Chapter 01

Basics Concepts of Thermodynamics

Thermodynamics is concerned with the ideas of heat and temperature, as well as
the exchange of heat and other forms of energy. The branch of science that
is known as thermodynamics is related to the study of various kinds of energy and
its interconversion. The behaviour of these quantities is governed by three main
laws of thermodynamics, which provide a quantitative description. The word
thermodynamics was coined by William Thomson in 1749. The following section
dives into some of the most commonly used thermodynamic terminologies.
What is Thermodynamics?
Thermodynamics is a field of science that investigates the links between heat,
work, and temperature, as well as their interactions with energy, radiation, and
the physical properties of matter. Thermodynamics, in its broadest sense, is
associated with the transfer of energy from one location to another and from one
form to another.
Heat is a type of energy that corresponds to a specific quantity of mechanical
work, which is the key concept. It discusses how thermal energy is transformed to
or from other forms of energy, as well as how this process affects matter. The
energy derived from heat is known as thermal energy.
The movement of microscopic particles within an object generates heat, and the
faster these particles move, the more heat is produced. Thermodynamics is
unconcerned about the rate at which these energy transformations occur. It is
based on the change occurring in the initial and final states. It’s also worth noting
that thermodynamics is a macroscopic field of study. This means it is concerned
with the bulk system rather than the molecular structure of matter.
Basic Concepts of Thermodynamics
Thermodynamics has its own set of terms related to it. A thorough
comprehension of the fundamental ideas ensures a deep understanding of the
numerous topics covered in thermodynamics, avoiding any misunderstandings.
Thermodynamic concepts are covered below.
System
The system refers to a specific part of the universe that is being observed. A
thermodynamic system is a part of matter with a defined boundary on which we
concentrate our attention. The system boundary can be real or imaginary, and it
can be fixed or movable.
Physical qualities and chemical compositions are said to be homogeneous if they
are consistent throughout the system. A system, on the other hand, is considered
to be heterogeneous if it is made up of parts with varied physical and chemical
properties. Depending on how matter and energy travel in and out of a system, it
can be divided into three categories. There are three different types of systems.
• Open System – An open system is one that can exchange matter as well as
energy with its surroundings. As a result, mass and energy can be
transmitted between the system and its surroundings in an open system.
Since it gains and loses matter as well as energy, hot coffee in an open flask
is an example of an open system. An open system is a steam turbine, for
example.
• Closed System – A closed system exchanges energy but does not exchange
matter with its surroundings. The transmission of energy takes place across
the closed system’s boundary, but the transfer of mass does not. Closed
systems include refrigerators and gas compression in piston-cylinder
assemblies. Coffee in a stainless flask is also an example of a closed system
because energy, but not matter, can flow through the steel walls.
• Isolated System – An isolated system is one that is unable to exchange
matter or energy with its surroundings. There is no such thing as a system
that is completely isolated. An isolated system, on the other hand, is one
that is entirely sealed to prevent matter intake or outflow and is thermally
insulated to prevent heat flow. The universe is believed to be self-
contained. Since it cannot gain or lose energy or matter, hot coffee in a
corked thermos flask is an example of an isolated system.
 Figure: Types of Systems

Surrounding
The remaining portion of the universe that is not a part of the system is known as
the surrounding. The term “surrounding” refers to everything outside the system
that has a direct impact on the system’s behaviour. In other words, anything

outside of the system is included in the surroundings. Together, the system and its
surroundings make up the universe.

Figure: System and Surroundings

The alterations in the system, on the other hand, have no effect on the entire
universe. As a result, the surroundings are that portion of the remaining universe
that can interact with the system for all practical purposes. In general,
the surroundings are defined as an area of space in its close surroundings.
Different Branches of Thermodynamics
The following are the four branches of thermodynamics.
1. Classical Thermodynamics– The behaviour of matter is studied using a
macroscopic approach in classical thermodynamics. Individuals consider
units such as temperature and pressure, which aids in the calculation of
other properties and the prediction of the characteristics of the matter
undergoing the process.
2. Statistical Thermodynamics– Every molecule is in the spotlight in statistical
thermodynamics, which means that the properties of each molecule and
how they interact are taken into account to characterise the behaviour of a
group of molecules.
3. Chemical Thermodynamics– The study of how work and heat interact in
chemical reactions and state transitions is known as chemical
thermodynamics.
4. Equilibrium Thermodynamics– Equilibrium thermodynamics is the study of
energy and matter transitions as they approach equilibrium.
Thermodynamic Properties
Thermodynamics is concerned with massive chemical entities such as atoms or
molecules. The macroscopic properties of a system are those that originate from
the bulk behaviour of matter. Thermodynamic properties are defined as system
characteristics that can be used to specify the system’s state. Thermodynamic
properties are classified into two categories, as shown below.
1. Extensive property– Extensive properties are system properties whose
value is dependent on the amount or size of material present in the system.
The value of extensive characteristics is dependent on the system’s mass.
Internal energy, entropy, free energy, and enthalpy are only a few of the
many properties.
 2. Intensive property- Intensive properties are system properties whose value
is independent of the amount or size of substance present in the system.
The properties of an intensive substance are those that are independent of
the amount of substance present. Vapour pressure, pressure, viscosity,
surface tension, and temperature are only a few of the many intensive
properties.
Thermodynamic Equilibrium
All properties of a system have fixed values at any given state. As a result, even if
the value of one property changes, the system’s state changes. While a system is
in equilibrium, the value of its properties does not change when it is isolated from
its surroundings.
• Thermal equilibrium– A system is said to be in thermal equilibrium when
the temperature is the same throughout the entire system.
• Mechanical equilibrium– A system is said to be in mechanical
equilibrium when there is no change in pressure at any point in the system.
• Chemical equilibrium– A chemical equilibrium is defined as a system in
which the chemical composition of a system does not change over time.
• Phase equilibrium– When the mass of each phase of a two-phase system
reaches an equilibrium level, it is called phase equilibrium.
If a thermodynamic system is in chemical equilibrium, mechanical equilibrium,
and thermal equilibrium, and the relevant parameters cease to vary with time,
then it is said to be in thermodynamic equilibrium.
Laws of Thermodynamics
Thermodynamic laws specify the essential physical qualities that characterise
thermodynamic systems in thermal equilibrium, such as energy, temperature, and
entropy. The laws of thermodynamics describe how these quantities react in
various situations.
Thermodynamics is governed by four laws, which are described below.
• Zeroth Law of Thermodynamics- According to the Zeroth Law of
Thermodynamics, if two bodies are separately in thermal equilibrium with a
 third body, then the first two bodies are likewise in thermal equilibrium
with each other. This indicates that if system A is in thermal equilibrium
with system B, and system C is likewise in thermal equilibrium with system
B, then both systems A and C are in thermal equilibrium.
• First Law of Thermodynamics- Energy cannot be generated or destroyed,
according to the first law of thermodynamics, but it can be converted from
one form to another. Heat, internal energy, and work are all addressed by
the first law of thermodynamics. Energy cannot be generated or destroyed,
according to the first law of thermodynamics, but it can be converted from
one form to another. According to this law, some of the heat provided to
the system is utilised to change the internal energy, while the remaining is
used to perform work.
Mathematically, it may be expressed as
ΔQ=ΔU+W
where,
• The heat given or lost is denoted by ΔQ.
• The change in internal energy is denoted by ΔU.
• W stands for work done.
The above equation can alternatively be written as follows:
ΔU=ΔQ−W
As a result of the above equation, we may deduce that the quantity (ΔQ – W) is
unaffected by the path taken to change the state. Furthermore, when heat is
applied to a system, internal energy tends to rise, and vice versa.
• Second Law of Thermodynamics- In an isolated system, the second law of
thermodynamics asserts that entropy always increases. Any isolated system
progresses spontaneously toward thermal equilibrium or the state of
maximum entropy. The universe’s entropy is always increasing and never
decreasing.
• Third Law of Thermodynamics- The third law of thermodynamics states
that when the temperature approaches absolute zero, the entropy of a
 system approaches a constant value. At absolute zero temperature, the
entropy of a pure crystalline solid is zero. If the perfect crystal has only one
state with minimum energy, this assertion holds true.
Sample Questions
Question 1: Is a cup of tea on a table a system that is open, closed, or isolated?
Answer:
Since it gains and loses matter as well as energy, a cup of tea on a table is an open
system.
Question 2: What are the differences between spontaneous and non-
spontaneous processes?
Answer:
A spontaneous process is irreversible and can only be reversed by an outside
force.
Non-spontaneous processes are those that do not occur on their own under
specified conditions and only occur when an external force is continuously
provided.
Question 3: What role does thermodynamics play in our daily life?
Answer:
Thermodynamics is a particularly essential branch of physics and chemistry since
it deals with the study of energy and its conversion, as well as the various forms
and abilities of this energy to accomplish work. It assists us in understanding the
heating and cooling systems in our homes and buildings in our daily lives. It also
aids in the investigation of the vehicle’s engines. The rules of thermodynamics
describe the process by which energy is turned into heat, which is subsequently
transported and converted into productive work.
Question 4: Which one of the properties between pressure and force is an
intensive property?
Answer:
Intensive properties are system properties whose value is independent of the
amount or size of substance present in the system. Since pressure is the force
exerted per unit area, it is an intense property.
Question 5: Which one of the properties between heat capacity and specific
heat is extensive and which is intensive?
Answer:
Heat capacity is a broad property that is determined by the mass of the substance.
However, since specific heat is a heat capacity per unit mass, it is independent of
the amount of substance. As a result, specific heat is an intensive property.
Internal Energy as a State of System
The various forms of energy are interconnected, and they can be converted from
one form to another under certain conditions. The field of science known as
thermodynamics is related to the study of various kinds of energy and its
conversion. In thermodynamics, the system refers to the part of the universe that
is being observed, whereas the surrounding refers to the rest of the universe that
isn’t part of the system. Every substance has a specific amount of energy that is
determined by the substance’s type, such as, temperature, and pressure. Internal
energy is the terminology for this. The internal energy change as a state function
or as a state of the system is described further down.
What is the State of a System?
A system’s state is defined as its state of existence when its macroscopic
characteristics have definite values. The state of the system is said to change if any
of the system’s macroscopic characteristics change. State variables are the
measurable properties needed to describe a system’s state. The state variables are
temperature, pressure, volume, composition, and so on. Consider the case of a
system formed of an ideal gas. Only three variables, such as temperature,
pressure, and volume, may define the state of this system.
A state function is a system property whose value is solely determined by the
system’s state and is unaffected by the path or method by which that state is
attained. The initial and final states of the system, not the path by which they are
obtained, determine the change in the value of these properties.
The system’s thermodynamic state is a crucial term. The system is in some
particular state at any given time, which may be described using values of
macroscopic properties that are relevant to our objectives. The current state of
the system is defined by the values of these characteristics at any given time. The
state changes whenever the value of any of these properties changes. If it can be
later discovered that each of the important properties has the same value as it did
at a previous point in time, it can be observed that the system has reverted to its
previous state.
The state of the system should not be mixed up with the type of physical state or
phase aggregation state. A change of state refers to a shift in the system’s state
rather than a phase transition.
Internal Energy
Every substance has a specific amount of energy that is determined by factors like
the chemical nature of the substance, temperature, and pressure. The term
“intrinsic energy” or “internal energy” refers to this type of energy. The letter U is
used to signify it (earlier it was represented by the symbol E). It is made up of the
individual particles’ kinetic energy and potential energy.
Translational energy, rational energy, vibrational energy, and other forms of kinetic
energy emerge from the motion of its particles. Electronic energy, energy due to
molecular interactions, nuclear energy, and other types of interactions between
particles all contribute to potential energy.
Although traditional thermodynamics is concerned with the macroscopic
characteristics of materials, such as temperature, pressure, and volume, thermal
energy is understood at the microscopic level as a rise in the kinetic energy of
motion of the molecules that make up a substance. The translational kinetic
energy of gas molecules, for example, is proportional to the temperature of the
gas, the molecules can rotate around their centre of mass, and the constituent
atoms can vibrate with respect to each other.
Chemical energy is also stored in the bonds that hold molecules together, and
weaker long-range interactions between molecules require even more energy. The
total internal energy of a substance in a particular thermodynamic state is the
sum of all these kinds of energy. A system’s total energy contains its internal
energy as well as any external sources of energy, such as kinetic energy from the
system’s overall motion, and gravitational potential energy from its elevation.
Internal energy is the sum of all forms of energy stored in atoms or molecules.
Depending on the nature of the constituent atoms, bonds, and various
temperatures, pressure, and other conditions, different substances have varying
internal energies. Even under equal temperature and pressure conditions, the
internal energy of 1 mole of carbon dioxide will differ from the internal energy of
1 mole of sulphur dioxide. Furthermore, under the same atmospheric pressure,
the internal energy of one mole of water at 300K differs from that of one mole of
water at 310K.
Internal Energy as the State of System
A variety of thermodynamic characteristics, such as pressure, volume,
temperature, internal energy, and enthalpy, can be used to define a
thermodynamic system. These are grouped into two categories: state functions
and path functions. A state function is a property of a system whose value is
determined by the system’s initial and final states. These types of functions
explain a function’s equilibrium state and are unaffected by how the system got
there. Internal energy, for example, is a state function that is independent of the
path taken to change the system’s state.
It is a system’s overall energy. This consists of a number of components, including
molecule translational kinetic energy, bond energy, electronic energy, and the
intermolecular interaction energy of the system’s constituents’ particles, among
others. Internal energy is affected by factors such as pressure, volume, and
temperature. All of the variables in this list are state functions. Mass, volume,
pressure, temperature, density, and entropy are all examples of state functions.
Some factors are influenced by the amount of matter present. Intensive
properties are factors that are independent of the amount of matter present.
Density is an example. A state function is a property of a system that is dependent
only on the system’s state and not on the process by which it is achieved. Internal
energy is independent of the path used to get from one condition to the next. It
depends on the system’s current state.
Since accurate values of different types of energies are stored in a system, such as
translational, vibrational, rational, chemical, and so on, it is impossible to compute
the absolute value of internal energy possessed by a substance. The difference
between the internal energies of the two states can be used to calculate the
change in the internal energy of a reaction.
Let’s denote the internal energies in states A and B as UA and UB, respectively. The
difference in internal energy between the two states will be,
∆U=UB – UA
The internal energy difference (∆U) has a set value and is unaffected by the path
followed between two states A and B. The difference between the products’ and
reactants’ internal energies, i.e. the change in internal energy, can be considered
for chemical reactions.
∆U=Uproducts – Ureactants
∆U =Up – Ur
where Up denotes the internal energy of the products, Ur denotes the internal
energy of the reactants, and ∆U denotes the internal energy change.
∆U is positive if the internal energy of the products is greater than the internal
energy of the reactants.
This means that if Up > Ur, then ∆U =Up – Ur = positive.
If the internal energy of the products is smaller than the internal energy of the
reactants, then ∆U will be negative.
This means that if Up < Ur, then ∆U =Up – Ur = negative.
As a result, the internal energy, U, is a state system, that is, the internal energy is a
property of the system whose value is solely determined by the system’s state.
This means that the difference in internal energy U is independent of the path and
only depends on the initial and final states.
Sample Questions
Question 1: What significance does internal energy have?
Answer:
Since the possible energies between molecules and atoms are crucial, the internal
energy is important for understanding phase shifts, chemical reactions, nuclear
events, and many other microscopic phenomena. In a vacuum, both objects have
macroscopic and microscopic energy.
Question 2: What affects internal energy?
Answer:
Internal energy can be changed by altering the temperature or volume of an
object without changing the number of particles inside. As the temperature of a
system rises, the molecules move faster, resulting in higher kinetic energy and
hence an increase in internal energy.
Question 3: Is internal energy a state function?
Answer:
A state function describes the equilibrium state of a system, as well as the system
itself. Since the internal energy U is defined by the quantities that determine the
state of the system at equilibrium, it is called a state function because any change
in energy is entirely determined by the system’s initial and final states.
Question 4: Is the internal energy affected by the system’s path?
Answer:
The internal energy U is totally defined by the quantities that determine the
equilibrium state of the system, therefore any change in energy is entirely
governed by the system’s initial and final states. As a result, the internal energy is
independent of the system’s path.
Question 5: When will the internal energy difference be negative?
Answer:
When the internal energy of the products is smaller than the internal energy of
the reactants, i.e. Up < Ur then the internal energy difference ∆U will be negative.
Applications of First Law of Thermodynamics
Energy, like matter, is always conserved, which means that it cannot be created or
destroyed, but it can be converted from one form to another. Internal energy is a
thermodynamic attribute of a system that refers to the energy associated with the
system’s molecules and comprises both kinetic and potential energy. Whenever a
system undergoes a change as a result of the interaction of heat, work, and
internal energy, it is followed by a series of energy transfers and conversions.
However, there is no net change in total energy throughout these exchanges.
Similarly, the fundamental law of thermodynamics confirms that heat is a type of
energy. This means that thermodynamic processes are guided by the concept of
energy conservation. The first law of thermodynamics is often known as the Law
of Energy Conservation.
First Law of Thermodynamics
A thermodynamic system in equilibrium has a state variable known as internal
energy (E). The difference in internal energy between two systems is equal to the
difference between heat transfer into the system and work done by the system.
The energy of the universe remains constant, according to the first law of
thermodynamics. It can be exchanged between the system and the environment,
but it cannot be generated or destroyed. The law is primarily concerned with
changes in energy states caused by work and heat transmission. It reimagines the
concept of energy conservation.
Heat is a kind of energy, according to the First Law of Thermodynamics, hence
thermodynamic processes are governed by the concept of energy conservation.
As a result, neither heat nor cold energy can be created or destroyed. It may,
however, be moved from one region to another and changed into and out of other
types of energy.
The equation for the first law of thermodynamics is given as;
ΔU = q + W
where: ΔU is the change in the internal energy of the system, q is the algebraic
sum of heat transfer between system and surroundings, W is the work interaction
of the system with its surroundings.
1. Energy (E) is always constant in an isolated system.
 2. Internal Energy is a system property and a point function. Internal energy is
a broad (mass-dependent) characteristic, whereas specific energy is a
narrow (mass-independent) attribute (independent of mass).
3. The internal energy of an ideal gas is just a function of temperature.
Significance of First Law of Thermodynamics: The first law of thermodynamics is
founded on the idea of energy conservation. This indicates that energy cannot be
generated or destroyed, but it can shift into different forms with no loss of energy.
When a system transitions from one state to another, both dQ and dW are
affected by the nature of the process. dU, on the other hand, is the same for all
operations.
Limitations of First Law of Thermodynamics
• When a system goes through a thermodynamic process, it must always
maintain a precise energy balance, according to the law. The first law, on
the other hand, fails to provide the feasibility of the process or change of
state that the system goes through.
• The first law, for example, does not explain why heat transfers from the hot
end to the cold end when a metallic rod is heated at one end but not the
other, and vice versa.
• The first law only quantifies the amount of energy transferred during this
process. The second law of thermodynamics serves as a benchmark for the
feasibility of various processes.
First law of Thermodynamics for a Closed System
Work done in a closed system is the product of pressure applied and volume
change caused by applied pressure.
W = − P ΔV
Where P is the constant external pressure on the system, and ΔV is the change in
volume of the system. This is specifically called pressure-volume work.
The internal energy of a system rises or falls in response to work contact that
occurs across its limits. Internal energy increases when work is performed on the
system and decreases when work is performed by the system. Any heat
interaction that occurs in the system with its surroundings modifies the system’s
internal energy. However, because energy is constant (as stated by the first law of
thermodynamics), the total change in internal energy is always zero. If the system
loses energy, it is absorbed by the environment. When energy is absorbed by a
system, it means that the energy was released by the environment:
ΔUsystem = −ΔUsurroundings
Where ΔUsystem is the change in the total internal energy of the system,
and ΔUsurroundings is the change in the total energy of the surrounding.
Applications of First Law of Thermodynamics
• Isothermal process: The temperature of an ideal gas remains constant
during an isothermal process. This means that the heat supplied to the
system is utilized to do work against the environment. So,
dQ = dU + dW
⇒ dQ = dW
• Melting process: When a solid melts to liquid, its internal energy increases.
Let m = mass of liquid and L = latent heat of the solid. Amount of heat
absorbed by the system, dQ = mL.
A small amount of expansion occurs, i.e., ΔV = 0
⇒ dW = PΔV = 0
So,
dQ = dU + dW
⇒ dU = mL
Thus, internal energy increases during the melting process.
• Heat engines:
The heat engine is the most common practical application of the First Law.
Thermal energy is converted into mechanical energy via heat engines and vice
versa. The vast majority of heat engines are open systems. A heat engine’s basic
idea makes use of the correlations between heat, volume, and pressure of a
working fluid. This fluid is normally a gas, however, it may transition from gas to
liquid and back to gas during a cycle in some instances.
When a gas is heated, it expands; nevertheless, when the same gas is confined, its
pressure rises. If the confinement chamber’s bottom wall is the top of a moving
piston, this pressure exerts a force on the piston’s surface, causing it to travel
downward. This movement can then be used to provide work equal to the total
force applied to the top of the piston multiplied by the distance traveled by the
piston.
Refrigerators, air conditioners, and heat pumps
Refrigerators and heat pumps are mechanical energy converters that convert
mechanical energy to heat. The majority of these are classified as closed systems.
When a gas is compressed, its temperature rises. This hot gas can then radiate
heat into its surroundings. When the compressed gas is allowed to expand, its
temperature drops below what it was before compression because some of its
heat energy was removed during the hot cycle. After then, the cold gas can absorb
heat energy from its surroundings. This is the operating principle of an air
conditioner. Air conditioners do not generate cold; rather, they remove heat. A
mechanical pump transports the working fluid outside, where it is compressed
and heated. The heat is then transferred to the outside environment, typically via
an air-cooled heat exchanger. Then it is delivered indoors to expand and cool
before taking heat from the internal air via another heat exchanger.
A heat pump is basically a reverse-cycle air conditioner. The compressed working
fluid’s heat is used to warm the building. It is then moved outdoors, where it
expands and cools, allowing it to absorb heat from the outside air, which is
normally warmer than the chilly working fluid even in winter.
Sample Questions
Question 1: What is the enthalpy of formation of the most stable form of an
element in its standard state?
Answer:
The enthalpy of formation of an element’s most stable form in its standard state is
zero.
Question 2: State Hess’s law.
Answer:
According to Hess’s law, the change in enthalpy of a reaction remains constant
whether the reaction is carried out in one step or numerous steps.
Question 3: Define the first law of thermodynamics.
Answer:
Energy cannot be created or destroyed, according to the first law of
thermodynamics. The energy of an isolated system remains constant.
Question 4: Many thermodynamically feasible reactions do not occur under
ordinary conditions. Why?
Answer:
The average energy of the reactants may be less than the threshold energy under
normal conditions. To start the reaction, they need some activation energy.
Enthalpy
Enthalpy is the measurement of heat or energy in the thermodynamic system. It is
the most fundamental concept in the branch of thermodynamics.

Let’s learn about Enthalpy in detail, including its Definition, Formulas, and other
related concepts.
• Enthalpy Definition
• Enthalpy Formula
• Relationship between ΔH and ΔU
• Difference between Entropy and Enthalpy
• Endothermic and Exothermic Reactions
Enthalpy Definition
Enthalpy is total energy of heat in the system which is equivalent to the sum of
total internal energy and resulting energy due to its pressure and volume.
The system has internal energy because of the molecule in motion and the state
of molecules as well. The molecules in motion generate kinetic energy and due to
vibrations and electric energy of atoms, the system can have energy in the
potential form as well.
Other than this, internal energy also includes energy stored in the form of
chemical bonds as we know the breaking of bonds releases energy in an
exothermic reaction.
Enthalpy Symbol
In thermodynamics and physical chemistry, Enthalpy is denoted as H. The
enthalpy change (ΔH) plays a crucial role in quantifying the heat exchange
between a system and its surroundings.
Enthalpy Units
Enthalpy is typically measured in units of energy per mole, such as joules per
mole (J/mol) in the International System of Units (SI) or calories per mole
(cal/mol) in the calorie-based system.
Enthalpy Formula
Enthalpy can be represented as:
H = U + PV
where,
• H is Enthalpy
• U is Internal Energy
• P is Pressure
• V is Volume
Enthalpy Change
Enthalpy is a state function (those functions which are only dependent on the
initial and final state of the process, not the path taken by the process) as its
constituents U, P, and V are state functions. As enthalpy is a state function, change
in enthalpy (ΔH) will depend on the initial and the final states of the system
Thus, change in enthalpy is represented by ΔH and is given by the following
formula:
ΔH = H2 – H1
Where,
• H1 is the Initial State Enthalpy of System
• H2 is the Final State Enthalpy of System
As we know, the formula for Enthalpy is H = U + PV, and then
H1 = U1 + P1V1
H2 = U2 + P2V2
Using, the values of H1 and H2, value of ΔH will be,
ΔH = (U2 + P2V2) – (U1+ P1V1)
⇒ ΔH = U2 + P2V2 – U1 -P1V1
⇒ ΔH = (U2 – U1) + (P2V2 -P1V1)
ΔH = ΔU + Δ(PV)
where,
• ΔU is the Change in Internal Energy
• Δ(PV) is the Change in Product of Pressure and Volume
Now, at a constant pressure P1 = P2 = P (Isobaric Process)
ΔH = ΔU + PΔV
Consider pressure inside and outside are the same for this isobaric process (i.e.
Pex = P) then the formula for the isobaric process will become,
Qp = ΔU +PΔV
Thus from the above two equations, we get,
ΔH = Qp
Thus from this derived formula, we understand that the increase in enthalpy of a
system is equal to the heat absorbed by it at a constant pressure.
Enthalpy of Vapourization
Enthalpy of Vaporization is the amount of heat energy required to convert a unit
mass of a liquid at its boiling point into a vapour state without an increase in
temperature. Its symbol is ∆H vap. Enthalpy of Vaporization changes with
increases with temperature and other parameter.
Enthalpy of Freezing Water
Enthaly of freezing water is the heat change required to change liquid ice to water
and the its is equal to -6.00 kJ/mole.
Relationship between ΔH and ΔU
As we already established that ΔH and ΔU are related by the equation ΔH = ΔU +
PΔV, at constant pressure. For reactions between solids and liquids, ΔV is very
small because as pressure varies, solids or liquids won`t get affected significantly.
So, for these reactions remove PΔV from the equation and write ΔH = ΔU
However, for the reactions involving gases, which are easily affected by the change
in pressure, ΔV should strictly be considered.
ΔH = ΔU + PΔV
⇒ ΔH = ΔU + P(V2 – V1)
⇒ ΔH = ΔU + PV2 – PV1
where,
• V1 is the Volume of Gas Reactants in Initial State
• V2 is the Volume of Gas Products in Final State
Requirements for ΔH to be equal to ΔU
There are two cases when ΔH and ΔU become equal, which are as follows:
 • When the reaction is conducted inside a closed container it prevents the
alteration of the volume of the system (ΔV = 0). Then change in enthalpy
will change as ΔH = ΔU.
• When there are only solids or liquids involved in the reactions then we can
neglect ΔV as the change in them due to the pressure is significant. So, ΔH =
ΔU.
Difference between Entropy and Enthalpy
Let’s understand the differences between Enthalpy and Entropy in the table
below:

Entropy vs. Enthalpy

Enthalpy Entropy

The total heat associated with a The measure of degree of randomness

system is called the enthalpy of the of the molecule is defined as the
system. entropy of the molecule.

Enthalpy is measured in regular Entropy is measured under controlled

conditions. conditions.

Enthalpy of any reaction is measured Entropy of any reaction is measured in

in Joule per Mole. Joule per Kelvin.

Enthalpy change of any reaction must Entropy change of the system must be
be minimum in any process. maximum in any process.
Figure: Entropy vs. Enthalpy

Endothermic and Exothermic Reactions

A reaction is a process in which two or more two reactants react to form some
products we can have a reaction in which we are required to give some energy on
the other hand some redactions can give energy to the products. So on this basis,
we can have two types of reactions that include
• Endothermic Reactions
• Exothermic Reactions
Endothermic Reactions
If in any chemical reaction heat is given to the reaction for it to proceed this
reaction is called the endothermic reaction. Thus, an endothermic reaction takes
heat from the surrounding and makes the surroundings cooler.
Exothermic Reactions
If in any chemical reaction heat is produced as the result of the reaction then it is
called the exothermic reaction. Thus, an exothermic reaction gives heat to the
surrounding and makes the surroundings warmer.
What Is Spontaneity?
The phrase spontaneity refers to a process’s viability. A spontaneous process is
one that can occur on its own or as a result of some kind of initiation under
certain conditions. In other terms, a spontaneous process is one that may happen
without any intervention. Feasible or probable processes are other names for
spontaneous processes.
Some real-life instances of spontaneous reactions:
• Water vaporisation
• The water flowed down the slope.
• Sugar or salt dissolves in water.
Types of Spontaneous Processes
• Processes that occur without the requirement for an initiator:
• Sugar makes a solution when it dissolves in water.
• The evaporation of water from bodies of water.
• Nitrogen dioxide is formed when nitric oxide and oxygen combine.
• Hydrogen iodide is formed when hydrogen and iodine react.
H2 + I2 → 2HI
• Processes that occur spontaneously but require some initiation:
• Ignition starts the process of lighting a candle that is burning wax.
• The heat initiates the heating of calcium carbonate to produce
calcium oxide and carbon dioxide. CaCO3 → CaO + CO2
• An electric spark was used to start the reaction between hydrogen
and oxygen, which resulted in the formation of water. 2H2 +
O2 → 2H2O
• Ignition starts the reaction between methane and oxygen, which
produces carbon dioxide and water. CH4 + 2O2 → CO2 + 2H2O
Spontaneity in Terms of Entropy Change
The entropy (S) of a system is defined as a measure of its unpredictability or
disorder. The entropy increases as the unpredictability increases. The order of
randomness or entropy of solid, liquid, and gas is Gas > Liquid > Solid.
• The entropy change is positive for spontaneous processes in isolated
systems (i.e., a system that cannot interchange matter or energy with its
surroundings).
For example, mixing two gases when the stopcock is opened, spreading a drop of
ink in a beaker filled with water, and so on.
• The total entropy change (Δstotal) must be positive for spontaneous
processes in open systems (i.e., a system that may interchange matter and
energy with the environment).
ΔStotal or ΔSUniverse=ΔSsystem + ΔSsurroundings>0
• When a cup of tea cools down, the water vapour and energy from the
teacup exchange with the environment.
• Entropy grows in all spontaneous reactions until an equilibrium is
established. As a result, at equilibrium, entropy is at its maximum, and
there is no further change in entropy. i.e., ΔS=0. Hence for a process in
equilibrium,
ΔStotal or ΔSUniverse=0
Second Law of Thermodynamics and Spontaneity
In terms of the second law of thermodynamics, the following is the connection
between entropy and spontaneity:
• Thermodynamically, all spontaneous or spontaneously occurring reactions
are irreversible. Non-reactive gases, for example, react with one another to
increase the entropy of constituent molecules. These, however, cannot be
separated from the rest of the combination.
• A spontaneous process cannot be reversed without the assistance of an
outside entity. Heat energy may move from a hot body to its own cold, but
not from a cold body to a hot one unless the cold body is heated first.
 • If an isolated system is to be spontaneous in a certain direction, its entropy
must grow, i.e.,
Ssystem>0 (Positive)
• Because the isolated system is blocked off from the rest of the world, no
energy exchange is conceivable. If it is to be spontaneous in this scenario,
the entropy must rise.
• The total entropy of both the system and its surroundings must grow or be
positive in a non-isolated system.
ΔSsystem+ΔSsurroundings>0(Positive)
Enthalpy
The enthalpy, often known as heat content, is represented by the letter H. Under
certain conditions, a system’s enthalpy may be defined as the sum of its internal
energy (U) and pressure-volume (PV) energy.
H=U+PV
H is negative in exothermic processes (energy is released by the system) and
positive in endothermic processes (energy is absorbed by the system).
Gibbs Energy
To forecast the direction of spontaneity, J. Willard Gibbs used the phrase “free
energy.” The quantity of energy available for accomplishing productive work under
constant temperature and pressure is known as free energy (G).
G=H–TS
H stands for the system’s enthalpy, S for the system’s entropy, and T for the
system’s temperature on the Kelvin scale.
The Gibbs free energy, G=H–TS
We know that enthalpy, H=U + PV
Therefore, G=U + PV-TS
Gibbs free energy changes can be represented as:
ΔG=ΔU+Δ(PV)–Δ(TS)
ΔG=ΔU+PΔV+VΔP–TΔS–SΔT
ΔT=0 and ΔP=0 if the change is carried out at a constant temperature and
constant pressure.
Therefore, ΔG=ΔU+PΔV–TΔS
Since, ΔH=ΔU+PΔV
ΔG=ΔH–TΔS
The equation ΔG=ΔH–TΔS is called Gibbs- Helmholtz equation.
Gibbs Energy and Spontaneity: According to Gibbs- Helmholtz equation,
ΔG=ΔH–TΔS
ΔG should be negative (ΔG<0) for the response to be spontaneous. Under the
following circumstances, ΔG can be negative:
• TΔS is positive while ΔH is negative.
• TΔS and ΔH are both negative. In this situation, ΔH favours the spontaneous
process whereas TΔS opposes it. If ΔH > TΔS, the process can be
spontaneous.
• TΔS and ΔH are both positive. TΔS is in favour of the spontaneous process in
this situation, whereas ΔH is against it. As a result, if ΔH <TΔS, the process
can be spontaneous.
The process does not occur if ΔH is 0, or the system is in equilibrium.
Effect of Temperature on Spontaneity: ΔG=ΔH–TΔS, according to Gibbs Helmholtz
equation. The magnitude of H does not vary much as the temperature rises, while
TΔS changes a lot as the temperature rises.
• ΔH is positive for endothermic processes, while ΔS is likewise positive. As a
result, whereas ΔH opposes the spontaneous reaction, TΔS favours it. At
low temperatures, an endothermic reaction may be non-spontaneous, but
at high temperatures, it may be spontaneous.
 • ΔH is negative for exothermic processes, and ΔS is also negative. As a result,
whereas ΔH favours the spontaneous reaction, TΔS opposes it. Exothermic
processes can therefore be spontaneous at low temperatures and non-
spontaneous at high temperatures.
Sample Questions
Question 1: What is the difference between spontaneity and disorder?
Answer:
The phrase spontaneity refers to a process’s viability. A spontaneous process is
one that can occur on its own or as a result of some kind of initiation under
certain conditions. Randomness or entropy are other terms for disorder. The
entropy (S) of a system is defined as a measure of its unpredictability or disorder.
The entropy increases as the unpredictability increases.
Question 2: What is spontaneity?
Answer:
The phrase spontaneity refers to a process’s viability. A spontaneous process is
one that can occur on its own or as a result of some kind of initiation under
certain conditions.
Example: Reaction between hydrogen and iodine to give hydrogen iodide.
H2+I2→2HI
Question 3: What is the relation between spontaneity and entropy?
Answer:
The isolated system’s entropy should be positive for spontaneity. The total entropy
change (ΔStotal) for spontaneous processes in open systems must be positive.
ΔStotal or ΔSUniverse=ΔSsystem+ΔSsurroundings>0
Question 4: What are the types of spontaneity?
Answer:
• Processes that occur without the requirement for an initiator.
 • Processes that occur spontaneously but require some initiation.
Question 5: What is the spontaneity of a reaction?
Answer:
The feasibility of a reaction is its spontaneity, i.e., whether the process can occur
on its own or with some initiation, given a set of conditions.