Balance on reactive processes

Principles and Calculations in Petrochemical Engineering, KMITL 1

Heat of reaction

The heat of reaction (or enthalpy of reaction), denoted ∆𝐻 ෡ 𝑟(T, P), is the
enthalpy change for a process in which stoichiometric quantities of reactants
at temperature T and pressure P react completely in a single reaction to
form products at the same temperature and pressure. For example, the heat
of the calcium carbide reaction at 25 oC and 1 atm is ;

෡ 𝑟(25 oC,1 atm) = - 125.4 kJ/mol

∆𝐻

𝑄= ∆𝐻 = 𝐻𝑝𝑜𝑟𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = - 125.4 kJ/mol

Noted : a negative Q implies flow of heat out of the system

Principles and Calculations in Petrochemical Engineering, KMITL 2

Heat of reaction

For example ;

2A + B 3C ෡ 𝑟(100 oC,1 atm) = - 50 kJ/mol

∆𝐻

means that the enthalpy change for the given reaction is;

- 50 kJ/mol - 50 kJ/mol - 50 kJ/mol

= =
2 mol A consumed 1 mol B consumed 3 mol C generated

If 15 mol of C/s was generated in the given reaction at 100 oC and 1 atm,
it means ;

- 50 kJ/mol 150 mol C generated

∆𝐻ሶ = = - 2500 kJ/s
3 mol C generated s

Principles and Calculations in Petrochemical Engineering, KMITL 3

Heat of reaction

Extent of reaction, ξ , as a measure of how far a reaction has proceeded.

Then ;

Principles and Calculations in Petrochemical Engineering, KMITL 4

Heat of reaction

Noted ; for a continuous process

𝑛ሶ A,r (mol) 𝑛ሶ A,r (mol/s)

𝜉 (mol) 𝜉ሶ (mol/s)

∆𝐻(kJ/s) ሶ
∆𝐻(kJ/s)

Remarks ;

1. ෡ 𝑟(T, P) is exothermic
Negative ∆𝐻

෡ 𝑟(T, P) is endothermic
Positive ∆𝐻

෡ 𝑟(T, P) is nearly independent of

2. At low and moderate pressure, ∆𝐻
pressure

෡ 𝑟(T)
then as ∆𝐻

Principles and Calculations in Petrochemical Engineering, KMITL 5

Heat of reaction

Remarks ;

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

equation is written. For example ;

4. The value of a heat of a reaction depends on the states of aggregation

(gas, liquid, or solid) of the reactants and products. For example ;

5. The standard heat of reaction, ∆𝐻෡𝑟𝑜 , is the heat of reaction when both the
reactants and products are at a specified reference temperature and pressure,
usually at 25 oC and 1 atm.

Principles and Calculations in Petrochemical Engineering, KMITL 6

Calculation heats of reaction

Example 12.1
(1)

Principles and Calculations in Petrochemical Engineering, KMITL 7

Example 12.1 (2)

Principles and Calculations in Petrochemical Engineering, KMITL 8

(3)

From ;

Find out ;

600 mol
Then; = - 1.58 × 106 kJ/s

Principles and Calculations in Petrochemical Engineering, KMITL 9

Measurement and calculation of heats of reaction : Hess’s Law

A heat of reaction may be measured in a calorimeter. The rise or fall of the

fluid temperature can be measured and used to determine the energy
released or absorbed by the reaction, and the value of ∆𝐻 ෡𝑟𝑜 may then be
calculated from that energy and known reactant and product heat
capacities.

෡𝑟𝑜 for this following reaction ;

Suppose, you wish to determine ∆𝐻

෡𝑟𝑜 = ?
∆𝐻

Principles and Calculations in Petrochemical Engineering, KMITL 10

Measurement and calculation of heats of reaction : Hess’s Law

You may construct a process path and carry out the reactions as ;

(1)
(2)
(3)

Principles and Calculations in Petrochemical Engineering, KMITL 11

Measurement and calculation of heats of reaction : Hess’s Law

From the previous equations, (1), (2), and (3) ; This result could have
obtained more concisely by treating the stoichiometric equations for
reactions (1) and (2) as algebraic equations.

………….(1) + (2)

………….(3)

Then ;

Principles and Calculations in Petrochemical Engineering, KMITL 12

 Hess’s Law

The standard heats of the following combustion reactions

Example 12.2 have been determined experimentally :

Use Hess’s Law and the given heats of reaction to determine the standard heat
of the reaction.

From above equations,

it can be implied that ; (4) = [2×(2)] + [3×(3)] - (1)

Principles and Calculations in Petrochemical Engineering, KMITL 13

Formation reactions and heats of formation

A formation reaction of compound is the reaction in which the compound

is formed from its elemental constituents as they normally occur in
nature (e.g., O2 rather than O)

Standard heats of formation, ∆𝐻 ෡𝑓𝑜 , for many compounds are listed in

Table B.1 (usually 25 oC and 1 atm )

Example for liquid benzene ;

Principles and Calculations in Petrochemical Engineering, KMITL 14

Formation reactions and heats of formation

It may be shown using Hess’s Law that if vi is stoichiometric coefficient of

the ith species participating in a reaction (+ for products, - for reactants)
𝑜
෡𝑓𝑖
and ∆𝐻 is the standard heat of formation of this species, then the
standard heat of the reaction is

Principles and Calculations in Petrochemical Engineering, KMITL 15

Formation reactions and heats of formation

Example 12.3 Determine the standard heat of reaction for the combustion of
liquid n-pentane, assuming water(l) is a combustion product.

Solutions ;

Heats of formation from Table B.1 ;

Principles and Calculations in Petrochemical Engineering, KMITL 16

Example 12.3
We may write the stoichiometric equations as following :

(1)
(2)
(3)

The desired reaction is ;

(4)

Then ; (4) = [2×(2)] + [6×(3)] - (1)

Principles and Calculations in Petrochemical Engineering, KMITL 17

Heats of combustion

The standard heat of combustion of substance, ∆𝐻 ෡𝑐𝑜 , is the heat of the

combustion of that substance with oxygen to yield specified products [e.g.,
CO2(g) and H2O(l)], with both reactants and products at 25 oC and 1 atm.

For example, the liquid ethanol is given in Table B.1 as following ;

෡𝑐𝑜 (25 oC, 1 atm) = -1,366.9 kJ/mol

: ∆𝐻

෡𝑐𝑜 in Table B.1, which equals the desired heat of reaction,

The value of ∆𝐻
can be determined entirely from heats of combustion as

Principles and Calculations in Petrochemical Engineering, KMITL 18

General Procedure

1. Complete the material balance calculations on the reactor to the

greatest extent possible.

2. Choose reference states for specific enthalpy calculations. (find

෡ or 𝑈
out 𝐻 ෡ to calculate ∆𝐻
෡ or ∆𝑈
෡)

classification

2.1) Heat of reaction method

2.2) Heat of formation method

෡𝑟𝑜 for ∆𝐻ሶ calculation

Find out an appropriate reaction to know the ∆𝐻
in the next step

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General Procedure

3. Calculate ∆𝐻ሶ for the reactor.

for single reaction

for multiple reactions

ሶ ሶ ሶ ሶ
When ;

vA is stoichiometric coefficient of the A species participating in a reaction

(+ for products, - for reactants)

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General Procedure

Process path for heat reaction method

Principles and Calculations in Petrochemical Engineering, KMITL 21

General Procedure

Process path for heat formation method

Principles and Calculations in Petrochemical Engineering, KMITL 22

Energy balance on reactive processes

Example 12.4 Calculate the heat transfer rate of the combustion as the
flowchart below,

Energy balance ;

For Opened System 𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

𝑄ሶ = ∆𝐻ሶ

Principles and Calculations in Petrochemical Engineering, KMITL 23

Example 12.4 Heat of reaction method

ሶ ሶ ሶ ሶ
From ;

If A is propane, then ;

If A is carbon dioxide, then ;

𝑛ሶ 𝐶𝑂2 𝑛ሶ 𝐶𝑂2 300 − 0

𝒗𝑪𝑶𝟐 3

*** 𝜉ሶ does not depend on species of reactants or products ***

Principles and Calculations in Petrochemical Engineering, KMITL 24

Example 12.4

Choose reference states

Principles and Calculations in Petrochemical Engineering, KMITL 25

Example 12.4
෡𝑖
Calculate the unknown 𝐻

of

of

of From Table B.8

of

of

of

Principles and Calculations in Petrochemical Engineering, KMITL 26

Example 12.4 Calculate ∆𝐻ሶ

for single reaction

Substitution of previously calculated values into above equation then gets ;

∆𝐻ሶ = - 1.26 × 105 kJ/s

REMARK !! 𝑄ሶ = ∆𝐻ሶ

Principles and Calculations in Petrochemical Engineering, KMITL 27

Example 12.4 Heat of formation method

Choose reference states

Noted!
- Heat capacity formulas is given from Table B.2
- Latent heats is given from Table B.1
- Specific enthalpies is given from Table B.8 or B.9

Principles and Calculations in Petrochemical Engineering, KMITL 28

Example 12.4
෡𝑖
Calculate the unknown 𝐻

of

From Table B.1

of

of
From Table B.8
of

of

Principles and Calculations in Petrochemical Engineering, KMITL 29

Example 12.4

of

From Table B.1 and B.2

of

From Table B.1 and B.8

Principles and Calculations in Petrochemical Engineering, KMITL 30

Example 12.4 Calculate ∆𝐻ሶ

for single reaction

Substitution of previously calculated values into above equation then gets ;

∆𝐻ሶ = - 1.26 × 105 kJ/s

REMARK !! 𝑄ሶ = ∆𝐻ሶ

Principles and Calculations in Petrochemical Engineering, KMITL 31

Energy balance on an ammonia oxidizer

100 mol NH3/s and 200 mol O2/s at 25 oC are fed into a reactor
Example 12.5
in which the ammonia is completely consumed. The product gas
emerges at 300 oC. Calculate the rate at which heat must be
transferred to or from reactor, assuming operation at
approximately 1 atm.

Principles and Calculations in Petrochemical Engineering, KMITL 32

Example 12.5 Heat of reaction method

Choose reference states

Calculate 𝜉ሶ

Principles and Calculations in Petrochemical Engineering, KMITL 33

Example 12.5 From Table B.8

From Table B.2

From Table B.8

Calculate ∆𝐻ሶ

∆𝐻ሶ = - 19,700 kJ/s

Energy balance ; 𝑄ሶ - 𝑊ሶ 𝑠 = ∆𝐻ሶ + ∆𝐸ሶ k + ∆𝐸ሶ p

𝑄ሶ = ∆𝐻ሶ = -19,700 kW

Principles and Calculations in Petrochemical Engineering, KMITL 34