ENERGETICS AND

THERMOCHEMISTRY
Sek Catalunya
1DP
Cristina Villaverde Basagoitia
 INTRODUCTION
What is thermodynamics?
The utilization of energy is central to our lives. Agricultural, industrial,
and domestic activities all consume vast amounts of energy daily.
Thermodynamics is the study of energy and how it is interconverted.
The first law of thermodynamics states that energy can be converted
from one form to another and that the total amount of energy for a
given system will remain constant.
This law is often called the law of conservation of energy and states
that energy can be neither created nor destroyed; it can only be
converted between different forms. This means that for a given system
we can account for and quantify all the energy changes. This is one of
the most fundamental principles of science.
Chemical potential energy, heat, and
entropy
In a chemical reaction total energy is conserved
Chemical potential energy is the energy stored in the chemical bonds
of a substance.
Heat, q, is a form of energy that is transferred from a warmer body to
a cooler body, as a result of the temperature gradient. Heat is
sometimes referred to as thermal energy. It can be transferred by the
processes of conduction, convection, and radiation. Heat has the
ability to do work. When heat is transferred to an object, the result is
an increase in the average kinetic energy of its particles and therefore
an increase in its temperature or a change in phase.
Entropy: is the measure of the disorder of a system
ENTROPY
 Chemical Energy
When examining the energy changes
involved in a chemical reaction, we
divide the universe into two parts: the
system in which the chemical reaction
is taking place, and its surroundings.
 You can think of the system as
being all the reactants, products,
and any solvents.
 The surroundings include the
apparatus that contains the
reaction, thermometers or other
measuring devices, the laboratory,
and everything external to the
reacting substances.
When a chemical reaction takes place, the atoms of the reactants are
rearranged to create new products. Chemical bonds in the reactants
are broken and new chemical bonds are made to form the products.
Energy is required to break the chemical bonds: bond breaking is an
endothermic process.
Energy is released when new chemical bonds are made: bond making is
an exothermic process.
The transfer of energy between the surroundings and the system is an
important part of understanding the energy changes in a reaction.

GCSE Chemistry - Exothermic and Endothermic Reactions #36 - YouTube

 Enthalpy and thermochemistry
Enthalpy is the measurement of energy in a thermodynamic system  

Thermochemistry is the study of heat changes that occur during

chemical reactions. At constant pressure, the change in enthalpy ∆H is
defined as the heat transferred by a closed system during a chemical
reaction.
The term “change in enthalpy” or “heat of reaction” is commonly used
when describing the thermodynamics of a reaction. The unit of
enthalpy change ∆H is kJ.
Open systems. They are those that freely exchange matter and energy with the
outside
Closed systems. They are those that freely exchange energy (but not matter) with their
environment.
Isolated systems. They are those that do not exchange matter or energy with the
environment
 Exothermic reactions

A chemical reaction in which heat is

transferred from the system to the
surroundings is defined as an
exothermic reaction with a negative
∆H. In contrast, chemical reactions
that absorb heat from their
surroundings are defined as
endothermic reactions with a positive
∆H

An exothermic reaction – YouTube

Endothermic reactions
Ammonium nitrate, NH4NO3 is an
important component of fertilizers. When
the solid dissolves in water to form
aqueous ammonium and nitrate ions, the
reaction requires heat to proceed. This
heat is absorbed by the system from the
surroundings, resulting in a decrease in
the temperature of the surroundings as
recorded by a thermometer. The
apparatus containing the reaction feels
cold to touch. This is an example of an
endothermic reaction (Figure 3).

Ammonium nitrate endothermic reaction - YouTube

 Calculating enthalpy changes in aqueous solutions
The change in enthalpy ∆H is defined as the heat transferred by a closed
system during a chemical reaction.
To calculate ∆H for a reaction we therefore need to find the heat change.
When calculating the heat change of a pure substance such as water, we
need to have an understanding of the physical quantity, the specific heat
capacity, c
The specific heat capacity of a pure substance is defined as the amount of heat
needed to raise the temperature of 1 g of the substance by 1 °C or 1 K.
For example, the specific heat capacity of copper is 0.385 J while that of ethanol is
2.44 J .
The lower the specific heat capacity of a given substance, the higher the
temperature rise achieved for the same amount of heat transferred to the
sample.
Specific heat capacity is an intensive property that does not vary in magnitude with
the size of the system being described. For example, a 10 sample of copper has the
same specific heat capacity as a 1 tonne block.
Specific heat capacity is used to calculate the heat q of a system using the
relationship:
q = mcΔT
where m is mass in kg and ∆T is the change in temperature.
Video Specific Heat Capacity
GCSE Physics - Internal Energy and Specific Heat Capacity #27 – You
dube

Exercise:
 An chunk of steel with a mass of 1.57 kg absorbs net thermal energy of 2.5x J
and rises its temperature by 355°C. What is the specific heat of the steel?
 The temperature of a 200-g sample of an unknown substance
changed from 40°C to 25°C. In the process, the substance released 569
calories of energy. What is the specific heat capacity of the substance? 
Exothermic vs. Endothermic Review

ENDOTHERMIC
EXOTHERMIC
 Enthalpy change of formation
The change in enthalpy during a reaction can be determined using the following
equation:
ΔHº reaction = ∑(ΔHfº products) – ∑(ΔHfº reactants)
ΔHfº is the standard enthalpy change of formation of a substance.
This is the energy change upon the formation of 1 mol of a substance from its
constituent elements in their standard state. We can use existing enthalpy of
formation data to calculate the enthalpy of reaction. The value and sign of the
calculated enthalpy of formation informs us about the energetics of the reaction.
For example, the standard enthalpy change of formation for methane is:
C(s) + 2H2 (g) → CH4 (g) ∆Hf = -74.9 kJ mol-1 It is important to note that the
elements carbon and hydrogen are represented in their standard states.
 Enthalpy change of combustion
The standard enthalpy change of combustion ∆Hc is the heat evolved upon the complete
combustion of 1 mol of substance. The enthalpies of combustion found in section 13 of the Data
booklet are values derived under standard conditions. Butane, one of the gases classified as
liquefied petroleum gas (LPG) is highly flammable:
C4H10 (g) + O2 (g) → 4CO2 (g) + 5H2O(l)
∆Hc = -2878 kJ
This thermochemical equation can also be written with the enthalpy of combustion value included
in the equation. The negative enthalpy change indicates an exothermic reaction so the value would
be included on the product side
C4H10 (g) + O2 (g) → 4CO2 (g) + 5H2O(l) + 2878 kJ
 Example: Calculate the enthapy change for the reaction:
C3H8(g) + 5 O2(g) 3CO2(g) + 4H2O (g)
From the following standard enthalpy changes of formation

Enthalpy of formation/Kjmol-1

C3H8 (g) -104

CO2(g) -394
H2O(l) -286
Calculate the enthalpy change for the reaction:
Fe3O4 (s) + 2C(graphite)  3Fe(s) + 2CO2(g)
From the data below:

Enthalpy of formation
(Kj mol-1)
Fe3O4 (s) -1118
CO2(g) -394
Benzene, C6H6 is highly flammable, producing a sooty flame:
2C6H6 (l) + 15O2 (g) → 12CO2 (g) + 6H2O(l)
∆H reaction = ∑(∆Hf products) - ∑(∆Hf reactants) =
[12 × ( 393.5) + 6 × ( 285.8) 2 × (+49.0) 15 × 0] kJ = ( 4722- 1714.8 -98.0)
kJ = -6535 kJ
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 changes.

Hess’s Law allows us to

calculate the overall change in
enthalpy by simply summing up
the changes for each step of the
way, until product is formed. All
steps have to proceed at the
same temperature and the
equations for the individual
steps must balance out.
 Definition of Hess’s Law
The heat of any reaction f for a specific reaction is
equal to the sum of the heats of reactions for any set of
reactions which in sum are equivalent to the overall
reaction.
EXAMPLE OF HESS’S LAW
Formation of carbon dioxide from carbon and oxygen can occur in one step or two
steps. In two steps it can be formed via the production of carbon monoxide.
• In one step,
C(s) + O2(g) → CO2 ΔH1 = -393 kJ/mol ……………..(i)
• In two steps,
step 1: C(s) + 1/2O2(g) → CO ΔH2 = -111 kJ/mol
Step 2: CO(g) + 1/2O2(g) → CO2 ΔH3 = -282 kJ/mol

Overall change: C(s) + O2(g) → CO2 ΔH2+3 = -393 kJ/mol = ΔH1

 Bond Enthalpy
The breaking of the hydrogen molecule into individual hydrogen atoms requires
energy. The bond enthalpy of a bond (the H-H bond in this example) is defined as the
energy required to break 1 mol of bonds in gaseous covalent molecules under
standard conditions.
Bond breaking is an endothermic process and has a positive enthalpy value, for
example:

Bond enthalpy is also referred to as bond dissociation enthalpy, and selected values
are provided in section 11 of the Data booklet and in table 1. These are average values
and are therefore only an approximation.
 Bond length
Consider the molecules hydrogen Fluoride HF, hydrogen chloride HCl, hydrogen
bromide HBr, and hydrogen iodide HI.
As you move down group 17 the atomic radius increases with increasing atomic
number, Z.
The consequence of this is that bond length increases, and bond strength
decreases, in the hydrogen halides as you move down group 17 (table 2).
Bond strength
The bond enthalpy
reflects the strength of
the covalent bond. As
we move from single
to double to triple
bonds the number of
electrons in the bond
increases resulting in
an increase in
electrostatic forces
and a shortening of
the bond length.
 Bond polarity
The polarity of a bond can be described by the
difference in electronegativity of the bonded atoms
(tables 3 and 4).
Example:using bond enthalpies to find the enthalpy change of reaction
Calculating enthalpy changes in aqueous solutions
The change in enthalpy ∆H is defined as the heat transferred by a closed system
during a chemical reaction.
To calculate ∆H for a reaction we therefore need to find the heat change. When
calculating the heat change of a pure substance such as water, we need to have
an understanding of the physical quantity, the specific heat capacity, C.
The specific heat capacity of a pure substance is defined as the amount of heat
needed to raise the temperature of 1 g of the substance by 1 °C or 1K. For
example, the specific heat capacity of copper is 0.385 J while that of ethanol is
2.44 J . The lower the specific heat capacity of a given substance, the higher the
temperature rise achieved for the same amount of heat transferred to the
sample.
 CALORIMETER
o Systematic Errors: a consequence of the
experimental procedure.
Not all the heat is just transferred to the
water:
- Walls of the coffee cup
- Stirrer
- The air surrounding the water
 OZONE
Ozone, O3 is both created
and destroyed in the
stratospheric layer of Earth’s
atmosphere. Ultraviolet (UV)
rays from the sun are
absorbed by oxygen, O2 ,
splitting the molecule into
single oxygen atoms. These
oxygen atoms can then
combine with oxygen
molecules to form ozone
Ozone is very effective at
absorbing harmful long- and short-
wavelength UV radiation.
Without the presence of ozone in
the stratosphere, life on Earth
would change forever, as harmful
UV radiation would damage cells
in both plants and animals.
The bond dissociation enthalpy of
an oxygen molecule is 498 kJ/mol .
In comparison, the energy
required to break an oxygen–
oxygen bond within an ozone
molecule is 364 kJ/mol .
The consequence of this is that an
ozone molecule is decomposed by
UV rays more readily than an
oxygen molecule. The ozone
photolysis is an endothermic
reaction with the required energy
coming from the UV radiation.
 Potential Energy Profile
Examination of this energy profile reveals that the oxygen molecule and oxygen
atom have a greater combined energy than the reactant ozone molecule. The
products of this reaction are said to be less stable, as they exist at a higher energy.
Depletion of the
ozone layer
Since the early 1980s
scientists have been
monitoring ozone
depletion globally,
particularly the giant holes
in the ozone layer which
have appeared above the
Arctic and Antarctic polar
icecaps
Chlorofuorocarbons (CFCs) are a type of hydrocarbon containing carbon, hydrogen, and halogen atoms.
Scientific research in 1973 discovered that while CFCs remained harmless close to the Earth’s surface, when
exposed to UV radiation in the stratosphere these compounds underwent chemical reactions resulting in the
release of chlorine.
The chlorine released then had a catalytic effect on the destruction of ozone in this layer of the atmosphere. As
the chlorine is not directly consumed in the reaction, small amounts of CFCs were found to be responsible for
the destruction of large quantities of ozone.