Examples

Nature of
Thermodynamics
4 Classical Macroscopic Physics
 mechanics
 electricity
 magnetism
 thermodynamics
o heat-related motion
 thermo is heat
 dynamics is motion

POVs
 Atomic point of view
o an agglomerate of an enormous number of
electrons, nuclei, and strings Model System
o use of the Schrodinger equation
 needs the coordinates of all electrons in the Given the example (hypothetical): a central
subject (1024 or 1025 coordinates are required heavy atom (+2 charge) and 10 symmetrically placed
to describe a cup of water) light atoms of equal mass with two having a +1 charge.
 Macroscopic point of view
In the normal modes (definition), the motions of
o statistical averaging
the individual atoms are strongly couples so that the
o fewer parameters
atoms tend to move in organized patterns.
“In the transition from the macroscopic level of
In the normal coordinates (definition), positions
description there is a tremendous simplification and
of each atom at instantaneous amplitude of each of each
a drastic reduction in the number of pertinent
normal mode.
variables.”
Other Hypothetical Normal Modes
In simplifying the atomic specification to
macroscopic specification, the slowness of macroscopic
measurements in comparison to the speed of atomic
motions is considered. In short, macroscopic are slower
than atomic in terms of POV.

To expound, during the very time that a  Normal Mode 1

macroscopic measurement is being made, the atoms of o Two charged atoms remain fixed while the
the system still go through enormously rapid and uncharged light atoms vibrate out of phase in
complex motions. pairs along the tangential directions.
“Macroscopic measurements sense only averages of  Normal Mode 2
the atomic coordinates.” o All light atoms vibrate in phase along the radial
direction.
Statistical averaging drastically reduces the  Normal Mode 3
number of pertinent variables. Of the original 1024 o Neighboring light atoms vibrate out of phase
atomic parameters, a few very special parameters along the tangential direction.
survive the averaging process and remain as the
appropriate parameters for a description of a “We are interested in understanding qualitatively
macroscopic system. These are the observable properties how most of these normal coordinates are lost in the
in a macroscopic system. statistical averaging, whereas a certain few unique
normal coordinates survive.”

Smoked Glass
 We think of macroscopic observation as a kind of
“hazy” illustration which concerns overall features
but not fine detail (insensitive to fine details)
 Qualitative way of statistical averaging
 Given the last example:
 o In the concept of energy, energy can be
transferred to a mechanical mode of a system.
 mechanical work: −P dV
 P is pressure, V is volume
o Energy can also be transferred to an electrical
mode of a system.
o Mode 1: Motion is indistinguishable with
 electrical work: −E d P
respect to mode 3
 E is electric field, P is a dipole
 this normal mode might be eliminated by
moment
statistical averaging
o It is equally possible to transfer energy to the
 this mode will be hidden during statistical
averaging process hidden atomic modes of motion (Hidden ≠
o Mode 2: motion is associated with gross change Lost)
in the size of the system o An energy transfer to the hidden atomic modes
 volume dilation is distinguishable; this is is called heat.
preserved through statistical averaging
o Mode 3: this motion is indistinguishable with
respect to Mode 1
The Internal Energy
 this mode of motion is associated with a
gross electric dipole moment  An ambiguous concept used in thermodynamics.
 negative charges suffer a net
displacement relative to the positive
Principle of Conservation of Energy
change  One of the most significant achievements in the
 if the smoked glass is electrically history of physics.
sensitive, then this mode might be  Developed for over two and a half centuries by
observable Leibnitz in 1693
 this mode of motion will survive the 1 2
o sum of the kinetic energy ( m v ) is conserved
statistical averaging process when the 2
electric dipole movement becomes a
In viewing a macroscopic system as an
valid parameter for the description of a
agglomerate of an enormous number of electrons and
macroscopic system
nuclei, interacting force which the energy conservation
“Under the statistical averaging process, one mode principle applies.
is lost, one survives as a mechanical parameter (V),
 With this, we conclude that macroscopic systems
and one survives as an electrical parameter (dipole
have definite and precise energies that subject to a
moment)”
definite conservation principle.
This is a very general result to illustrate the o We now accept the existence of a “well-defined”
situation where enormous number of atomic coordinates energy of a thermodynamic system.
where only a very, very, very few with unique o Absolute vs Difference values of energy
symmetric properties survive the statistical averaging  The absolute values of any form of energy
process (transition to a macroscopic description). do not have any physically meaningful
concepts until it has some differences
 Some of these surviving coordinates are mechanical compared to a reference state.
(V), and electrical (dipole moment).  Only differences of energy have physical
o mechanics is the study of surviving mechanical significance in either atomic or macroscopic
parameters level.
o electrics is the study of surviving electrical
parameters In understanding the concept of energy, to apply
the difference, we use some particular standard state of a
Thermodynamics is the study of the macroscopic system (energy is taken as zero), then this will be the
observations of numerous of atomic coordinates, which reference state. The energy of a system in any other state
do not appear explicitly in a macroscopic parameter relative to the energy of the standard state is then defined
(such as hidden atomic mode, mode #1) of a system due as “Internal Energy” (denoted by: U).
to the statistical averaging process.
Internal energy is defined as the energy relative
 Thermodynamics is the study of hidden existing to the energy of the standard state plus the internal
atomic modes. Thermodynamics is concerned energy is an extensive parameter.
with processes of heat transfer.
 Intensive Properties
 o Intensive properties are independent of the size from the other by some work done on the system. This
or mass of the system. leads to the measurability of the internal energy
o They describe the system's state and are often difference. In other words, the work done is the
related to the system's temperature, pressure, difference in the internal energy of the two states in
density, and composition. adiabatic system.
o Examples include temperature (T), pressure (P),
“The heat flux to a system in any process (at
density (ρ), and specific volume.
constant mole numbers) is simply the difference in
 Extensive Properties
internal energy between the final and initial states,
o Extensive properties depend on the size or extent
diminished by the work done in that process.”
of the system.
o These properties are additive and scale with the In this situation, work and heat are
size or amount of material present in the system. interchangeable.
o Examples include mass (m), volume (V),
internal energy (U), and enthalpy (H).
The Basic Problem of
Measurability of Internal Energy
 There exist a macroscopic conservative energy Thermodynamics
function (U internal energy)
o This energy function must be macroscopically Thermodynamic Equilibrium
controllable and measurable  We choose to restrict our discussion to simple
Example: Ice and water in a glass container systems. These simple states in thermodynamics are
 In this system, when the system is vigorously stirred, called “equilibrium states.” The following is an
then the ice melts rapidly since energy is transferred. example:
In this case, mechanically. o Fluid at rest (for example, in a cup) is at a
 If it is left outside on a sunny day, ice melts simpler state than a fluid in laminar flow (for
spontaneously despite no work is put onto the example, water from a tap).
system. Energy in this situation is transferred in the  Note: Laminar flow can be defined as the
form of heat. motion of a fluid where every particle in the
fluid follows the same path of its previous
Example: Ice and water in an insulated bottle particles.
 The rate of ice melting is decreased o Fluid in laminar flow is in a simpler state than a
 If melting rate turns into a negligible value, then the fluid in turbulent flow.
wall is impermeable to the flow of heat.  Note: Turbulence or turbulent flow is fluid
o This system is called adiabatic (opposite is motion characterized by chaotic changes in
called diathermal) pressure and flow velocity.
 Observation: Isolated systems generally tend to
Results: if a wall allows the flux of neither work nor evolve spontaneously toward simpler states.
heat, then it is “restrictive with respect to the o Turbulences in fluid will eventually damp out
energy.” and concentration inhomogeneities ultimately
are destroyed by diffusion currents.
This means that a system enclosed by a wall that
 In here, we will assume that there exist equilibrium
is restrictive with respect to energy, volume, and mole
states. These are macroscopically characterized
numbers is said to be “closed.” Consequently, energy is
completely by internal energy (U), the volume (V),
macroscopically “controllable.” Energy can be trapped
and the mole numbers (N1…Nn) of the chemical
by adiabatic walls (restrictive to energy) and
component.
manipulated by diathermal walls.
 What systems are in equilibrium?
In the case of adiabatic walls, with the same o Systems in absolute and true equilibrium are few
example, work is the only permissible energy transfer. in number.
Work is well-defined by the theory of mechanics.  In absolute equilibrium, all radioactive
materials would have completely decayed
 If the work is done via compression ( = displacement and all nuclear reactions would have come
of piston in a cylinder): to completion.
o W =F × Displacement  These reactions would take cosmic times.
 If the force is done by stirring: o Systems that are static and at rest
o W =Torque × ω ( angular rotation )

We are able to measure the energy difference of

two states by knowing that one state may be reached
The Basic Problem of Thermodynamics  For each constrained equilibrium state, there
is entropy of the composite system.
 Additionally, for some particular values of
U(1) and U(2), entropy is maximum

“The basic problem of thermodynamics can be

Example
solved with the aid of extremum principle if the
Assumptions – What ifs entropy of the system is known as a function of the
 If the piston is freed, in general, the piston will seek extensive parameters.”
some new position.
”The relation that gives the entropy as a function of
 If the adiabatic coating is stripped from the piston, the extensive parameters is known as a fundamental
the heat can flow between the two systems. There relation.”
will then be a redistribution of energy between the
two systems. S=S ( U ,V , N 1 ,… N n ) → U=U (S ,V , N 1 ,… N n)
 If holes are punched in the piston, then there will be
 These are alternative forms of the fundamental
redistribution of matter (and also of energy) between
relation.
the two systems.
 Each of these contains all thermodynamic
“The removal of a constraint in each can result in information about the system.
the beginning of some spontaneous (natural)
process, and when the systems fully settle into new
equilibrium states they do so with new values of the
FAQs
parameters.”
1) What is the intrinsic meaning of “thermodynamics”?
“The basic problem of thermodynamics is the
calculation of the equilibrium values of these - Answer : “thermo-“ means the heat and “dynamics”
parameters.” means the motion, so it means that the motion of heat.

Final Equilibrium State 2) In the transition from the atomic to the macroscopic
 The most economical form for the equilibrium level of description, there is a tremendous simplification
criterion is in terms of an extremum principle. and a drastic reduction in the number of pertinent
o Developed by Fermat (1602) – says that light variables. Then, how do we simplify the atomic
travels between two given points along the path specification to macroscopic specification?
of shortest time (or at fastest speed)
- Answer : It can be possible because of “the slowness”
o When applied to equilibrium criterion, the
of macroscopic measurements in comparison to the
values of the extensive parameters in the final
speed of atomic motions. Macroscopic measurements
equilibrium state are simply those that maximize
sense only the averages of the atomic coordinates.
(or minimize; purely a matter of sign
convention) some function. 3) Which mode of atomic coordination will be
 This function would also have several eliminated (hidden; not lost) at the macroscopic point of
particular mathematical properties. view? (Assumption : the smoked glass is electrically
sensitive)
The Entropy Maximum Postulate
“There exists a function, called the entropy (S), of - Answer : the normal mode 1 is eliminated. Other
the extensive parameters of any composite system, atomic modes are survived as mechanical and electrical
defined for all equilibrium states and having the parameters.
following property.”
4) What’s the concept of “heat”?
“The values assumed by the extensive parameters in
- Answer : an energy transfer to the hidden atomic
the absence of an internal constraint are those that
modes.
maximize the entropy over the constrained
equilibrium states.” 5) What’s the definition of the “Internal energy (U)”?
 This does not apply to non-equilibrium states. - Answer : The energy of a system in any other state
 Entropy of particular state is definite and dependent relative to the energy of the standard state.
on the constraints.
o For example, a composite system with the 6) If a system is enclosed by adiabatic wall
internal adiabatic wall and with particular values (impermeable to the flow of heat), what types of energy
of U(1) and U(2) can be transferred in this system? And how can we
measure the amount of energy differences in this case?
- Answer : The permissible energy transfer is in the form Q= -8 kJ, indicating that the heat is transferred to
of “work”. We are able to measure the energy difference surroundings from system.
of two states by knowing one state may be reached from
the other by some work done. The work done is the 3)What’s the difference of extensive parameters and
difference in the internal energy of the two states in intensive parameters?
adiabatic system.
- Answer : Extensive parameters are dependent on
7) What is the simplest criterion for the determination of the size of the system such as Ut and Vt, while
the final equilibrium state? intensive parameters are independent of the size of
the system such as Temperature and Pressure.
- Answer : The function (called Entropy, S) of extensive
parameters will be maximized at the equilibrium state.
4)1kg of oxygen is heated reversibly at constant
8) Liquid/vapor saturation pressure Psat is often pressure from an initial state of 300K and 1 bar until
represented as a function of temperature by the Antoine
its volume double. Calculate W, Q, ∆U, ∆H for the
process.
equation, which can be written in the form:

ln ⁡〖 Psat /kPa 〗 =A−B/(T /K +C ) (Assume for oxygen that PV/T = 83.14 bar·cm3·mol-
1
·K-1 and Cp = 29 J·mol-1·K-1, and Mw = 32 g·mol-1)

- Answer : at the constant pressure, temperature is

increased to double during the volume becomes
twice (∆T=300K).

Then, ∆H=Cp∆T= 8700 J·mol-1 = 271.9 J·g-1 =

271.9 kJ·kg-1.

∆U=∆(H−PV)=∆H−P∆V=∆H−83.14

∆T= 193.9 kJ·kg . -1

W=−P∆V= -61 kJ·kg . -1

Correlate the data by fitting them to the above equation,

and then find numerical value of parameters A, B, and C Q=∆H = 271.9 kJ·kg . -1

by an appropriate regression procedure.

5)An incompressible fluid (= constants) is
- Answer : A = 13.9142, B = 2569.4534, C = -53.2307 contained in an insulated container fitted with a
frictionless piston. Can energy as work be
transferred to the fluid?
WEEK 2 Quiz 2. Problem & Solution
Quiz 2. -Answer : There is not any volume change of
incompressible fluid, so the work value is same to
1)What is the 1st law of thermodynamics? zero (W=−P∆V), which means that the energy
cannot be transferred to the fluid as work.
- Answer : 1st law of thermodynamics defines the
energy, it contains the meaning of conservation of 6) In the following take CV = 20.8 and CP = 29.1
energy, “Energy can’t be lost or gain”. J⋅mol−1⋅°C−1 for nitrogen gas:
2)Heat in the amount of 5 kJ is added to a closed (a) Three moles of nitrogen at 30°C, contained in a
system while its internal energy decreases by 8 kJ. rigid vessel, is heated to 250°C. How much heat is
How much energy is transferred as work? For a required if the vessel has a negligible heat capacity?
process causing the same change of state but for If the vessel weighs 100 kg and has a heat capacity
which the work is zero, how much heat is of 0.5 kJ⋅kg−1⋅°C−1, how much heat is required?
transferred?
(b) Four moles of nitrogen at 200°C is contained in
- Answer : From the 1st law of thermodynamics, a piston/cylinder arrangement. How much heat must
∆U=Q−W. In this case, Q= 5 kJ, and ∆U= -8 kJ, be extracted from this system, which is kept at
then the W value is -13 kJ which means that 13 kJ constant pressure, to cool it to 40°C if the heat
of work is transferred to surroundings from the capacity of the piston and cylinder is neglected?
system. If the work is zero,∆U=∆Q is valid, so
-Answer :
(a) In this system, the constant volume is
maintained. ()

If the vessel has a negligible heat capacity, the heat

equation is as follows:

Q1 = nCv∆T= 13.728 kJ.

If the vessel has a heat capacity, the heat equation is

as follows:

Qtot = Q1+Q2 = 13.728 kJ + mCVessel ∆T= 11013.728

kJ.

(b) In this system, the constant pressure is

maintained. Q=nCp∆T= -18.624 kJ.

So, 18.624 kJ must be extracted from this system.