Advanced Thermodynamics

Lecture 2

Yaguo Wang
Assistant Professor
Mechanical Engineering

Review Table _ Posted on Canvas

Ideal Gas _ Heat Capacities and Specific Heats

Approximately,
Energy
C
T
Heat capacity (CV) and specific heat capacity
(cV) for constant volume process
U
u
Cv and cv
T v
T v
Heat capacity (CP) and specific heat capacity
(cP) for constant pressure process

H
CP

T P

h
and cP
T P

Specific Heats for Ideal Gases

For an ideal gas, h = h(T)
dh
h
cP
T P dT

T2

cP dT Always

T1

Similarly, for ideal gas u = u(T)

cV

du
u

T V dT

T2

T1

cV dT Always

Specific Heats for Monoatomic Ideal Gases

Constant Specific Heat for Monoatomic Ideal Gas

Isentropic Process for Monoatomic Ideal Gases

Define k = cP/cV

1
R=cp -c v =cp (1- )=c v (k-1)
k

If cP and cV independent of temperature

dT
dP
dT
dv
ds [c p
R ]

ds

[c

R
]
vT
T
P
v
dT
1 dP
dT
dv
=c p
c p (1- )
=c v
+c v (k-1)
T
k
P
T
v
=0
=0
k 1

T2 v1

T1 s v 2 s

k 1
k

T2 P2

T1 s P1 s

Quasi-static Processes
Assume massless, frictionless and well-insulated piston
Slowly apply increasing force (FP)
to piston causing piston to move
down in compression process,
PCM = (FP/AP + PATM) at all times

Process approximately
reversible by slowly removing
each infinitesimal mass

Exp. A_Quasi-static Isothermal Compression

Uninsulated piston cylinder sitting in a constanttemperature water bath, a force applied on top of
piston compress the monoatomic gases very slowly
(quasi-static) from position 1 to 2.
1. Calculate the work in this process with 1st and 2nd
law
2. Verify that same result is reached with =

Exp. A_Quasi-static Isothermal Compression

Exp. A_Quasi-static Isothermal Compression

Exp. A_Quasi-static Isothermal Compression

Exp. B_Quasi-static Adiabatic Compression

Insulated piston cylinder, a force applied on top of
piston compress the monoatomic gases very slowly
(quasi-static) from position 1 to 2.
1. Calculate the work in this process with 1st and 2nd
law
2. Verify that same result is reached with =

Exp. B_Quasi-static Adiabatic Compression

Exp. B_Quasi-static Adiabatic Compression

Exp. B_Quasi-static Adiabatic Compression

Introduction to Statistical Thermo.

Ways of Arranging Objectives

Problem 1: How many ways can we arrange N
Distinguishable objects? For example, we wish to
arrange N books in various ways on a shelf?

Ways of Arranging Objectives

Problem 2: How many ways can we arrange N
distinguishable objects into r distinguishable boxes?
Such that there are N1 objects in the first box, N2 in
the second, , and Nr in the rth box?

Ways of Arranging Objectives

Problem 2: What if without regard to order within the boxes?

Ways of Arranging Objectives

Problem 3: How many ways can we select N
distinguishable objects from a set of g
distinguishable objects? e.g. putting N books on
one of two shelves and g-N books on the other.

Ways of Arranging Objectives

Problem 4: How many ways we can put N
indistinguishable objects into g distinguishable
boxes? There is no limit on the number of objects in
any box?

Ways of Arranging Objectives

Ways of Arranging Objectives

Problem 5: How many ways we can put N
distinguishable objects into g distinguishable
boxes? Each of N different books can be put on any
of g shelves.

Quantum States_Bohr Hydrogen Atom

Main Idea:
Electron energy
States are discrete

Thermodynamic Probability
The issue in Thermo is manner in which a fixed
number of particles are distributed among the
available quantum states (microstates).
Many quantum states have same energy __
number of quantum states at each energy level is
called degeneracy.

Thermodynamic Probability
Microstate: description of a system which relies on
the states of each element of the system.
Q1: how many coordinates do we need to describe a
system containing ONE particle?
Q2: how many coordinates do we need to describe a
system containing N=100 particles?

)=

Thermodynamic Probability
Macrostate: description of a system which relies on
some macroscopic properties.
Think about the 100 particles, each is labeled as 1, 2,
100. Put these 100 particles into five boxes, each
with N1, N2, N3, N4, N5 particles.
If we dont care about the label of individual particle,
but only the total number in each box.
Q: how many coordinates do we need to describe
this system?

)=

Thermodynamic Probability
The number of microstates in a given Macrostate

Principle of Equal Priori Probabilities

All microstates of motion

occur with equal frequency.

Specification of Molecular Microstates

An array of N particles has a total energy U. The
energies of the individual particles are assumed to
take on the discrete values, , , , , . The
number of particles with energy is .
Thus:

Example:
An array of 2 particles has a total energy of 2, each
energy level has a degeneracy of 2. The energies of the
individual particles are assumed to take on the discrete
values, , , . The number of particles with energy
is .
How many possible macrostates for this system?

Molecular Distributions