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Thermodynamics, statistical mechanics, and the philosophy of this course

1.1

Thermodynamics

The study of bulk properties of macroscopic quantities of matter, and the processes by
which they are changed. Anything big enough to see with our eyes or even a microscope.
Avogadros number. In strict classical TDs we take a top-down approach and force ourselves to be
ignorant of microscopic physics!
How properties of bulk matter depend on temperature, mechanical conditions, and other changes
in the objects environment (for example dynamics).
The goal here is to derive connections/relationships between bulk/global properties/variables
such as an objects pressure, volume, energy, its capacity to store heat, its compressibility (change
in objects volume due to changes in pressure), etc. [DEMO: RUBBER BAND.]
Remarkably, many bulk properties of matter are constrained in universal relations that depend
weakly, or not at all, on the microscopic nature of the matter. Most striking, the laws of TDs are
universal: they apply regardless of the atomic nature of the particular macroscopic object.
E.g.:
Heat always flows spontaneously from a hot macroscopic object to a cold macro
object, and never the other way around. Heat flows from my hot cup of coffee to the room.
Particles diffuse from the cream into my coffee, mixing the two, a mixed cup of coffee and
cream never spontaneously separates into distinct regions of coffee and cream. Particles
diffusively mix.
Liquids always boil easier at a lower pressure.
Maximum efficiency of all heat engines operating between two temperatures are
the same, whatever they use as a working substance (air, steam, etc.).
Historically, TDs arose in large part in an effort to improve the efficiency of steam engines in
the early 19th century, and its laws were largely complete by the mid 19th century, long
before atoms/molecular theories of matter were established. It is a relatively self-contained,
self-consistent set of physical relations. You dont need to understand the microstructure to apply
TDs, which is good if the systems are complex: we can still predict things with an incomplete
microscopic theory.
In classical TDs, some properties or relationships must be measured as input to the laws, which
then provide universal connections to other properties. E.g.: measured ideal gas law (approximate
for low-density gas)
P V nRT .
(1)
P is the pressure, V is the volume, n is the number of moles of gas, T is temperature, and R
8.31J/(molK) is the universal gas constant. It was established empirically, providing an equation
of state that relates pressure, volume, and temperature for dilute gases at equilibrium,
meaning all parts of the system are at the same T, P , etc.
So you tell me n = 1 mole, T = 300K, and V = 1L = 103 m3 , and now we know
P = 2.5 106 N/m2 (Pascals) = 25bars 25atm .
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(2)

Notice that the laws of TDs dont predict P from V and T without additional input.
What happens if a hole develops in the container? [DRAWING] Free expansion into larger
volume. A nonequilibrium process, so the gas law is invalid during the process. BUT the laws of
TDs allow us to predict that Tf = Ti for essentially all non-viscous fluids (ideal fluids not just ideal
gases).

1.2

Statistical mechanics

Developed in the late 19th through early 20th century, this is a bottom-up approach. We can,
in principle, start with the properties of individual atoms, then use the detailed microscopic laws
of physics (quantum mechanics), and a statistical description of the random interactions of large
numbers of particles, to derive all the properties of bulk matter, and some of the universal laws of
TDs! E.g., we can derive the ideal gas law and explain the 2nd law of TDs! Stat mech is useful both
for this direction of inference, using the laws of probability/statistics to connect atoms to
macroscopic phenomena and predict behavior, and the opposite direction: measure bulk
properties and infer something about particles.
A common attitude is that it all makes sense once we have stat mech: a statistical description
of the microscopic interactions of a macroscopic number of particles. Which is why many students
(like me) find a first course on classical TDs (thou shalt not use any knowledge of the micro-world)
to be very mystifying in parts, especially when it comes to entropy and the 2nd law of TDs. And I
should say here that, for its time, this was the hardest science class I ever took.
BUT, one only needs a LITTLE stat mech (and basically no quantum) to have classical TDs
make sense - once you have used statistical mechanics to establish some basic TD results, you can
forget the microscopic details and understand a wide variety of beautiful phenomena, making for an
astounding and very deep achievement of 19th century physics that one should find very enjoyable.
US/Schroeder: This middle of the road approach, mainly classical TDs, but with some
insight from stat mech, is followed in our textbook by Schroeder. We will generally move stat
mech considerations into the background and treat the system with classical TDs. And we will
occasionally borrow from Carringtons more classical approach where we find it most useful.

Survey of the Course

Concepts
We are going to learn about energy, and about different forms of energy flows between objects,
most prominently work and heat. We are going to spend a lot of time thinking about temperature and pressure and something called chemical potential, and what these ideas really mean.
We are going to use these ideas in more precise ways than you are used to doing, but with that
precision will come the ability to understand and even predict the behavior of real systems.
We are going to get down and dirty with the concept of ENTROPY. By the end of this course
I hope that you can appreciate that entropy is a profound and yet trivial concept all at the
same time. It gives great predictive power and yet, once you really get it, entropy becomes almost
a tautology.
Equilibrium will come to have a very precise meaning. We will essentially confine our attention
to equilibrium properties.

Thermodynamic limit. Great predictive power comes when you know you are dealing with
many many (many!) atoms behaving collectively. Combined with some basic statistical reasoning,
this gives us the ability to make bewilderingly precise statements about what will happen.

Physical Laws
Thermodynamics is about physical laws that place constraints on how real objects can behave. We
will become very intimate with the First and Second Laws of Thermodynamics. We will even
get to know the Zeroth and Third Laws of TDs. You will be sick and tired of these things.
But they place important checks on what is possible. These and other principles that we develop
throughout this course will give us guidance toward very fundamental questions. What processes
happen spontaneously, and what processes require a shove to happen? By processes, we can
mean all kinds of things, but think of the motion of a piston, the mixing of two different fluids,
phase transformations (water freezing), and chemical reactions.

Machines
Thermodynamics, as I said earlier, was originally developed in the 19th century to give guidance
to the design of steam engines. What are the design principles of machines like car engines,
refrigerators, pumps, or the photosynthetic machinery in green plants? What are the limits on
the efficiency of real machines? What kinds of designs can achieve those best efficiencies?

Model Systems
Ideal gas.
Einstein model of a solid.
Occasionally, paramagnets that can adopt two different magnetic moments.

Applications
TD methods, language, and thinking are present in almost all contemporary scientific fields: atmospheric science; astronomy; chemistry and chemical engineering; geology; biophysics (my own
field).