Energy Balances on

Reactive Processes

1
 Energy Balances on Reactive
Processes Objectives
 Explain the concepts of heat of reaction (exothermic & endothermic), Hess’s
Law, heat of formation, heat of combustion
 Explain the concepts of combustion related knowledge; heating value, adiabatic
flame temperature, flammability limit, flash point and flame properties
 Calculate the enthalpy (and internal energy) change due to reaction using Hess’s
and from tabulated data of the standard heat of formation and the standard heat
of combustion.
 Write and solve an energy balance on a chemical reactor using either the heat of
reaction method or the heat of formation method
 Write and solve a reactive-energy system for the heat transfer for specified
inlet / outlet conditions, the outlet temperature for a specified heat input and
product composition for a specified outlet temperature
 Solve energy problems for processes involving solutions for which heats of
solution are significant
 Convert a higher heating value of a fuel to a lower heating value vice versa

2
 Chemical Composition

 When chemical systems react we need to deal with the composition of

the mixtures.
 The feed stream (or state) will have various reactants and non
reactive diluents. The reactants may or may not be in stoichiometric
proportions.

 The product stream (or state) will have the reaction products, all the
non-reactive species present in the feed. Also, some of the reactants
will be present if the reaction does not go to completion and/or the
feed ratio of the reactants is not stoichiometric.

 There are a large number of measures used for chemical composition

(next slide), but in this class we will focus primarily on mole fraction.
3
 Chemical Stoichiometry
 Balanced chemical reaction - same number of atoms on each side.

 Example: ammonia synthesis:

 1/2 N2 + 3/2 H2 → NH3.
 N2 + 3 H2 → 2 NH3.
 Which one is correct?

 Most chemical reactions can be balanced by inspection. About the most difficult
balancing task will come in combustion reactions.

 Example: Write a balanced chemical reaction for benzene (C6H6) complete

combustion.
C6H6 + 15/2O2 = 6CO2 + 3H2O
 Write the species without coefficients.
 Balance CO2 and H2O.
 Balance O2.

4
 Diluents (Inert)

 Chemical reactions can be thought of as algebraic expressions.

 We treat a diluent like a constant added to both sides of an equation:
 It can be kept if it is convenient to illustrate a point, or removed for
simplicity.

 The most common diluent we deal with is N2 which enters into reactive
streams as part of air.
 Air: 21% O2/79% N2 or 3.76 moles of N2 per 1 mole O2.

 This is lumping all the minor components of air (Ar, CO2, …) into the N2
column.

 Extend the benzene example to include the stoichiometric combustion of

benzene in air:
C6H6 + 15/2(O2 + 3.76 N2) = 6 CO2 + 3 H2O + 28.2 N2
5
 Chemical Stoichiometry Example

 Balance the reaction for stoichiometric acetone (CH3COCH3)

combustion in air.
 Find the mole fraction of CO2 (yCO2) in the effluent gas assuming
complete combustion.

moles of A
ya =
total stream moles

 Use Dalton’s and Amagat’s Law for ideal gas mixtures and Raoult’s
Law for ideal gas and liquid equilibrium

pA vA
ya = = p A = yaP = x Ap A*  T 
P V
6
 Chemical Stoichiometry - Solution

 Balance the reaction:

C3H6O + 4(O2 + 3.76 N2) = 3 CO2 + 3 H2O + 15.04 N2

 A common mistake in balancing reactions is to forget that the

fuel sometimes carries oxygen too.

 Compute the mole fraction of CO2:

3 moles CO 2 moles CO 2
yCO 2 = = 0.143
21.04 moles total moles total

7
 Heats of Reaction
 One of the most common engineering measures of a chemical reaction is its “heat of
reaction”.

 Heat of reaction (a.k.a. enthalpy of reaction) -- ∆H Reaction(T,P)

 “The enthalpy change for a process in which stoichiometric quantities of reactants
at T and P react completely in a single reaction to form products at the same T and
P.”
 Usually, T = 25°C and P = 1 atm. Standard heat of reaction ∆H° Reaction

 This definition is very useful for analysis of enthalpy changes in reactions in a general
sense.
 ∆HReaction < 0 – exothermic (“gets hot”).
 ∆HReaction > 0 – endothermic (“gets cold”).

 We won’t use heat of reaction directly in our first law analyses of reactions, but it is a
useful and often-tabulated property.

8
 Heats of Reaction

∆HR = -ve (exothermic)

∆HR = +ve (endothermic)
Tin, Pin, Hreac Tout, Pout, Hprod
Qin/Qout

Tin, Pin = Tout, Pout 2A + B 3C

Hprod  Hreac

∆HR = Hproduct - Hreactant

(heat/reaction enthalpy)
9
 Heats of Reaction

2A + B 3C  ĤR = -50 kJ/mol

= -50 kJ/2 mol A reacted
ĤR = -50 kJ/1 mol B reacted
= -50 kJ/3 mol C produced

Ĥr  To ,Po 
Difference in overall enthalpy H = nA,r
A

nA,out - nA,in nA,r

Extend of reaction is defined as = =
A A

x associated with enthalpy becomes H = Hr  To ,Po 

10
 Example

 Say that 150 mol of C was generated in the given reaction at 100oC and 1 atm,
the enthalpy change is

-50 kJ 150 mol C generated

H
 = = - 2500 kJ/ s
3 mol C generated s

11
 Features Heats of Reaction

0
ˆ
H r • Heats of reaction for reactant and product at reference
temperature of 25°C and 1 atm.
• Do not depend on pressure for low and moderate pressure (i.e. < 10
atm)
• Depend on the phase (gas, liquid, solid)

0
CH4(g) + 2O2(g) CO(g) + 2H2O(l) H ˆ
= -890.3kJ/mol
r (A)
0
CH4(g) + 2O2(g) CO(g) + 2H2O(g) =Hˆ-802.3kJ/mol
r (B)

ˆ o = H
H rB
ˆ o + 2 H
rA
ˆv  H2 0
(25o C)

12
 Heat of Reaction
(or Enthalpy of Reaction)
Ĥr (T,P)

Ĥro

ˆ ° = - 890.3 kJ
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2O (l) H r
mol

13
 Example of Heat of Reaction
(or Enthalpy of Reaction)
Example 2

ˆ ° = + 48.66 kJ
6C(s) + 3H2 (g)  C 6H6 (l) H r
mol

6 g-moles of solid carbon and 3 g-moles of gaseous hydrogen at 25 oC and 1 atm

react completely to form 1 g-mole of liquid benzene the product is brought
back to 25oC and 1 atm the specific enthalpy would be + 44.86 kJ. Q = ∆H ,
44.86 KJ of heat would have to be added into the reactor to keep the product at
25oC.

Note : At low and moderate pressures is

Ĥr (T,P) nearly independent of pressure .
Hence the heat of reaction may be written as Ĥr (T)

14
 Types of Heat of Reaction
 If Ĥr (T, P) < 0 => the reaction is exothermic .. Example 1
°

 less energy is required to break the reactant bonds than is released when the
product bonds form, resulting in a net heat release as the reaction proceeds
(i.e. Enthalpy of Reactants > Enthalpy of Products).
 This energy may be transferred from the reactor or else may serve to raise
the temperature of the reaction mixture
 Recall Example 1; ˆ ˆ (P,T) - H
ˆ (P,T) = - 890.3 kJ/ mol
H (P,T) = H
r prod react

 If Ĥ°r (T, P) > 0 => the reaction endothermic .. Example 2

 more energy is required to break the reactant bonds than is released when
the product bonds form, resulting in a net heat release, resulting in a net
absorption of energy as the reaction proceeds (i.e. Enthalpy of Reactants <
Enthalpy of Products)
 Unless this energy is supplied to the reactor as heat, the temperature
decreases ˆ (P,T) = H
ˆ (P,T) - H
ˆ (P,T) = + 48.66 kJ/ mol
 Recall Example 2; H r prod react 15
 Total Enthalpy Change
Due to Reaction
Recall Example 1; CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2O (l) ˆ ° = - 890.3 kJ
H r
mol

The standard (T = 25oC, P = 1 atm) heat of reaction is - 890.3 kJ per mol of

WHAT?
- 890.3 kJ - 890.3 kJ
Ĥ°r = =
1mol of CH4 reacted 2 mols of O 2 reacted
- 890.3 kJ - 890.3 kJ
= =
1mol of CO 2 generated 2 mols of liquid H2 O generated

and if for example, 2 mols /s of CH4 was reacted, the associated enthalpy
change is
kJ mols kJ
H = -890.3 x2 of CH4 reacted = 1780.6
1mol of CH4 reacted s s
16
 Total Enthalpy Change
Due to Reaction
and if for example, 4 mols /s of O2 was reacted the associated enthalpy
change is
kJ mols kJ
H = -890.3 x4 of O 2 reacted = 1780.6
2 mols of O 2 reacted s s

and if for example, 2 mols /s of CO2 was generated, the associated enthalpy
change is
kJ mols kJ
H = -890.3 x2 of CO 2 generated = 1780.6
1mols of CO 2 generated s s

and if for example, 4 mols /s of H2O was generated, the associated enthalpy
change is
kJ mols kJ
H = -890.3 x4 of H2O generated = 1780.6
2 mols of H2 O generated s s

17
 Total Enthalpy Change
Due to Reaction
 In general, if vA is the stoichiometric coefficient of a reactant or reaction
product A (negative if it is a reactant, positive if it is a product) and n A,r
moles of A are consumed / reacted or generated at T = To and P = Po, the
associated enthalpy change is
Ĥr  To ,Po 
H = nA,r
A

nA,out - nA,in nA,r

 Recall Chapter 4, the extent of reaction, ξ ; = =
A A

ˆ (T ,P )
H  H
 Then the associated enthalpy change is r o o
18
 The Value of Heat of Reaction
Depends on How Stoichiometric Equation
is Written

ˆ kJ
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (l) Hr = - 890.3
°

mol

1 g-mole of gaseous methane and 2 g-moles of gaseous oxygen at 25 oC and 1 atm react
completely to form 1 g-mole of gaseous carbon dioxide and 2 g-moles of liquid water
and the products are brought back to 25oC and 1 atm and the net enthalpy would be –
890.3 kJ. Q = ∆H , 890.3 KJ of heat would have to be transferred away from the reactor
to keep the products at 25oC.
ˆ ° = - 1780.6 kJ
2CH4 (g) + 4O 2 (g)  2CO 2 (g) + 4H2 O (l) H r
mol
2g-moles of gaseous methane and 4 g-moles of gaseous oxygen at 25 oC and 1 atm react
completely to form 2 g-moles of gaseous carbon dioxide and 4 g-moles of liquid water
and the products are brought back to 25oC and 1 atm and the net enthalpy would be –
1780.6 kJ. Q = ∆H , 1780.6 KJ of heat would have to be transferred away from the
reactor to keep the products at 25oC. 19
 The Value of Heat of Reaction Depends on the States
of Aggregation of Reactants and Products

ˆ ° = - 890.3 kJ
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (l) H r
mol
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (g) ˆ ° = - 802.3 kJ
H r
mol

The only difference between the reactions is that the water formed as a liquid in
the first reaction and as a vapor in the second reaction

hence the difference between the two heats of reaction must be the enthalpy
change associated with the vaporization of 2 mols of water at 25oC

i.e. ˆ = 2H
H ˆ
vap 
H2
O , 25 o

C = - 802.3 - (-890.3) = 88
kJ
mol
20
 Heat of Reaction of Propane
(State of Aggregation)

ˆ ° = - 2204 kJ
C 3H8 (l) + 5O 2 (g)  3CO 2 (g) + 4H2 O (l) H r
mol
C 3H8 (g) + 5O 2 (g)  3CO 2 (g) + 4H2 O (l) ˆ ° = - 2220 kJ
H r
mol

The only difference between the reactions is that propane exists as a liquid in the
first reaction and as a vapor in the second reaction

hence the difference between the two heats of reaction must be the enthalpy
change associated with the vaporization of 1 mol of propane at 25 oC

i.e. ˆ = H
H ˆ
vapC H
3 8
, 25o
C 
= - 2204 - (-2220) = 16
kJ
mol

21
 Heat of Reaction of Propane
(State of Aggregation)

ˆ ° = - 2204 kJ
C 3H8 (l) + 5O 2 (g)  3CO 2 (g) + 4H2O (l) H r
mol
C 3H8 (l) + 5O 2 (g)  3CO 2 (g) + 4H2O (g) ˆ ° = - 2028 kJ
H r
mol

The only difference between the reactions is that the water formed as a liquid in
the first reaction and as a vapor in the second reaction

hence the difference between the two heats of reaction must be the enthalpy
change associated with the vaporization of 4 mols of water at 25oC

i.e.
ˆ = 4 H
H ˆ
vapH 2
O , 25 o
C = - 2028 - (-2204) =176
kJ
mol

22
 Working Session 1 - Problem 9.3
The standard heat of the combustion reaction of liquid n-Hexane to
form CO2(g) and H2O(l) with all reactants and products at 77oF and 1
atm, is -1.791 x 106 Btu/lb-mole. The heat of vaporization of hexane
and water at 77oF is 13,550 Btu/lb-mole and 18,934 Btu/lb-mole,
respectively.

a. Use the given data to calculate the standard heat of reaction at

77oF for the combustion of n-hexane vapor to form CO2(g) and
H2O(g).

b. At what rate in Btu/s is heat absorbed or released (state which) if

120 lbm/s of O2 is consumed in the combustion of n-hexane vapor ,
water vapor is the products, and the reactants and products are all
23
at 77oF.
 Working Session 1 - Problem 9.3

a. Use the given data to calculate the standard heat of reaction at 77 oF

for the combustion of n-hexane vapor to form CO2(g) and H2O(g).

ˆ ° = - 1.791 x 106 Btu

C 6H14 (l) + 9.5O 2 (g)  6CO 2 (g) + 7H2 O (l) H r1
lb - mole
ˆ° = ? Btu
C 6H14 (g) + 9.5O 2 (g)  6CO 2 (g) + 7H2 O (g) Hr2
lb - mole

(Hypothetical reaction steps)

ˆo
ΔH r2
C6H14 (g), 77oF H2 O (g), 77oF,
O2 (g), 77oF CO2 (g), 77oF
Hˆ 1 = -Hˆ vap., C6H14 Hˆ 3 = 7 Hˆ vap., H2O
ˆ = H
H ˆo
C6H14 (l), 77 F o 2 r1 H2 O (l), 77oF
O2 (g), 77oF CO2 (g), 77oF
24
 Working Session 1 - Problem 9.3

Btu ˆ° Btu
Ĥ°vap, C6H6 (77 o F) = 13,550 H vap, H2 O
(77 o F) = 18,934
lb - mole lb - mole

ˆ ° = H
H ˆ + H ˆ + H ˆ
r2 1 2 3

= - Hˆ + H ˆ + 7 H
ˆ
vap., C 6H14 r1 vap., H2O

 Btu   6 Btu 
=  -13,550  +  -1.791 x 10 
 lb - mole C 6H14   lb - mole C 6H14 
 Btu   7 lb - moles H2 O formed 
+ 18,934   
 lb - mole H2 O   lb - mole C 6H14 reacted 
Btu
= -1.672 x 106
lb - mole

25
 Working Session 1 - Problem 9.3

b. If Q = ∆H, at what rate in Btu/s is heat absorbed or released (state which) if 120
lbm/s of O2 is consumed in the combustion of n-hexane vapor , water vapor is the
products, and the reactants and products are all at 77oF.

ˆ (77 o F)
  H
Q  H r2

lb m lb - mole
-120 x
n O 2 ,in s 32 lb m lb - mole
= = = 0.395
O 2 -9.5 s

 lb - mole   Btu  Btu

Q =  0.395  - 1.672 x 10 6
 = - 660,440
 s  lb - mole  s

Negative enthalpy indicates

an exothermic process
(i.e. heat is released )
26
 Working Session 2

ˆ ° = - 326 kJ
2CH3O H(l) + O 2 (g)  2CH2 O (g) + 2H2 O (l) H r
mol
2CH3O H(v) + O 2 (g)  2CH2 O (g) + 2H2 O (v) ˆ ° = ? kJ
H r
mol

a) Liquid methanol react with O2 as shown in the 1st reaction.

Calculate heat of reaction for the 2nd reaction

b) Suppose 200 mol/s of liquid methanol and 30% excess oxygen

are fed to the reactor at 25oC, a 50% fractional conversion
of methanol is obtained, and the products are brought back down
to 25oC. Calculate the output flowrate and heat.
(Consider the 1st reaction only)
27
 The Heat of Reaction
at Constant Volume
 Determined by the change on internal energy (∆U) between reactants and
products
 
ˆ (T)  H
Ur r  
ˆ (T)   PV
r
ˆ (T)  RT 
ˆ  H
r  i  gaseous
 gaseous
 products
 i 


 reactants 

Note: This last relation assumes that the gases behave as ideal gases, and
that the molar volumes of the liquid or solid components are small. If there
are no gaseous species involved in the reaction, Uˆ (T) » H
ˆ (T)
r r

C 6H14 (g) + 9.5O 2 (g)  6CO 2 (g) + 7H2 O (g)

Example :
 
ˆ (T)  RT    H
ˆ (T)  RT  7  6  9.5-1
ˆ (T)  H
Ur r  i  gaseous
 gaseous  i  r
 products 
 reactants 
28
 Hess’s Law (1840)

 The total heat liberated in a

series of chemical reactions is
equal to the sum of the heats
liberated in the individual steps.

 The heat liberated by ∆Ho,

(enthalpy) which is a state
function.

 State functions are independent

Germain Henri Hess of path.
(1802 - 1850)
29
 Difficulties for Measuring
Heat of Reaction
 Some reactions cannot be accomplished.
 Example 2C + O2(g)  2 CO (incomplete combustion)

 Alternative method
C + O2  CO2 ∆Hr1 = -393.51 kJ/mol
CO + ½ O2  CO2 ∆Hr2 = -282.99 kJ/mol

Ĥr3
0

C + ½ O2 (+ ½ O2) CO (+ ½ O2) ˆ 0 = H
H r3
ˆ 0 + (-H
r1
ˆ0 )
r2

= -393.51+ 282.99
ˆ0 ˆ0
H = -H = -110.52kJ/ mol
H = H r2
r1
CO2

30
 Hess’s Law

Just as the species in a chemical reaction can be treated as algebraic

quantities, so can the heats of reaction (and other thermodynamic
properties). Example:

Reaction 1: A+B C+D ∆HoReaction,1

Reaction 2: C+E F ∆HoReaction,2

Reaction 3 = Reaction 1 + Reaction 2 A+B+ED+F

∆HoReaction,3 = ∆HoReaction,1 + ∆HoReaction,2

31
 Hess’s Law

 Hess’s Law:
 “If the stoichiometric equation for Reaction 1 can be obtained by
algebraic operations on stoichiometric equations for Reactions 2,3,
…, then the heat of reaction of Reaction 1 can be found by the
same operations on the heat of reaction of Reactions 2,3,…”

 This concept allows us to compute heats of reaction from heats of

formation.
 Although there are a large number of molecules we deal with as
engineers, we can generally find heats of formation for them in
reference tables.
 However, the set of chemical reactions of interest to engineers is
virtually infinite, so creating tables of heats of reaction is not
practical.
32
 Hess’s Law - Example

B+ 6E  2D ˆo = ?
H r

2A + B  2C Hˆ o = -1000 kJ/ mol (1)

r1

A + D  C + 3E ˆ o = -2000 kJ/ mol

H (2)
r2

Equation (2) × -2 : -2A - 2D  -2C - 6E (2A)

Equation (2A) + Equation (1) : B+ 6E = 2D

Hˆ ro = (-2)Hˆ r2o + Hˆ r1o = + 3000 kJ/ mol

33
 Hess’ Law Example

Find the heat of reaction of the water gas shift reaction:

CO + H2O  CO2 + H2
A. For each species in the reaction of interest, write the reaction forming it
from the elements:
1. C + 1/2 O2  CO H°Reaction1 = H°f, CO
2. H2 + 1/2 O2  H2O H°Reaction2 = H°f, H2O
3. C + O2  CO2 H°Reaction3 = H°f, CO2

B. Combine the element reactions to form the reaction of interest (note the
sign):
Reaction3 - Reaction1 - Reaction2 = CO + H2O  CO2 + H2

C. Combine the heats of formation in the same way.

H°Reaction = - H°f, CO - H°f, H2O + H°f, CO2
34
 Hess’s Law/Hof Example

 The heat of formation is defined as the heat of reaction from the

elements.

 Practically, however, contacting elements rarely results in the

reaction of interest.

 A mixture of graphite, oxygen, and hydrogen won’t form

methanol.
 But lots of materials will react with oxygen – heats of combustion.

 Employ Hess’s Law to find heats of formation by indirect routes.

35
 Hess’s Law/Hof Example

 Find H°f for methanol from heat of combustion data.

Reaction 1. CH3OH + 3/2 O2  CO2 + 2 H2O

Reaction 2. C + O2(g)  CO2(g)
Reaction 3. H2(g) + 1/2 O2  H2O(g)

 Methanol from the elements:

C + 1/2 O2 + 2 H2  CH3OH.
Reaction 2 + 2(Reaction 3) – Reaction 1.

H°f(CH3OH) = H°Reaction2 + 2H°Reaction3 - H°Reaction1

36
 Hess’s Law

 HESS’s law :- If the stoichiometric equation for a reaction can be derived

from other reaction equations (by multiplication by constants, addition and
subtraction) then the heat of reaction for the first reaction can be derived by
performing the same algebraic operations on the heats of reaction for the
other reactions.
kJ
Rxn1 ... C  O 2  CO 2 Hr1
o
 393.5
Example : mol
1 kJ
Rxn2 ... CO  O 2  CO 2 Hr2
o
 282.99
2 mol
1 kJ
Rxn3 ... C  O 2  CO Hr3
o
 ?
2 mol
______________________________________________ __________
According to Hess's law:
1
Rxn3  Rxn1 - Rxn2 C  O  CO
2 2
kJ
and Hr3o  Hr1o -Hr2o Hr3o  110.52
mo l
________________________________________________________ 37
 Example 3 – Problem 9.6

 Formaldehyde may be produced in the reaction between methanol and oxygen

2CH3OH (l) + O2(g)  2HCHO (g) + 2H2O(l) Hor = -326.2 kJ/mol

The standard heat of combustion of hydrogen is

H2(g) + ½ O2(g)  H2O (l) Hor = -285.8 kJ/mol

Use these heats of reaction and Hess’s law to estimate the standard heat of
direct decomposition of methanol to form formaldehyde

CH3OH (l)  HCHO (g) + H2 (g)

38
 Example 3 – Problem 9.6

Rxn 1 : 2CH3OH (l) + O2(g)  2HCHO (g) + 2H2O(l) Horxn1 = -326.2 kJ/mol
Rxn 2 : H2(g) + ½ O2(g)  H2O (l) Horxn2 = -285.8 kJ/mol

Rxn 3 : CH3OH (l)  HCHO (g) + H2 (g) Horxn3 = ? kJ/mol

________________________________________________________________

According to Hess’s law

Rxn 3 = ½ Rxn 1 – Rxn2

Horxn3 = ½ Horxn1 - Horxn2

Horxn3 = ½ (-326.2)- (-285.8) = 122.7 kJ/mol

39
 Working Session 2 – Test 3 (2005/06)

a) Calculate Ĥ (kJ/mol) for the following reaction using the listed

standard enthalpy of reaction data

2N2(g) + 5O2(g)  2N2O5(s)

N2(g) + 3O2(g) + H2(g)  2HNO3(aq) Ĥo= -414 kJ/mol

N2O5(s) + H2O(l)  2HNO3(aq) Ĥo= -86 kJ/mol
O2(g) + 2H2(g)  2 H2O(l) Ĥo= -571.6 kJ/mol

40
 Heats of Formation

 Definition: “The enthalpy change (i.e., heat of reaction) associated with the formation of
one mole of a compound from the elements as they normally occur in nature at a reference
temperature and pressure (usually 25°C/1 atm).”
 Symbol: ∆H°f
 “°” refers to standard state. Usually pure, but could be in solution. T = 25°.
 Strictly speaking, the standard state is not specified to be 1 atm, but in practice is almost
always is.

 1/2 N2 + 3/2 H2 = NH3(v)

 ∆HReaction = - 46.19 kJ/mol, so
 ∆H°f,(NH3) = - 46.19 kJ/mol.

 Using this definition we can see that the heats of formation of the elements “as they
normally occur in nature” create the arbitrary zero enthalpy reference point for chemical
reactions.
 ∆H°f,(H2) = 0 kJ/mol at 25°C/1 atm.

41
 Heats of Formation
 The heat of formation, H ˆ, for a chemical species is equal to the heat of reaction
f
for the reaction forming 1 mol of this species from its “elements” at standard
conditions.

Note: Elements may be monoatomic (e.g., C) or diatomic (e.g., H 2), and the
standard state may be any phase (c, l, or g). In this notation, “c” means
crystalline or solid phase.

 The standard heat of formation ( H ˆ o) of the compound is the enthalpy change

f
associated with the formation of 1 mole of the compound at a reference
temperature and pressure (usually 25oC and 1 atm)

 Do not depend on pressure for low and moderate pressure (i.e. < 10 atm)
 Depend on the phase (gas, liquid, solid)
 The standard heat of formation an elemental species (e.g. O 2, N2, H2) is
zero. (WHY?)
 The standard heat of formation of some substances is given in Table B-1 42
 Heats of Formation

 An example - heat of formation for liquid propane:

3C  c  + 4H2 (g)  C 3H8 (l)
ˆ o = -119.8 kJ/ mol
H f  25 o
C, 1atm 

Note: This value is from Table B.1. Values for the heats of formation for
C(c) and H2(g) are listed in Table B.1 as zero, indicating that these are
elements. The heat of formation for propane as a gas is different (-103.8
kJ/mol). Why?

 Heats of reaction from heats of formation (by Hess’s law):

H r i f
ˆ o =  H
ˆo =
i
  i

products
 ˆo -
i H f   
i
reactants
ˆo
i H f  i

43
 Heat of Reactions from
Heats of Formation
ˆo =
H r

products

ˆo -
i H f     Hˆ 
i
reactants
i
o
f
i

C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l)

H r

ˆ o = 5 H
ˆo
f  CO 2
 ˆo
+ 6 H f  H2 O (l)
 ˆo
- 6 H f  C5H12 (l)

= 5[(-393.5) + 6(-285.84) -(-173.0)] kJ/mol

= -3509 kJ/mol

Ĥ 
o
f are obtained from Table B.1

44
 Heats of Reaction from
Heats of Formation- Example
 Find the standard heat of reaction for the reaction of hydrogenate
acetylene from ethane using heat of formation data from appropriate
table :
 C2H2 + 2 H2  C2H6.

Solution :
 Reaction 1: 2 C + H2 = C2H2
 Reaction 2: 2 C + 3 H2 = C2H6

 Acetylene hydrogenation = Reaction 2 – Reaction 1 (by Hess’ Law).

 Hof,Reaction = Hof,Reaction2 - Hof,Reaction1 = - 311.41 kJ/mol (exothermic).
45
 Calculation of a Heat of Reaction from
Heats of Formation
 An example - consider the reaction

CH4  g  + 2O 2  g   CO 2  g  + 2H2O (v)

Write the formula for H ˆ °in terms of the standard heats of formation of
r
the reactants and products
C(s) + 2H2 (g)  CH4 (g) ˆ ° = H
H r1
ˆ°
f  CH4 (g)

C(s) + O 2 (g)  CO 2 (g) ˆ ° = H

H r2
ˆ°
f   CO 2 (g)

H2 (g) +
1
2
O 2 (g)  H2O (g) ˆ ° = H
H r3
ˆ°
f   H2 O(g)

  
Hˆ °r = 2 Hˆ °f
H2 O(g)
 
+ Hˆ °f
CO 2 (g) 
 
 -  Hˆ °
 
f

CH4 (g) 
 46
 Calculation of a Heat of Reaction from
Heats of Formation

 An example - The standard heat of reaction for methane if the water

is formed as a liquid:
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (l)

 
Hˆ °r = 2 Hˆ °f
H2 O(l)
 
+ Hˆ °f
CO 2 (g) 
 
 -  Hˆ °
 
f
CH4 (g)
 
+ 2 Hˆ °f 
O 2 (g) 

Read the standard heat of formation of respective species from Table
B.1.
ˆ   kJ   kJ    kJ   kJ  
Hr = 2  -285.84
°
 +  -393.5   -  -74.85 +20 
  mol   mol    mol   mol  
ˆ ° = -890.33 kJ
H r
mol 47
 Example: Heats of Formation

 An example - The standard heat of reaction for methane if the water

is formed as a vapor:
CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (g)

 
Hˆ °r = 2 Hˆ °f
H2 O(g)
 
+ 2 Hˆ °f
CO 2 (g) 
 
 -  Hˆ °
 
f
CH4 (g)
 
+ 2 Hˆ °f 
O 2 (g) 

Read the standard heat of formation of respective species from Table
B.1.

ˆ ° = 2  -241.83 kJ  +  -393.5 kJ   -  -74.85 kJ  + 2  0 kJ  

H r   mol
 
mol
  
mol
 
mol

          
ˆ ° = -802.31 kJ
H r
mol 48
 Solution of Example:
Heats of Formation

Rxn1: CH4 (g)+ 2O 2 (g)  CO 2 (g) + 2H2O(l)  Hˆ ro

Rxn1
 kJ
= -890.3
mol
Rxn2 : CH4 (g)+ 2O 2 (g)  CO 2 (g) + 2H2O(g) Hˆ ro
Rxn2
= -802.3
kJ
mol
 Rxn1- Rxn2 = 2H2O(l)  2H2O (g)  
Hˆ = ?
vap

 
Hˆ
vap

ˆo
= Hr  Rxn2

- Hˆ ro  Rxn1
= 88
kJ
mol
 Hˆ 
o
r
Rxn2

ˆo
= Hr  Rxn1
ˆ
+ 2H vap

kJ
where, Hˆ vap = 44 is the heat of vaporization of water at 25o C and 1 atm
mol

49
 Working Session 1 - Problem 9.8
 Trichloroethylene, C2HCl3 , may be produced in a two-step reaction sequence as follows;

C2H4 (g) + 2Cl2(g)  C2H2Cl4 (l) + H2(g) Hor = -385.76 kJ/mol

C2H2Cl4(l)  C2HCl3(l) + HCl (g)

The standard heat of formation of liquid trichloroethylene is -276.2 kJ/mol

a) Calculate the standard heat of formation of tetrachloroethane, C2H2Cl4 (l) and the
standard heat of the second reaction
b) Use Hess’s law to calculate the standard heat of reaction of

C2H4 (g) + 2Cl2(g)  C2HCl3 (l) + H2(g) + HCl(g)

c) If 300 mol/h of C2HCl3 (l) is produced in the reaction of part (b) and the reactants and
products are all at 25oC and 1 atm, how much heat is evolved or absorbed in the
process?

50
 Working session 1 - Problem 9.8

a) Calculate the standard heat of formation of tetrachloroethane, C2H2Cl4 (l)

C2H4 (g) + 2Cl2(g)  C2H2Cl4 (l) + H2(g) Hor = -385.76 kJ/mol

Hor = (Hof) H2(g) + (Hof) C2H2Cl4(l) - (Hof) C2H4(g) - 2(Hof) Cl2(g)

read the standard heat of formation of ethylene, chlorine and hydrogen from Table B-1

-385.76 = [0 + (Hof) C2H2Cl4(l) ] - [(52.28 - 2(0)]

(Hof) C2H2Cl4(l) = - 333.48 kJ/mol

51
 Working Session 1 - Problem 9.8

Calculate the standard heat of the second reaction

C2H2Cl4(l)  C2HCl3(l) + HCl (g)

Hor = (Hof) HCl(g) + (Hof) C2HCl3(l) - (Hof) C2H4Cl4(l)

Read the standard heat of formation of hydrochloric acid from Table B-1 & the
standard heat of formation of liquid trichloroethylene and tetrachloroethane are -276.2
kJ/mol and -333.48 kJ/mol, respectively.

Hor = -92.31 - 276.2 – (- 333.48) = - 35.03 kJ/mol

52
 Working Session 1 - Problem 9.8

b) Use Hess’s law to calculate the standard heat of reaction of

C2H4 (g) + 2Cl2(g)  C2HCl3 (l) + H2(g) + HCl(g)

According to Hess’s law

Rxn 1 : C2H4 (g) + 2Cl2(g)  C2H2Cl4 (l) + H2(g) Horxn1 = -385.76 kJ/mol

Rxn 2 : C2H2Cl4(l)  C2HCl3(l) + HCl (g) Horxn2 = -35.08 kJ/mol

Rxn 3 : C2H4 (g) + 2Cl2(g)  C2HCl3 (l) + H2(g) + HCl(g) Horxn3 = ? kJ/mol
_________________________________________________________________

Rxn 3 = Rxn 1 + Rxn 2

Horxn3 = - 35.03 - 385.76 = - 420.76 kJ/mol

53
 Working Session 1 - Problem 9.8

c) If 300 mol/h of C2HCl3 (l) is produced in the reaction of part (b) and
the reactants and products are all at 25oC and 1 atm, how much heat
is evolved or absorbed in the process?

C2H4 (g) + 2Cl2(g)  C2HCl3 (l) + H2(g) + HCl(g)

Hor = -420.76 kJ/mol

Hˆo
Q = H
 = r
nA,r
A
kJ
-420.76
mol C 2HCl3 formed mol C 2HCl3 formed hr kJ
= x 300 x = - 35.06
1 hr 3600 s s

54
 Heats of Combustion

 Combustion involves a chemical reaction between combustible species and oxygen

(usually from air) to produce heat and combustion products (mainly water and carbon
dioxide plus some other by-products such as carbon monoxide, oxides of nitrogen /
sulphur , unburned fuels and radicals)

 The standard heat of combustion, H°c, is the heat released when one mole of a
substance reacts with oxygen to yield specified products in a specified phase:

 CO2 is always gas phase.

 H2O can be liquid or vapor with the reactants and products at 25°C, 1 atm.

The standard heat of full combustion of some substances is given in Table B-1

55
 Heats of Combustion

 The standard heat of combustion of liquid ethanol is given in Table B1 as –

H°c = -1366.9 kJ/mol which signifies

C2H5OH (l) + 3O2 (g)  2 CO2 (g) + 3 H2O (l) : Hr (25oC, 1 atm) = -1366.9 kJ/mol

 Based on the assumptions:

 a) All carbons in the fuel forms CO2 (g)
 b) All hydrogen forms H2O (l)
 c) All sulfur forms SO2 (g)
 d) All nitrogen forms N2 (g)

56
 Heat of Reactions from
Heat of Combustion
 The standard heat of combustion in Table B-1

 The standard heats of reactions that involve only combustible

substances and combustion products can be calculated from tabulated
standard heats of combustion, in another application of Hess’s law

H r
 i c
ˆ o = -  H
i

ˆo  i
= 
reactants
   
ˆo -
i H c
i
products
ˆo
i H c  i

If any of reactants or products are themselves combustion products

Hˆo
(CO2, H2O(l), SO2(g)…) their c terms in the above equation should
be set equal to zero
57
 Heat of Reaction from
Heat of Combustion

Calculate the standard heat of reaction for the dehydrogenation of ethane

C 2 H6  C 2 H4 + H 2
From Table B1

 Ĥ o
c
C 2H6
= -1559.9 kJ/ mol

 Ĥ o
c
C 2 H4
= -1411.0 kJ/ mol

 Ĥ o
c
H2
= - 285.84 kJ/ mol

Then the Hr will be

r 
ˆ o = H
H ˆo
c  C 2H6
 ˆo
- H c  C 2H4
 ˆo
- H c  H2
= 136.9 kJ/ mol

58
 Hess’s Law/Hoc Example

 Find the HoReaction for the partial oxidation of methane reaction (forming
methanol) from heat of combustion data.

Reaction 1: CH4 + 1/2 O2  CH3OH HReaction1

 Combustion reactions :

Reaction 2: CH4 + 2 O2  CO2 + 2 H2O HReaction2

Reaction 3: CH3OH + 3/2 O2  CO2 + 2 H2O HReaction3

 We can find the heat of reaction of Reaction 2 and Reaction 3 using a bomb
calorimeter.
Reaction 1 = Reaction 2 – Reaction 3.
HReaction1 = HReaction2 - HReaction3
59
 Calculation of the Heat of Reactions from
Heat of Combustion & Heat of Formation

 Calculate the standard heat of the acetylene hydrogenation reaction

C2H2 (g) + 2H2(g)  C2H6 (g) Hor = ? kJ/mol

a) using the standard heat of combustion (Table B-1)

H r 
ˆ o = H
ˆo
c  C 2H2
 ˆo
+ 2 Hc  
H2
ˆo
- H c  C 2H6

= -1299.6 + 2(-285.84) - (-1559.9)

kJ
= - 311.38
mol
60
 Solution

b) using the standard heat of formation (Table B-1)

H r 
ˆ o = H
ˆo
f  C 2H6
 ˆo
- H f  C 2H2
 ˆo
+ 2 H f  H2

= - 84.67 - 226.75 - 2(0)

kJ
= - 311.42
mol

61
 Solution

c) Standard Heat of Combustion + Hess’s law

Rxn 1 : C2H2 (g) + 2.5O2(g)  2CO2 (g) + H2O (l) Hoc = -1299.6 kJ/mol
Rxn 2 : H2(g) + 0.5O2(g)  H2O (l) Hoc = -285.84 kJ/mol
Rnx 3 : C2H6 (g) + 3.5O2(g)  2CO2 (g) + 3H2O (l) Hoc = -1559.9 kJ/mol

_________________________________________________________________

Rxn 4 : C2H2 (g) + 2H2(g)  C2H6 (g) Hoc = ? kJ/mol

Rxn 4 = Rxn 1 + 2Rxn2 – Rxn3

Hoc = -1299.6 + 2(-285.84) – (-1559.9) kJ/mol = -311.38 kJ/mol

62
 Working Session

Methane and oxygen react in the presence of a catalyst to form

formaldehyde. In a parallel reaction, methane is oxidized to CO2 & H2O

CH4 (g) + O 2 (g)  HCHO (g) + H2 O (g) ˆ° =

Hr1

CH4 (g) + 2O 2 (g)  CO 2 (g) + 2H2 O (g) ˆ° =

H r2

a) Calculate the standard heat of reaction for both reaction

a) If mole of CO2 in the effluent gases is 0.15 and there is no remaining

O2, determine the composition of effluent gases and the amount of
heat remove from the reactor

63