Energy Balances on

Reactive Processes
∆HR = -ve (exothermic)
∆HR = +ve (endothermic)

Tin, Pin, Hreac Tout, Pout, Hprod

Qin/Qout

2A + B 3C

ˆo +
 = H
Q = H r  nΔ
 H
outlet
 ˆ
ˆ - n H
i i
inlet
i i ..... Single Reaction

Q = H
 =

reactions, j
 jHˆ r,jo +  n Hˆ -  n Hˆ
outlet
i i
inlet
i i ..... Multiple Reactions

1
 Energy Balances on
Reactive Processes
 There are two common approaches to choose reference conditions for energy
balance calculation and to estimate enthalpies and internal energies.
1. Heat of Reaction Method - The reactants and products are considered as
molecular species at To, which is the reference temperature for the heat of
reaction (usually 25 oC, 1 atm). Nonreactive species may be considered at any
convenient reference temperature Tref.
 This method is generally preferable when a single reaction for which Hor
is known
 For steady-state flow process with negligible stream kinetic and potential
energies:
Q = H
…… single reaction
Q = Hˆo +
r 
all species
iˆi -
nH 
all species
iˆi
nH
going out coming in

2
 Energy Balances on Reactive
Processes Multiple Reaction
 = H
Q 
…… Multiple reactions
 =
Q 
reactions, j
ˆo +
 jHr,j 
outlet
n iHi  i
ˆ - n H
ˆ
i
inlet

Note: In the last two terms of this equation, the enthalpies are the enthalpies of
species i, relative to a reference temperature T o.

 For batch process (constant volume / pressure)

Q = U
ˆo +
Q = U =  Ur 
all species
iˆi -
nU 
all species
iˆi
nU
at final state at initial state

3
 Energy Balances –
Heat of Formation Method
2. Heat of Formation Method - The reference is taken as the elements that make up the
reactants and products at reference temperature T o. Nonreactive species may be considered
at any convenient reference temperature T ref.

 This method is generally preferable for a single reaction and multiple reactions
where Hor is not readily available
 For steady-state flow process (negligible stream kinetic and potential energies)

Q = H

Q = H
=

all species
iˆi -
nH 
all species
iˆi
nH
going out coming in

Note: In this equation, the enthalpies are equal to the heat of formation of species i at
To, plus the enthalpy of that species relative to the reference temperature T o.

4
 Comparison of Methods

Comparison of the hypothetical process paths that correspond to the heat of

reaction and heat of formation methods

5
 Energy Balance – Example 1

The standard heat of reaction at 25oC and 1 atm for the oxidation of
ammonia is -904.7 kJ/mol. 100 moles/hr ammonia and 200 moles/hr
oxygen at 25oC are fed in a reactor in which the ammonia is completely
consumed. The product stream emerges as a gas at 300oC. Calculate the
heat transferred to or from the reactor, assuming operation at
approximately 1 atm.

kJ
4NH3 (g) + 5O2 (g)  4NO (g) + 6H2O (g) Ĥro = - 904.7
mol

6
 Energy Balance - Example

ˆ in , Hˆ out & Q
1. Mass balances have been completed, calculate H

E.g. Ammonia Oxidation Process

100 mol NH3/h 100 mol NO/h

200 mol O2/h 150 mol H2O/h
ˆ in
H 75 mol O2/h
25 °C, ?
300 °C, Hˆ out ?
Q = ? (kJ/h)

Solution-page 453
7
 Energy Balance – Problem 9.11

n-Butane is converted to iso-butane in a continuous isomerization

reactor that operates isothermally at 149oC. The feed to the reactor
contains 93 mole % n-butane, 5 mole % iso-butane and 2 mole % HCl
at 149oC and a 40% conversion of n-butane is achieved.

a. Taking a basis of 1 mol of feed gas, calculate the moles of each

component in the feed and product mixtures and the extent of reaction,
ξ (mol)
b. Calculate the standard heat of polymerization reaction (kJ/mol). Then,
feed and product species at 25oC as references, prepare an inlet-outlet
enthalpy table.
c. Calculate the required heat transfer (kW) to or from the reactor for a
reactor feed of 325 mol/h.
d. Determine the heat of the isomerization reaction at 149oC,
(kJ/mol) 8
 Energy Balance – Solution to
Problem 9.11

Basis: 1 mol of feed gas

93 mole % n-butane n3 mol n-butane

5 mole % i-butane n4 mol i-butane
2 mole % HCl n5 mol HCl
149 °C
149 °C

Q = + / - ? (kJ/s)

Given : % conversion of n-butane = 40%

9
 Energy Balance – Solution to
Problem 9.11
a. Taking a basis of 1 mol of feed gas, calculate the moles of each component in the feed and
product mixtures and the extent of reaction, ξ (mol)

Isomerization reaction : n-C4H10 (g)  i-C4H10 (g)

Feed components : 0.93 mol n-C4H10, 0.05 mol i-C4H10 , 0.02 mol HCl

Product components :

n-butane balance :
0.4 mol n - C 4H10 reacted
n3 = 0.93 mol n - C 4 H12 - 0.93 mol n - C 4 H10 fed x = 0.558 mol n - C4 H10
mol n - C 4H10 fed

i-butane balance :
0.4 mol i- C 4H10 produced
n4 = 0.05 mol i- C 4 H12 + 0.93 mol n - C 4 H10 fed x = 0.422 mol i- C4 H10
mol n - C 4H10 fed
10
HCl balance : n5 = 0.02 mol HCl
 Energy Balance – Solution to
Problem 9.11
The extent of reaction, ξ (mol)

 nn-butane  out -  nn-butane  in 0.558-0.93

= = = 0.372 mol
n-butane -1

b. Calculate the standard heat of polymerization reaction (kJ/mol) taking the feed and
product species at 25oC as references.

n-C4H10 (g)  i-C4H10 (g)  

Ĥor 25 o C = ?
kJ
mol
Use the standard heat of formation (Table b-1) :

∆Hor = (∆H ) - (∆H )

i-C4H10 (g) f n-C4H10 (g) f

o
∆H r (25oC) = -134.5 – (-124.7) = - 9.8 kJ/mol
11
 Energy Balance – Solution to
Problem 9.11
Basis : 1 mol of feed gas

References : n-C4H12 (g), i-C4H12 (g) , HCl (g) at 25oC and 1 atm
nin Hin nout Hout
Substance
(mol) (kJ/mol) (mol) (kJ/mol)
n-C4H12 (g) H1 H4
0.93 0.558
i-C4H12 (g)
0.05 0.422
H2 H5
HCl (g)
0.02 0.02
H3 H6
c. Calculate the required heat transfer (kW) to or from the reactor for a reactor feed of
325 mol/h.

Q = H r i ii i
ˆ 0 + nH
 ˆ - nH

out
ˆ
in
12
 Energy Balance – Solution to
Problem 9.11
Basis : 325 mol/h of feed gas

References : n-C4H12 (g), i-C4H12 (g) , HCl (g) at 25oC and 1 atm
nin Hin nout Hout
Substance
(mol/h) (kJ/mol) (mol/h) (kJ/mol)
n-C4H12 (g) 302.25 H1 181.35 H4

i-C4H12 (g) 16.25 137.15

H2 H5
HCl (g) 6.5 6.5

H3 H6
ˆ  137.15 -16.25  mol  kJ  h kJ
Hr = 
0
 x  -9.8  x = - 0.329
 1  h  mol  3600 s s

13
 Energy Balance – Solution to
Problem 9.11

 C 
149
ˆ &H
H ˆ = dT
1 4 25 p n-butane(g)

  
ˆ &Hˆ = 149 Heat of capacities are
H 2 5
Cp dT given in Table B-2
25 i-butane(g)

 C 
149
ˆ &H
H ˆ = dT
3 6 25 p HCl(g)

H ˆ = 14.287 kJ
ˆ &H ˆ = 14.142 kJ
ˆ &H
H ˆ = 3.608 kJ
ˆ &H
H
1 4 2 5 3 6
mol mol mol

-0.329 kJ/s + [181.35(14.287) + 137.15(14.142) + 6.5(3.608)

Q =
– 302.25(14.287) – 16.25(14.142)-6.5(3.608)] kJ/h x h/3600s
= -0.334 kJ/s

14
 Energy Balance – Solution to
Problem 9.11
d. Determine the heat of the isomerization reaction at 149 oC,  
Ĥr 149 o C(kJ/mol)

Hypothetical reaction paths

 Hˆ
r
o
n-C4H12 (g), 149 C i-C4H12 (g), 149oC

Ĥ1 Ĥ2
Ĥor
n-C4H12 (g), 25oC i-C4H12 (g), 25oC

ˆ (149 o C) = H
H ˆ + H
ˆ o + H
ˆ
r 1 r 2

From previous calculations

H r 
ˆ 149 o C =  -14.287 + (-9.8) + 14.142 = -9.945 kJ/mol

Repeat question (c) using the heat of isomerization at 149 oC and the following reference
states : n-C4H12 (g), i-C4H12 (g) , HCl (g) at 149oC and 1 atm

15
 Energy Balance – Heat of Formation

Basis : 325 mol/h of feed gas

References : C (s), H2 (g) , Cl2 (g) at 25oC and 1 atm

nin Hin nout Hout

Substance
(mol/h) (kJ/mol) (mol/h) (kJ/mol)
n-C4H12 (g) 302.25 H1 181.35 H4

i-C4H12 (g) 16.25 137.15

H2 H5
HCl (g) 6.5 6.5

H3 H6

16
 Evaluation of Hi using Heat of
Formation

 
149
ˆ ˆ
H1,H4 =  C p dT -124.7
25 n-butane(g)

kJ kJ
= 14.287 -124.7  = -110.41
mol mol

H2 ,H5 =   C p 
149
ˆ ˆ dT -134.5
25 i-butane(g)

kJ kJ
= 14.142 -134.5  = -120.358
mol mol

 
149
ˆ ˆ
H3 ,H6 =  C p dT - 92.31
25 HCl(g)

kJ kJ
=  3.608 - 92.31 = -88.702
mol mol
17
 Energy Balance – Heat of Formation
Basis : 325 mol/h of feed gas
References : C (s), H2 (g) , Cl (g) at 25oC and 1 atm
nin Hin nout Hout
Substance
(mol/h) (kJ/mol) (mol/h) (kJ/mol)
n-C4H12 (g) 302.25 -110.41 181.35 -110.41

i-C4H12 (g) 16.25 137.15

-120.358 -120.358
HCl (g) 6.5 6.5
-88.702
Q = H
 =

all species
iˆi -
nH 
all species
iˆi
nH -88.702
going out coming in

kJ
= -110.41(181.35 - 302.25) -120.358(137.15 -16.25) = -1202.71
hr
kJ hr kJ
= -1202.71 * = - 0.334
hr 3600s s 18
 Working Session 2

Ethyl alcohol is produced by fermenting maltose (a sugar) in a continuous

Fermentation process. The reaction is:

C12H22 O11(s) + H2O (l)  4C2H5OH (l) + 4CO2(g)

Maltose at 40oC and 50% excess water at 25oC are fed to the process. The
Maltose reacts completely. The process effluents are liquid ethanol and liquid
water at 40oC and carbon dioxide at 100oC. The standard heat of combustion of
Maltose to form CO2(g) and H2O(l) is -5649.1 KJ/mol.

a)Calculate the standard heat of the reaction

b)Calculate net heat transfer to or from the process using the heat
of reaction method

19
 Working Session 3

1 mole/s of a fuel containing methane and ethane in an equimolar mixture is

fed to a boiler.

CH4 (g) + 2O2 (g)  CO2(g) + 2H2O (g)

C2H6 (g) + 7/2O2 (g)  2CO2(g) + 3H2O (g)
0.5 mol CH4 18.62 mol N2
0.5 mol C2H6 2.2 mol O2
23.7 mol air 2.5 mol H2O
25 °C 1.5 mol CO2
269 °C
Q = ? (kJ/s)

Calculate net heat transfer to or from the process

Ans: Q = -928 KJ/s

20