18CHO101T

SUSTAINABLE ENERGY ENGINEERING

Unit 4. Energy calculations and other
chemical energy transfer processes
• Introduction • Other chemical processes for energy
• Basic thermodynamic functions and transfer
• Microwave-assisted reactions
applications
• Sonochemistry
• Calculation of heat of reaction • Electrochemistry
• Photochemistry and photovoltaic cells
• Application of Hess law
• Problems on heat of reaction and
Hess law

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 Introduction
• Most chemical reactions require an energy input for the reaction to occur in a timely fashion
on an industrial scale.
• Given that one of the principles of green chemistry states that “energy requirements of
chemical processes should be recognized for their environmental and economic impacts and
should be minimized,” it is important to understand energy needs of the chemical
process.
• To do so requires one to know first how energy is produced in chemical reactions and
second how it can be measured through basic thermodynamic functions.

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Basic thermodynamic functions and applications
• When a reaction occurs, there is an energy change in going from the
reactants to the products; this energy change is termed the heat of
reaction.
• To measure the total heat or energy emitted or consumed by a reaction, we
use a thermodynamic function called enthalpy (H).

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 Heat of reaction
• Heat of reaction, also called enthalpy of reaction, is the
amount of heat evolved or absorbed in a reaction
carried out at constant pressure.
• If the pressure in the vessel containing the reacting
system is kept at a constant value, the measured heat of
reaction represents the change in the thermodynamic
quantity called enthalpy, or heat content, ΔH
accompanying the process—i.e., the difference
between the enthalpy of the substances present at the
end of the reaction and the enthalpy of the substances
present at the start of the reaction.
• Heat of Reaction, ΔH = ΔH (products) – ΔH (reactants)
• If the heat of reaction is positive, the reaction is said to
be endothermic.
• If the heat of reaction is negative, the reaction is said to
be exothermic.
• The units for ΔH is kJ/mol.
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Heat of reaction
• The heat of a reaction is the NET amount of heat that is taken in or given off by a reaction.
• Every reaction that occurs takes in heat and gives off heat. For instance, to get a piece of paper to burn,
the paper must be heated. This can be done with a match or a magnifying glass, or by adding it to an
existing fire. The heat that must be added to make the reaction occur is called the activation energy.

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Heat of reaction
• One simple way to express this idea (that all reactions both take in and give off heat) is to show it
graphically.

For an exothermic reaction (one that gives off heat):

1. Everything has some energy (nothing is at 0 on the energy scale). So, the
reactants have some energy and the products have some energy (but a different
amount)
2. Energy must be put in to make the reaction happen. This is the energy shown in Exothermic reaction
red on the left side and is called the activation energy.
3. Energy is released by the production of the products. This is shown in purple on
the right side of the reaction. There is no special name for this energy.
4. The difference between the energy put in (activation energy) and the energy
released is the heat of the reaction. This is indicated by the green arrow in the
middle. Specifically, we subtract the energy out from the energy in, resulting in a
negative number (exothermic)
For an endothermic reaction:
• The graph is similar, but the products have more energy than the reactants. As a
result, more heat is put in than comes out. When the energy out is subtracted
from the larger energy in value, the result is positive (endothermic).

Endothermic reaction
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Exothermic and endothermic reactions

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Exothermic and endothermic reactions
*

* Formation of clouds is due to condensation of water vapour. As heat is released during the conversion of
gas into liquid and from liquid to solid (snow), it is an exothermic reaction.
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Calculation of heat of reaction
Consider an isomerization reaction, where butylene is converted to isobutylene.

If we define the reactant and the product with a common standard state, then the energy change associated
with this process is the difference between the enthalpy of the product and the enthalpy of the reactant. This is
defined as the heat of reaction, ΔHr, with Δ symbolizing a change in energy between the enthalpy of the
products and the enthalpy of the reactants. According to the energy balance then,

with n being the number of moles of the products and reactants

When there are multiple reactants and products,

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Calculation of heat of reaction
We can put this definition on a molar basis, by dividing by the number of moles,

to put this in terms of the stoichiometric coefficient, νi.

Recall that νi is negative for a reactant and positive for a product.
Note: Stoichiometric coefficient is the number written in front of atoms, ion and molecules in a chemical reaction to
balance the number of each element on both the reactant and product sides of the equation.

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Calculation of heat of reaction
We can put this definition on a molar basis, by dividing by the number of moles,

to put this in terms of the stoichiometric coefficient, νi.

Recall that νi is negative for a reactant and positive for a product.
Note: Stoichiometric coefficient is the number written in front of atoms, ion and molecules in a chemical reaction to
balance the number of each element on both the reactant and product sides of the equation.

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Calculation of heat of reaction
The enthalpy of an elemental species, in its standard state at 25 °C, is equal to zero.

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Calculation of heat of reaction - Problem

Solution:

Exothermic!

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Heat of formation
• A reaction that leads to the formation of the compound from its elements is termed a formation
reaction.
• The heat of formation ΔHf is the energy generated (or consumed) through the formation of the
component from its elements.
• The standard enthalpy of formation, ΔHf° of a compound is the change in enthalpy for the reaction
that forms 1 mole of the compound from its elements, with all substances in their standard states.
We usually report ΔHf° values at 298 K.

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Heat of combustion
• Heat of combustion is the heat of formation of a species through a combustion reaction.
• For the combustion of methane,

• Remember that ΔHf for O2 is equal to zero.

• The heat of combustion is just a specific case of heat of reaction.

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Heat of reaction – Concluding remarks
• It is important to note that the heat of reaction is dependent on the phase of the species in
the reacting system.
• Thus, it is essential to use the heat of formation for liquid water if liquid water is produced.
• The difference between the heat of formation of the liquid andthe vapor species will be
identical to the heat of vaporization of that component.
• It is not possible to measure values of heat of reaction for every conceivable reaction.
• Fortunately, it is possible to develop equivalent chemical reactions for complex systems
based on simpler reactions.
• Hess’s law states that for an equation of a reaction which is the sum of two or more
equations: ΔHr of the total reaction is equal to the sum of ΔHr values of the underlying
reactions.

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Hess’s law
Hess's Law of Constant Heat Summation (or just Hess's Law) states that regardless of the multiple stages
or steps of a reaction, the total enthalpy change for the reaction is the sum of all the changes.

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Problems on Hess law

Solution:

(3)

(4)
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Problems on Hess law
Adding equations (3) and (4)

The overall heat of reaction for the target expression is

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Surprise test
1. The enthalpies of formation of CO (g), CO2 (g), N2O (g) and N2O4 (g) are − 110, − 393,
81 and 9.7 kJ/mol, respectively. Find the value of ΔH for the reaction, N2O4 (g) + 3 CO
→ N2O (g) + 3 CO2 (g).

2. Calculate ΔH for the process

Hg2Cl2 (s) 2Hg (l) + Cl2 (g)
from the following information:
Hg (l) + Cl2 (g) HgCl2 (s) ΔH = − 224 kJ
Hg (l) + HgCl2 (s) Hg2Cl2 (s) ΔH = − 41.2 kJ

3. The heat of combus on for the gases hydrogen, methane and ethane are −285.8, −890.4
and −1559.9 kJ/mol respectively at 298K. Calculate (at the same temperature) the heat of
reaction for the following reaction 2CH4(g) ---> C2H6(g) + H2(g)
Given:

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Other chemical processes for energy transfer
• Traditional chemical processing relies on the transfer of energy in the
form of heat or work, but it is also possible to use other processes to
transfer the necessary energy to promote a chemical reaction.
• Because the energy transfer may be more efficient or targeted, the
yield and selectivity can be improved, often eliminating the need for a
catalyst, reducing the separation requirements, and eliminating
waste.
• This section evaluates several of these less common energy transfer
techniques.

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Other chemical processes for energy transfer
• Microwave-assisted reactions

• Sonochemistry

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Other chemical processes for energy transfer
• Electrochemistry

• Photochemistry and photovoltaic cells

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Microwave-assisted reactions https://cem.com/uk/microwave-chemistry/theory

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Microwave-assisted reactions

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Microwave-assisted reactions
• Microwave frequencies are part of the electromagnetic spectrum and typically range from 110 to 140 GHz, between
infrared radiation and radio waves; Energy can be transported through microwave radiation.
• Most kitchens now include a microwave oven, which converts electrical energy into microwaves that are transmitted
to food. The absorption of the microwave energy by the food leads to an increase in the temperature of the food.
• Similar processes are also found in industrial processes for drying and curing products, or to generate plasma such as
in the plasma enhanced chemical vapor deposition (PECVD).
• Because the microwave energy allows for efficient energy transfer directly into materials, it can be used to provide
higher yields in shorter reaction times when compared to conventional thermal heating.
• Features of microwave heating:
• Instantaneous high temperatures at the surface of the solid.
• Facilitation of contact between solid and liquid reagents.

• The use of microwave chemistry is spreading rapidly wherever polar materials are present and often no solvent is
required.
• When a polar solvent is present, the success of the chemical reaction depends on the efficient conversion of energy
absorbed by the solvent.
• Because of the increased efficiency of energy transfer, reactions can happen in a microwave without the presence of a
catalyst.
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Sonochemistry

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Sonochemistry
• Ultrasound, or high intensity sound, provides another means of transferring energy through a
fluid. The key element of ultrasound is the creation of acoustic cavitation, which is defined as
the collapse of gas bubbles in a liquid and which generates very high local temperatures (about
5000 °C) and high pressures (over 1000 atm).
• Ultrasound is fairly common for processes involving solids in a liquid or two immiscible liquids.
• Reactions involving ultrasound require shorter reaction times with improving rates and superior
selectivity.
• Most of these reactions require quality mixing between species.
• Ultrasonic baths are used to clean the surface of jewelry pieces by cavitation.
• Sonication has also been used widely in the field of microbiology and biochemistry (to help with
digestion of cells).
• In the polymer field, copolymers of polyethylene and acrylamide have been built using ultrasonic
cleavage of polyethylene in the presence of acrylamide.
• Most recently, sonochemistry was used as an efficient extraction technique. Extraction of carvone
and limonene from caraway seeds has been successful. Sonochemistry helped increase the yield,
lower the extraction temperature, and produce a purer extract than those obtained with
conventional methods.
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Electrochemistry
Electrochemical cells

Electrolytic cell Galvanic cell

(Electrical energy  Chemical energy) (Chemical energy  Electrical energy)

https://www.toppr.com/ask/content/story/amp/types-of-electrochemical-cells-43694/
https://saylordotorg.github.io/text_general-chemistry-principles-patterns-and-applications-v1.0/s23-01-describing-electrochemical-cel.html
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Electrochemistry

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 Electrochemistry – A Galvanic cell
• According to the first law of thermodynamics, the energy given
off in a chemical reaction can be converted into heat, work, or a
mixture of heat and work. By running the half-reactions in
separate containers, we can force the electrons to flow from the
oxidation to the reduction half-reaction through an external
wire, which allows us to capture as much as possible of the
energy given off in the reaction as electrical work.
• We can start by immersing a strip of zinc metal into a 1 M Zn2+
ion solution. We then immerse a piece of platinum wire in a
second beaker filled with 1 M HCl and bubble H2 gas over the Pt
wire. Finally, we connect the zinc metal and platinum wire to
form an electric circuit.
• We've now made a system in which electrons can flow from one
half-reaction, or half-cell, to another. Zinc atoms on the metal
surface lose electrons to form Zn2+ ions, which go into solution.

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 Electrochemistry – A Galvanic cell
• The electrons given off in this half-reaction flow through the circuit and eventually accumulate on the
platinum wire to give this wire a net negative charge.
• The H+ ions from the hydrochloric acid are attracted to this negative charge and migrate toward the
platinum wire. When the H+ ions touch the platinum wire, they pick up electrons to form hydrogen atoms,
which immediately combine to form H2 molecules.

• The oxidation of zinc metal releases Zn2+ ions into the Zn/Zn2+ half-cell. This half-cell therefore picks up a
positive charge that interferes with the transfer of more electrons.
• The reduction of H+ ions in the H2/H+ half-cell leads to a net negative charge as these H+ ions are removed
from the solution. This negative charge also interferes with the transfer of more electrons.

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 Electrochemistry – A Galvanic cell
• To overcome this problem, we complete the circuit by adding a U-tube filled with a saturated solution of a
soluble salt such as KCl. Negatively charged Cl- ions flow out of one end of the U-tube to balance the
positive charge on the Zn2+ ions created in one half-cell. Positively charged K+ ions flow out of the other end
of the tube to replace the H+ ions consumed in the other half cell. The U-tube is called a salt bridge,
because it contains a solution of a salt that literally serves as a bridge to complete the electric circuit.
• Why salt bridge?
 The charge of all ions in both half-cells must remain zero to maintain the electron flow.
 The purpose of the salt bridge is to act as a source of spectator ions that can migrate into each of the
half cells to preserve neutrality.
 Any charge buildup in the solutions of the two half cells is known as a junction potential.
 Therefore, the purpose of a salt bridge is to reduce the junction potential between the solution
interface of the two half cells, and the salt bridge allows ions to move between half-cells and keep the
charge in each container zero.

https://quizlet.com/gb/344688142/required-practical-8-measuring-the-emf-of-an-electrochemical-cell-
flash-cards/
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Analytical_Che
mistry)/Analytical_Sciences_Digital_Library/In_Class_Activities/Electrochemical_Methods_of_Analysis/0
2_Text/5._Electrochemical_Cells
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 Electrochemistry
• Electrochemistry is defined as oxidation/reduction reactions involving electron transfer between electrodes (usually
metals, conductors of electricity) and ionic solutions (or electrolytes).
• It was founded by John Daniell and Michael Faraday in the 1830s.
• Electrochemistry involves redox reactions, essentially an exchange of electrons between species. The redox reaction
can be promoted through the application of an external voltage.
• An electrochemical process can promote a chemical reaction through the application of electricity across a cell, or one
in which current is generated through the chemical reaction.
1. The best example of an electrochemical reaction is in the traditional battery. The earliest batteries, and those still
used in automobiles, contained a liquid electrolyte, usually an acid, which would react with a solid surface, for
example, lead, promoting a chemical reaction that transferred electrons through an electric circuit.
2. Electrochemical processes can be seen in action in nature (photosynthesis is an electrochemical process).
3. Commercial applications such as the coating of objects with metals through electrodeposition or through
electroplating to protect metals from corrosion.
4. It can also be used as a greener way to recover metal ions from waste streams, to remove low-molecular-weight
ionic compounds through electrodeionization for the production of pure drinking water, or to regenerate an
expensive metal or toxic compound in situ.
5. The fuel cell represents another electrochemical reaction. The fuel cell requires a constant source of fuel, usually
hydrogen, in order to continue to produce electricity. The electrochemical reaction involves the oxidation of
hydrogen to produce water, representing the greenest energy opportunity (except that the production of hydrogen
to power the fuel cell may not be as green as desired).

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 Photochemistry
Photochemical processes use photons from light sources as the
source of energy.
Advantages:
• clean with no waste production,
• the reaction temperatures are lower than in traditional
thermal processes, and
• they may provide higher selectivity as light is directly
shining on the essential reagents.
1. Photochemistry is used by nature for photosynthesis
(conversion of carbon dioxide and water into glucose using
sunlight).
2. It is also used in the commercial production of vitamin A
and vitamin D3; this is one of the only industrial processes
relying on photochemistry since there is no viable thermal
alternative to the production of these two valuable
products. 37
Photochemistry
3. Many organic and inorganic chemical reactions are induced by light.
A. An example of an organic photochemical reaction is the preparation of benzyl chloride
(C6H5CH2Cl) from toluene (C6H5CH3) and chlorine (Cl2). When the diatomic molecule of chlorine is
exposed to light, breakage of the Cl–Cl bond occurs and two chlorine radicals are then formed:

Approximately 100,000 tons of benzyl chloride is produced annually using this gas-phase photochemical
reaction.
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Photochemistry
B. An example of a photoreactive organometallic reaction is a decarbonylation reaction (removal of
a carbonyl group). When organometallic compounds (containing a metal center and organic-based
ligands) are subjected to UV irradiation, their ligands are dissociated upon irradiation with UV
light.
• For example, a solution of molybdenum hexacarbonyl (Mo(CO)6) in tetrahydrofuran (THF) will
become Mo(CO)5(THF) upon UV irradiation.
• In this case one of the CO ligands is removed and replaced by THF.
• Since THF is easily dissociated, it can be replaced by another ligand in the second reaction step.
• This reaction is particularly useful for carbonylation chemistry since metal carbonyls resist
thermal substitution and do not dissociate when heated.

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Photochemistry
4. Photochemically activated reactions are finding uses in modern applications such as
the combustion of carbon nanotubes at high temperatures, which then break open
and reorganize in the shape of horns giving the popular name “nanohorns,” promising
materials for chemical and bio-sensors. Their strong catalytic property is suitable for
fuel cell applications and their porosity is ideal for gas storage.

Another application of converting light to electricity is photovoltaic cells.

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 Photovoltaic cells (Also refer Unit 1)
• Sunlight can also be converted directly into
electricity using the photovoltaic effect (based on
the creation of a p-n junction; p for positively
doped (lack of electrons and creation of holes) and
n for negatively doped (presence of extra negative
charges).
• For a semiconductor in the presence of light, an
electron can be excited and moves from p-silicon
into the n-silicon.
• As the electrons move, the p-silicon becomes
positively charged and the n-silicon becomes
negatively charged, creating a net electric field.
• In the photovoltaic cell, this semiconductor device
Electron–hole movement in a p-n junction
is connected to an electric circuit through which
the electrons migrate back to the p-silicon, creating
an electric current that can be used for power.

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Photovoltaic cells (Also refer Unit 1)
• Photovoltaic cells are often made of silicon-based semiconductor materials, which efficiently absorb
light and release free electrons, but they can also be made from more complex and less
environmentally friendly materials such as cadmium and tellurium.
• Photovoltaic cells are typically from 1 to 10 cm wide and are connected together in modules to bring
the current and voltage to acceptable levels.
• The amount of electricity produced depends on the amount of solar radiation, which varies depending
on the weather and time of the day.
• Usually only about 25% of the solar energy is converted into electricity under ideal conditions; the
remainder is dissipated as heat.
• Produced electricity can be used directly to power devices such as small calculators or road signs and
lighting or communication equipment, or it may be placed directly onto the electric grid.
• Because solar power is intermittent, a solar energy system must include battery storage that can
provide energy when it is cloudy outside. The photovoltaic cells usually produce a direct current (DC),
which needs to be converted to alternating current (AC) for most households and appliances through
an inverter.

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Photovoltaic cells (Also refer Unit 1)
How Much Does It Cost?
• A typical domestic solar-thermal hot water heater system costs between $1000
and $2000.
• In parts of the globe where it is mostly sunny all year, a solar-photovoltaic
installation can supply about 40% of all electricity needs at a cost of about
$50,000. If more electricity is generated than needed, owners can sell it back to
the electric utility provider and make a profit.
• For commercial solar-thermal power plants, construction costs are estimated to
be twice those associated with a modern coal power station and three times the
costs of a gas power station.
• Residential solar electricity is more expensive than the average grid electricity.

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• If an element exists in more than
one form under standard
conditions, the most stable form of
the element is used for the
formation reaction.
• The elemental source of oxygen is
O2, not O or O3, because O2 is the
stable form of oxygen at 298 K and
standard atmospheric pressure.
• Similarly, the elemental source of
carbon is graphite and not diamond,
because the former is the more
stable (lower energy) form at 298 K
and standard atmospheric pressure.
• Likewise, the most stable form of
hydrogen under standard conditions
is H2(g), so this is used as the source
of hydrogen.

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