Table of Contents

Thermodynamic States
Thermodynamic Processes
Heat Capacities
Thermodynamic Cycles
Calorimetry
Entropy
Misuses of the Laws of Thermodynamics
Thermodynamic States
The ideal gas law relates the pressure (P), olume (!), num"er of moles (n) and
temperature (T) of a gas#
P! $ n%T
&n S& units, % $ '#() *+(mol,-)# .e especially careful to use S& units e/clusiely as this
e0uation is often used in chemistry with a different set of units#
1ote that this law is appro/imate# &t only applies to cases where the temperature is well
a"oe the condensation point and the olume of the molecules is much less than the
olume of the container# The term 2law3 does not ma4e it uniersally applica"le or e/act#
% is a constant and n is often held constant (a sealed container)# This normally leaes
three aria"les in this e0uation# 5o not assume that one of the three is held constant
unless you hae eidence# Sometimes all three change# 6sing Charles7 law or .oyle7s
law (special cases of the ideal gas law) inappropriately are common ways to ma4e
mista4es#
Thermodynamic Processes
8E
th
$ 9 : ;
s

The first law of thermodynamics is a statement of conseration of energy# < system can
e/change energy with its enironment with heat (9), a microscopic transfer of energy, or
wor4 (;
s
, also denoted as ;
gas
), a macroscopic transfer of energy# This results in changes
in its internal or thermal energy (E
th
, also denoted as 6 in some te/ts)# .y conention,
heat coming into the system is considered positie and heat going out of the system is
considered negatie# ;or4 done "y the system (e/pansion) is considered positie, while
wor4 done on the system (compression) is considered negatie (note that this is the
opposite of the classical mechanics sign conention for wor4, thus the minus sign in the
first law)#
;
s
$ =Pd! (> the area under the cure in the P! diagram) always# ?or an isochoric
process, ;
s
$ @# ?or an iso"aric process, ;
s
$ P=d! $ P8!# ?or an isothermal process,
the ideal gas law can "e used to find P as a function of ! and su"stituted into the e0uation
for wor4# ;
s
$ =(n%T+!)d! $ n%T,ln(!
f
+!
i
)#
The definitions of C
p
and C

can "e used to o"tain a formula for heat during iso"aric and
isochoric processes# ?or an iso"aric process, d9 $ nC
p
dT# &f C
p
and n are constant
(usually the case, at least appro/imately), then 9 $ nC
p
8T# Li4ewise, for an isochoric
process, d9 $ nC

dT# &f C

and n are constant (usually the case, at least appro/imately),

then 9 $ nC

8T#
This formula for heat during an isochoric process can "e used with the first law and the
formula for wor4 to o"tain e/pressions for the change in thermal energy for any process#
?or an isochoric process, ;
s
$ @, so 8E
th
$ 9 $ nC

8T# This formula for 8E

th
can "e
generaliAed to all processes since thermal energy is path independent#
Plausible Physical
Situations
Name State
Variables
P V T Eth Q Ws W
&nsulated
sleee or
rapid
process
<dd
weight to
or push
down on
piston
<dia"atic
compression
P!
B
$
constantC
T!
BD)
$
constant
6p 5own 6p nC8T
E @
@ DnC8T F @ nC8T E @
&nsulated
sleee or
rapid
process
%emoe
weight
from or
pull up on
piston
<dia"atic
e/pansion
P!
B
$
constantC
T!
BD)
$
constant
5own 6p 5own nC8T
F @
@ DnC8T E @ nC8T F @
Heat gas Loc4ed
piston or
rigid
container
&sochoric ! fi/edC P
G T
6p ?i/ed 6p nC8T
E @
nC8T
E @
@ @
Cool gas Loc4ed
piston or
rigid
container
&sochoric ! fi/edC P
G T
5own ?i/ed 5own nC8T
F @
nC8T
F @
@ @
Heat gas Piston free
to moe,
load
unchanged
&so"aric
e/pansion
P fi/edC !
G T
?i/ed 6p 6p nC8T
E @
nCp8T
E @
P8! E @ DP8! F @
Cool gas Piston free
to moe,
load
unchanged
&so"aric
compression
P fi/edC !
G T
?i/ed 5own 5own nC8T
F @
nCp8T
F @
P8! F @ DP8! E @
&mmerse
gas in
large "ath
<dd
weight to
piston
&sothermal
compression
T fi/ed at
temperatur
e of "ath,
P! $
constant
6p 5own ?i/ed nC8T
$ @
n%T,ln
(!f+!i)
F @
n%T,ln(!f+
!i) F @
Dn%T
,ln(!f+!i)
E @
&mmerse
gas in
large "ath
%emoe
weight
from piston
&sothermal
e/pansion
T fi/ed at
temperatur
e of "ath,
P! $
constant
5own 6p ?i/ed nC8T
$ @
n%T,ln
(!f+!i)
E @
n%T,ln(!f+
!i) E @
Dn%T,
ln(!f+!i) F
@
6n4nown 6n4nown 1o 1ame P!+T $
constant
H H H nC8T 8Eth I
;s
=Pd! $ >
area under
cure in
P!
diagram
D=Pd! $ >
area under
cure in P!
diagram
TipsJ -now which formulas are specific to a particular process and which are true for any
process# See the ne/t section for notes on C
p
, C

and B#
Heat Capacities
C

, the molar heat capacity at constant olume (Aero wor4), can "e estimated using the
num"er of degrees of freedom multiplied "y K%# ?or a monatomic gas, there are three
degrees of freedom from the translation of the particles in three dimensions, so C

$
(+L,%# ?or a diatomic gas, there are fie degrees of freedom from the three directions of
translation and two a/es of rotation# The third possi"le a/is does not hae a significant
rotational 4inetic energy and is therefore insignificant# Therefore, C

$ M+L,%# ?or solids,

there are three degrees of freedom from translation and three from i"ration, so C

$ (%
(5ulongDPetit)# <ll three formulas are theoretical and classical, and generally gie
reasona"le agreement with empirical ealuations# 5eiations from these formulas can "e
e/plained with 0uantum mechanics which is "eyond the scope of this course#
C
p
, the molar heat capacity at constant pressure, can "e calculated for an ideal gas# ?or an
iso"aric process where n and C
p
are constant, 9 $ nC
p
8T# The change in thermal energy
can "e calculated with the general formula 8E
th
$ nC

8T# ;
s
$ P=d! $ P8! "y the
definition of wor4# 6sing the ideal gas law, P8! $ n%8T# 8E
th
$ 9 : ;
s
"y the first law
of thermodynamics# Com"ine the a"oe formulas to o"tain an e/pression for C
p
#
8E
th
$ 9 : ;
s
nC

8T $ nC
p
8T : n%8T
C
p
$ C

I %
The ratio of heat capacities is denoted "y the letter gamma (B), and is defined "y the
following formulaJ
B $ C
p
+C

?or a monatomic ideal gas, B $ ((+L,% I %)+((+L,%) $ M+(# ?or a diatomic ideal gas, B $
(M+L,% I %)+(M+L,%) $ N+M#
Oas C

C
p
B E/amples
monatomi
c
(+L,% M+L,% M+( He, 1e,
<r
diatomic M+L,% N+L,% N+M H
L
, 1
L
, P
L
Thermodynamic Cycles
< cycle must hae a total 8E
th
$ @# Therefore Q9 $ Q;
s
"y the first law# 1ormally, it is
useful to separate the alues of 9 that are positie from those that are negatie# Positie
alues represent heat input into the system and negatie alues represent heat output from
the system#
The total wor4 for a cycle can "e calculated graphically with the area enclosed in the P!
diagram# &f the cycle is cloc4wise, then the deice is a heat engine and Q;
s
E @# &f the
cycle is counterDcloc4wise, then the deice is a refrigerator+air conditioner or heat pump
and Q;
s
F @#
Heat Engines
< heat engine has a characteristic called efficiency, e (also denoted R)#
e $ Q;
s
+Q9
H
The summation of wor4 includes all processes, regardless of sign# The summation for
heat includes only heat input from the 2hot reseroir3 which in this case includes only the
processes with positie heat#
There is a theoretical upper limit on the efficiency of an engine operating "etween two
temperature e/tremes# This is the Carnot or ma/imum efficiency#
e
carnot
$ ) : T
c
+T
h
Heat Pumps !efrigerators and "ir Conditioners
&f a cycle has a total wor4 less than Aero, then the deice might "e a refrigerator+air
conditioner or a heat pump# These deices hae heat input from a lower temperature
system and hae heat output to a higher temperature system# The physical construction
for these two deices can "e e/actly the same, "ut the use and desired outcomes are
different# ;ith a refrigerator+air conditioner, the goal is to transfer heat from the colder
system# ;ith a heat pump, the goal is to transfer heat to the hotter system# ;ith any of
these deices, the energy input is in the form of wor4# This wor4 is typically done "y a
compressor (you pay for the energy to run this)#
< refrigerator+air conditioner has a characteristic called the coefficient of performance,
C#P#P# or -#
- $ Q9
c
+SQ;
s
S
The summation for heat includes only the heat input from the 2cold reseroir3 which in
this case includes only the processes with positie heat# The summation of wor4 includes
all processes, regardless of sign#
There is a theoretical upper limit on the coefficient of performance for a refrigerator+air
conditioner operating "etween two temperature e/tremes# This is the Carnot coefficient
of performance and is "ased on the second law of thermodynamics#
-
carnot
$ T
c
+(T
h
: T
c
)
< heat pump also has a characteristic called the coefficient of performance, C#P#P# or -#
- $ Q9
h
+Q;
s
The summation for heat includes only the heat output to the 2hot reseroir3 which in this
case includes only the processes with negatie heat# The summation of wor4 includes all
processes, regardless of sign#
There is a theoretical upper limit on the coefficient of performance for a heat pump
operating "etween two temperature e/tremes# This is the Carnot coefficient of
performance and is "ased on the second law of thermodynamics#
-
carnot
$ T
h
+(T
h
: T
c
)
Calorimetry
Calorimetry is an application of conseration of energy# ?or an isolated system, the total
energy does not change# &ndiidual mem"ers of the system with different temperatures
may e/change energy through the mechanism of heat# <ny gain in energy "y one is a loss
"y another# So the starting e0uation for an isolated system should "e the followingJ
Q9 $ @
?or each mem"er of the system, use one or "oth of the following e0uations, depending on
the situationJ
9 $ mc8T (temperature change in response to heat)
9 $ >mL (phase change in response to heat)
m $ mass
c $ specific heat capacity
8T $ change in temperature
L $ heat of fusion or heat of aporiAation
> depends on direction of phase change
The first e0uation is 0uite possi"ly the most misused e0uation in physics# &t is not true
that heat always leads to temperature change (see the second e0uation)# &t is also not true
that the only mechanism for changing temperature is heat (see adia"atic processes
a"oe)#
Entropy
Entropy, S, is often characteriAed as a measure of disorder, though this is a loose
definition# The second law of thermodynamics states that for an isolated system
(no energy or matter e/changed with e/ternal agents), the total entropy of the
system cannot decreaseJ
8S T @
There are two general methods for calculating entropy# The first is useful when there are
e/changes of energy in the form of heat# The second is useful when there is mi/ing of
particlesJ
8S $ =(d9+T) U 9+T
S $ 4,ln(w)
S $ entropy
4 $ .oltAmann7s constant $ )#('EDL( *+-
w $ num"er of possi"le microscopic states consistent with
the macroscopic state
#isuses of the $a%s of Thermodynamics
Some nonDscientists and a few willfully ignorant 2scientists3 claim that the laws of
thermodynamics falsify "oth cosmic and "iological eolution# These claims are not
supported "y eidence#
The &ig &ang 'oes Not Violate the (irst $a%
Pne claim unsupported "y eidence is that the .ig .ang couldn7t possi"ly "e correct
"ecause it iolates the first law of thermodynamics# The claim is that there is o"iously a
lot of energy now and there couldn7t "e any energy "efore the .ig .ang# The total energy
apparently increased thus iolating the first law of thermodynamics#
?or this alleged iolation to "e true, we must 4now the total energy of the unierse "oth
"efore and after the .ig .ang and show that they are different (putting aside o"Vections
that there might "e no such thing as 2"efore the .ig .ang3)# 1o one has calculated the
energy of the unierse 2"efore the .ig .ang#3 .ut een if one assumes that the energy is
Aero 2"efore the .ig .ang3, a calculation of the total energy of the unierse "ased on
classical physics also yields a total energy of AeroW This was shown in a paper written "y
E# Tryon in a )XN( article in the Vournal 1ature (and not refuted to date)# How can that "e
so with all the stuff moing around (4inetic energy), light energy, etc#H &t turns out that
the negatie graitational potential energy "alances out the positie energy and the net
sum is Aero#
Een if we assume that there is such a thing as 2"efore the .ig .ang3 and that the total
energy of the unierse "efore the .ig .ang is Aero, there is no proen iolation of the
first law of thermodynamics#
E)olution 'oes Not Violate the Second $a%
<nother claim unsupported "y eidence is that the second law of thermodynamics
prohi"its the eolution of chemicals to simple organisms (a"iogenesis) or of simple
organisms to more comple/ organisms, an apparent decrease in entropy#
There are two important o"Vections to the Ylife iolates the second lawY claim# ?irst, there
is no calculation that shows that comple/ life forms are always lower entropy than less
comple/ forms or nonDliing things# Hand waing metaphors are no su"stitute for a
proper calculation of entropy# Second, life forms are not closed systems# They
continuously e/change energy and particles with their enironments, so the second law
has nothing to say a"out them unless you include their enironments in the calculation of
entropy# Eolution has not "een proen to iolate the second law of thermodynamics#
There are similar claims "ased on illDdefined and uncalculated 2information3 which
should not "e confused with science#