Thermochemistry

FSC 112

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Thermochemistry and simply calculations
based on Hess’s Law

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 Scope
• Introduction

• Systems and surroundings

• Energy

• Work

• Heat

• Internal energy

• First law of thermodynamics 3

 Introduction
Thermochemistry is a branch of chemistry that deals with the study of heat
energy.

 Associated with chemical reactions and/or phase changes such as melting and
boiling.

Energy exchange between a system and its surroundings

It is useful in predicting reactant and product quantities throughout the course
of a given reaction.
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Used to predict whether a reaction is spontaneous or non-spontaneous
• Thermochemistry is a branch of thermodynamics

• It is the study of the energy changes in the form of heat associated with chemical

reactions.

• Thermodynamics is the study of energy as it changes from one form to another

• Energy is the capability to do work

• Occurs in different forms: heat, mechanical, chemical etc….

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 Some definitions…
• A system is the specific part of the universe that is being
studied.
• Everything outside the system is considered the surrounding
or environment.
• The system is separated from the surrounding by a boundary
• A system may be:
• isolated — when it cannot exchange energy or matter with the
surroundings; e.g. gas in a cylinder
• closed— when it can exchange energy but not matter with the
surroundings; e.g. radiator engine
• open— when it can exchange both matter and energy with the
surroundings, e.g. a pot of boiling water.

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 Energy
• Energy is generally defined as the capacity to do work or transfer heat.
• The energy possessed by matter is usually a sum of its kinetic and potential energy.
• Kinetic energy, is the energy possessed by an object in motion and is usually called energy in motion.
• It depends on the mass and velocity of the object,
• .
• If two objects are moving at the same velocity, the one with the greater mass will have a greater
kinetic energy and thus a greater capacity to do work.
• In chemistry, the kinetic energy of atoms and molecules is characterized by mass and constant
motion.
• Kinetic energy is also associated with energy possessed as a result of its temperature or thermal
energy.
• This is because of internal motion (vibration, rotation…) within the molecule increases with
temperature 7
 Energy
• The potential energy is energy possessed by the object as a result of its state or
position relative to other objects.
• Potential energy exists whenever an object with mass has a position within a
force field with respect to the other object.
• The gravitational potential (mgh). The "stored" energy is held within the
gravitational field e.g. water at the top of the mountain
• In chemistry, the most important potential energy is the electrostatic potential
energy.
• It arises as a result of the interactions between charged particles.
• It is a measure of the strength of the nearby charges, nuclei and electrons, at a
particular position. 8
 Radiant Energy
• It’s solar energy and comes from sun

• It’s the primary Energy source for Earth

• It heats the atmosphere and surface of earth

• Vegetation through photosynthesis

 Chemical Energy

• It is stored within the structural units of chemical substances. (It’s a kind of

potential energy)

• When substances participate in chemical reactions chemical energy is released,

stored, or converted to other form of energies.

© 2012 Pearson Education, Inc.

 Units of energy
• The SI unit for energy is the Joule, , in honour of james joule who investigated

work and heat

• another common unit is the calorie, cal.

• A calorie is defined as the amount of energy required to raise the temperature of

water from to 11
Question
A person weighing 75.0 kg (165 lbs) runs a course at 1.78 m/s (4.00 mph). What is
the person’s kinetic energy?

m = 75.0 kg EK = ½ mv2
v = 1.78 m/s
2
1  m
E K  (75.0 kg) 1.78 
2  s
kg  m 2
E K  119 2
 119 J
s
(3 significant figures)
Copyright © Cengage Learning. All rights reserved. 6 | 12
Question
What is the potential energy of a 1360 kg automobile parked on the top
level of a parking garage 36.6 m (120 ft) high

•The automobile is in the gravitational field with potential energy given as

•; ;

•the potential energy is

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Question
Find the distance between two spheres of charges, and , respectively, if
the electrostatic potential energy is .

•; ;

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SECOND LECTURE

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 Work
• Work is the energy used to cause an object with mass to move through a distance
against a force

• The most common type of work encountered in chemistry is the pressure-volume

work.

• The negative sign is to show that the system is doing work. This is the general
convention.
• is the pressure acting on the system
• is the change in volume.

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 Heat,
• Heat, is energy that causes a change in the temperature of a system.

• Energy that flows in and out of a system due to temperature difference

• Heat is the transfer of thermal energy between two bodies that are at different
temperatures

• Heat flows from a region of higher temperature to one of lower temperature; once
the temperatures become equal, heat flow stops.

• Work and heat are forms of energy and have the units of energy

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 Heat capacity

• It is defined as the amount of heat required to raise a mass of the substance by

• Mathematically, heat capacity, C
• with unit or
• Specific heat capacity is the amount of heat required to raise of the substance
through
• with unit or
• Molar heat capacity is the amount of heat required to raise of the substance
through
• with unit or

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 Concept check

• Calculate the work associated with the expansion of a gas from 46 L to 64 L at a

constant external pressure of 15 atm.

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Concept check
• Calculate the heat absorbed by of water to raise its temperature from to (at
constant pressure). The specific heat of water is 4.18
• Recall

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Endothermic and Exothermic
Processes
In an endothermic reaction:
The reaction vessel cools.
Heat is absorbed.
Energy is added to the system.
q is positive.

In an exothermic reaction:
The reaction vessel warms.
Heat is evolved.
Energy is subtracted from the system.
q is negative.
Copyright © Cengage Learning. All rights reserved. 6 | 21
 Internal Energy

• Internal energy, U, of a system is the energy possessed as a result of the spatial

arrangement of its constituent atoms or molecule.

• It is a sum of the kinetic energy and potential energy.

• The kinetic energy is due to the motion of the system's particles (translations,
rotations, vibrations which increase with temperature)

• the potential energy is associated with the static constituents of matter, static
electric energy of atoms within molecules or crystals, and the static energy of
chemical bonds. 22
 Internal energy / State functions
• The absolute value of the internal energy is difficult to obtain
• The change in internal energy, when the system undergoes a process is
more useful thermodynamically and is easier to obtain

• Similarly for a reaction

• The internal energy can be changed by doing work or supplying heat

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 First law of Thermodynamics
• In its simplest form, it states that neither matter nor energy can be created or
destroyed.
• Same as law of conservation of energy
• The amount of energy in the universe is constant – energy can be changed,
moved, controlled, stored, or dissipated.
• For a closed system

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 Sign convention
heat transfer in
heat transfer out
(endothermic), +q
(exothermic), -q
SYSTEM

∆E = q + w

w transfer in w transfer out

(+w) (-w)
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 Concept check
• Calculate E for a system undergoing an endothermic process in which of heat
flows and where of work is done on the system

• where , since the process is endothermic, and , since work is done on the system.

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 Concept check
• When a spring was wound of work was done on it, but escaped as heat to the
surroundings. What is the change in internal energy of the spring?

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 Enthalpy
• Enthalpy is a measure of the total energy of a thermodynamic system.
• It includes the internal energy and the amount of energy required to make room
for it by displacing its environment and establishing its volume at a constant
pressure.

• Absolute enthalpy value is usually difficult to measure; however, the change in

enthalpy, ΔH, is a more useful quantity than its absolute value. It is defined by the
following equation:

• where
• is the final enthalpy of the system, expressed in joules.
• is the initial enthalpy of the system, expressed in joules.
• The change in Enthalpy is also the heat of reaction at constant pressure 28
 Enthalpy of reaction,
• This is the enthalpy change associated with a chemical
reaction.
• Here, is the enthalpy of the products and is the enthalpy of
the reactants. thus

• If is positive and the reaction is said to be endothermic

• If is negative and the reaction is said to be exothermic

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 Thermochemical equations
• Balanced chemical equations that show the associated enthalpy change in this
way are called thermochemical equations

• Or

• Or

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 Characteristics H

• Both internal energy and enthalpy are state functions. This means they depend
only on the state of the system and not on how it was achieved. For example, the
internal energy of cooked rice is the same regardless of how it was cooked, boiled
in oven, over kerosene stove or gas, it is immaterial.

• They are extensive. This means that they depend on the amount and state or
phase of substance present. For example, the energy of 5g of ice is different from
that of 10g of ice; 5g of ice(H2O(s)) has a different internal energy from 5g of

water(H2O(l)). The implication of this is as follows

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• i.e. The change in enthalpy is multiplied by any factor that multiplies the reaction

• The enthalpy change of a reaction is equal in magnitude, but opposite in sign to

the enthalpy change for the reverse reaction.

• This is a consequence of the first characteristic

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 Concept check
• How much heat is released when of methane gas is burned in a constant-
pressure system?

• One mole gives of of energy

• Strategy is to know how many moles is contained in of methane

• Heat given of will be

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 Concept check
• When 2 mol of ) and 1 mol of react to • FOR
give liquid water, 572 kJ of heat evolves.

• What is the amount of heat evolved for • THIS IS FOR THE REACTION
1 mole of water MULTIPLIED BY ½

• FOR

• THIS IS THE REVERSE REACTION

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Don't forget that the enthalpy change of reaction must be negative here to illustrate the fact that heat if being given
off by the reaction.
Now, in order for this reaction to produce 1 mole of water, all the coefficients of the chemical equation must
be halved.
(12⋅2)H2(g)+12O2(g)→(12⋅2)H2O(l)
This will get you
H2(g)+12O2(g)→H2O(l)
Now, the enthalpy change for this reaction will be half the value of the enthalpy change for the reaction that
produced 2 moles of water.
ΔH1 mole H2O=12⋅ΔH2 moles H2O
ΔH1 mole H−2O=−572 kJ2=−286 kJ
This means that the thermochemical equation that describes the formation of 1 mole of water looks like this
H2(g)+12O2(g)→H2O(l) ΔH=−276 kJ
To write the thermochemical equation that describes the decomposition of 1 mole of water into hydrogen gas and
oxygen gas, you need to reverse the chemical equation
H2O(l)→H2(g)+12O2(g)
and change the sign of the enthalpy change of reaction.
ΔHreverse=−ΔHforward
This means that the thermochemical equation will look like this
H2O(l)→H2(g)+12O2(g) ΔH=+276 kJ
This means that when 1 mole of water undergoes decomposition, 276 kJ of heat are being absorbed!
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THIRD LECTURE

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 calorimetry
• Calorimetry is the science of measuring heat

• It is based on observing the temperature change when a body absorbs or discharges

energy as heat.

• The instrument used in calorimetry is called a calorimeter

• It can be done at constant volume or at constant pressure

• Constant volume calorimetry measures the internal energy while the constant
pressure measures the enthalpy

• A constant volume calorimeter is called a bomb calorimeter

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 Concept check
• When a student mixes 50 mL of 1.0 M and 50 mL of 1.0 M in a coffee-cup
calorimeter, the temperature of the resultant solution increases from 21.0oC to
27.5oC. Calculate the enthalpy change for the reaction in kj/mol HCl, assuming
that the calorimeter loses only a negligible quantity of heat, that the total volume
of the solution is 100 mL, that its density is 1.00 g/mL, and that its specific heat is
4.18 J/g-K.

• total volume of the solution is 100 mL, its mass is

• The temperature change is
• Recall 38
• "Since the temperature increases the reaction must be exothermic"

• Because it is a constant pressure process

• To express the enthalpy change on a molar basis, we use the fact that the number
of moles of HCl is given by the product of the volume (50mL = 0.050 L) and
concentration (1.0 M = 1.0 mol/L) of the HCl solution:

• (0.050 L)(1.0 mol/L) = 0.050 mol

• Thus, the enthalpy change per mole of HCl is H = –2.7 kJ/0.050 mol = –54 kJ/mol

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Hess' law
• Hess’s law states that the enthalpy change for a
reaction that is carried out in a series of steps is
equal to the enthalpy changes of all individual
steps.
• It is based on the fact that energy change for
any chemical or physical process is
independent of the pathway or number of
steps required to complete the process,
• i.e. enthalpy is a state function.
• Consider the conversion of A to B
• ΔH1 is the change in enthalpy for a direct
conversion of A to B.
• ΔH1 = ΔH2 + ΔH3.
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Concept check
• Given:
• I.
• II.
• Determine the enthalpy change of following reaction.

• Solution
• The sign of also changes since the equation was reverse. Since one mole of CO2
was produced, this second equation is also multiplied by ½ giving:

• Adding to the first equation

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Concept check
• WE HAVE
• Given • – IV

• I. • –V
• – VI
• II.
• REACTION IV MULTIPLIED BY 2
• III. • VII.
• find enthalpy change for: • SUMMING THESE THREE REACTIONS – V, VI AND VII; GIVES

• Solution. note that the enthalpies of • THUS .

reactions are included with the
reaction Reactions I and III are
endothermic. Reaction II is
exothermic.

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 𝑥
𝑁 2 𝑂 4 (𝑔) →2 𝑁 𝑂 2 ( 𝑔)
−2 𝑘𝑐𝑎𝑙
𝑁 2 ( 𝑔 ) +2 𝑂 2 ( 𝑔
−2)(13 .5)𝑘𝑐𝑎𝑙

+ 43 𝑘𝑐𝑎𝑙

I. I.
II. II.
III. III. 43
 Enthalpy of formation, , or
• Enthalpy of formation is the standard enthalpy of reaction for the formation of
one mole of the substance from its elements in their reference state.

• The reference state of an element is its most stable form at the specified
temperature, usually 25oC and 1 bar.
• the reference state of hydrogen is a gas of H2 molecules, that of mercury is liquid
and carbon is graphite.
• Some elements exist in more than one form; when this happens, the most stable
form is the reference state. E.g. the standard enthalpy of formation for ethanol
(C2H5OH) is the enthalpy change for the following reaction

• The standard enthalpy of formation of the most stable form of any element is
defined as zero. This is because the elements need no formation
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Some enthalpy of
formation
• These values may be used to calculate
ΔH for any chemical reaction so long
as all the compounds involved appear
in the tables. This is obtained by

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Sample Exercise
• For which of the following reactions at 25oC would the enthalpy change represent
a standard enthalpy of formation? For those where it does not, what changes
would need to be made in the reaction conditions?

• a) 2 Na(s) + ½ O2(g)  Na2O(s)

• b) 2 K(l) + Cl2(g)  2 KCl(s)

• c) C6H12O6(s)  6 C(diamond) + 6 H2(g) + 3 O2(g)

• Write the equation corresponding to the standard enthalpy of formation of liquid

carbon tetrachloride (CCl4). 46
 Concept check

• Calculate for the reaction:

• Given that:

• The last three equations are enthalpies of formation

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Concept check
• Use standard enthalpies of formation to calculate ΔH for the reaction

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 Fuel: Sources of Energy
• A fuel is any substance that is burned or similarly reacted to provide heat and other
forms of energy
• Food supplies the raw materials that your body needs to replace cells and the energy
that keeps those cells functioning.
•Foods fill three needs of the body: they supply substances for the growth and repair of
tissue, they supply substances for the synthesis of compounds used in the regulation of
body processes, and they supply energy. About 80% of the energy we need is for heat.
The rest is used for muscular action, chemical processes, and other body processes.
•The body generates energy from food by the same overall process as combustion, so the
overall enthalpy change is the same as the heat of combustion, which can be determined
in a calorimeter. 49
 Chemistry in Action:
Fuel Values of Foods and Other Substances
C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol

1 cal = 4.184 J
1 Cal = 1000 cal = 4184 J

Substance DHcombustion (kJ/g)

Apple -2

Beef -8

Beer -1.5

Gasoline -34
 Fossil fuels
• Coal, petroleum, and natural gas, which are the world’s major sources of energy, are
known as fossil fuels.
•Anthracite, or hard coal, the oldest variety of coal, was laid down as long as 250
million years ago and may contain over 80% carbon. Bituminous coal, a younger
variety of coal, has between 45% and 65% carbon.
•Natural gas consists of gaseous hydrocarbons, compounds of hydrogen and carbon. It
•contains primarily methane CH4, with small amounts of ethane C2H6, propane C3H8,

and butane C4H10.

• Petroleum is a liquid composed of hundreds of compounds, most of which are
hydrocarbons, with the remainder being chiefly organic compounds containing sulfur,
nitrogen, or oxygen.
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 Sources of Energy
•Nuclear energy is the energy released in either the fission (splitting) or the fusion

(combining) of atomic nuclei.

• Renewable energy sources include solar energy from the Sun, wind energy

harnessed by windmills, geothermal energy from the heat stored inside Earth,

hydroelectric energy from flowing rivers, and biomass energy from crops and

biological waste matter

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END

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