Ch.

12 Thermodynamics

Internal energy – all the energy of a stationary system (chemical, nuclear, kinetic, etc.)
Thermal energy – That part of the internal energy that changes T

Gases – translational, vibrational, rotational all contribute to thermal energy

(monatomic gases have only translational)

Ways to change internal energy of gas system:

Heat Q
Work W
Both!

State: the values of P, V, T, U of the system at a given time (PVTU – “state variables”)
Change of State: altering P, V, T, and/or U

12.1 Work in Thermodynamic Processes

Compress gas with (approximately)

constant pressure P:

W = !F"y = ! PA"y = ! P"V

NOTE : "y is negative, "V is negative
(
so W is positive work done ON gas )
Work has been done on the gas to
compress it to a smaller volume.

If compressed gas expands against the

piston, work is done BY the gas (W is then
negative).

PV Diagrams & “PV Work”

In above case, P=constant - “isobaric”

The amount of work involved is equal to

the area under the curve. In compression,
!V is negative and the work done on the
gas, W = !P"V will be positive.

If the process went the other way, !V is

positive, and the work done ON the
gas W = !P"V is negative, i.e. work is
actually done BY the gas.
Other possible cases:

Decrease V at constant P Increase P at constant V P and V both change

Then increase P Then decrease V simultaneously

Note: the work in (b) is larger than in (a) because the change in V occurred at higher P in
(b), so the force required was larger. W depends on the way the system goes from one
state to another.

How to change P or V without doing W? Add/subtract Q!

Example: Problem #6
Sketch a PV diagram of the following processes:
(a) A gas expands at constant pressure P1 from volume V1 to volume V2. It is then
kept at constant volume while the pressure is reduced to P2.
(b) A gas is reduced in pressure from P1 to P2 while its volume is held constant at V1.
It is then expanded at constant pressure to a final volume V2.
(c) In which process is more work done by the gas? Why?
 12.2 The First law of Thermodynamics

If positive Q is energy transferred to system, positive W is work done on system, then:

!U = U final " U initial = Q + W

Isolated System: where Q and W are ZERO. Here U = const. ! "U = 0 .

Cyclic Process: !U = 0 " Q + W = 0 i.e. Q = #W

Note that a cyclic process only requires that the SUM of Q and W is zero, not both Q and
W individually. (READ Tip 12.2 regarding the sign convention here).

Isothermal Process: another special case where !U = 0 . Here !T = 0 .

Example: ideal monatomic gas in cylinder in contact with heat reservoir:

Add heat carefully, keeping T constant and

allowing V to increase and P to drop.
3
U= nRT For !T = 0 " !U = 0
2
But !U = Q + W " 0 = Q + W
So Q = #W
Since we added heat, Q is positive and W is
negative. Work is done BY the gas on the outside
world.

Adiabatic Process: Q = 0 .

Example: Ignition phase in internal combustion engine. Hot gas expands air against
piston so quickly that little Q has time to be lost.

Example: Problem #14

A monatomic ideal gas undergoes the thermodynamic

process shown in the PV diagram here. Determine
whether each of the following values of !U, Q, and W
for the gas is positive, negative, or zero.
Example: Problem #17
A thermodynamic system undergoes a process in which its internal energy decreases by
500 J. If at the same time 220 J of work is done on the system. Find the energy
transferred to or from it by heat.

Example: Problem #22

One mole of gas is initially at a pressure of

2.00 atm, volume of 0.300 L and has an
internal energy equal to 91.0 J. It its final
state the gas is at a pressure of 1.50 atm
and a volume of 0.800 L and its internal
energy equals 180 J. For the paths IAF,
IBF, and IF in this figure, calculate: (a) the
work done on the gas and (b) the net
energy transferred to the gas by heat in the
process.

12.3 The First Law and Human Metabolism

What is important here is not simply the total body heat Q and work W: Q + W = !U but
the rate at which they are “performed”:
!U Q W
= +
!t !t !t
In order to radiate body heat and perform work on the outside world (note that Q and W
will be negative, in general), the body’s internal energy must be re-supplied by food and
oxygen.

Average rate of oxygen used in metabolizing food – 1 liter for every 4.8 kcal (= 4.8 Cal =
20 J).

!U !VO
= 4.8 2

!t
! !!t
kcal / s L/ s
NOTE: Extreme activity produces a lot of Watts of power, but most individuals cannot
do this for very long! You burn up almost as many Calories sleeping 8 hours as you
would in 1 hour of heavy activity!

Example: Jog 1 mile = burn 120 Calories = 2 slices of bread

Efficiency

Not everybody can produce as much work

for the same intake of energy. The more fit
you are, the more efficient you will be at
producing power.

W
!t
Efficiency e =
!U
!t
Smooth activity,
without a lot of
stops & starts
(when no W is
done but Q is
still lost) is more
efficient as well.

12.4 Heat Engines and the Second law of Thermodynamics

During heat transfer from a hot reservoir to a cold reservoir, a portion of the randomized
kinetic energy of a gas can be converted into directed non-randomized work. Example:
coal-fired or gas-fired electrical power plants.

Heat Engine – A device that converts part of the internal energy into work.

Cyclic Process – Gas returned to its initial state, so that its !U = Q + W = 0 . So the work
done on the engine is W = !Q , and so the work done by the engine is We = !W

Engine absorbs net

Qe, net = Qhot ! Qcold which is converted to
work done by the engine
We = Qe, net = Qhot ! Qcold .
 The work done by the engine for a cyclic
process is the area enclosed by the cyclic
curve in its PV diagram. Think of this as
PV work.

Thermal Efficiency: the fraction of the heat flowing in that is converted to work in 1
cycle:
W Qhot ! Qcold Qcold
e= e = = 1!
Qhot Qhot Qhot

2nd Law of Thermodynamics: It is impossible to construct a heat engine that, operating

in a cycle, produces no other effect than the absorption of energy from a reservoir and
the performance of an equal amount of work.

In essence: it is always true that e < 1 and Qcold > 0 and Qhot < ! . No heat
engine is 100% efficient.

Applications: power generators, etc.

Reverse process: Heat Pumps. Examples: refrigerators heat pumps for home
heating/cooling.

12.5 Reversible & Irreversible Processes

Reversible – every state along the path is in equilibrium, and can return to initial state
along same path. In practice, needs to be slow & have no “unwanted” losses (such as
friction).

Irreversible – the real world.

12.6 The Carnot Engine

An idealized engine of maximum efficiency, working in reversible cycle. (Does not really
exist).

Tcold
e = 1!
Thot
For Tcold = Thot e=0
Tcold
For " 0 e"1
Thot

All real engines are less efficient than the Carnot Engine because they operate
irreversibly (due to friction) and because they complete a cycle in a brief time period (are
never in a state of equilibrium).

Example: Problem#27

One of the most efficient engines ever built is a coal-fired steam turbine in the Ohio
valley, driving an electric generator as it operates between 1870°C and 430°C.
(a) What is its maximum theoretical efficiency?
(b) Its actual efficiency is 42%. How much mechanical power does the engine deliver
if it absorbs 1.40x105 J of energy each second from the hot reservoir?
12.7 Entropy

For a reversible system, if Qr is the heat absorbed or expelled by the system:

Qr
!S =
T
Strictly speaking, Qr is for a reversible path. For real (irreversible) systems, we must
model he process by a reversible one (with the same initial and final states, of course!).

The entropy of the Universe increases in all natural processes.

Perpetual Motion Machines – ain’t no such thing!

1st kind – violate the First Law of Thermodynamics by having !U = 0 but Q + W < 1
(puts out more energy than is put in).

2nd kind – violate the Second Law of Thermodynamics by having no heat loss from the
system Qr = 0 (having e ! 1 ).

12.8 Entropy and Disorder

Observation: A disorderly arrangement is much more probable than an orderly one if the
laws of nature are allowed to operate without interference.

Isolated (“closed”) systems tend toward greater disorder and entropy is a measure of
that disorder.

NOTE: within such an isolated system, some parts might experience a decrease in
entropy, but only at the expense of an even greater increase in entropy by the rest of the
system.

Entropy a la Boltzmann: S = k B lnW where W represents the probability of the system

having that specific configuration.

Example: Drawing colored marbles from a bag with equal numbers of Red & Green:

The 2R2G result is most probable, having 6 ways to get that result. Also most disordered.
The second law of thermodynamics is really a statement of what is most probable,
rather than of what must be. In terms of entropy & the bag of marbles, sometimes you
really will pull 4 red ones in a row!

Implicit with our statement that entropy increases during a process is the definition of the
“arrow of time”. One often sees a dropped plate shatter on the floor. One never sees a
broken plate self-assemble and jump off the floor into our hand!

Degradation of Energy

In all real processes, the energy available for doing work decreases. As time progresses,
higher-grade energy (that which can do useful work) generally gets transformed into
lower-grade energy (that which can do less useful work).

Example: Dropping a ball to do work. Mechanically, a ball can do mgh work. But if all
the mgh were first transformed into heat, less work could be done, because no heat
engine operates with 100% efficiency.

Example: Problem #37

A 70-kg log falls from a height of 25 m into a lake. If the log, the lake, and the air are all
at 300 K, find the change in entropy of the universe for this process.

Example: Problem #39

The surface of the Sun is at approximately 5700 K, and the temperature of the Earth’s
surface is approximately 290 K. What entropy change occurs when 1000 J of energy is
transferred by heat from the Sun to Earth?

Question: If entropy continually increases, how is it that complex living organisms can
form and grow out of simpler molecules on the Earth?