Rosales, Twinkle Anne G.

ChE 2201
HISTORY OF THERMODYNAMICS

Basic physical notions of heat and temperature were established in the 1600s, and scientists
of the time appear to have thought correctly that heat is associated with the motion of microscopic
constituents of matter. But in the 1700s it became widely believed that heat was instead a separate
fluid-like substance. Experiments by James Joule and others in the 1840s put this in doubt, and
finally in the 1850s it became accepted that heat is in fact a form of energy. The relation between
heat and energy was important for the development of steam engines, and in 1824 Sadi
Carnot had captured some of the ideas of thermodynamics in his discussion of the efficiency of
an idealized engine. Around 1850 Rudolf Clausius and William Thomson (Kelvin) stated both
the First Law - that total energy is conserved - and the Second Law of Thermodynamics. The
Second Law was originally formulated in terms of the fact that heat does not spontaneously flow
from a colder body to a hotter. Other formulations followed quickly, and Kelvin in particular
understood some of the law’s general implications.

The idea that gases consist of molecules in motion had been discussed in some detail
by Daniel Bernoulli in 1738, but had fallen out of favor, and was revived by Clausius in 1857.
Following this, James Clerk Maxwell in 1860 derived from the mechanics of individual
molecular collisions the expected distribution of molecular speeds in a gas. Over the next several
years the kinetic theory of gases developed rapidly, and many macroscopic properties of gases in
equilibrium were computed. In 1872 Ludwig Boltzmann constructed an equation that he thought
could describe the detailed time development of a gas, whether in equilibrium or not. In the 1860s
Clausius had introduced entropy as a ratio of heat to temperature, and had stated the Second Law
in terms of the increase of this quantity. Boltzmann then showed that his equation implied the so-
called H Theorem, which states that a quantity equal to entropy in equilibrium must always
increase with time. At first, it seemed that Boltzmann had successfully proved the Second Law.
But then it was noticed that since molecular collisions were assumed reversible, his derivation
could be run in reverse, and would then imply the opposite of the Second Law. Much later it was
realized that Boltzmann’s original equation implicitly assumed that molecules are uncorrelated
before each collision, but not afterwards, thereby introducing a fundamental asymmetry in time.

Early in the 1870s Maxwell and Kelvin appear to have already understood that the Second
Law could not formally be derived from microscopic physics, but must somehow be a consequence
of human inability to track large numbers of molecules. In responding to objections concerning
reversibility Boltzmann realized around 1876 that in a gas there are many more states that seem
random than seem orderly. This realization led him to argue that entropy must be proportional to
the logarithm of the number of possible states of a system, and to formulate ideas about ergodicity.
The statistical mechanics of systems of particles was put in a more general context by Willard
Gibbs, beginning around 1900. Gibbs introduced the notion of an ensemble - a collection of many
possible states of a system, each assigned a certain probability. He argued that if the time evolution
of a single state were to visit all other states in the ensemble - the so-called ergodic hypothesis -
then averaged over a sufficiently long time a single state would behave in a way that was typical
of the ensemble. Gibbs also gave qualitative arguments that entropy would increase if it were
measured in a "coarse-grained" way in which nearby states were not distinguished.

In the early 1900s the development of thermodynamics was largely overshadowed by

quantum theory and little fundamental work was done on it. Nevertheless, by the 1930s, the Second
Law had somehow come to be generally regarded as a principle of physics whose foundations
should be questioned only as a curiosity. Despite neglect in physics, however, ergodic theory
became an active area of pure mathematics, and from the 1920s to the 1960s properties related to
ergodicity were established for many kinds of simple systems. When electronic computers became
available in the 1950s, Enrico Fermi and others began to investigate the ergodic properties of
nonlinear systems of springs. But they ended up concentrating on recurrence phenomena related
to solitons, and not looking at general questions related to the Second Law. Much the same
happened in the 1960s, when the first simulations of hard sphere gases were led to concentrate on
the specific phenomenon of long-time tails. And by the 1970s, computer experiments were mostly
oriented towards ordinary differential equations and strange attractors, rather than towards systems
with large numbers of components, to which the Second Law might apply.

Starting in the 1950s, it was recognized that entropy is simply the negative of the
information quantity introduced in the 1940s by Claude Shannon. Following statements by John
von Neumann, it was thought that any computational process must necessarily increase entropy,
but by the early 1970s, notably with work by Charles Bennett, it became accepted that this is not
so, laying some early groundwork for relating computational and thermodynamic ideas.
Reference: https://www.wolframscience.com/reference/notes/1019b

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 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. Davy
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.

Other scientists liked the fluid theory. Lavoisier thought heat was a fluid that caused the
atoms it surrounded to separate (which is why, he said, density usually decreases as you heat a
substance). One important contribution he made was to show that the heat generated by human or
animal metabolism (oxidizing food with oxygen from breathing) produces the same amount of
energy as combusting the food (which is often if not always true). Carnot, who will be very
important later (in the development of the second law of thermodynamics), 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
(change in temperature) determine the available power. However, later he realized that some of
the heat is lost when it is converted to mechanical energy (work), which means it can't be a fluid
like water (water isn't lost when falling water is used to drive a motor).

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 (like
the modern unit joule) and energy defined by change in temperature of a substance (like the modern
unit calorie, the energy needed to raise the temperature of 1g of water 1°C). 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.

Joule (for whom the unit joule is named) was an English beer-brewer who did the studies
mentioned earlier that lead to the first law. You might have learned Joule's law in a physics class,
that heat produced by electricity, Q, is

where I is current and R is resistance. He compared heat produced by electricity and heat produced
by mechanical work (heating water using a paddlewheel powered by a falling weight) 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 (like in a power plant) and work can be used to
generate heat (like with the cannon drills or paddlewheel). Kelvin combined these ideas and used
them to propose the Kelvin temperature scale (but the details of that can wait until we study
Carnot's discoveries in more detail).
Reference:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Book%3A_General_Chemistry_Sup
plement_(Eames)/Thermochemistry/History_of_Thermodynamics