Thermodynamics: 1. The Zeroth Law
Thermodynamics: 1. The Zeroth Law
Thermodynamics: 1. The Zeroth Law
REMARK: work and heat are not properties belonging to bodies. Tey're ways of
transferring energy, in an ordered or disordered way.
Moreover, temperature is not related to the kinetic energy of particles (this is
valid only for perfect gas).
The laws of thermodinamic are 4. The zeroth law is the last one to be redacted.
1. The zeroth law
Before citing the zeroth law, we nedd several definitions.
Once you choose the preferred thermodynamic system, the others are called surroundings
or environments. The universe is the maximal set of all thermodynamic systems
interacting with each other. There MUST be no other physical systems interacting with the
one in the universe.
Universe
Thermodynamic system
Environments
Definition 3 Two systems or part of a system separated by a diathermic wall are said to
be in thermal equilibrium when their thermodynamic coordinates have reached values
which are constant in time
Theorem 1 [The zeroth law] If a system A is found to be in thermal equilibrium with B
and B is found to be in thermal equilibrium with C, then it is also true that C will be found
to be in thermal equilibrium with A.
2 2 2 1 1 1
2
mv mgh
2
<
Q-W U B -U A U (3)
Q- W dU
= ( ) ( ) = 𝛥
𝛿 𝛿 =
You can change internal energy either by thermal contact, which is called heat exchange,
or by work made on the system
The symbol 𝛿 is due to the fact that it is not a mathematical differential, it means "a small
amount of exchange".
Work is considered negative when it is don on the sistem, which explains the negative sign in
the formula (3).
For hydrostatic systems, F = Pext A, and the work is W = F ⋅ d = Pext (A ⋅ d) , for
d the height of the fluid, Pext the pressure exerced on the system, so:
W Pext V
W PextdV
= 𝛥
𝛿 =
𝛥 U Q nCV
= = 𝛥𝜃 is a function of state, so it doesn't depend on the path.
• We say that a transformation is isobaric if it happen at constant pressure.
P
Vi Vf
V
P nRV=
𝜃
All the amount of heat exchanged will be absorbed by the gas and it is used to increase
the volume, in such a way it will mantain the temperature constant. It means 𝛥U = 0,
but
it doesn't mean that the heat exchange is zero!
U Q-W
Q W
𝛥 = = 0
as expected, so:
𝛿W pdV nRV dV
= =
𝜃
W
f nR𝜃
dV nR ln Vf Q
= ∫
i V Vi = 𝜃 =
d
𝜃
𝜃
= - CRV dVV Cp -C
=
V dV
(
CV V - - dV
V
)
= (𝛾 1)
C
with 𝛾 = p , so integrating:
CV
-
f V f
ln 𝜃i = ln Vi = 0
𝜃
𝛾 1
𝜃f V
f = 𝜃i Vi
- 𝛾 1 - 𝛾 1
(4)
𝜃V
- = constant
𝛾 1
PV
𝜃 =
nR
PV 𝛾
= constant
The relation will lead to a steeper graph.
If we open the wall, the gas will distribute uniformly in the whole space. We wait until
a final equilibrium state, in which the gas will be expansed without a heat exchange
(the system is isolated). What is the amount of work?
Pext W
U
= 0→ = 0
nCV U
𝛥 = 0
𝛥𝜃 = 𝛥 = 0 → 𝛥𝜃 = 0
The intermediate state are not equilibrium state, we know nothing. This is an
irreversible transformation, and it is the most irreversible transformation: nothing
changes, you know only the initial and the final states, nothing in between.
| QH W QC
| = | |+| |
The meaning of the second statement is that you cannot convert all heat released from a hot
body into work, you always need two bodies, another colder to receive a small amount of heat.
This means that it cannot happen that 𝜂 = 1 or 𝜔 = +∞, becouse |QC |, |W | can never be
0, and
W QH - QC
= | | | | (5)
The second law is valid also for reversible transformation! For every physical process, |QC |
and |W| can never be zero.
Figure 1: Second law of thermodynamics
The only transformations are in the reservoirs.
PROOF. Suppose is valid the first statement, and suppose that a cold body realeases |QC |
into a hot body, and there is a cyclic machine that doesn't violate the second statement
through which the cold body releases a quantity of heat of |QC | to the cold body. In
definitive, the heat transferred by the cold body is 0...
The converse: create a machine that violates the second statement, so the cold body releases
|Q | to a machine that converses it entirely into work spend by another machine to pass |Q |
1 2
from the same cold body to a hotter body. The total amount of work is 0, the heat extracted
by the cold body is |Q | + |Q | and it is the same received by the hot body with 0 work.
1 2
𝜂 irr ⩽ 𝜂 rev
PROOF. Suppose that there are two reversible engines with two different efficiency, for
example 𝜂 < 𝜂 , this means that
2 1
W W | | | |
𝜂2 =
QH QH
| |
<
| |
= 𝜂1
This means |Q H | > |Q H |, |Q C | > | | Q C . Now let flow this quantity between two
2 1
reservoirs, so |Q H | = |W| + |Q C | and the same for the other engines, but in the reverse
2 1 2 1
2 2
in which the work produced by one system is used to power the second (the work is zero).
You're violating the second law of thermodynamics (the clausius statement). This means
𝜂 ⩾ 𝜂 . Use the same argument with swapped engine.
2 1 □
W |QH - QC
- QQHC
| | | | |
𝜂 =
QH
| |
=
QH | |
= 1
| |
QH nR H VVab
= 𝜃 ln
QC C | | 𝜃
ln
Vc
Vd
QC nR C VVdc QH H Vb
⇒ = ⋅
𝜃
| | = 𝜃 ln ln
Va
𝜃H Vb
- 𝛾 1
= 𝜃 C VC
𝛾
Vb Vc
𝜃H Va
- 𝛾 1
= 𝜃C V
d
𝛾
⟹
Va Vd =
Vb - Vc
ln
Va Vd = 1
𝜃C
riv = 1 - 𝜃 (6)
𝜂
H
It is a very important result, showing that every reversible machine has this efficiency. To
calculate this, you have to use the thermal scale of perfect gas!
You see that if 𝜃C approaches the absoulte zero, then the efficiency would become 1 (which is
impossible).
30/11/21
Since the efficiency is independent from the substance (see (6)), we can give a new definition
of temperature. Before, we need to choose a substance and a property changing with
temperature, and we associated a number to this property that is changing. It contains a
number of arbitrary choiches.
We can do something better of the scale of temperature for the ideal gas. It contains the
absolute zero for gas, that is the zero also for all other substances! Tis is becouse the
efficiency is the same for all bodies. I am extending the meaning of the scale of temperature
for gas ⟹ absolute scale of temeprature. I create a Carnot cycle to study the temperature of
a body, using water at the triple point 273.16 K as T and I define the new temperature as
Q K. The scale is the same as the celcius degrees scale, but the zero is
2
T 1 = 273.16
Q
| 1|
shifted to - K. The absolute zero is an actual zero! you cannot pass through it, it's
| 2|
273.15
TH QH
=
T Q
system, so C - C . Tis amounts to say that, if the process is reversible,
TH QH =
QC QH
TC TH+ = 0
case becouse if we take the same amount of heat from the col body, QC irr QC rev , so
| | > | |
QC QH
T⏡⏣⏣
⏠⏣⏣
C TH
⏢
+ ⩽ 0
<0
and it will be equal to zero only in the reversible case. Generalizing, ∑ QTii ⩽ 0 , and for a
continuous cycle:
Theorem 7 [Clausius' inequality] For continuous cycles, ∮
𝛿 Q ,where the
equality holds only for reversible cycles.
T ⩽ 0
3.3. Entropy
B
Remember from Joul's experiment ∮𝛿Q- 𝛿W = 0 ⟹ ∫A 𝛿Q- 𝛿W = U(B) -U(A) .
But we have made a choice on the name of U, it's not an absolute choice. But this leads us to
say that
B 𝛿Q
∫
A T rev = S(B) -S(A)
since it is 0 if the cycle is reversible. This new function S is called entropy. This is the
macroscopic definition of entropy and we measure it in [J / K] .
For the irreversible case, we close the cycle with a reversible transformation and obtain
𝛿Q B 𝛿Q A 𝛿Q
∮
T irr = ∫A T irr + ∫B T rev ⩽ 0
B 𝛿Q B 𝛿Q
∫
A T irr A T rev = S(B) -S(A)
⩽ ∫
S B -S A
( ) ( ) ⩾ 0 .
The universal entropy difference is positive in the case of an irreversible transformation, zero
for a reversible transformation. The universe entropy increas es in every irreversible
transformation.
We define dS =
Q dU
T rev T rev V constant , since Q dU for constant volume. So
𝛿
= 𝛿 =
dU
1
(7)
T Q rev V constant
=
𝛿
,
In the general case,
S Q ∫ nCV dT nR dV
f 𝛿
𝛥 =
i T rev
∫
T V = +
01/12/21
In an isothermal process, Ti = Tf , while for the volume, it has increased with the law
Pf / Pi = Vi / Vf . Now we want to calculate 𝛥Sf i in an adiabatic transformation:
→
f 𝛿Q
𝛥S f i = ∫i T
→
rev
P
isot
her
mal
Vi Vf V
We are sure that the initial and final position will lie on an isothermal tranformation, also
if it isn't. The adiabatic free expansion is an irreversible process, while the isothermal is a
reversible transformation. So their difference is not in the initial and final state, it's the way
the system relates with the surroundings. In the process where a gas expands,
𝛥 Ssystem = 0, becouse the system is isolated, so it isn't exchanging heat nor work.
Substitute the vacuum with a piston, so the expansion is very low, and a source of heat to
compensate the loss of heat and lead to a stable temperature.
Piston
Gas
The difference between reversible and irreversible is all in the universe! Is it isolated? Does it
wxchange heat with others?
This means that 𝛥S > 0 in any spontaneous process. If the Kelvin statement wouldn't
hold, the system will have 𝛥S < 0, becouse there is only loss of heat, which is converted
entirely into work. If the clausius' statement would be false, we still would have 𝛥S < 0,
becouse TC < TH and the same amount of heat, so |𝛥SC | > |𝛥SH | but the first is
negative...
Spontaneous processes leads to a tendency to thermal equilibrium.
In the final state, Ti = Tf . If the process involves an increasing entropy, the final state
(thermal equilibrium state) will have the maximum amount of entropy of the universe.
The probability to find a molecule decrases in time. The initial state is asymmetric and
ordered. The final state is symmetric, uniform and disordered. Pay attention to the
terms you use!
We have a discrete finite number of particles N and states. Each particle will be defined
to be in a certain state. You place the particles in a certain state of energy. Take an energy
level and say how much particles have this value of energy; then calculate alll the possible
permutations (it is a mathematical intuition!). If the internal energy is associated to a
thermal equilibrium state (so to the temperature), I have the restriction that the total
internal energy must be U. The equilibrium distribution is the distribution that maximize
the number of way I can permutate the energy states. In fact, in the previous experiment, the
final equilibrium state corresponds to the maximum disorder.
Maximum S [J / K] corresponds to thermal equilibrium, which corresponds to
maximum 𝛺, so there must be a relationship between entropy and thermodynamic
probability, that is microscopical. How to relate entropy to a number of probability? It must
eb S = f(𝛺), but which kind of function? Let's compare entropy property to the probability
property. Suppose we understand the absolute meaning of entropy, not only the difference in
it (𝛥S), and take two different physical systems with SA and SB . it's an extensive property
of the system. The total entropy is S = SA + SB = f(𝛺) = f(𝛺A ) + f(𝛺B ) . In
probability, 𝛺 = 𝛺A · 𝛺B , so
f(𝛺A · 𝛺B ) = f(𝛺A ) + f(𝛺B )
And the only function with this property is the logarithm, so
S ⏠⏣⏣
const
=
⏡⏣⏣
⏢
· ln 𝛺
J
K
Remember that PV = nR𝜃 =
N R Nk k R J the Boltzmann constant.
NA NA K
𝜃 = 𝜃, =
S k= ln 𝛺 (9)
07/12/21
This is called the Bolzmann identity. (9) refers to the entropy of the whole system. This
definition is based on the identification of 𝛥S = ∫𝛿Q / Trev . Then we were able to relate
the entropy to the so called thermodynamic probability represented by 𝛺, and we also
considered a constant that connects the number to the physical quantity (k = R / NA ) using
the behavior of the ideal gas.
Now, this definition of entropy opens the way to the statystical thermodynamic. You have
to recognize the existence of a finite number of energy states. We were able to identify
the probability with the entropy.
Now, given a certain temperature (a state of thermal equilibrium), which is the distribution
of states that corresponds to this temperature? Thermal equilibrium corresponds to masimum
entropy, that is maximum distribution. So calculate 𝛺 and find the maximum of this function
with the constraint of the internal energy given by the thermal equilibrium and of the
number
of particles that must be fixed. We will number the energy levels (𝜖i ) and add the
degeneracy gi and count how many particles ni occupy every state, but you have the
restriction that
i
∑
ni = N and the restriction on the total energy.
In the non degenerate case 𝛺 =
0n !n !n ! … nN !
1 2
i
∑
N! , with ni𝜖i = E. How is this
calculation done? It can be demonstrated (see the file, Lagrange multiplier...) that this result
depends on a parameter 𝛽:
ni e - i P i 𝛽𝜖
N ∑j e - j
=
𝛽𝜖
= (𝜖 )
1
𝛽 =
kT
- kTi
e = P(𝜖i).
𝜖
and so j
∑j e- kT
𝜖
Keeping constant the number of particles, if you decrease temperature, this leads to increase
the number of particles that occupy the lowest energy levels and decreasing those which
occupy the highest value of energy, and viceversa. If T → 0, the particles will be all in one
level, if T → ∞, the distribution will be uniform among all the possible states.
E N
/ = ni i N . It depends on the temperature, and this allows us to say that
𝜖 /
temperature is related to internal energy. If we change physical system, energy states might
change: the sequence depends on the physical system. Also if the temperature is the same, it
doesn't mean that the total energy is the same! The temperature says only how to distribute
the atoms in that specific sequence of energy level, that change from physical system to
physical system.
Two physical system at the same temperature do not necessarily have the same average
internal energy becouse their energy levels are different.
Internal energy doesn't mean kinetic energy, temperature is not a measure of the kinetic
energy of a system of particles: this is true only for the ideal gas. In the pther case, we also
have potential energy due to the interactions of the particles of the system (configurational
energy).
Suppose now we have a continuous distribution of energy levels.
- kTE
P E dE e dE
- kTE
( ) =
∫
∞
0
e dE
This is the probability distribution of occupation of an energy level in a continuous
distribution of the value of E. This is consideren in non quantum physics. Each state
containes both the kinetic part and the configurational part of the energy. Calculating the
average internal energy we get:
- kTE
∞
Ee dE
E kT
∫
0
- kTE
< > = =
∫
∞
0
e dE
3.6. Microscopic significance of work and heat
Work means that the system exchanges energy with the surroundings making use of the
uniform motion and uniform potential energy in an external field: it is an order
way. Heat makes use of the internal energy random motion and internal
configurational energy of the atoms. From a mathematical point of view, the result is that
in the case of work there is a uniform shift in the energy levels, while the number of particles
in a state remains the same. It means that temperature changes. Heating means that the
sequence of energy levels remains the same, while the number of particles per state changes.
• Work:∑ ni d i ;
• Heat:∑ dni i .
( 𝜖 )
( ) 𝜖
𝜔 = | QC W QC QH - QC
|/| | = | | / (| | | QH - QC QC
|) = 1 / (| | | TH TC -
|) / | | = 1/( / 1)
It means that in a practical refigerator you cannot obtain TC , otherwise this shall be
= 0
infinite.
14/12/21
From the microscopical point of view we have a discrete number of particles and find the
possible distribution on the discrete energy states in the thermal equilibrium, which
corresponds to the maximum of the distribution.
T : all the particles are in the ground state. If T , then nE n N and it's
0
= 0 →∞ = 0 = /2
a uniform distribution.
E E
T T T
E E
= ∞ > 0 = 0
0 0
n
| |
If T - , nE n N , but if T
→ ∞ = 0 = /2 →0
- this means that n 0 = 0, nE N .
=
E E
T - T T
E E
= ∞ < 0
= 0
0 0
The behavior of 𝛽(E) is more informative of what is happening (see the slides for graphs):
Negative values of absolute temperature has only a microscopical meaning, but negative
temperatures are "higher" than the positive ones! This is becouse the particles occupy higher
energy states. We would have a flow of heat from the negative temperatures to higher
temperatures. You can obtain such a state, but this can be reached only in a restricted finite
time.
This is the end...?