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

Reference: https://chem.libretexts.org/Bookshelves/General_Chemistry/Book
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).