Chemical Process Principles

(CLB10904)
Chapter 4
Energy Balance (Part 4)
Energy Balance on Reactive
Process
Dr. Kelly Yong Tau Len
SCET UniKL MICET
Tel: 06-5512051
Email: kytlen@unikl.edu.my
E-Learning: CLB 10904 – Kelly Yong
 Heat of Reaction/Enthalpy of Reaction, ΔĤr
• Enthalpy change for a process in which stoichiometric quantities of
reactants at T & P react completely in single reaction to form
products at the same temperature and pressure.
• For example, given the following calcium carbide reaction

CaC2 (s)+ 2H 2O(l) ® Ca(OH)2 (s)+C2 H 2 (g)

• The heat of the reaction at 25 oC and 1 atm is

Hˆ r (25C,1 atm)  125.4 kJ / mol

• If ΔĤr is negative, the reaction releases heat (exothermic reaction).

• If ΔĤr is positive, reaction requires heat (endothermic reaction).
• The standard heat of reaction, ΔĤor is the heat of reaction when
both reactants and products are at specific reference T and P of
25˚C and 1 atm. 2
 Heat of Reaction/Enthalpy of Reaction, ΔĤr
• The relationships between enthalpy change, ΔH and heat of
reaction/enthalpy of reaction, ΔĤr is given as following
νA=
DH r,(T ,P )
Stoichiometric coefficient of a reactant or
reaction product A
DH = o o
nA,r nA,r = Number of moles of A consumed or
nA generated at T0 and P0

• In addition, we know that extent of reaction, ξ (measure of how far a

reaction has proceed) is given as:
nAout - nAin nA,r
Modulus sign: Values x= =
must be positive! nA nA
• Therefore we can combine these 2 equations. If a reaction takes
place at T0 and P0 and the extent of reaction is ξ, the enthalpy
change is

DH = eDĤr(T ,P )
3 0 0
 Heat of Formation, ΔĤof
• A formation reaction of a compound is the reaction in which the
compound is formed from its elemental constituents as they normally
occur in nature.
• The enthalpy change associated with the formation of 1 mole of the
compound at a reference temperature and pressure (usually 25 oC
and 1 atm) is the standard heat of formation of the compound, ΔĤof
• Standard heats of formation for many compounds are listed in Table
B.1

• For example, ΔĤof for crystalline ammonium nitrate is given in Table

B.1 as -364.14 kJ/mol, signifying

3
4 N 2 (g) + 2H 2 (g) + O2 ® NH 4 NO3 (c) : DĤ of = -365.14kJ / mol
2
 Method 1: Method 2:
Heat of Heat of
Reaction Formation
(ΔĤr) Method (ΔĤf) Method

Energy
Balance on
Reactive
Process
5
 Heat of Reaction (ΔĤr) Method
This method is preferable when there is a SINGLE
reaction for which ΔĤor is known or given.
Procedures:
1. Complete the material balance calculations on the
reactor as much as possible.
2. Choose reference state for specific enthalpy, ΔĤ
calculations. The best choice are generally 25oC and 1
atm.
3. Calculate the extent of reaction, ξ.

nAout - nAin νA = Stoichiometric coefficient

nA,r
x= = nA,r = Molar flow rate of a species
nA nA consumed or generated
4. Prepare the inlet-outlet enthalpy table, inserting the known 6
values.
 Heat of Reaction (ΔĤr) Method
This method is preferable when there is a single
reaction for which ΔĤor is known.
Procedures:
5. Calculate ΔĤ for the reactor. For a single reaction in a
continuous process we can use:

DH = xDĤ r + å ni Ĥ i - å ni Ĥ i
We add this for out in
reactive process

5. Substitute the calculated values into the energy balance

equation for open system.

7
Heat of Reaction (ΔĤr) Method (Example)
The standard heat of reaction for the propane combustion
process is given below:

C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l) : DĤ ro = -2220kJ / mol

100 mol C3H8 (g)/s

25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
2256 mol N2(g)/s
300ºC, 1atm

Question: Calculate the rate at which heat, Q must be

transfer to or from the reactor.
8
Heat of Reaction (ΔĤr) Method (Example)
SOLUTION
1. Usually we choose reference state 25 oC and 1 atm because the specific
enthalpy for most of the compounds in this example (O2(g), N2(g), CO2(g),
and H2O(g)) is available from the Physical Property Table (Table B.8).
2. Prepare the inlet-outlet enthalpy table, inserting the known amounts for
all components. Remember if the components is at its reference state
(E.g. C3H8(g) inlet condition is 25 oC and 1 atm (= Reference state),
therefore the enthalpy value for this stream is 0.

9
Heat of Reaction (ΔĤr) Method (Example)
SOLUTION
3. Calculate the extent of reaction, ξ. When we want to calculate
extent of reaction, choose ANY species A (can be any product or
reactant) in which the feed and product flow rates are known. In
this example, we choose C3H8 as species A. Therefore ξ can be
calculated as

C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l) : DĤ ro = -2220kJ / mol

Outlet Molar Inlet Molar
flow rate flow rate

Stoichiometric
10
Coefficient
Heat of Reaction (ΔĤr) Method (Example)
SOLUTION
3. Calculate each unknown stream component enthalpy, Ĥi, as
ΔĤ for the species going from its reference state to the process
state, and insert the enthalpies in the table.
From Table B.8 Specific Enthalpies of Selected Gases
• Ĥ2 = ΔĤ for O2 (25 oC) —> O2 (300 oC) = 8.47 kJ/mol
Inlet
• Ĥ3 = ΔĤ for N2 (25 C) —> N2 (300 C) = 8.12 kJ/mol
o o

• Ĥ4 = ΔĤ for O2 (25 oC) —> O2 (1000 oC) = 32.47 kJ/mol

• Ĥ5 = ΔĤ for N2 (25 oC) —> n2 (1000 oC) = 30.56 kJ/mol
Outlet
• Ĥ6 = ΔĤ for CO2 (25 C) —> CO2 (1000 C) = 48.60 kJ/mol
o o

• Ĥ7 = ΔĤ for H2O (25 oC, l) —> H2O (1000 oC, g) = ?? (At

reference state, 25 oC, water is in liquid phase but at
1000 oC, it will be in gas phase). Therefore;
100 1000

11
Ĥ 7 = ò p,l
C dT + DĤ v
(100 o
C) + òC p,v
dT = 81.71kJ / mol
25 100
Heat of Reaction (ΔĤr) Method (Example)
4. Calculate ΔH for the reactor using this formula.

8.47 32.47
8.12 30.56
48.60
81.71

C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l) : DĤ ro = -2220kJ / mol

5. Substitute the calculated value (ΔH) in the energy balance equation to

obtain the heat transfer rate, Q 12
 Heat of Formation (ΔĤof) Method
This method is preferable for MULTIPLE reactions and
single reaction for which ΔĤor is not known.
Procedures:
1. Complete the material balance calculations on the
reactor as much as possible.
2. Choose reference state for specific enthalpy, ΔĤ
calculations.
 This is the step that distinguishes the Heat of Reaction
Method with this one.
 Choose the elemental species that constitute the reactants
and products in the state in which the elements are found
at 25ºC and 1 atm [C(s), H2(g),etc].
3. Prepare the inlet-outlet enthalpy table, inserting the known
values. 13
 Heat of Formation (ΔĤof) Method
Procedures:
4. Calculate each unknown ΔĤ for the species.
 For a reactant or product, START with the ELEMENTAL
SPECIES at 25ºC and 1 atm (references) and form 1 mol of the
process species at 25ºC and 1 atm (ΔĤ=ΔĤof from Table B1).
 Then bring the species from 25ºC and 1 atm to its process state
(Can use heat capacities from Table B.2, specific enthalpies
from Table B.8 and B.9, and latent heats from Table B.1).
5. CalculateH for the reactor. For both single and multiple

DH = å ni Ĥi - å ni Ĥi
reactions, the formula is

out in

6. Substitute the calculated values into the energy balance equation

for open system.

14
Heat of Formation (ΔĤof) Method (Example)

C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)

100 mol C3H8 (g)/s

25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
2256 mol N2(g)/s
300ºC, 1atm

Question: Calculate the rate at which heat must be transfer

to or from the reactor.

15
Heat of Formation (ΔĤof) Method (Example)
SOLUTION
1. The reference states would be C(s), and O2(g) at 25oC (the elemental
species constituting the reactants and products) and N2 at 25oC (the
reference temperature of Table B.8).
2. Prepare the inlet-outlet enthalpy table, inserting the known amounts for
all components.

16
Heat of Formation (ΔĤof) Method (Example)
C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)

Ĥ1 100 mol C3H8 (g)/s

25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
2256 mol N2(g)/s
300ºC, 1atm

3C(s)(25 oC,1atm) + 4H 2 (g)(25 oC,1atm)

ß Ĥ a = (DĤ f )C3H8 ( g )
O
Ĥ1 = Ĥ a + Ĥb
ß
Ĥ b = 0
C3 H8 (g)(25 C,1atm) ÞÞ C3 H8 (g)(25 oC,1atm)(Inlet condition)
o

17
Heat of Formation (ΔĤof) Method (Example)
4. Calculate each unknown ΔĤ for the species.

Calculate Ĥ1 for the entering propane (C3 H 8 )

1.START with C and H 2 (elemental species) at 25ºC and 1 atm (references)
and form 1 mol of C3 H 8 at 25ºC and 1 atm
3C(s)(25 oC,1atm) + 4H 2 (g)(25 oC,1atm) ® C3 H 8 (g)(25 oC,1atm)
ß Ĥ a = (DĤ Of )C H ( g ) = -103.8kJ / mol(From Table B.1)
3 8

2.Bring C3 H 8 from 25ºC and 1 atm to its inlet state (25ºC,1atm)

DĤ b = 0 (since C3 H 8 inlet temperature is 25oC)
18 Therefore Ĥ1 = DĤ a = -103.8kJ / mol
Heat of Formation (ΔĤof) Method (Example)
C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)
100 mol C3H8 (g)/s
25ºC, 1atm 100 mol O2(g)/s Ĥ 4
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s
400 mol H2O(v)/s
Ĥ 2 600 mol O2 (g)/s 1000ºC, 1atm
2256 mol N2(g)/s
300ºC, 1atm

Ĥ 2 = DHO2,300 oC
O2 (g)(25 oC,1atm) ÞÞÞ O2 (g)(300 oC,1atm)

O2 is elemental Ĥ 4 = DHO2,1000 C
o

species so zero ΔĤof O2 (g)(25 oC,1atm) ÞÞÞ O2 (g)(1000 oC,1atm) 19

Heat of Formation (ΔĤof) Method (Example)
Calculate Ĥ 2
O2 (g)(25 oC,1atm) ® O2 (g)(300 oC,1atm)
1.No DĤ of , since O 2 is elemental species
2. Bring O 2from 25ºC and 1 atm
to 300ºC and 1 atm
Ĥ 2 = DH = DH O 2,300 o C ® Table B.8
Ĥ 2 = 8.47kJ / mol
20 Try yourself!
Calculate Ĥ 2
O2 (g)(25 oC,1atm) ® O2 (g)(1000 oC,1atm)
1.No DĤ of , since O 2 is elemental species
2. Bring O 2from 25ºC and 1 atm
to 1000ºC and 1 atm
Ĥ 4 = DH = DH O 2,1000 oC ® Table B.8
Ĥ 4 = 32.47kJ / mol
Try yourself!
Heat of Formation (ΔĤof) Method (Example)
C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)
100 mol C3H8 (g)/s
25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s Ĥ 5
Furnace 300 mol CO2(g)/s
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
Ĥ 3
2256 mol N2(g)/s
300ºC, 1atm

Ĥ 3 = DH N 2,300 oC
N 2 (g)(25 oC,1atm) ÞÞÞ N 2 (g)(300 oC,1atm)

N2 is elemental Ĥ5 = DH N 2,1000 oC

species so zero
ΔĤof N 2 (g)(25 oC,1atm) ÞÞÞ N 2 (g)(1000 oC,1atm)
21
Heat of Formation (ΔĤof) Method (Example)

Calculate Ĥ 3 Calculate Ĥ 5
N 2 (g)(25 oC,1atm) ® N 2 (g)(300 oC,1atm) N 2 (g)(25 oC,1atm) ® N 2 (g)(1000 oC,1atm)
1.No DĤ of , since N 2 is elemental species 1.No DĤ of , since N 2 is elemental species
2. Bring N 2from 25ºC and 1 atm 2. Bring N 2from 25ºC and 1 atm
to 300ºC and 1 atm to 1000ºC and 1 atm
Ĥ 3 = DH = DH N 2,300 o C ® Table B.8 Ĥ 5 = DH = DH N 2,1000 o C ® Table B.8

Ĥ 3 = 8.12kJ / mol Ĥ 5 = 30.56kJ / mol

Try yourself! Try yourself! 22
Heat of Formation (ΔĤof) Method (Example)
C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)
100 mol C3H8 (g)/s
25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s Ĥ 6
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
2256 mol N2(g)/s
300ºC, 1atm

C(s)(25 oC,1atm) + O2 (g)(25 oC,1atm)

ß Ĥ a = (DĤOf )CO ( g )
2 Ĥ6 = Ĥ a + Ĥb
ß Ĥb = DĤCO2,1000
CO2 (g)(25 oC,1atm) ÞÞ CO2 (g)(1000 oC,1atm)(Outlet condition)
23 23
Heat of Formation (ΔĤof) Method (Example)

Calculate Ĥ 6 for the exiting CO 2

1.START with C and O2 (elemental species) at 25ºC and 1 atm (references) and form 1 mol
of CO 2 at 25ºC and 1 atm
C(s)(25 oC,1atm) + O2 (g)(25 oC,1atm) ® CO 2 (g)(25 oC,1atm)
ß Ĥ a = (DĤ Of )CO = -393.5kJ / mol(From Table B.1)
2(g)

2.Bring CO 2 from 25ºC and 1 atm to its output conditions (1000ºC)

DĤ b = 48.60kJ/mol ® Table B.8
Therefore Ĥ 6 = DĤ a + DĤ b = -393.5+ 48.60 = -344.9kJ / mol
24 24
Heat of Formation (ΔĤof) Method (Example)
C3 H8 (g) +5O2 (g) ® 3CO2 (g) + 4H2O(l)
100 mol C3H8 (g)/s
25ºC, 1atm 100 mol O2(g)/s
2256 mol N2(g)/s
Furnace 300 mol CO2(g)/s Ĥ 7
400 mol H2O(v)/s
1000ºC, 1atm
600 mol O2 (g)/s
2256 mol N2(g)/s
300ºC, 1atm

1
H 2 (g)(25 oC,1atm) + O2 (g)(25 oC,1atm)
2
ß Ĥ a = (DĤOf ) H O( g )
2
Ĥ7 = Ĥ a + Ĥb
ß Ĥ b = DĤ H 2O,1000
25
H 2
O(g)(25 o
C,1atm) ÞÞ H 2
O(g)(1000 o
C,1atm)(Outlet condition) 25
Heat of Formation (ΔĤof) Method (Example)

Calculate Ĥ 7 for the exiting H 2O

1.START with H 2and O2 (elemental species) at 25ºC and 1 atm (references) and form 1 mol
of H 2O at 25ºC and 1 atm
1
H 2 (g)(25 oC,1atm) + O2 (g)(25 oC,1atm) ® H 2O(v)(25 oC,1atm)
2
ß Ĥ a = (DĤ Of ) H O(v) = -241.83kJ / mol(From Table B.1)
2

2.Bring H 2O from 25ºC and 1 atm to its output conditions (1000ºC)

DĤ b = 37.69kJ/mol ® Table B.8
Therefore Ĥ 7 = DĤ a + DĤ b = -241.83+ 37.69 = -204.14kJ / mol 26
Heat of Formation (ΔĤof) Method (Example)
5. Calculate H for the reactor

–103.8
8.47 32.47
8.12 30.56
–344.9
–204.1

27 27