond is
formed

 Consider water formation reaction

2 H2 (g) + O2 (g) 2 H2O (v)

 One O-O bond and two H-H bonds broken. System absorbs
energy.
 4 O-H bonds are formed. System releases energy.
+ Exothermic and Endothermic Reaction
4

 Exothermic reaction
 If energy required to break the reactant chemical bond is LESS
THAN energy released when product chemical bond is formed.
 Heat of reaction must be released as heat or work or else the
temperature of the system will increase.
 The net energy, ΔHr=-ve

 Endothermic reaction
 If energy required to break the reactant chemical bond is
LARGER THAN energy released when product chemical bond is
formed.
 Energy is needed by the process else the temperature of the
system will decrease.
 The net energy, ΔHr=+ve
+ Heat of Reaction (or Enthalpy of Reaction): ΔĤr (T,P)
5

 Heat of reaction (or enthalpy of reaction)

 Enthalpy change for a process in which stoichiometric
quantities of reactants at T & P reacted completely in single
reaction to form products at the same T & P.
 Stoichiometric quantities of reactant means molar amount of
the reactant numerically equal to their stoichiometric
coefficient.
 Example: Heat of reaction between calcium carbide and water.
Hˆ  r (25 C,1 atm)  -125.4 kJ/mol


 In simple word;
 Reactants and products: stoichiometric quantities
 Complete Reaction
 Reactants are fed at T,P
 Products are produced at T,P
+ Relationship Between Heat of Reaction and
6

Enthalpy Change
 Although the heat of reaction Ĥ
is rdefined so, the actual enthalpy
change H
depends on how many moles of reactant has been
consumed. Therefore:

H  Hˆ r (T , P)

(n A,out  n A,in ) n A, r
 
vA vA

 Where:
vA - stoichiometric coefficient
ξ - extent of reaction
nA,r - moles of A consumed
+ Properties of Heat of Reaction
7

 Exothermic (ΔĤr= -ve) and Endothermic (ΔĤr= +ve)

 At low and moderate pressure, ΔĤr is nearly independent of
pressure
 ΔĤr depends on how the stoichiometric equation is written
CH4 (g) + 2O2(g)  CO2(g) + 2H2O(l)
ΔĤr1 (25°C)= -890.3 kJ/mol  for 1 CH4

2CH4 (g) + 4O2(g)  2CO2(g) + 4H2O(l)

ΔĤr2 (25°C)= -1780.6 kJ/mol  for 2 CH4

 ΔĤr depends on the states of aggregation (gas, liquid, or solid)

CH4 (g) + 2O2(g)  CO2(g) + 2H2O(l)
ΔĤr1 (25°C)= -890.3 kJ/mol
CH4 (g) + 2O2(g)  CO2(g) + 2H2O(g)
ΔĤr2 (25°C)= -802.3 kJ/mol
+ Determination of Heat of reaction: Calorimeter

 Normal procedure to measured the heat of reaction is using

calorimeter – a closed reactor immersed in a fluid contained a
well-insulated vessel
 However it has a limitation

 Considered this reaction

C (s) + ½ O2 (g)  CO (g)

 Theproduct would be either pure CO2 or mixture of CO and

CO2, making it impossible to determine heat of CO
formation reaction alones.
+ Determination of Heat of reaction : Hess’s Law
9

C + ½ O2(g)  CO ΔHr1= ?
Alternative reactions
C + O2  CO2 ΔHr2 = -393.51 kJ/mol
CO + ½ O2  CO2 ΔHr3 = -282.99 kJ/mol

Hˆ 0 r1  Hˆ 0 r 2  ( Hˆ 0 r 3 )

 393.51  282.99
 110 .52kJ / mol

 If the stoichiometric equation for reaction 1 can be obtained by algebraic

operations (multiplication by constant, addition, and subtraction) on
stoichiometric equation for reactions 2, 3….., then the heat of reaction
ΔĤr1 can be obtained by performing the same operations on the heats of
reactions ΔĤr2 , ΔĤr3 ….
+ Determination of Heat of reaction: 10

Using Standard Heats of Formation (ΔĤ°f)

 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 (ΔĤ°f)
 Enthalpy
change associated with the formation of 1 mole of
compound at a reference temperature (25°C) 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

 Calculating heat of reaction from standard heat of formation:

Hˆ r   vi Hˆ  fi   v Hˆ i fi   v Hˆ  i fi
i products reac tan t
+ Determination of Heat of reaction: 11

Using Standard Heats of Combustion (ΔĤ°c)

 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 25°C and 1 atm.
 All carbon in the fuel forms CO2
 All hydrogen forms H2O
 All sulfur form SO2
 All nitrogen forms N2

 Several values are listed in Table B.1

 Calculating heat of reaction from standard heat of
combustion :
Hˆ r   vi Hˆ ci   v Hˆ  i ci   v Hˆ  i ci
i reac tan ts products
+ 12

Problems from your textbook

 Problem 9.9 (c) page 478.
+ Methods for Energy Balance Calculation 13

for Reactive System

Heat of Heat of
Reaction Formation
Method Method
+ Methods for Energy Balance Calculation 14

for Reactive System

Heat of
Reaction H  Hˆ ro   nout Hˆ out  nin Hˆ in (single reaction)
Method H   j rj   nout Hˆ out  nin Hˆ in (multiple reactions)
 Hˆ
reaction
o

Heat of
Formation H   n out Hˆ out   n in Hˆ in
Method
+ Energy Balance on Reactive Processes
15

 Method 1: Heat of Reaction Method

preferable when there is a single reaction for which ΔĤ°r is known
(or calculated from standard heat of formation)

Reactants ΔH Products
Tin Tout

ΔH1 ΔH2

Reactants ΔHro Products

T=25 oC T=25 oC
+ Method 1: Heat of Reaction Method
16

1. Complete the material balance

2. Choose reference states for specific enthalpy changes
 reactant and products species at 25°C and 1 atm for which
 ΔĤ°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 as any reactant or product for which the
feed and product flow rates are known
(n A,out - n A ,in )
x=
vA

4. Prepare inlet-outlet enthalpy table

H unknown stream component enthalpy (Ĥ)
5. Calculate each
6. Calculate
H  for
 Hˆ o the reactor:
r  out out 
n Hˆ  n Hˆ (single reaction)
in in

H   j rj   nout Hˆ out  nin Hˆ in (multiple reactions)

 Hˆ
reaction
o
+ Energy balance on reactive processes
17
+
 HEAT OF REACTION METHOD
18
19
20
+ Energy Balance on Reactive Processes
21

 Method 2: Heat of Formation Method

preferable when there is a multiple reaction and single reaction
for which ΔĤ°r is not calculated directly from standard heat of
formation.

Reactants ΔH Products
Tin Tout

ΔH1 ΔH2

Elements
25 oC
+ Method 2: Heat of Formation Method
22

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 25°C and
1 atm
- For nonreacting species at any convenient temperature
3. Prepare inlet-outlet enthalpy table
4. Calculate each unknown stream component enthalpy
H
5. Calculate for the reactor for single or multiple reaction. Note
that heat of reaction terms are not required since the elements
are chosen as references ; use following eq.

H   n out Hˆ out   n in Hˆ in

+ Heat of Formation method 23
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Example 9.5-2
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+ 30

Try Problem from your textbook

Problem 9.23 page 483
+ 31

Try Problem from your textbook

Problem 9.56 page 496