Chemical Process Calculations

Autumn 2020

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
 Energy Balances
Mon 11/02/2020

Laws of Thermochemistry:

At a given temperature and pressure, the quantity of energy required to decompose a chemical
compound into its elements is precisely equal to that evolved in the formation of that compound
from its elements.

Law of Constant-heat Summation:

It states that the net heat evolved or absorbed in a chemical process is the same whether the
reaction takes place in one or in several steps. The total change in enthalpy of a system is
dependent on the temperature, pressure, state of aggregation, and state of combination at the
beginning and at the end of the reaction and is independent of the number of intermediate
chemical reactions involved. This principle is known as the law of Hess.

Hence, using this principle, it is possible to calculate the heat of formation of a compound from
a series of reactions not involving the direction formation of the compound from the elements.
the majority of chemical compounds cannot be formed in the pure state directly from the
elements (such as CO):
𝐶 + 𝑂2 = 𝐶𝑂2 ∆𝐻1
𝐶𝑂 + 0.5𝑂2 = 𝐶𝑂2 ∆𝐻2

Heat of formation of CO = ∆𝐻1 − ∆𝐻2 2

 Energy Balances

Standard Heat of Combustion:

The heat of combustion of a substance is the heat of reaction resulting from the oxidation
of the substance with molecular oxygen. Note: the heat of combustion is negative.

The standard heat of combustion is that resulting from the combustion of a substance, in the
state that is normal to 25°C and atmospheric pressure, with the combustion beginning and
ending at a temperature of 25°C.

Calculation of the Standard Heat of Reaction from Heats of Formation:

[∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = σ ∆𝐻𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − σ ∆𝐻𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) ]25℃

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 Energy Balances

Ques. 1: Calculate the standard heat of reaction, ∆𝐻25 of the following:

CaC2 (s) + 2H2O (l) = Ca(OH)2 (s) + C2H2 (g)

Heat of formation:
Species ∆𝑯𝒇
CaC2 (s) -15000 cal
2H2O (l) -68317.4 cal
C2H2 (g) -54182.6 cal
Ca(OH)2 (s) -235800 cal

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 Energy Balances

Calculation of the Standard Heat of Reaction from Heats of Combustion:

For organic compounds, the standard heat of reaction can be conveniently calculated by using
directly the standard heats of combustion instead of standard heats of formation.

[∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = σ ∆𝐻𝑐(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) − σ ∆𝐻𝑐(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) ]25℃

Note:
1. Heat of formation of organic compounds are small in comparison to the heats of combustion
2. Heats of reaction are small in the systems involving only combinations of organic compounds

General equation to calculate the heat of formation of a compound CaHbBrcCldFeIfNgOhSi

from its heat of combustion:

If ∆𝐻𝑐 is the heat of combustion of this compound corresponding to the final products,
CO2(g), H2O(l), Br(l), Cl2(g), HF(aq), I(s), N2(g), SO2(g), and ∆𝐻𝑓 its heat of formation, then,

∆𝐻𝑓 = - ∆𝐻𝑐 − 94501.8a − 34158.7b − 41502e − 70960i

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 Energy Balances

If ∆𝐻′𝑐 is the heat of combustion of this compound corresponding to the final products,
CO2(g), H2O(l), Br2(g), HCl(aq), I(s), HNO3(aq), H2SO4(aq), and ∆𝐻𝑓 its heat of formation, then,

∆𝐻𝑓 = - ∆𝐻′𝑐 − 94501.8a − 34158.7b + 3670C − 5864.3d − 44502e − 15213.3g − 148582.6i

Ques. 2: Calculate the standard heat of formation for (a) CH3Cl (g) (b) CH3OH (l)

Given: standard heat of combustion, ∆𝐻𝑐 for (a) 182.81 kcal (b) 173.65 kcal

Answer:
𝑎 ∆𝐻𝑓 = 182810−94501.8 1 − 34158.7 3 − 5864.3 1 = −19582 cal

𝑏 ∆𝐻𝑓 = 173650−94501.8 1 − 34158.7 4 = −57037 cal

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 Energy Balances

Ques. 3: Calculate the standard heat of reaction ∆𝐻25 of the following:

CH3Cl (g) + KOH (s) = CH3OH (l) + KCl(s)

The heats of formation of the inorganic compounds:

KOH(s) , ∆𝐻𝑓 = −101780cal ; KCl(s) , ∆𝐻𝑓 = −104175cal

Answer: ∆𝐻25 = -37455 cal

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 Energy Balances

Heat of reaction for incomplete reaction:

For each species associated with the reaction for an unsteady-state, closed system (no
flow in or out):

𝑓𝑖𝑛𝑎𝑙
𝑛𝑖 = 𝑛𝑖 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 + ν𝑖 ε

The equivalent for a steady-state flow system is

𝑛𝑖 𝑜𝑢𝑡 = 𝑛𝑖 𝑖𝑛 + ν𝑖 ε
Thus, for a steady-state flow system

𝐹𝑙𝑜𝑤 𝑜𝑢𝑡 𝐹𝑙𝑜𝑤 𝑖𝑛

∆𝐻𝑟𝑥𝑛 25°𝐶, 1 𝑎𝑡𝑚 = ෍ (𝑛𝑖 𝑖𝑛 + ν𝑖 ε ) ∆𝐻෢ ෢

𝑓,𝑖 − ෍ (𝑛𝑖 𝑖𝑛 ) ∆𝐻𝑓,𝑖
𝑖 𝑖

= ε σ ν𝑖 ∆𝐻෢
𝑓,𝑖 = ε∆𝐻𝑟𝑥𝑛

For species not present as a product or reactant, use 𝑛𝑖 = 0 and ν𝑖 = 0

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 Energy Balances
X= 0.8
C6H6 (g) , 25°C, 1 atm
C6H12 (g) , 25°C, 1 atm
Reactor
3H2 (g) , 25°C, 1 atm

C6H6 (g) + 3H2 (g) = C6H12 (g)

Limiting reactant: C6H6 (g)
Compound Specific Enthalpy
(kJ/g mol)
C6H6 (g) 82.927
H2 (g) 0
C6H12 (g) -123.1

Solution:
−𝑓 (𝑛𝑖𝐿𝑅 ) −0.8 (1)
ε= = = 0.8
ν𝐿𝑅 −1

∆𝐻𝑟𝑥𝑛 25°𝐶, 1 𝑎𝑡𝑚 = 0.8 1 −123.1 + −3 0 + −1 82.927 = −164.8kJ

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 Energy Balances

Ques. 4: Calculate ∆𝐻°𝑟𝑥𝑛 𝑝𝑒𝑟 𝑔𝑚𝑜𝑙 𝑜𝑓 𝑁𝐻3𝑓𝑜𝑟 𝑡ℎ𝑒 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓

4 𝑔𝑚𝑜𝑙 𝑜𝑓 𝑁𝐻3 𝑎𝑛𝑑 5g mol of O2:
4NH3 (g) + 5O2 (g) → 4NO(g) + 6H2O(g)

Given:
Compound ∆𝐻°𝑓 (kJ/gmol) [ 25°C, 1 atm)
NH3 (g) -46.191
O2 (g) 0
NO(g) +90.374
H2O(g) -241.826

Answer: -226.174kJ/g mol NH3

6*(-241.826) +4*(+90.374) = heat of formation for product =-1089.46kJ

5*(0) +4*(-46.191) = heat of formation for reactant = -184.764kJ
Heat of reaction = product-reactant = -904.696
Per mol of NH3= -904.696/4= -226.174kJ
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 Energy Balances

Calculate heat of reaction for a process in which the reactants enter and products exit
at temperature other than 25°C and 1 atm.
Note: Enthalpy is a state variable (path independent).

Reactants at Ti ∆𝐻𝑟𝑥𝑛 (T) Products at T

(1) (2)

Reactants :
{Sensible heats} Products :
∆𝑯 = 𝑯 𝟐𝟓°𝑪 − 𝑯(𝑻𝒊)
∆𝑯 = 𝑯 𝑻 − 𝑯(𝟐𝟓°𝑪)

Reactants at 25°C ∆𝐻𝑟𝑥𝑛 (25°C) Products at 25°C

(3) (4)

R-> P
Enthalpy change (in the given T) of product-reactant = heat of reaction 11
 Energy Balances

Objective: Calculate ∆𝐻𝑟𝑥𝑛 (the enthalpy change) from state 1 to state 2.

This value is the same as summing the values of all of the enthalpy changes 1 to 3, 3 to 4,
and 4 to 2. The enthalpy change for the reactant and products is the combination of the
sensible and latent heat (enthalpy) changes that might be taken from a table, or be
calculated using a heat capacity equation for each species. In the figure (previous slide),
the products are shown leaving the reactor at a common temperature, but each reactant
might exist at a separate temperature Ti .
Then the sensible heat plus any phase change for each component would be
𝑇𝑖
𝐻𝑖 𝑇𝑖 − 𝐻𝑖 25°𝐶 = 𝑛𝑖 න ෣𝑐ℎ𝑎𝑛𝑔𝑒
𝐶𝑝,𝑖 𝑑𝑇 + 𝑛𝑖 ∆𝐻𝑖,𝑝ℎ𝑎𝑠𝑒
25°𝐶

If any slight pressure and mixing effects are ignored, for a steady-state system, the heat of
reaction at temperature T other than the reference temperature is
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠

∆𝐻𝑟𝑥𝑛 T = ෍ ෢𝑖 25°𝐶 − 𝐻
𝑛𝑖 𝐻 ෢𝑖 𝑇 + ∆𝐻𝑟𝑥𝑛 25°𝐶 + ෍ ෢𝑖 𝑇 − 𝐻
𝑛𝑖 𝐻 ෢𝑖 25°𝐶
𝑖 𝑖

And in shorter notation,

∆𝐻𝑟𝑥𝑛 T = H T − H 25°𝐶 products − H T − H 25°𝐶 reactants + ∆𝐻𝑟𝑥𝑛 25°𝐶

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 Energy Balances

Ques. 5: Public concern about the increase in the carbon dioxide in the atmosphere has led
to numerous proposals to sequester or eliminate the carbon dioxide. An inventor believes
he has developed a new catalyst that can make the gas phase reaction

CO2 (g) + 4H2 (g) → CH4(g) + 2H2O(g)

proceed with 40% conversion of the CO2. The source of hydrogen would be from the
electrolysis of water using electricity generated from solar cells. Assume that 1.5mol CO2
enter the reactor at 700°C together with 4 mol of H2 at 100°C. Determine the heat of reaction
if the exit gases leave at 1 atm and 500°C.

X=0.4
1.5 mol 700°C, 1 atm, CO2 (g)
500°C, 1 atm, H2O(g)
Reactor
4 mol CO2 (g), CH4 (g), H2(g)
100°C, 1 atm, H2 (g)
CO2=0.9
Inlet (two)have Outlet (04)have CH4 = 0.6
energy Energy; 500C H2 = 1.6
H2O= 1.2
Heat of reaction
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 Energy Balances

Compounds 𝒌𝑱 𝒌𝑱
∆𝑯𝒇 ( ) ∆𝑯𝑻𝟐𝟓𝑪 ( )
𝒈𝒎𝒐𝒍 𝒈𝒎𝒐𝒍
25°C 100°C 500°C 700°C

CO2(g) -393.250 20.996 30.975

H2(g) 0 2.123 13.826

H2O(g) -241.835 17.010

CH4(g) -74.848 23.126

Answer: ?kJ/g mol CO2

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 Energy Balances
Thu 11/05/2020

Heats of Neutralization of Acids and Bases:

The neutralization of a dilute aqueous solution of NaOH with a dilute solution of HCl may
be represented by the following thermochemical equation: H+ +OH- = H2O
Na+, Cl- are present
NaOH (aq) + HCl (aq) = NaCl (aq) + H2O(l)In both reactant and produ
Side
The heat of reaction ∆𝐻25 may be calculated from the respective heats of formation.

Note: The net result of the neutralization of dilute solutions of strong acids and bases is the
production of water from hydrogen and hydroxyl ions. The evolved heat is 13.36kcal/g-mol.
However, in the neutralization of dilute solutions of weak acids and weak bases, the heat
given off is less than 13.36kcal/g-mol.

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 Energy Balances

Thermoneutrality of salt solutions:

When dilute aqueous solutions of two neutral salts are mixed, there is no thermal effect
provided there is no precipitation, or evolution of gas.

NaCl (aq) + KNO3 (aq) = NaNO3 (aq) + KCl(aq) ∆𝐻 = 0

Heat of formation of ions:

H2 (g) + 0.5O2 (g) = H2O (l) ∆𝐻 = −68317.4 𝑐𝑎𝑙

OH- (aq) + H+ (aq) = H2O(l) ∆𝐻 = −13360 𝑐𝑎𝑙

Subtracting the above two equations:

H2 (g) + 0.5O2 (g) = OH- (aq) + H+ (aq)

∆𝐻𝑓 = −68317.4 − −13360 = −54957 cal

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 Energy Balances

Heat of formation of ions:

At high temperature, the elementary gases are known to dissociate into their atomic states
with absorption of great amounts of energy. Upon cooling, these monatomic gases rapidly
recombine to form the original molecular gas. An interesting phenomenon of this type is
the association of monatomic hydrogen, H(g), to form molecular gas, H2(g) in the hydrogen
welding process.

Dissolution of solids:

Dissolution of solids in water is very common process in the industry, for instance, dissolution
of caustic soda.
Crystallization is the reverse process of dissolution. For all practical purposes, the heat of
solution with a reverse sign is taken as heat of crystallization. Heat of dissolution of solids can
also be calculated using standard heat of formation data of crystalline solids and their solutions.

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 Energy Balances

Ques. 6: (a) Making use of heat of formation data, calculate the heat of solution of ZnSO4
in 15H2O by dissolving crystals of ZnSO4 in water at 25°C.
(b) Instead of ZnSO4 crystals, if ZnSO4.7H2O (hydrated crystals) is used to prepare that same
solution, what would be the heat of solution at 25°C?

Given: Compounds ∆𝑯𝒐𝒇 (kJ/mol)

ZnSO4 -982.8

ZnSO4.15H2O -1053.904

ZnSO4.7H2O -3077.75

Answer: (a) -71.104 kJ/mol (exothermic) (b) 23.036kJ/mol (endothermic)

ZnSO4 +7H2O ZnSO4.15H2O
ZnSO4
Crystal of H2o will also have to dissolve
ZnSO4.7H2O + 8H2O ZnSO4.15H2O + 7H2O
(crystal) -285.83
for 1mole
ZnSO4 +15H2O = ZnSO4.15H2O -3077.75 -1053.904
-982.8 -1053.904
Hf = -1053.904-(-982.8) = -71.104 18
 Energy Balances

Sensible heat changes in gases at constant pressure

𝑇2
𝑄 = න 𝐶 ∙ 𝑑𝑇
𝑇1
Where,

𝐶 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2

Sensible heat changes in liquids and solids

Heat capacities at constant pressure and constant volume of a liquid are nearly equal. In
general, the heat capacity of a liquid increases with an increase in temperature, although
the variation of the heat capacity of a liquid with temperature is considered to be of less
importance.
For liquids,
𝑑𝐻 = 𝑚𝐶𝑙 𝑑𝑇
Where,
𝐶𝑙 is the heat capacity of the liquid [kJ/(kg.K)]
𝑚 is the mass of the liquid (kg)
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 Energy Balances

Ques. 7: Chlorinated diphenyl is heated from 40°C to 280°C at the rate of 4000kg/h in an indirectly
fired heater. In this particular range, the heat capacity of the fluid is given by the equation

𝑘𝐽
−3
𝐶𝑙 = 0.7511 + 1.465 ∗ 10 𝑇
𝑘𝑔. 𝐾
Where, T is in K

Also, the heat capacity data of diphenyl at 40°C and 280°C are 1.1807 and 1.5198kJ/kg.K,
respectively.

Calculate the heat to be supplied to the fluid in the heater using the heat capacity equation.
Also calculate the %error involved in using the mean heat capacity data for the heat change
calculations.

% error = {(polynomial)-(mean)/(polynomial)}*100
Answer: 2.54% error

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Sensible heat changes in gas mixtures

The sensible heat change of an ideal gaseous mixture can be calculated by calculating the
mixture properties from the properties of pure gases present in the mixture. For an ideal
gas mixture, the molar heat capacity of a gas mixture at a constant pressure is given by

𝐶𝑚𝑖𝑥 = ෍ 𝑦𝑖 ∙ 𝐶𝑖
1

Where,
𝑦𝑖 is the mole fraction of the ith component
𝐶𝑖 is the molar heat capacity of the ith component

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 Energy Balances

Ques. 8: Pyrites fines are roasted in a chamber plant for making sulphuric acid. The gases
leaving the roaster are at 502°C and have molar composition SO2 7.09%, O2 10.55%,
SO3 0.45% and N2 81.91%. Calculate the heat content of 1kmol gas mixture over 25°C,
using the heat capacity data provided below:

Compounds a bx103 cx106 dx109

SO2 24.7706 62.9481 -44.2582 11.122

O2 26.0257 11.7551 -2.3426 -0.5623

SO3 22.0376 121.624 -91.8673 24.3691

N2 29.5909 -5.141 13.1829 -4.968

𝑤ℎ𝑒𝑟𝑒, 𝐶 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3

Answer: 15016.7 kJ/mol

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 Energy Balances

Ques. 9: Below table shows the compositions of the incoming and outgoing gas mixtures to
and from a converter are given. Assume that the sulphur burner gases enter the converter
at 800K and the outgoing gas leave it at 875K. Intercoolers are installed in the catalyst
beds of the converter.
Compounds Inlet gas, kmol/h Outlet gas, kmol/h
SO2 8.851 0.351

O2 13.2 8.95

SO3 0.984 9.484

N2 102.4 102.4

Calculate the heat transfer taking place in the intercoolers using heat capacity data.
Given: Standard heat of reaction = -98910kJ/kmol SO2

Compounds a bx103 cx106 dx109

SO2 24.7706 62.9481 -44.2582 11.122

O2 26.0257 11.7551 -2.3426 -0.5623

SO3 22.0376 121.624 -91.8673 24.3691

N2 29.5909 -5.141 13.1829 -4.968

Answer: -143.66kW 23