+

CHEMICAL PROCESS
PRINCIPLES II

Energy Balance on
Reactive System
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Content
Chemical Reaction
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
General procedure of energy balance on reactive
systems.
Adiabatic Reactors. (9.5b)
Thermochemistry of solutions
Fuels and Combustion (9.6)
+ Methods for Energy Balance Calculation
for Reactive System

Heat of
Formation H noutH out nin H in
Method

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

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

Use different reference condition

+ Chemical Reaction

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)

Each times reaction occurred, 3 chemical bond are broken and 4

bonds are formed more energy is released
The net energy release must be transferred away from reactor for
the reactor temperature to remain constant
+ Exothermic and Endothermic Reaction

Exothermic reaction
If energy required to break the reactant chemical bond is
LOWER 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 needed 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 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
Standard heat of reaction, H o (always at 25oC and 1 atm)
r
+
Heat of reaction
(T, P)
H r

negative exothermic
positive indothermi c
(T )
low and moderate pressure H r

The value of the heat of a reaction depends on how the stoichiometric

equation is written.
The value of a heat of reaction depends on the states of component
(gas, liquid, solid)
+ 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:

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

Where: H H r (T , P)
vA - stoichiometric coefficient
- extent of reaction
nA,r - moles of A consumed or generated
+ Properties of Heat of Reaction
Standard heat of reaction (r)

Exothermic (r= -ve) and Endothermic (r= +ve)

At low and moderate pressure, r is nearly independent of pressure
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

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
reaction when both reactants and products are at REFERENCE CONDITION
(usually 25 C and 1 atm)
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Example 9.1-1
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+ Internal Energy of Reaction
For a reaction takes place in a closed reactor or constant volume

(T) U
U r products U reactant

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


gaseous gaseous
products reactants
Assumption : ideal gas behavior and specific volume of solid and liquid of
reactants and products are negligible compare to the gases
Example for the reaction
C6H14 (l) + 19/2 O2 (g) 6 CO (g) + 7 H2O (v)
+
Example 9.1-2
+
Hesss Law
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) + O2 (g) CO (g)

- If the reactant at 25oC or lower, nothing would occur since
the rate of reaction at this temperature is immeasurably
low
- If the mixture were heated to a temperature at which C
and O2 react at a measurable rate, the product would be
either pure CO2 or mixture of CO and CO2, making it
impossible to determine heat of CO formation reaction
alones
- Hess Law can be used
+
Hesss Law
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 + O2(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 r 3 393.51 282.99
H H 0
r1 H H 0 r 2 110.52kJ / mol
CO2
To determine final (T, P)
H
from several Hr (T, P)
r
+
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 (25oC) 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 reactan t
+ Example 9.3-1
+
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 25oC and 1 atm.
All carbon in the fuel forms CO2
All hydrogen forms H2O
All sulfur form SO2
All nitrogen forms N2
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 reactan ts products
+
Example 9.4-1
Calculate the standard heat of reaction for the
dehydrogenation of ethane
C2 H 6 C2 H4 + H2
+

Methods for Energy Balance Calculation

for Reactive System

Heat of Heat of
Reaction Formation
Method Method
+ 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 )
x=
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 j rj noutH out nin H in (multiple reactions)
H
reaction
o

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 25oC 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 noutH out nin H in

6. Substitute calculated H value in the energy balance equation
and complete the required calculations.
+
Example
+
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.
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Example 9.5-2
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Example 9.5-3
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Example 9.5-4
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+
General procedures :
Energy balances on reactive processes
Heat of Reaction method:
1. Complete material balances
2. Choose the suitable reference
states (components)
3. Calculate the extent reaction,
reactant or product of known
flow in and flow out
4. Prepare input and output
stream
5. Calculate the unknown
enthalpy for each components
6. Calculate enthalpy of the
reactor (eq 9.5-1a and 9.5-1b)
7. Calculate the heat
Heat of Formation method:
1. Complete material
balances
2. Choose the suitable
reference states (elements)
3. Prepare input and output
stream
4. Calculate the unknown
enthalpy for each
components using
standard heat of formation
*****
5. Calculate enthalpy of the
reactor (eq 9.5-2)
6. Calculate the heat
+STEP BY STEP TO SOLVE ENERGY BALANCE
FOR REACTIVE SYSTEM

STEP 1 - SOLVE MATERIAL BALANCES FIRST

Follow reactive material balance procedures
STEP 2 - DRAW ENTHALPY TABLE
STEP 3- WRITE REFERENCE STATES
(COMPONENT OR ATOM, TEMP. AND 1 ATM)
STEP 4 - WRITE ENERGY BALANCE EQUATION
STEP 5 - DETERMINE ENTHALPY FOR EACH
COMPONENT IN EACH INPUT AND OUTPUT
STREAM
STEP 6 -DETERMINE Q
+ STEP 1 - SOLVE MATERIAL
BALANCES FIRST
Follow Reactivematerial balance
procedures
BUT in your flow diagram you must indicate states,
temperature and pressure
Example
CH4 (g), 100 mol/s,
25C and 1 atm

n1 mol CH4 (g)

n2 mol O2 (g)
Reactor 300C and 1
atm n3 mol N2 (g)
Air, 100C and
1 atm n4 mol CO2 (g)
n5 mol H2O (g)

NOTE: IF YOU CANNOT SOLVE MATERIAL BALANCE YOU CAN STILL PROCEED WITH ENERGY
BALANCE
BY FOLOWING STEPS 2 TO 6
+ STEP 2 - DRAW ENTHALPY TABLE
Example
Component Input Output
Enthalpy, Enthalpy,
mol kJ/mol mol kJ/mol
CH4 (g) 6.5 1 n1 4
O2 (g) 19.7 2 n2 5
N2 (g) 73.8 3 n3 6
CO2 (g) - - n4 7
H2O(v) - - n5 8
STEP 3 - WRITE REFERENCE STATES (COMPONENT OR
ATOM, TEMP. AND 1 ATM)
Example: Reference states CH4 (g), O2 (g), N2(g), CO2(g), H2O(v) at25C and
1 atm (Heat of reaction method)

Reference states C (g) H2 (g), O2 (g), N2(g), at25C and 1 atm (Heat of forma
tion method)
+STEP 4 - WRITE ENERGY BALANCE EQUATION
OPEN SYSTEM: Q - Ws = H + KE + PE
ignore KE + PE = 0
Include phase change, Hvap or Hmelting

STEP 5 - DETERMINE ENTHALPY FOR EACH

COMPONENT IN EACH INPUT AND OUTPUT STREAM
Heat of Reaction Method
rxn = lilfiproducts - lilfireactant, kJ/mol
i= Cp(T)dT - between T and Tref, kJ/mol
Q = rxn + (nii)out - (nii)in, kJ or kJ/s

extent of reaction = (Limiting reactant out -Limiting reactant in)

/stoichiometric coefficient of limiting reactant

Heat of Formation Method

i= fi + Cp(T)dT - between T and Tref, kJ/mol
Q = (nii)out - (nii)in, kJ or kJ/s
+ STEP 6 -DETERMINE Q

See STEP 5
+ PAST YEAR QUESTION
+ PAST YEAR QUESTION
+
Adiabatic Reactors (9.5b)
When input and output conditions are specified, H = 0, and
outlet temperature.
Method of calculating the is similar to heat for reaction
method or heat of formation method
Refer to Example 9.5-3 and 9.5-4
+
Fuels and combustion (9.6)
Higher heating value (HHV) is -Hc with H2O(l) as the
combustion product
Low heating value (LHV) with H2O (v) as the combustion
product

HHV = LHV + nH (eq 9.6-1)