THERMODYNAMICS

Thermodynamics deals with the concepts of heat and temperature and the inter-
conversion of heat and other forms of energy. The four laws of thermodynamics govern
the behavior of these quantities and provide a quantitative description. William
Thomson, in 1749, coined the term thermodynamics.

•To be specific, it explains how thermal energy is converted to or from other forms of
energy and how matter is affected by this process. Thermal energy is the energy that
comes from heat. This heat is generated by the movement of tiny particles within an
object, and the faster these particles move, the more heat is generated.

•Thermodynamics is not concerned about how and at what rate these energy
transformations are carried out. It is based on the initial and final states undergoing the
change.

•It should also be noted that Thermodynamics is a macroscopic science. This means that
it deals with the bulk system and does not deal with the molecular constitution of matter.

Different Branches of Thermodynamics

Classical Thermodynamics - the behavior of matter is analyzed with a macroscopic

approach. Units such as temperature and pressure are taken into consideration, which
helps the individuals calculate other properties and predict the characteristics of the
matter undergoing the process.

Statistical Thermodynamics - every molecule is under the spotlight, i.e. the properties
of every molecule and how they interact are taken into consideration to characterize the
behavior of a group of molecules.

Chemical Thermodynamics - is the study of how work and heat relate to each other
in chemical reactions and in changes of states.

Equilibrium Thermodynamics - is the study of transformations of energy and matter

as they approach the state of equilibrium.

System - is a specific portion of matter with a definite boundary on which our attention
is focused. The system boundary may be real or imaginary, fixed or deformable.

Three types of systems

Isolated System – cannot exchange energy and mass with its surroundings. The
universe is considered an isolated system.
Closed System – Across the boundary of the closed system, the transfer of energy
takes place but the transfer of mass doesn’t take place. Refrigerator, compression of gas
in the piston-cylinder assembly are examples of closed systems.

Open System – the mass and energy both may be transferred between the system and
surroundings. A steam turbine is an example of an open system.

Basic Concepts of Thermodynamics – Thermodynamic Terms

Thermodynamics has its own unique vocabulary associated with it. A good
understanding of the basic concepts forms a sound understanding of various topics
discussed in thermodynamics preventing possible misunderstandings.

System boundary - is a closed surface surrounding a system through which energy and
mass may enter or leave the system.

Surroundings - Everything that interacts with the system.

- Everything outside the system that has a direct influence on the

behavior of the system.

System - is a region containing energy and/or matter that is separated from its
surroundings by arbitrarily imposed walls or boundaries

Thermodynamics - A system undergoes a thermodynamic process when there is some

energetic change within the system that is associated with changes in pressure, volume
and internal energy.

Four types of thermodynamic processes

Adiabatic Process – A process where no heat transfer into or out of the system occurs.

Isochoric Process – A process where no change in volume occurs and the system does
no work.

Isobaric Process – A process in which no change in pressure occurs.

Isothermal Process – A process in which no change in temperature occurs.

Thermodynamic Equilibrium

At a given state, all properties of a system have fixed values. Thus, if the value of even
one property changes, the system’s state changes to a different one. In a system that is
in equilibrium, no changes in the value of properties occur when it is isolated from its
surroundings.
Thermal equilibrium - when the temperature is the same throughout the entire
system.

Mechanical equilibrium - when there is no change in pressure at any point of the

system.

Chemical equilibrium - when the chemical composition of a system does not vary with
time.

Phase equilibrium in a two-phase system - is when the mass of each phase reaches
an equilibrium level.

Thermodynamics Properties - are defined as characteristic features of a system,

capable of specifying the system’s state. Thermodynamic properties may be extensive or
intensive.

• Intensive properties - are properties that do not depend on the quantity of matter.
Pressure and temperature are intensive properties.

• Extensive properties - their values depends on the mass of the system. Volume,
energy, and enthalpy are extensive properties.

Enthalpy - is the measurement of energy in a thermodynamic system. The quantity of

enthalpy equals the total heat content of a system, equivalent to the system’s internal
energy plus the product of volume and pressure.

H = E + PV

E - sum of the internal energy

P - pressure of the system

V - volume of the system

Entropy - is a thermodynamic quantity whose value depends on the physical state or

condition of a system. In other words, it is a thermodynamic function used to measure
the randomness or disorder.

For example, the entropy of a solid, where the particles are not free to move, is less than
the entropy of a gas, where the particles will fill the container.

Thermodynamic potentials - are quantitative measures of the stored energy in a

system. Potentials measure the energy changes in a system as they evolve from the
initial state to the final state. Different potentials are used based on the system
constraints, such as temperature and pressure.
Different forms of thermodynamic potentials along with their formula are

tabulated below:

Thermodynamics Solved Problems

Calculate ∆G at 290 K for the following reaction:

2NO(g) +O2(g) +2NO2(g)

Solution:

Given:

∆H = -120kJ and ∆S = -150JK^ – 1

To make the unit of ∆S the same as ∆H, we have to convert the unit of ∆S as follows:

∆S = -150J/K(1kJ÷1000J) → ∆S = -0.15kj/K

We know that, G = U + PV - TS → ∆G = ∆H – T∆S

So, ∆G = -120kJ - (290K) (-0.150kJ/K) = -120 kJ + 43kJ

Therefore, ∆G is – 77kJ.

Laws of Thermodynamics

Thermodynamics laws define the fundamental physical quantities like energy,

temperature and entropy that characterize thermodynamic systems at thermal
equilibrium. These thermodynamics laws represent how these quantities behave under
various circumstances.

Four laws of thermodynamics

Zeroth law of thermodynamics

-states that if two bodies are individually in equilibrium with a separate third body, then
the first two bodies are also in thermal equilibrium with each other.

-enables us to use thermometers to compare the temperature of any two objects that we
like.

First law of thermodynamics

-also known as the law of conservation of energy, states that energy can neither be
created nor destroyed, but it can be changed from one form to another.

Examples:

• Plants convert the radiant energy of sunlight to chemical energy through

photosynthesis. • We eat plants and convert the chemical energy into kinetic energy
while we swim, walk, breathe, and scroll through this page.

• Switching on light may seem to produce energy, but it is electrical energy that is
converted.

Second law of thermodynamics

-states that the entropy in an isolated system always increases. Any isolated system
spontaneously evolves towards thermal equilibrium—the state of maximum entropy of
the system.

-If a room is not tidied or cleaned, it invariably becomes more messy and disorderly with
time. When the room is cleaned, its entropy decreases, but the effort to clean it has
resulted in increased entropy outside the room exceeding the entropy lost.

Third law of thermodynamics

-states that the entropy of a system approaches a constant value as the temperature
approaches absolute zero.

Examples:

Let us consider steam as an example to understand the third law of thermodynamics

step by step:

1. The molecules within it move freely and have high entropy.

2. If one decreases the temperature below 100 °C, the steam gets converted to water,
where the movement of molecules is restricted, decreasing the entropy of water.

3. When water is further cooled below 0 °C, it gets converted to solid ice. In this state,
the movement of molecules is further restricted and the entropy of the system reduces
more.
4. As the temperature of the ice further reduces, the movement of the molecules in them
is restricted further and the entropy of the substance goes on decreasing.

5. When the ice is cooled to absolute zero, ideally, the entropy should be zero. But in
reality, it is impossible to cool any substance to zero.

Thermodynamics – Summary and Overview

Thermodynamics - deals with the transfer of energy from one form to another.

Laws of thermodynamics are:

• First law of thermodynamics: Energy can neither be created nor be destroyed, it

can only be transferred from one form to another.

• Second law of thermodynamics: The entropy of any isolated system always

increases.

• Third law of thermodynamics: The entropy of a system approaches a constant

value as the temperature approaches absolute zero.

• Zeroth law of thermodynamics: If two thermodynamic systems are in thermal

equilibrium with a third system separately, then they are in thermal equilibrium with
each other.

Entropy - is the measure of the number of possible arrangements the atoms in a system
can have.

Enthalpy - is the measurement of energy in a thermodynamic system.

THE FIRST LAW OF THERMODYNAMICS AND

EXOTHERMIC & ENDOTHERMIC REACTIONS
Thermodynamics is the study of the relations between heat, work, temperature, and
energy. The laws of thermodynamics describe how the energy in a system changes and
whether the system can perform useful work on its surroundings.

The first law of thermodynamics states that energy can neither be created nor
destroyed, only altered in form. For any system, energy transfer is associated with mass
crossing the control boundary. These produce the control volume. The mass flow of a
fluid is associated with the kinetic, potential, internal, and “flow” energies that affect the
overall energy balance.
That is why the first law of thermodynamics is referred to as the conservation of energy
principle, meaning that energy can neither be created nor destroyed, but rather
transformed into various forms as the fluid within the control volume changes.

Example:

Conservation of heat energy into chemical energy (sunlight – plant)

Conservation of mechanical energy into electrical energy (generator)

Conservation of chemical energy into heat and sound energy (fireworks)

Conservation of electrical energy into mechanical energy (electric appliances)

∆E = Q + W

ΔE is the change in internal energy of a system,

Q is the net heat transfer (the sum of all heat transfer into and out of the system), and

W is the net work done (the sum of all work done on or by the system).

Exothermic Reaction

-When a reaction makes and releases its own heat, that’s called an exothermic reaction.

-You’ll know it makes its own heat because it will feel hot to you!

Endothermic Reaction

-When a reaction absorbs heat from the surroundings, it’s called an endothermic
reaction.

-You’ll know it’s absorbing heat because it feels cold to you!

THERMOCHEMICAL
H₂ + O₂ (Reactant) → H₂O (Product)

Thermochemical Equation

-is a balanced chemical equation that shows not only the reactants and products but also
the enthalpy change (ΔH) of the reaction.

-It provides information on the heat absorbed(endothermic) or released (exothermic)

during the reaction under constant pressure.
Enthalpy (∆H) - is a measure of the total heat content of a system. In chemical
reactions, ΔH represents the heat change at constant pressure.

Negative ΔH - heat release (exothermic)

Positive ΔH - heat absorption (endothermic).

CH₄ + 2O₂ → CO₂ + 2H₂O ΔH= −890 kJ

-This reaction represents methane (CH4) burning in oxygen (O₂) to produce carbon
dioxide (CO₂) and water (H₂O).

-ΔH = -890 kJ: The negative sign indicates that heat is released, so it’s an exothermic
reaction.

-Energy Released: 890 kJ of heat is released for every 1 mole of methane burned.

CaCO₃ → CaO + CO₂ ΔH= +178kJ

-This reaction, calcium carbonate (CaCO₃) decomposes into calcium oxide (CaO) and
carbon dioxide (CO₂) when heat is absorbed.

-ΔH = +178 kJ: The positive sign indicates that heat is absorbed, making this an
endothermic reaction.

-Energy Absorbed: 178 kJ of heat is absorbed for every 1 mole of calcium carbonate
decomposed.

Properties of Thermochemical Equation

• Can be REVERSED

-If you reverse a chemical equation,

The sign of ΔH (energy change) also reverses.

Example:

N₂ + 3H₂ → 2NH₃ ΔH = -92 kJ

2NH₃ → N₂ + 3H₂ ΔH = +92 kJ

• Can be ADDED/SUBTRACTED

-You can treat thermochemical equations like math problems: you can add, subtract, or
even multiply them.

This is how we use Hess’s Law to calculate ΔH in reactions that happen in multiple steps.
Types of Chemical Reactions

1. Combination Reaction - A + B → C

2. Decomposition Reaction – A B+C

3. Replacement Reaction – A + B → C + D

4. Replacement Reaction – AB + CD → AD + CB