Chemical Process Calculations

Autumn 2021

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
 Energy Balances
Thu 10/21/2021

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 = -39850 cal

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 Energy Balances

Ques. 4: Calculate the standard heat of reaction at 25°C when gaseous ammonia is dissolved
in water to form 2% by mass of its solution for the generation of weak anion exchanger of
a water treatment plant.

NH3(g) + H2O (l) = NH4OH (l)

The heats of formation of the compounds:

361.2kJ
NH4OH(l) , ∆𝐻𝑓 = − mol
NH3 ; H2O(l) , ∆𝐻𝑓 = −285.83kJ/mol ;

NH4OH (l), ∆𝐻𝑓 = −45.94kJ/mol

Answer: ∆𝐻25 = 3456.1kJ/100kg solution at 298.15K

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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. 5: 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

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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)

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 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
Thu 10/28/2021

Ques. 6: 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 they 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.

700°C, 1 atm, CO2 (g)

500°C, 1 atm, H2O(g)
Reactor
CO2 (g), CH4 (g), H2(g)
100°C, 1 atm, H2 (g)

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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

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:

NaOH (aq) + HCl (aq) = NaCl (aq) + H2O(l)

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.

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 Energy Balances

Q. 7 Chlorinated diphenyl (Diphyl A-30) is heated from 40°C to 280°C at the rate of 4000 kg/h in
an indirectly fired heater. In this particular temperature range, the heat capacity of the
fluid is given by the equation
𝐶𝑙 = 0.7511 + 1.465 ∗ 10−3 𝑇 𝑘𝐽/ 𝑘𝑔. 𝐾
Also, the heat capacity data of Diphyl A-30 at 40°C and 280°C are 1.1807 and 1.5198 kJ/(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.

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 Energy Balances

Q. 8 Obtain an expression relating the heat of reaction and the temperature of the reaction

SO2 (g) +1/2O2(g) = SO3 (g)

Using the same expression, calculate the heat of reaction at 502°C.

a bx103 cx106 dx109

SO3 22.036 121.624 -91.867 24.369
SO2 24.771 62.948 -44.258 11.122
O2 26.026 11.755 -2.343 -0.562

∆𝐻𝑟0 = −98910𝑘𝐽/𝑚𝑜𝑙

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 Energy Balances

Q. 9 Acetic acid is esterified in the liquid phase with ethanol at 100C and atmospheric pressure
to produce ethyl acetate and water.

CH3COOH(l) + C2H5OH(l)= CH3COOC2H5(l) + H2O(l)

(a) Calculate the heat of reaction at 100C using heat capacity of reactants and products at
mean temperature.

Component Mean heat capacity at 62.5C,kJ/(kmol.K)

Ethylacetate 146.89
Water 75.76
Ethanol 119.55
Acetic acid 129.7

∆𝐻𝑟0 = −4.43𝑘𝐽/𝑚𝑜𝑙

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 Energy Balances

Q. 9 (b) Develop an expression of calculation of heat capacity equation constants, as a function

of temperature.

Component a bx103 cx106 dx109

Ethylacetate 4.2905 934.378 -2640.0 3342.58

Water 50.845 213.08 -631.398 648.746

Ethanol 100.92 -111.83 498.54 0
Acetic acid 155.48 -326.59 744.199 0

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 Energy Balances

Q. 10 In a commercial process, chlorine is manufactured by burning hydrogen chloride gas

using air. The reaction taking place in the burner is
4HCl(g) + O2(g)= 2H2O(g) + 2Cl2(g)
For good conversion, air is used in 35% excess of that theoretically required. Assume that
the oxidation is 80% complete and the dry air and hydrogen chloride gas enter the
burner at 25°C. Calculate
(a) the composition of dry gases leaving the burner,
(b) the adiabatic reaction temperature of the product gas stream
Component Product gas a.n n.bx103 n.cx106 n.dx109
stream
(kmol)

HCl 0.8 24.247 -6.087 10.609 -3.467

O2 0.55 14.314 6.465 -1.288 -0.309

Cl2 1.6 45.674 38.207 -34.181 10.356
H2O 1.6 51.987 0.127 21.137 -7.276

N2 5.08 150.322 -26.116 66.969 -25.237

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