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Lecture 8
Lecture 8
3)
We have been considering the entropy changes in the processes where
two interacting systems exchanged the thermal energy but the volume and
the number of particles in these systems were fixed. In general, however,
we need more than just one parameter to specify a macrostate:
S kB ln U ,V , N
We are familiar with only one partial derivative of entropy:
S 1
U V , N T
Today we will explore what happens if we let the other two parameters (V
and N) vary, and analyze the physical meaning of two partial derivatives of
the entropy:
S S
V U , N N U ,V
General Approach:
S S U,V , N
if monotonic as a function of U
(“quadratic” degrees of freedom!), may U U S,V , N
be inverted to give
S S S
dS d U d V d N
U N ,V V N ,U N U ,V
U U U
dU dS dV dN
S V , N V S , N N S ,V
S 1
So far, we have abbreviated one of these partial derivatives:
The other partial derivatives are: U N ,V T
U U U
T P
S N ,V V N ,S N V , S
pressure chemical potential
Thermodynamic Identities
d U T d S P dV d N
- the so-called
With these abbreviations:
thermodynamic identity
shows how much the system’s energy changes when one particle is added to the
system at fixed S and V. The chemical potential units – J.
is an intensive variable, independent of the size of the system (like P, T, density).
Extensive variables (U, N, S,V...) have a magnitude proportional to the size of the
system. If two identical systems are combined into one, each extensive variable is
doubled in value.
The thermodynamic identity holds for the quasi-static processes (T, P, are well-
define throughout the system)
The 1st Law for quasi-static processes (N = const): d U T d S P dV
S S S 1 P
dS d U d V d N dS d U dV d N
U N ,V V N ,U N U ,V T T T
This identity holds for small changes S provided T and P are well defined.
S 1 S P S
The coefficients may
be identified as: U N ,V T V N ,U T N V ,U T
Quasi-static Adiabatic Processes
Let’s compare two forms of the 1st Law :
Q T d S Q
Thus, for quasi-static processes : dS
T
Quasistatic adiabatic (Q = 0) processes: d S 0 isentropic processes
W
P(V )dV PV const PiVi
1
V V dV Vf
Vi i W P dV P Vi V f
1
PiVi
1 1
PiVi Vi Vi
1 1 1 2 105 Pa 102 m 2 103 m 2
1 V f
Vi 1 V f
1
2J
PiVi x
1 1
1 x The non-quasistatic process results
x in a higher T and a greater entropy
PiVi 1 105 Pa 10 3 m3 10 2 1 J of the final state.
x
S U ,V , N N k B ln V N k B ln U k B ln f N
f
Direct approach:
2
f
adiabatic quasistatic isentropic Q0 U W N k B T PV
2 2/ f
f N k BT T f Vi
N k B T V VT f /2
const
2 V Ti V f
Vf f 2 Vf
S N k B ln N k B ln 0
Vi 2 f Vi
adiabatic non-quasistatic
Vf
f Uf
S N k B ln N k B ln
Vi 2 Ui
V f Vi f T f Ti Pi Vi 2 5 2
N kB 10
Vi 2 Ti Ti 2 250
105 Pa 10-3 m 3 10-2 1
J/K
300K 300
V f 5 5
10 2 U W 2 J Ui N k BTi Pi Vi 105 Pa 10-3 m 3 250 J
V 2 2 2
2
P To calculate S, we can consider any quasistatic
U = Q = 1J process that would bring the gas into the final state (S is
a state function). For example, along the red line that
coincides with the adiabata and then shoots straight up.
Let’s neglect small variations of T along this path ( U <<
U, so it won’t be a big mistake to assume T const):
1
Q 2J 1J 1
S 0 (adiabata) J/K
Vf Vi V T 300K 300
The work done on the gas is negative, the gas does positive work on the piston in an
amount equal to the heat transfer into the system
Qrev Wrev V P V x 1
Qrev Wrev 0 S N k B ln i i i J/K
T T Vf Ti x 300
2
Thus, by going 1 2 3 , we will increase the gas entropy by S123 J/K
300
Comment on State Functions
1 S
thermal energy temperature
T U V , N
P S
mechanical volume pressure
T V U , N
S
diffusive particles
chemical
potential T N U ,V
The last column provides the connection between statistical physics and
thermodynamics.
To discuss the physical meaning of these
Temperature partial derivatives of S, let’s consider an
ideal gas isolated from the environment, and
consider two sub-systems, A and B,
UA, VA, NA UB, VB, NB separated by a membrane, which, initially, is
insulating, impermeable for gas molecules,
and fixed at a certain position. Thus, the
sub-systems are isolated from each other.
(We have already considered such a system
when we discussed T, but we want to
proceed with P and )
Assume that the membrane becomes thermally conducting (allow exchange U while
V and N remain fixed). The system will evolve to the state of equilibrium that is
characterized by a maximum entropy. One of the sub-systems can increase its
energy only at the expense of the other sub-system, and it’s crucial that the sub-
system receiving energy increases its entropy more than the donor loses. Thus, the
sub-system with a larger S/U should
S AB S A S B S A S B
receive energy, and this process will continue 0
until SA/UA and SB/UB become the same: U A U A U A U A U B
Ideal gas: U ,V , N g N V NU f N / 2
(fN degrees of freedom)
S U ,V , N N k B ln g N V U f / 2
The “energy” equation of state (U T):
1 S f 1 f
N kB U N kB T
T U V , N 2 U 2
S N kB
P T T PV N kBT
V U , N V
- we have finally derived the equation of state of an ideal gas from first principles!
In other words, we can calculate the thermodynamic information for an isolated
system by counting all the accessible microstates as a function of N, V, and U.
Problem: (all the processes are quasi-static)
Q
You should be able to do this using (a) Sackur-Tetrode eq. and (b) d S
T
f T Q f dT dV
Q dU PdV Nk B dT dV dS dU PdV Nk B
2 V T 2 T V
U ,V , N f N V NU f N / 2
S NkB ln g N VT f / 2
Vf f Tf
(a) S NkB ln (b) S NkB ln
Vi 2 Ti
S A SB S
N A NB N U ,V T
S
In equilibrium, TA TB A B
NA
S - the chemical
T
N U ,V potential
UA
Sign “-”: out of equilibrium, the system with the larger S/N will get more
particles. In other words, particles will flow from from a high /T to a low /T.
U
Chemical Potential: examples
N V , S
Einstein solid: consider a small one, with N = 3 and q = 3.
( N 3, q 3)
q N 1 ! 10 S ( N 3, q 3) kB ln 10
q !( N 1) !
let’s add one more oscillator: S ( N 4, q 3) kB ln 20
U 1
dS d U d N To keep dS = 0, we need to decrease the
N S T T energy, by subtracting one energy quantum.
U
Thus, for this system
N S
4 m
3/ 2
5
Monatomic ideal gas: S ( N ,V ,U ) N k B ln V U ln N 5/ 2
2
3h 2
S V 2 m
3/ 2
VT 3 / 2
T k BT ln 2 k BT k BT ln g m
N U ,V N h N
At normal T and P, ln(...) > 0, and < 0 (e.g., for He, ~ - 5·10-20 J ~ - 0.3 eV.
Sign “-”: usually, by adding particles to the system, we increase its entropy.
To keep dS = 0, we need to subtract some energy, thus U is negative.
The Quantum Concentration
V 2 m
3/ 2
h 2
3/ 2
h3 P
k BT ln 2 k BT k BT ln n k BT ln
5/ 2
N h 2 mkBT 2m k BT
3/ 2
n=N/V – the concentration of molecules
0
when n
The chemical potential increases with the density of the gas or with increases
its pressure. Thus, the molecules will flow from regions of high
density to regions of lower density or from regions of high pressure
to those of low pressure .
h 2
3/ 2
n
k BT ln n
k BT ln when n nQ, 0
2 mkBT n
Q
- the so-called quantum concentration (one particle per
2 m
3/ 2
nQ 2 k BT cube of side equal to the thermal de Broglie wavelength).
h When nQ >> n, the gas is in the classical regime.
3/ 2
h h 1 mkBT
dB nQ
p mkBT dB 3 h
2
At T=300K, P=105 Pa , n << nQ. When n nQ, the quantum statistics comes into play.
Ideal Gas in a Gravitational Field
Pr. 3.37. Consider a monatomic ideal gas at a height z above sea level, so each
molecule has potential energy mgz in addition to its kinetic energy. Assuming that
the atmosphere is isothermal (not quite right), find and re-derive the barometric
equation.
dU V 2 m
3/ 2
( z 0) mgz k BT ln 2 k BT mgz
d N S ,V N h
V 2 m
3/ 2
V 2 m
3/ 2
k BT ln 2 k BT mgz k BT ln 2 k BT
N ( z ) h N (0) h
mgz
kBT ln N ( z) mgz kBT ln N (0) N ( z ) N (0)e k BT
S and CP
Q T d S - this is a useful result that removes the restriction of constant volume.
Tf
S P CP dT S C S
P
T T P T
T
Future Directions
Although the microcanonical ensemble is conceptually simple, it is not
the most practical ensemble. The major problem is that we must specify
U - isolated systems are very difficult to realize experimentally, and T
rather than U is a more natural independent variable.
S U ,V , N kB ln
micro- U, V, N 1
Pn
canonical (T fluctuates)
F T ,V , N kB T ln Z
En
T, V, N 1 kB T
canonical Pn e
(U fluctuates) Z
En N n
U, V,
grand 1
Pn e kB T T ,V , kB T ln Z
canonical (N fluctuates) Z