Thermodynamics

Thermodynamics is a branch of physics that deals with the relationship between heat and other
properties (such as pressure, density, temperature, etc.) in a substance. Specifically, thermodynamics
focuses largely on how a heat transfer is related to various energy changes within a physical system
undergoing a thermodynamic process. Such processes usually result in work being done by the system
and are guided by the laws of thermodynamics.

(https://www.thoughtco.com/thermodynamics-overview-2699427)

History of Thermodynamics
For a long time, physicists and chemists debated whether heat was a fluid (like a mysterious
liquid) or came from the motion of particles. Many early scientists, like Newton, had thought that heat
might be caused by small movement of particles, and greater heat meant greater velocities or kinetic
energies. Lavoisier, however, thought that heat was a massless fluid that he called "caloric."

Count Rumford, a British physicist, observed that the process of boring cannon (drilling the hole
in the middle of the brass cannon) produced a lot of heat, especially when the drill was dull or blunt. He
showed that the heat produced was related to the amount of mechanical work done by the drill.
Humphry Davy, an English chemical physicist, showed that even at 0°C, two ice cubes would melt when
rubbed together. This frictional heating is also a way that people sometimes start fires in the wilderness.

Antoine Lavoisier thought heat was a fluid that caused the atoms it surrounded to separate. One
important contribution he made was to show that the heat generated by human or animal metabolism
produces the same amount of energy as combusting the food. Nicolas Léonard Sadi Carnot also thought
that heat was a liquid, because like liquids it "flows downhill" from hot objects to cold objects. He
thought that like power generation from a waterfall, the amount of heat that moves and the distance it
falls determine the available power. However, later he realized that some of the heat is lost when it is
converted to mechanical energy, which means it can't be a fluid like water.

Julius Robert von Mayer used data other people collected on heat capacities of air at constant
pressure or constant volume to calculate the relationship between the energy defined as force x
distance and energy defined by change in temperature of a substance. Imagine heating a sample of air in
a fixed volume container or in a chamber with a piston, so that it is always at atmospheric pressure. One
sample does work when heated (by expanding against atmospheric pressure) and the other does not.
The difference in heat required to get the same temperature change in the 2 containers must be
equivalent to the work done by the system with the piston. Mayer argued that heat, work, and chemical
energy are all interconvertible, meaning they are all energy in different forms.

James Prescott Joule was an English beer-brewer studied the nature of heat, and discovered its
relationship to mechanical work. This led to the law of conservation of energy, which in turn led to the
development of the first law of thermodynamics.

heat produced by electricity, Q, is

QαI2R
 where I is current and R is resistance. He compared heat produced by electricity and heat
produced by mechanical work and thus showed the equivalence of mechanical work and heat. In other
words, Joule and Carnot had showed that heat can be used to generate work and work can be used to
generate heat. Kelvin combined these ideas and used them to propose the Kelvin temperature scale.

(https://chem.libretexts.org/Bookshelves/General_Chemistry/Book
%3A_General_Chemistry_Supplement_(Eames)/Thermochemistry/History_of_Thermodynamics)

(https://en.wikipedia.org/wiki/James_Prescott_Joule)

The Four Laws of Thermodynamics

The fundamental principles of thermodynamics were originally expressed in three laws. Later, it
was determined that a more fundamental law had been neglected, apparently because it had seemed so
obvious that it did not need to be stated explicitly. To form a complete set of rules, scientists decided
this most fundamental law needed to be included. The problem, though, was that the first three laws
had already been established and were well known by their assigned numbers. When faced with the
prospect of renumbering the existing laws, which would cause considerable confusion, or placing the
pre-eminent law at the end of the list, which would make no logical sense, a British physicist, Ralph H.
Fowler, came up with an alternative that solved the dilemma: he called the new law the “Zeroth Law.”
In brief, these laws are:

The Zeroth Law

Zeroth law states that if two bodies are in thermal equilibrium with some third body, then they
are also in equilibrium with each other. This establishes temperature as a fundamental and measurable
property of matter.

The law is intended to allow the existence of an empirical parameter, the temperature, as a
property of a system such that systems in thermal equilibrium with each other have the same
temperature. The law as stated here is compatible with the use of a particular physical body, for
example a mass of gas, to match temperatures of other bodies, but does not justify regarding
temperature as a quantity that can be measured on a scale of real numbers.

The First Law

First law states that the total increase in the energy of a system is equal to the increase in
thermal energy plus the work done on the system. This states that heat is a form of energy and is
therefore subject to the principle of conservation.

For a thermodynamic process without transfer of matter, the first law is often formulated

Δ Usystem = Q + W.

where ΔUsystem denotes the change in the internal energy of a closed system, Q denotes the
quantity of energy supplied to the system as heat, and W denotes the amount of thermodynamic work
(expressed here with a negative sign) done by the system on its surroundings.
 In the case of a thermodynamic cycle of a closed system, which returns to its original state, the
heat Q in supplied to the system in one stage of the cycle, minus the heat Q out removed from it in
another stage of the cycle, plus the thermodynamic work added to the system, W in, equals the
thermodynamic work that leaves the system W out.

ΔUsystem(fullcycle) = 0

hence, for a full cycle,

Q = Qin − Qout + Win − Wout = Wnet

For the particular case of a thermally isolated system (adiabatically isolated), the change of the
internal energy of an adiabatically isolated system can only be the result of the work added to the
system, because the adiabatic assumption is: Q = 0.

ΔUsystem = Ufinal − Uinitial = Win − Wout

For processes that include transfer of matter, a further statement is needed: 'With due account
of the respective fiducial reference states of the systems, when two systems, which may be of different
chemical compositions, initially separated only by an impermeable wall, and otherwise isolated, are
combined into a new system by the thermodynamic operation of removal of the wall, then

Usystem = U1 + U2,

where Usystem denotes the internal energy of the combined system, and U 1 and U2 denote the
internal energies of the respective separated systems.

The Second Law

Second law states that heat energy cannot be transferred from a body at a lower temperature
to a body at a higher temperature without the addition of energy. This is why it costs money to run an
air conditioner.

The second law is applicable to a wide variety of processes, reversible and irreversible. All
natural processes are irreversible. Reversible processes are a useful and convenient theoretical fiction,
but do not occur in nature.

A prime example of irreversibility is in the transfer of heat by conduction or radiation. It was

known long before the discovery of the notion of entropy that when two bodies initially of different
temperatures come into thermal connection, then heat always flows from the hotter body to the colder
one.

The second law tells also about kinds of irreversibility other than heat transfer, for example
those of friction and viscosity, and those of chemical reactions. The notion of entropy is needed to
provide that wider scope of the law.

According to the second law of thermodynamics, in a theoretical and fictive reversible heat
transfer, an element of heat transferred, δQ, is the product of the temperature (T), both of the system
and of the sources or destination of the heat, with the increment (dS) of the system's conjugate variable,
its entropy (S)
 δQ = TdS .

Entropy may also be viewed as a physical measure of the lack of physical information about the
microscopic details of the motion and configuration of a system, when only the macroscopic states are
known. This lack of information is often described as disorder on a microscopic or molecular scale. The
law asserts that for two given macroscopically specified states of a system, there is a quantity called the
difference of information entropy between them. This information entropy difference defines how much
additional microscopic physical information is needed to specify one of the macroscopically specified
states, given the macroscopic specification of the other – often a conveniently chosen reference state
which may be presupposed to exist rather than explicitly stated. A final condition of a natural process
always contains microscopically specifiable effects which are not fully and exactly predictable from the
macroscopic specification of the initial condition of the process. This is why entropy increases in natural
processes – the increase tells how much extra microscopic information is needed to distinguish the final
macroscopically specified state from the initial macroscopically specified state.

The Third Law

The third law of thermodynamics is sometimes stated as follows:

The entropy of a perfect crystal of any pure substance approaches zero as the
temperature approaches absolute zero.

At zero temperature the system must be in a state with the minimum thermal energy. This
statement holds true if the perfect crystal has only one state with minimum energy. Entropy is related to
the number of possible microstates according to:

S = kB ln Ω

Where S is the entropy of the system, k B Boltzmann's constant, and Ω the number of microstates
(e.g. possible configurations of atoms). At absolute zero there is only 1 microstate possible (Ω=1 as all
the atoms are identical for a pure substance and as a result all orders are identical as there is only one
combination) and ln(1) = 0.

A more general form of the third law that applies to a system such as a glass that may have
more than one minimum microscopically distinct energy state, or may have a microscopically distinct
state that is "frozen in" though not a strictly minimum energy state and not strictly speaking a state of
thermodynamic equilibrium, at absolute zero temperature:

The entropy of a system approaches a constant value as the temperature approaches

zero.

(https://www.livescience.com/50776-thermodynamics.html)

(https://en.wikipedia.org/wiki/Laws_of_thermodynamics)