CHEMICAL PROCESS

CALCULATIONS

Dr.V.Sangeetha
Associate professor,
Department of Chemical Engineering,
Kongu Engineering College,
Perundurai, Erode.

Feb 1, 2024
 UNIT IV Energy Balance:

Thermal physics: Heat capacity - enthalpy

changes of solids, liquids, gases and solutions -
Thermal chemistry: Heat of reaction, formation,
solution, mixing and combustion - Effect of
pressure and temperature on heat of reaction-
Adiabatic flame temperature.

Feb 1, 2024
Thermochemistry

 Thermochemistry is the study of the heat

changes that occur during chemical reactions
and physical changes of state.
 The law of conservation of energy states that
in any chemical or physical process, energy
is neither created nor destroyed.
 Energy
 Energy is defined as the capacity to do work or to
produce heat.
 The 1st Law of Thermodynamics …. Energy is
conserved as it is converted between one form and
another, it will be neither created or destroyed, but
simply change form…thus making the energy of the
universe constant!
 Energy can be classified a
 Kinetic
 Potential
 Flow / Pressure
 Internal
 Heat and work
 absorbed by
In endothermic processes, heat is _________
the system.
energy + 2HgO (s) 2Hg (l) + O2
(g)
energy + H2O (s) H2O (l)

In exothermic processes, heat is ________

released by
the system.
2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

 Enthalpy is used to measure the heat that is
either gained or lost by a system that is at
constant pressure.

ΔH = Hproducts – Hreactants

When ΔH is +, the system...has gained heat. (ENDO)

When ΔH is –, the system... has lost heat. (EXO)

• Enthalpy is an extensive property, meaning that…the

amount of material affects its value
 Sensible heat: Heat must be transferred to raise or lower
the temperature of a substance
specific heat (capacity): amt. of heat needed to raise
temp. of 1 g of a substance

J/ C *g or J/ K*g
molar heat (capacity): amt. of heat needed to raise
temp. of 1 mol of a substance
J/ C *mol or J/ K*mol
Relationship between
-=R
Heat capacity of gases at constant pressure

Feb 1, 2024
 Enthalpy changes accompanying Chemical Reaction
 Heat of Reaction ()
 Standard Heat of reaction ()
 Heat of Formation()
 Standard Heat of Formation ()
 Heat of combustion ()
 Standard heat of Combustion ()

Hess's Law :
The overall enthalpy change will be exactly the
same whether reaction take place in one step or
two steps or however many steps.
Feb 1, 2024
  Standard heat of reaction from heat of Formation

 ΔHorxn = Σ (ΔH fproducts) – Σ (ΔH f reactants)

 Standard heat of reaction from heat of combustion

 ΔHorxn = Σ (ΔH creactants) – Σ (ΔH cproducts)

Feb 1, 2024
 Approximate the enthalpy change for the
combustion of 246 g of liquid methanol.

2 CH3OH(l) + 3 O2(g) 2 CO2(g) + 4 H2O(g)

–238.6 kJ/mol 0 kJ/mol –393.5 kJ/mol –241.8 kJ/mol
X2 X2 X4

–477.2 kJ –1754.2 kJ
ΔHorxn = (–1754.2 kJ) – (–477.2) = –1277 kJ
kJ)
So… for 2 mol
(i.e., 64
g)
X = ΔH = –4910 kJ
of CH3OH
Water Phase Change Diagram
 Thermochemical Equations

H2O (s) H2O (l) ΔH = 6.01 kJ/mol ΔH = 6.01 kJ

If you reverse a reaction, the sign of ΔH changes

H2O (l) H2O (s) ΔH =- 6.01 kJ

If you multiply both sides of the equation by a factor n,

then ΔH must change by the same factor n.

2H2O (s) 2H2O (l)

ΔH = 2 mol x 6.01 kJ/mol = 12.0 kJ

Calculate the enthalpy for this reaction

2C(s) + H2(g) ---> C2H2(g) ΔH° = ??? kJ

Given the following thermochemical equations:

C2H2(g) + (5/2)O2(g) ---> 2CO2(g) + H2O(ℓ) ΔH° = -1299.5 kJ

C(s) + O2(g) ---> CO2(g) ΔH° = -393.5 kJ

H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

2CO2(g) + H2O(ℓ) ---> C2H2(g) + (5/2)O2(g) ΔH° = +1299.5 kJ
2C(s) + 2O2(g) ---> 2CO2(g) ΔH° = -787.0 kJ
H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

Notice that the ΔH values changed as well

Add up ΔH values for our answer:
+1299.5 kJ + (-787 kJ) + (-285.8 kJ) = +226.7 kJ
Thermodynamics: the study of energy and
its transformations
Thermochemistry: the sub discipline involving
chemical reactions and
energy changes
 Energy
 Energy is defined as the capacity to do work or to
produce heat.

 The 1st Law of Thermodynamics …. Energy is

conserved as it is converted between one form and
another, it will be neither created or destroyed, but
simply change form…thus making the energy of the
universe constant!

 Energy can be classified as either Kinetic or

Potential
Kinetic energy: energy associated with the motion of
atoms and molecules in a system.

KE = ½ mv2

Temperature is a measure of the average KE of a

collection of particles in a system.
 Heat vs Energy

 Thermal energy is the energy of the object and is

not in the process of being transferred or moved.

 Heat is kinetic energy being transferred

 It moves from a hotter object towards cooler
object until the temperatures are the same.
 At this point the KE’s are at equilibrium.
 It is not a property of the substance.
 System: the part of the universe we are
studying
Surroundings: everything else
In chemistry the system is the reaction that
we are interested in and the surroundings
could be the container that the reaction
takes place in.

Usually, energy is transferred to...

Change an object’s state of motion
(1)
like fuel in a vehicle.
Cause a temperature change like
(2) a furnace warming a house.
Units of energy are either
joules (J)
kilojoules (kJ)

James
CONVERSIONS: Prescott
Divide by 1000 to convert from J to KJ Joule
Multiply by 1000 to convert from KJ to J (1818-1889)

4184 J = 4.184 kJ
 absorbed by
In endothermic processes, heat is _________
the system.
melting
boiling
sublimation

released by
In exothermic processes, heat is ________
the system.
freezing
condensation
deposition
 Enthalpy is used to measure the heat that is
either gained or lost by a system that is at
constant pressure.

ΔH = Hproducts – Hreactants

When ΔH is +, the system... has gained heat.(ENDO)

When ΔH is –, the system... has lost heat. (EXO)

• Enthalpy is an extensive property, meaning that…the

amount of material affects its value
Enthalpy (H)
 Thermochemical Equations

H2O (s) H2O (l) ΔH = 6.01 kJ/mol ΔH = 6.01 kJ

If you reverse a reaction, the sign of ΔH changes

H2O (l) H2O (s) ΔH =- 6.01 kJ

If you multiply both sides of the equation by a factor n,

then ΔH must change by the same factor n.

2H2O(s) 2H2O (l)

ΔH = 2 mol x 6.01 kJ/mol = 12.0 kJ

Thermochemical Equations
The physical states of all reactants and products must be
specified in thermochemical equations.
H2O (s) H2O (l) ΔH = 6.01KJ
H2O (l) H2O (g) ΔH = 44.0 KJ

Practice Question:
How much heat is evolved when 266 g of white
phosphorus (P4) burns in air? ΔHreaction = -3013 kJ
 2 H2(g) + O2(g) → 2 H2O(g) ΔH = – 483.6 kJ

What is the enthalpy change when 178 g of H 2O(g)

are produced?

The space shuttle was powered

by the reaction above.
Calorimetry: the measurement of heat flow

A Calorimeter is used to measure the heat changes

molar heat (capacity): amt. of heat needed to raise

temp. of 1 mol of a substance
J/ C *mol or J/ K*mol

specific heat (capacity): amt. of heat needed to raise

temp. of 1 g of a substance
J/ C *g or J/ K*g
 We calculate the heat a substance loses or gains using:
q = m c ΔT AND q = m cX

(for within a given (for between two states

state of matter) of matter when temp is
constant)
q = heat
m = amount of substance
c = substance’s heat capacity
ΔT = temperature change
cX = heat of fusion (s/l)
or heat of vaporization (l/g)
Heat capacities of metals are very low when
compared to water or other substances.
In an experiment it was determined that 59.8 J was required
to change the temperature of 25.0 g of ethylene glycol (a
compound used as antifreeze in automobile engines) by
10.0 C.

Calculate the specific heat capacity of ethylene glycol.

q = m c ΔT
 Typical Heating Curve

– q )
d (
o ve g
r em l/g
e a t
h
Temp.

← l
q ) →
s/l d (+
d e
s a t ad
h e

HEAT
 Constant Pressure Calorimetry
Calorimetry:
The measurement of heat flow • Commonly called
“COFFEE CUP” calorimetry

• It’s used to determine any

changes in enthalpy for
reactions occurring in
solution.

• Atmospheric pressure
remains constant during the
reaction .
Practice Problem
A lead (Pb) pellet having a mass of 26.47 g at
89.98°C was placed in a constant-pressure
calorimeter containing 100.0 mL of water. The water
temperature rose from 22.50°C to 23.17°C.

What is the specific heat of the lead pellet?

 A sketch of the initial and final situation is as follows:

We know the masses of water and the lead pellet as well as the initial and final
temperatures. Assuming no heat is lost to the surroundings, we can equate the
heat lost by the lead pellet to the heat gained by the water. Knowing the specific
heat of water, we can then calculate the specific heat of lead.
Because the heat lost by the lead pellet is equal to the heat
gained by the water,
qPb = −280.3 J.
Combustion reactions
are studied using constant
volume calorimetry.

It requires a BOMB
CALORIMETER.
We assume that no energy escapes into the
surroundings, so that the heat absorbed by the bomb
calorimeter equals the heat given off by the reaction.
Hess’ Law 1840

 The change of enthalpy in a chemical reaction

is independent of the route by which the
chemical change occurs.

 This is true because enthalpy is a state function , which is a

value that does not depend on the path taken
 How Hess’s Law works
● The ΔHrxns have been calculated and tabulated
for many basic reactions.

● Hess’s law allows us to put these simple

reactions together like puzzle pieces so that they
can add up to a more complicated reaction.

● By adding or subtracting the ΔHrxns, we can

determine the ΔHrxn of the more complicated
reaction.
Hess's Law is saying:

If you convert reactants A into products B, the overall

enthalpy change will be exactly the same whether you do
it in one step or two steps or however many steps.
Important things to remember when using Hess’s Law:

● If a reaction is reversed, the sign of H is also reversed.

● The size of H is directly related to the quantities of

reactants and products

● If the coefficients in a balanced reaction are multiplied

by an integer, the value of H is multiplied by the same
integer.
Calculate the enthalpy for this reaction

2C(s) + H2(g) ---> C2H2(g) ΔH° = ??? kJ

Given the following thermochemical equations:

C2H2(g) + (5/2)O2(g) ---> 2CO2(g) + H2O(ℓ) ΔH° = -1299.5 kJ

C(s) + O2(g) ---> CO2(g) ΔH° = -393.5 kJ

H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

1) Determine what must be done to the given equations to get the target equation:

a) first eq: flip it so as to put C2H2 on the product side

b) second eq: multiply it by two to get 2C
c) third eq: do nothing. We need one H2 on the reactant side and that's what we
have.

2CO2(g) + H2O(ℓ) ---> C2H2(g) + (5/2)O2(g) ΔH° = +1299.5 kJ

2C(s) + 2O2(g) ---> 2CO2(g) ΔH° = -787.0 kJ
H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

Notice that the ΔH values changed as well

Add up ΔH values for our answer:
+1299.5 kJ + (-787 kJ) + (-285.8 kJ) = +226.7 kJ
Standard enthalpy of formation (ΔHf0) is the heat
change that results when one mole of a compound is
formed from its elements at STP.

Whenever a standard enthalpy change is quoted,

standard conditions are assumed.
The standard enthalpy of formation of any element in its
most stable form is zero.

ΔHf0 (O2) = 0 ΔHf0 (C, graphite) = 0

ΔH0f (O3) = 142kJ/mol ΔHf0 (C, diamond) = 1.90 kJ/mol

Some other important types of enthalpy changes

Standard enthalpy change of combustion, ΔH°c

The standard enthalpy change of combustion of a

compound is the enthalpy change which occurs
when one mole of the compound is burned
completely in oxygen at STP .

The enthalpy change of solution (ΔH soln) is the

heat generated or absorbed when a certain amount
of solute dissolves in a certain amount of solvent at
STP.
Standard enthalpy of a reaction (ΔHorxn):

Using Hess’s law, we can easily calculate

ΔHorxn from the ΔHfo of all reactants and products by
using the following equation:

ΔHorxn = Σ (ΔH fproducts) – Σ (ΔH f reactants)

 (Look these up.
Approximate the enthalpy change for the See App. 4,
combustion of 246 g of liquid methanol. P A19.)

2 CH3OH(l) + 3 O2(g) 2 CO2(g) + 4 H2O(g)

–238.6 kJ/mol 0 kJ/mol –393.5 kJ/mol –241.8 kJ/mol
X2 X2 X4

–477.2 kJ –1754.2 kJ
ΔHorxn = (–1754.2 kJ) – (–477.2) = –1277 kJ
kJ)
So… for 2 mol
(i.e., 64
g)
X = ΔH = –4910 kJ
of CH3OH
Practice problem #1

Benzene (C6H6) burns in air to produce carbon dioxide and liquid

water. How much heat is released per mole of benzene
combusted?

The standard enthalpy of formation of benzene is 49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (g)

Practice Problem # 2
What is the Δ Hrxn for the complete
combustion of Butane, C4H10 (g)?

2 C4H10 (g) + 13 O 2(g) 8CO2 (g) + 10 H2O (g)