熱力學

Chapter 14 Lecture
Chapter 16:
Temperature and
Heat
© 2016 Pearson Education, Ltd.

What You're Learning
• A precise definition of temperature

and heat
• How temperature is measured
• How a material's specific heat
determines the energy needed to
change its temperature
• Three mechanisms of heat transfer:
• Conduction
• Convection
• Radiation
• To determine the temperature of a
system in thermal energy balance
with its surroundings
Thermodynamic Equilibrium and
Temperature
• Two systems placed in contact may undergo changes in
macroscopic properties like length, pressure, electrical
resistance, etc.
• When such macroscopic changes cease, the two
systems are in thermodynamic equilibrium.
• By definition, systems in thermodynamic equilibrium are
at the same temperature.
• Any convenient macroscopic property can be used as a
measure of temperature.
• A thermometer is a system with some macroscopic
property whose value is used as an indication of
temperature.

Gas Thermometers
• One of the most versatile thermometers is the constant-

volume gas thermometer.
• The pressure of the gas provides
an indication of temperature.
• Absolute zero is defined to be the
temperature at which the gas
pressure would become zero.
• Gas thermometers are the current
basis of the SI definition of the
Kelvin temperature scale.
• Gas Thermometers can be used
over a wide range of temperatures.
!" = $%&
$% A constant-volume gas thermometer
!= &
"
The Kelvin Scale
• The current SI temperature scale is defined using the triple point of

water, the unique temperature where solid, liquid, and gas can coexist.
• The temperature at the triple point is currently defined to be
273.16 K.
• The point of zero pressure in a gas defines a second temperature,
namely absolute zero.
• Together, the two defined temperatures establish the kelvin scale.
• The SI definition of temperature is currently being revised. The new
definition will make the triple point of water a measured quantity.
Two points establish the kelvin temperature scale

Heat Capacity and Specific Heat
• Heat is energy being transferred from one object to

another because of a temperature difference alone.
• In SI, heat is measured in joules (J).
• An older unit, the calorie (cal), is equal to 4.184 J.
• The heat capacity C of an object is a measure of the heat
∆Q required per unit temperature change: ∆Q = C ∆T.
• The specific heat c of a substance is the heat capacity
per unit mass: ∆Q = mc ∆T.
' = ()
heat capacity specific heat capacity
Heavier object is more difficult to heat up.
Equilibrium Temperature
• When two substances at different temperatures are

brought into thermal contact without any loss of energy,
they come to equilibrium at a temperature determined by
their masses and specific heats:
m1c1ΔT1 + m2 c2 ΔT2 = 0
• For the hotter object ∆T is negative.
• Heat flows from the hotter object into the cooler object.
Heat Transfer: Three Common Mechanisms
• Conduction is heat transfer through direct physical contact.

• Occurs as molecules in a hotter region collide with and transfer
energy to those in an adjacent cooler region.
• Convection is heat transfer through the bulk flow of a fluid.
• Occurs when a heated fluid becomes less dense and rises.
• Radiation is heat transfer by electromagnetic radiation.
• Occurs when the surface of an object emits or absorbs
electromagnetic radiation.

Heat Transfer
• Conduction: The rate of heat flow through a slab of & + ∆&
thickness Δx, uniform cross-sectional area A, and A
thermal conductivity k is given by
ΔT
H = −kA Δ+
Δx
where ΔT is the temperature difference across its
thickness. Thermal resistance ∆+ &
.=
/0
• Radiation: The power loss from a surface area A at
temperature T is given by the Stefan-Boltzmann law:
P = e AT 4
• Here e is the emissivity, which lies between 0 and 1,
and = 5.67 10 8 W / m 2 K 4 is the Stefan-Boltzmann
constant.
Thermal Energy Balance
• A system is in thermal energy balance when its rate of

energy gain is equal to its rate of energy loss.
• A system in energy balance maintains a constant
temperature.
• If loss exceeds gain, the system cools.
• If gain exceeds loss, the system warms.
A house in thermal-energy balance

Intensity of sunshine
!=1 43.!" &# = 5.67 10 8
W / m2 K 4
!
4=
435" Earth
d Sun surface temperature: T=?

sun radius: Rs=?
Earth-sun distance: d=?
sun
! = 1 43.!" & #
!
4=
435"
d Sun surface temperature: T=5778K

sun radius: Rs=6.955 x 108m
Earth-sun distance: d=1.496 x 1011m
! = 1 43.!" & #
= 5.67×10$% 43×6.955"×10&' ×5778# = 3.84×10"'@
! 3.84×10"' @
4= " = && " = 1366 "
435 43 1.496×10 (
d Sun surface temperature: T=5778K

sun radius: Rs=6.955 x 108m
Earth-sun distance: d=1.496 x 1011m
Example: Earth's Temperature
• INTERPRET: This is a problem about energy balance.

The heat loss mechanism is radiation.
• DEVELOP: In energy balance, the rate of energy arriving
per square meter equals the rate radiated. Writing e = 1
and S = 1366 W/m2 we have
RE2 S = e⇥ ( 4 RE2 T 4)
! 3.(" 4 ! 4 ! 1366
&= " = = $% = 278.58%
A1×43.( 41 4×5.67×10
• Earth absorbs energy from the Sun at the

average rate of about 960 W/m2 for each square
meter of its cross-sectional area R 2E . Assuming
Earth's emissivity is 1, what should be its
average temperature?

• INTERPRET: This is a problem about energy balance.

The heat loss mechanism is radiation.
• DEVELOP: In energy balance, the rate of energy arriving
per square meter equals the rate radiated. Writing e = 1
and S = 960 W/m2 we have
)
RE2 S = e⇥ ( 4 RE2 T 4
• EVALUATE: Solving gives
1/4
⎛ 960 W/m2
⎞
T =⎜ 4 ⎟
= 255 K
⎝ 4(5.67 × 10 W/m ·K ) ⎠
−8 2
• ASSESS: Makes sense? This temperature (–18ºC or 0ºF)

seems in the right ballpark, but a bit low for a global
average. In fact, the natural greenhouse effect keeps
Earth some 33ºC warmer, at about 288 K or 15ºC.

Summary
• Thermodynamic equilibrium is the state reached when

macroscopic properties of a system or systems don't change.
• Systems in thermodynamic equilibrium are at the same
temperature.
• The kelvin (K) is the SI unit of temperature.
• Heat is energy in transit because of a temperature difference
alone.
• The heat required to heat an object by an amount ∆T
depends on its mass and its specific heat, c: Q = mc ∆T.
• Heat transfer mechanisms include conduction, convection,
and radiation.
• Thermal energy balance is a state in which the rate at
which energy is delivered to a system is equal to the rate at
which the system loses energy. A system in energy balance
maintains a constant temperature.
Chapter 14 Lecture
Chapter 17:
The Thermal
Behavior
of Matter

• To understand ideal gases by

using both experimental results
and Newtonian physics applied
to gas molecules
• How temperature and molecular
energy are related
• To describe the three principle
phases of matter
• To calculate the energies involved
in phase transitions
• To interpret phase diagrams
• To calculate thermal expansion
of solids, liquids, and gases

The Ideal-Gas Law
• Experiment shows that a gas of N molecules in a closed

container obeys a simple relation between pressure p,
volume V, and temperature T:
pV = NkT
• This is the ideal-gas law, and the
behavior of most real gases closely
approximates this ideal. A piston-cylinder system
−23
• Here k = 1.38 × 10 J / K is Boltzmann's constant.
• The ideal-gas law may also be written as
pV = nRT
where n is the number of moles of gas, and
R = N A k = 8.314 J / K ⋅ mol is the universal gas constant.

Kinetic Theory of the Ideal Gas
• The ideal-gas law follows by assuming a gas consists of
particles that obey Newton's laws. For analysis we assume
• N identical particles of mass m and no internal structure
• No intermolecular forces and molecules only have kinetic
energy
• Molecular motion is random
• Collisions with the wall of the container are elastic
• Gas pressure arises from the average force the particles
exert when they collide with the container walls.
Gas molecules confined to a rectangular box

• Consider the elastic collision shown in the figure:

• The magnitude of vx and vy do not change.
• During collision the magnitude of the change in
momentum is 2mvx.
• Collisions recur in a time 2L/vx.
• The average force exerted by the
ith particle is
2mvxi mvxi2
Fi = =
2L / vxi L
• Summing over N particles we obtain
F
p= =
∑ Fi =
∑ xi / L
mv 2
=
∑ xi
mv 2
=
m∑ vxi2
=
mN ∑ vxi mN 2
⋅
2
= vx
A A A AL V V N V
• The previous slide showed
• However, the molecules are moving randomly so their speeds

are independent of their direction of motion. Thus, we can
eliminate reference to the x-component by using
• Thus,
• Note that this is the ideal gas law if we make the substitution
The Maxwell-Boltzmann Distribution
• Molecules in a gas exhibit a range of speeds that result

from random collisions among the molecules.
• This is the Maxwell-Boltzmann distribution.
• At high temperatures the distribution is broader and
peaks at a higher speed.
• The average kinetic energy is
• The thermal speed is
where m is the molecular mass.

Phase Changes
• Most substances occur in three phases—solid, liquid, gas.

• It takes energy, called the heat of transformation, L, to
effect phase changes from solid to liquid and liquid to gas.
• Heat of transformation measures
the energy Q required to change
the phase of a mass m: Q = mL.
• Energy must be removed to go
the other way.
• The solid-liquid transition involves
the heat of fusion (熔化), Lf.
• The liquid-gas transition involves
the heat of vaporization (汽化), Lv.
• The direct transition from solid to gas involves the heat of
sublimation (昇華), Ls.
• During a phase change, temperature remains constant as
energy goes into breaking molecular bonds.
Phase Diagrams
• The phases of a substance can be displayed on a plot of pressure

versus temperature.
• Curves separate regions characterizing the different phases.
• The curves meet at the triple point,
where all three phases coexist in
equilibrium.
• The liquid-gas curve ends at the
critical point, where the sharp
distinction between liquid and
gas disappears.
• Different paths in the phase diagram
take the material through different
phase sequences:
– Path CD shows the familiar solid-liquid-gas transitions.
– Path AB goes directly from solid to gas.
– Path GH shows that changing pressure can result in phase
changes.
Phase diagram for water
~ 1atm
Thermal Expansion
• Most materials expand when heated.

• Liquids are best characterized by
the coefficient of volume
expansion, β, which is the
fractional change in volume per unit
temperature change:
• Solids are best characterized by the

coefficient of linear expansion, α,
which is the fractional change in
length per unit temperature change:
• Typical values are

Invar 36% nickel and 64% iron mass (不變鋼)
Charles Édouard Guillaume

Nobel Prize in Physics (1920)
The Anomalous Behavior of Water
Why? Homework
• Between 0˚C and 4˚C, water contracts on heating.
• This is a residual effect of the hydrogen bonds that form
ice crystals.
• The open structure of the ice crystal makes ice less dense
than liquid water.
• Hence solid water, unlike most substances, floats in its
liquid phase.
• This fact has enormous consequences for aquatic life.
Summary
• The ideal-gas law relates pressure, temperature, and

volume:
• Derivation of the ideal-gas law from Newtonian mechanics
shows that temperature measures the average kinetic
energy of the gas molecules.
• Phase changes take substances
between solid and liquid, liquid and
gas, solid and gas.
• Phase changes require energy,
described by the heats of
transformation.
• The phase structure of a substance
is described in its phase diagram.
• Thermal expansion occurs as most substances are heated.
• An exception is water in the range from 0˚C to 4˚C.
Chapter 14 Lecture
Chapter 18:
Heat, Work, and
the First Law of
Thermodynamics
Slide 20-1
• The first law of thermodynamics
and how it extends the principle of
conservation of energy to thermal
phenomena
• To understand the work and heat
involved in basic thermodynamic
processes:
– Isothermal
– Constant volume
– Isobaric
– Adiabatic
• To understand how molecular
structure determines the specific
heat of an ideal gas
Slide 20-2
How to make a balloon smaller or bigger ?
A pin or pump is NOT allowed!
Slide 20-3
Slide 20-4
Slide 20-5
1st law of thermodynamics
∆"!" = $ + &
change of system’s thermal energy.
internal energy.
()∆+
external work on the system(+) !"

or ! = − $ %&'
work done by the system(-). !!
Slide 20-6
The First Law of Thermodynamics
• Two ways to raise temperature:
• Thermally: flow of heat
• Energy flow resulting
from a temperature
difference
• Mechanically: doing work
• End result is the same for the same energy input:
• An increase ∆Eint in the system's internal energy Eint
• First law of thermodynamics
• Change in internal energy of a system is the heat added to the
system plus the work done on the system:
ΔEint = Q + W
• Extends conservation of energy to include thermal processes
Slide 20-7
Doing Work
• A piston-cylinder system is a useful device for describing the
thermodynamic behavior of a gas.
• The piston seals the cylinder, allowing the gas volume to change
without any gas escaping.
• Work can be done on or by the gas as the piston moves.
• If the bottom is uninsulated, heat can flow in or out.
• The work done on the gas is the negative of the area under the pV
curve: V2
W = − ∫ p dV
V1
Slide 20-8
Reversible and Irreversible Processes
• Changing the state of a system can be done
• Reversibly
• In which case the system remains
always in thermodynamic equilibrium
and follows a path in its
pressure-versus-volume (pV) diagram.
– Any process carried out slowly enough
to be quasi-static is reversible.
– It's possible to reverse the system's path
in its pV diagram.
• Irreversibly
• In which case the system goes temporarily out of equilibrium,
without well-defined values for temperature, pressure, and other
quantities.
– Although the system has no well-defined path in the pV diagram, it
may end up in a definite state, back in equilibrium.
Slide 20-9
Four ideal gas processes
Slide 20-10
Isothermal Processes and the Ideal Gas
• An isothermal process takes place at
constant temperature.
• One way to achieve this is to keep the
system in thermal contact with a heat
reservoir — a much larger system held at
constant temperature.
• The ideal gas law gives P = nRT/V.
• Then, with constant T, the work done is
dV
( )
V2 V2
W = − ∫ p dV = −nRT ∫ = −nRT ln V2 V1
V1 V1 V
• Since the temperature doesn't change,
neither does the internal energy of an ideal
gas. Therefore the first law gives
Q = −W = nRT ln V2 V1( )
Slide 20-11
Constant-Volume Processes
• In a constant-volume process (also called isometric, isochoric,

or isovolumic), the heat added to the gas and the resulting
temperature change are related by
Q = nCV ∆T
• Here CV is the molar specific heat at constant volume.
• Its units are J/K·mol.
• No work is done in a constant-volume process, so W = 0 and
the first law reads ∆Eint = Q.
• Therefore ∆Eint = nCV ∆T.
• For an ideal gas, internal energy depends on temperature
alone, so this relationship ∆Eint = nCV ∆T between ∆Eint
and ∆T holds for any process. The internal energy of ideal
gas can always be represented by constant-volume process.
Slide 20-12
Isobaric Processes
• An isobaric process takes place at constant pressure.
• Then the work done (on the gas) is W = –p ∆V.
• Adding heat to an ideal gas results both in a temperature change and in
work being done.
• Therefore it takes more heat to
effect a given temperature change:
Q = nCV ΔT + pΔV
• The molar specific heat at
constant pressure, Cp, expresses
this extra work (using pΔV = nRΔT):
nCp ΔT = nCV ΔT + nRΔT
• Thus Cp = CV + R.
ΔEint = Q + W
∆,"# = ! + . %∆' = /1∆+
/)$ ∆+ = −%∆' + . → . = /)$ ∆+ + %∆' = /)% ∆+ → )% = )$ + 1
Slide 20-13
Ideal-Gas Processes: a Comparison
Slide 20-14
Slide 20-1
Section 20.4: PV diagrams and processes
• Let us now turn our

attention to the
transformation of a system
from one equilibrium state
to another via a quasistatic
process.
• During a quasistatic
process, the system
remains near equilibrium
at all instants.
• Such a process can be
represented by a
continuous path on a
PV diagram.
© 2015 Pearson Education, Ltd. Slide 20-2
Isobaric process
∆𝐸 = 𝑊 + 𝑄
𝑛𝐶 ∆𝑇 = −𝑃∆𝑉 + 𝑛𝐶 ∆𝑇

Isobaric process
∆𝐸 = 𝑊 + 𝑄
𝑛𝐶 ∆𝑇 = 𝑃∆𝑉 + 𝑛𝐶 ∆𝑇
𝑊 = −𝑃∆𝑉
𝑄 = 𝑛𝐶 ∆𝑇

The change of internal energy is
path-independent.
𝑑
∆𝐸 = 𝑁𝑘 𝑇 −𝑇
2
Only depends on the temperature
of initial state and final state.
d: degrees of freedom Slide 20-5

Lecture Outline
Chapter 19
Entropy

Chapter 19: Entropy
Chapter Goal: Study the causes for the observed

irreversibility of many physical phenomena and
understand that the concept of entropy is connected
to our sense of irreversibility.
Section 19.1: States
Two issues:
(1) how to distribute energy?
(2) how to distribute space?
Slide 20-8
Energy distribution
Slide 20-9
• Now consider a swinging pendulum

inside a box containing three
indistinguishable gas particles.
• Quantum mechanics tells us that the
energy of a confined system can
only change by discrete units called
quanta.
• Let us assume that there are six
identical energy units to be
distributed among the pendulum
and the three particles.
• We will further assume that the
collisions distribute the energy units
randomly throughout the system.

Distribute 6 identical balls to 4 different boxes.
• If we describe the system’s macrostate by the number of energy
units in the pendulum, then there are 7 macrostates.
• The figure shows how, for each of the macrostates, the energy units
can be distributed.

Slide 20-12
• Since collisions are

randomized, each
basic state is equally
likely to occur.
• Because there are 84
likely basic states, the
probability of any one
basic state is 1/84.
• The figure shows how
the probability of a
given macrostate
depends on the
fraction of energy in
the pendulum.
• The graph shows what

happens if we increase the
number of particles.
• We can see that the relative
probability of all 50 energy
units in the pendulum
drops precipitously.
• With 100 particles, this
probability drops to 10–40.
• So, if we release a
pendulum in a box
containing many particles,
the mechanical energy of
the pendulum will transfer
to the particles.
Section 19.2: Equipartition of energy
Section Goal
You will learn to
• Establish the concept of equipartition of energy as
resulting from randomization the energy exchanges
that occur between particles in a system via
interactions.

• Suppose now instead of a

pendulum and three
particles, we have four gas
particles inside the box.
• As illustrated in the figure,
the configuration of
macrostates and basic states
is identical to the previous
case of the pendulum.
• On average, each part of
the system has an equal
share E/4 if the system’s
energy E.

Energy expectation value: Equipartition
1 3 6 10 15 21 28 6
×6+ ×5+ ×4+ ×3+ ×2+ ×1+ ×0=
84 84 84 84 84 84 84 4
equipartition of energy!
Slide 20-17
• This situation is the same for the pendulum and three

particles, or if we replace the pendulum with some
other object.
• Therefore we can state:
• As long as the interactions between different
parts of a system randomize the distribution of
energy, each part of the system tends to have
equal share of the system’s energy.
• This equal distribution of energy among the parts of a
system is called equipartition of energy.

Section 19.3: Equipartition of space
Space distribution
Slide 20-19
Section Goal
You will learn to
• Establish the concept of equipartition of space as
resulting from randomization of the energy exchanges
that occur between particles in a system via
interactions.

• Consider the figure, where one half of the container has gas in it and
the other is a vacuum, separated by a partition.
• When the partition is removed, the gas expands irreversibly into the
vacuum.
• This irreversible diffusion is due to the incoherent motion of
particles.

• Now consider a box containing

six identical particles.
• Assume that the container is
divided into four equal
compartments, as shown.
• Let us define the macrostate of
the system as the number of
particles in the upper left
compartment.
• If all six particles are in the
upper left compartment, then
the basic state is specified by
(6,0,0,0).
Example 19.5 Particles in a box

Use the data in Figure
19.12 to determine the
average number of
particles in the top left
compartment of the
four-compartment box
shown there.

• Determining the distribution of six particles in four

compartments is identical to the energy distribution in
the previous section and is illustrated in the table.
• The tendency to distribute particles uniformly over
space is called equipartition of space.

Section 19.4: Evolution toward the most probable
macrostate
• As the previous checkpoint illustrated, only the
neighboring macrostates are accessible to the system
after each collision.
• If we start with all the energy in the pendulum, the
system can only gradually evolve toward the most
probable macrostate.
• Once the system reaches the most probable
macrostate, it will remain near this state.
• The macrostate that has the greatest number of
microstates and is therefore the most probable
macrostate is the equilibrium state.
macrostate
• To get a better
understanding of the 10 units of energy
evolution of a system
toward equilibrium, let
us consider 20 particles
in a box that is divided
into two compartments.
• The partition while
preventing particles from
crossing from one
compartment to the next,
allows exchange of
energy via collisions. 14 particles 6 particles

macrostate
• Suppose A contains 14 particles, B contains 6
particles, and the box contains 10 units of energy.
• The number of basic states associated with each
compartment is represented by Ω.
10 units of energy

macrostate

macrostate
• For a given macrostate, the
number Ω of basic states
available to the system is
Ω = Ω A Ω B.
• The probability of each
macrostate is obtained by
dividing Ω by Ω tot.
• The figure shows this
probability as a function of
the fraction of energy.

macrostate
• Because the number of
basic states is a very
large number, it is more
convenient to work
with natural logarithms.
• The figure illustrates
how ln(Ω A), ln(Ω B),
and ln(Ω) vary with the
number of energy units
in compartment A.
• We can see that the
number of basic states
is a maximum when the
energy is
equipartitioned.
macrostate
• The irreversible evolution of a system toward
equilibrium can be quantified by the number of basic
states Ω :
• A closed system always evolves so as to
maximize the number of basic states Ω.
• When this number has reached a maximum,
the system is at equilibrium.
• The irreversible tendency of a closed system to
maximize Ω is called the second law of
thermodynamics.
Why it happens? Because chance is HIGH!!
Lecture Outline
Chapter 20
Energy
Transferred
Thermally
Slide 20-32
Chapter 19: Entropy
microscopic Macroscopic
connection
atomic parameters volume (V)

position pressure (P)
velocity temperature (T)
so on…
Section 19.5: Dependence of entropy on volume
• To count the basic states,

let us divide the
container into M equal-
sized compartments.
• The number of basic
states for the N particles
in the container is
Ω = MN(closed system)
Each particle has M choices.
Slide 20-34
• Entropy is a unitless quantity that is a measure of the

number of basic states in a system. It is defined as
S ≡ ln Ω.
• For a closed system evolving toward equilibrium,
ΔS > 0 (closed system evolving toward equilibrium)
• For a closed system at equilibrium, Ω = Ω max and
ΔS = 0 (closed system at equilibrium)
• The second and third equations are a mathematical
expression of the second law of thermodynamics,
called the entropy law.

• For a system of N gas particles equipartitoned over a volume V,

S = ln Ω = ln(MN ) = N ln M
• If the volume of these equal sized compartments is ΔV, then
S = N ln(V/ΔV) = N ln V – N ln ΔV
• If the volume of the gas changes from Vi to Vf, then the entropy
change of the gas is
ΔS = Sf – Si = (N ln Vf – N ln ΔV ) – (N ln Vi – N ln ΔV)
= N ln Vf – N ln Vi = N ln  Vf  (closed system at equilibrium)

 V 
i
Slide 20-36
• Consider two gases inside a

container with a partition separating
the gases, as shown.
• The number of basic states of the
system is Ω = Ω A Ω B.
• Using the definition of entropy we
get
S = ln (Ω A Ω B)
= ln Ω A + ln Ω B = SA + SB
• The entropy of a combined system
is the sum of the entropies of the
individual systems.
Section 19.6: Dependence of entropy on energy
(kinetic energy)
Section Goals
You will learn to
• Define the root-mean-square speed and thermal
equilibrium for a system of identical particles.
• Derive the relationship between average kinetic
energy and thermal energy for a monatomic ideal
gas.
• Define the absolute temperature for a system from
the entropy perspective.

(kinetic energy)
• Let us now calculate how entropy depends on the
energy of the system.
• We will restrict ourselves to ideal gases.
• The incoherent kinetic energy of all atoms makes up
the internal energy of a gas.
• A single atom moving at speed v contributes 2 1
m u 2
to
Eth.
• A basic state is specified by the components vx, vy,
and vz of all N atoms.

(kinetic energy)
• We will divide the available
“velocity space” shown in the
figure into small
compartments and count the
number of ways we can
distribute N atoms among
these compartments.
• To determine the available
velocity space, we introduce
the root-mean-square speed,
or the rms speed:
u rms º (u 2 )av
• where (v2)av is the average of
the square of the speeds of all
atoms.
(kinetic energy)
1 1 ∑ 𝑣 1
𝐸 = 𝑚𝑣 = 𝑁 𝑚 = 𝑁 𝑚𝑣
2 2 𝑁 2
r1 m v2
m
r2
v1
∑ 𝑣⃑ 2𝐸 vy
𝑣 = =
𝑁 𝑚𝑁
vx
(kinetic energy)
• To determine the volume of the velocity space, let us start by
assuming that –avrms ≤ vx ≤ avrms, and likewise for y and z.
• Then velocities of all atoms in our system lies within the cube of
volume shown in the figure.

(kinetic energy)
• The average kinetic energy Kav of one atom is
Eth
Kav º 2 m(u )av = 2 mu rms =
1 2 1 2
(monatomic ideal gas)
N
• Now we can rewrite rms speed as
1/ 2
 2Eth 
rms   
 mN 
• So we see that the volume of velocity
1/2 3
  2 Eth  
 (2arms )   2a  3
 
  mN  
3/2
 8a  2
  ( Eth )3/ 2  b( Eth )3/2
 mN 

(kinetic energy)
• Now we divide the velocity space volume into smaller
compartments. The number of velocity-space compartment is
b
Mu = = (Eth )3/ 2
dE dE
• Then the number of ways we can distribute N distinguishable atoms
in these Mv compartments is
dE
S  ln Wu = N ln Eth - N ln
3
2
(monatomic ideal gas at
b equilibrium)
• Now, if the thermal energy of the gas changes from Eth,i to Eth,f, the
resulting entropy change is
 Eth,f 
S  Sf  Si  N ln Eth,f  N ln Eth,i
3
2
3
2  N ln 
3
2 
 Eth,i 
∆𝐸 = ∆𝑊 + ∆𝑄
internal energy.
external work on the system(+)

or ∆𝑊 = − 𝑃𝑑𝑉
work done by the system(-).
Slide 20-45
2nd law of thermodynamics
for an isolated system
Δ𝑆 ≥ 0
arrow of time, only ONE way!
(P1, V1, T1) Ω = 1
(P2, V2, T2) Ω = 3
(P3, V3, T3) Ω = 10
Slide 20-46
Entropy for ideal gas
Distribute N particles
into phase space.
Ω∝𝑉 𝐸
𝑉 x 𝐸
real space volume velocity space volume
d: degrees of freedom phase space

Slide 20-47
What is degrees of freedom?
𝑥, 𝑦, 𝑧
d=3 𝑉 ,𝑉 ,𝑉
𝑥, 𝑦
d=2 𝑉 ,𝑉
𝑥
d=1 𝑉
Slide 20-48
Lecture Outline
Chapter 20
Energy
Transferred
Thermally
Slide 20-1
Slide 20-2
∆𝐸 = ∆𝑊 + ∆𝑄
internal energy.
external work on the system(+)

or ∆𝑊 = − 𝑃𝑑𝑉
work done by the system(-).
Slide 20-3
Δ𝑆 ≥ 0
(P1, V1, T1) Ω = 1
(P2, V2, T2) Ω = 3
(P3, V3, T3) Ω = 10
Slide 20-4
into phase space.
Ω∝𝑉 𝐸
𝑉 x 𝐸

Slide 20-5
What is degrees of freedom?
𝑥, 𝑦, 𝑧
d=3 𝑉 ,𝑉 ,𝑉
𝑥, 𝑦
d=2 𝑉 ,𝑉
𝑥
d=1 𝑉
Slide 20-6
𝑆 = 𝑙𝑛 Ω
= 𝑁𝑙𝑛 𝑉 + 𝑁𝑙𝑛 𝐸 +A
𝑑
= 𝑁𝑘 𝑇 at equilibrium
𝐸
2 𝑑
= 𝑁𝑙𝑛 𝑉 + 𝑁𝑙𝑛 𝑇 +B
2
𝑉 𝑑 𝑇 𝑉 𝑑 𝐸
∆𝑆 = 𝑁𝑙𝑛 + 𝑁𝑙𝑛 = 𝑁𝑙𝑛 + 𝑁𝑙𝑛
𝑉 2 𝑇 𝑉 2 𝐸
d: degrees of freedom Slide 20-7

into phase space.
Ω∝𝑉 𝐸
𝑉 x 𝐸

Slide 20-8
Isentropic processes Δ𝑆 = 0
𝑉𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉 x 𝐸

phase space
Slide 20-9
𝑉𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉 x 𝐸

phase space
Slide 20-10
𝑉𝐸 = 𝑐𝑜𝑛𝑠𝑡.
𝑉𝑇 = 𝑐𝑜𝑛𝑠𝑡.
𝑑
𝑃 𝑉 = 𝑐𝑜𝑛𝑠𝑡. 𝐸 = 𝑁𝑘 𝑇
𝑃𝑉 2
𝑃 𝑉 =𝑇
𝑁𝑘
𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡.
2
𝛾 =1+
𝑑
Slide 20-11
Isentropic processes
Quantitative Tools: Entropy in ideal gas

processes
• For any isentropic process:
g -1 g -1
TiVi = TfVf
g g
PiVi = PfVf
1 -1 1 -1
Pi Ti = Pf Tf .
g g

Work for Isentropic processes Δ𝑆 = 0
𝑃𝑉 = 𝑐 → 𝑃 = 𝑐𝑉
v1 5ǎ
𝑉 −𝑉 𝑃 𝑉 −𝑃 𝑉
𝑊=− 𝑃 𝑑𝑉 = −𝐶 𝑉 𝑑𝑉 = −𝐶 =−
1−𝛾 1−𝛾
𝑛𝑅 𝑇 − 𝑇 𝑛𝑅𝑑 𝑇 − 𝑇
= =−
𝛾−1 2
Work depends only on initial

and final temperature along
isentropic processes.
Slide 20-13
Diesel engine 1
Fuel ignites in a diesel engine because of the temperature rise

that results from compression as the piston moves toward the top
of the cylinder; there's no spark plug as in a gasoline engine.
Compression is fast enough that the process is essentially
adiabatic. If the ignition temperature is 500°C, what compression
ratio 𝑉 /𝑉 is needed? Air's specific-heat ratio is 𝛾 = 1.4, and
before compression the air is at 20°C.
Slide 20-14
Diesel engine 1
Fuel ignites in a diesel engine because of the temperature rise

that results from compression as the piston moves toward the top
of the cylinder; there's no spark plug as in a gasoline engine.
Compression is fast enough that the process is essentially
adiabatic. If the ignition temperature is 500°C, what compression
ratio 𝑉 /𝑉 is needed? Air's specific-heat ratio is 𝛾 = 1.4, and
before compression the air is at 20°C.
𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡.
𝑇𝑉 =𝑇𝑉
𝑉 𝑇 𝑉 𝑇 773 .
= → = = = 11.3
𝑉 𝑇 𝑉 𝑇 293
Slide 20-15
Diesel engine 2
Air at 20.0°C in the cylinder of a diesel engine is compressed

from an initial pressure of 1.00 atm and volume of 800 cm3 to a
volume of 60 cm3. Assume that air behaves as an ideal gas with
𝛾 = 1.4 and that the compression is adiabatic. Find the final
pressure and temperature of the air.
Slide 20-16
Diesel engine 2

(1) the final pressure:
𝑃𝑉 =𝑃 𝑉
.
𝑃 =𝑃 =1 = 37.6 atm
Slide 20-17
Diesel engine 2

(2) the final temperature :
𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡.
𝑇𝑉 =𝑇𝑉
.
𝑉 800
𝑇 =𝑇 = 293 = 825.74𝐾
𝑉 60
Slide 20-18
Isothermal process
A scuba diver is 25 m down, where the pressure is 3.5 atm or

about 350 kPa. The air she exhales forms bubbles 8.0 mm in
radius. How much work does each bubble do as it rises to the
surface, assuming the bubbles remain at the uniform 300 K
temperature of the water?
Slide 20-19
Isothermal process
A scuba diver is 25 m down, where the pressure is 3.5 atm or

about 350 kPa. The air she exhales forms bubbles 8.0 mm in
radius. How much work does each bubble do as it rises to the
surface, assuming the bubbles remain at the uniform 300 K
temperature of the water?
𝑉 𝑃
𝑃𝑉 =𝑃𝑉 → =
𝑉 𝑃
𝑉 𝑃
𝑊 = −𝑛𝑅𝑇𝑙𝑛 = −𝑃 𝑉 𝑙𝑛
𝑉 𝑃
4 3.5
= −350 × 1000 × 𝜋 8 × 10 𝑙𝑛 = −0.94𝐽
3 1
Slide 20-20
Cyclic process
An ideal gas with 𝛾 = 1.4 occupies 4.0 L at 300 K and 100 kPa
pressure. It's compressed adiabatically to one-fourth of its original
volume, then cooled at constant volume back to 300 K, and finally
allowed to expand isothermally to its original volume. How much
work is done on the gas?
Is w
0ˇ9 Ith
nkthǚ
∆𝑉 = 0 pV5 const
Pzkh4
∆𝑆 = 0
100.4h4
∆𝑇 = 0
1w 笇4 696.44clapy 554.517
696.44 1 100.4
W
741 555
1.4 1
17
oii44 741.1 Slide 20-21
1
Cyclic process
An ideal gas with 𝛾 = 1.4 occupies 4.0 L at 300 K and 100 kPa
pressure. It's compressed adiabatically to one-fourth of its original
volume, then cooled at constant volume back to 300 K, and finally
allowed to expand isothermally to its original volume. How much
.
work is done on the gas? 𝑃 = 𝑃 = 100 = 696.4kPa
𝑃 𝑉 −𝑃 𝑉 696.4 × 1 − 100 × 4
𝑊 =− =
∆𝑉 = 0 1−𝛾 1.4 − 1
∆𝑆 = 0 = 741𝐽
∆𝑇 = 0
𝑊 =0
𝑉 4
𝑊 = −𝑛𝑅𝑇𝑙𝑛 = −𝑃 𝑉 𝑙𝑛 = −555𝐽
𝑉 1
𝑊 =𝑊 +𝑊 +𝑊 = 740 − 555 = 186J
Slide 20-22
Lecture Outline
Chapter 20
Energy
Transferred
Thermally
Slide 20-1
Slide 20-2
∆"!" = ∆$ + ∆&
internal energy.
external work on the system(+) !"

or ∆" = − % &'(
work done by the system(-). !!
Slide 20-3
Δ( ≥ 0
(P1, V1, T1) Ω = 1
(P2, V2, T2) Ω = 3
(P3, V3, T3) Ω = 10
Slide 20-4
2
- =1+
'

Section 20.4: PV diagrams and processes
• The figure shows four important constrained

quasistatic processes in ideal gases that we will study
next.

Carnot Efficiency
(Thermal energy becomes work)
• The efficiency of an engine, defined as the ratio of work
delivered to heat extracted from the hot reservoir, is
W Qh − Qc Qc
e= = = 1−
Qh Qh Qh
• For a Carnot engine,
Qc/Qh = Tc/Th, and the
efficiency is
W Tc
eCarnot = = 1−
Qh Th

The Carnot Engine
• A conceptually important heat-engine design is
the Carnot engine, whose cycle consists of two
adiabatic and two isothermal steps.
∆" = 0
∆% = 0
∆% = 0
∆" = 0
Proof of Carnot Efficiency 0"#$%&' = 1 − 1( = 1 − 2(
1) 2)
"#(
"(*
1( 2(
0"#$%&' =1− =1−
1) 2)
Proof of Carnot Efficiency
0 = − "#* + "*( + "(, + ",# /1#*
(* 34 2" − 2+ (, 34 2+ − 2"
−342+ 53 + − 342" 53 +
(# -−1 (( -−1
=−
(*
342+ 53
(#
(* (,
−342+ 53 ( − 342" 53 (
# (
=−
(*
342+ 53 (
#
-./ -./
2+ (* = 2" (( (* ((
2( -./ = 67389. → < -./ -./ → =
2+ (# = 2" (, (# (,
(* ((
342+ 53 ( − 342" 53 ( 2(
# ,
0"#$%&' = =1−
(* 2+
342+ 53
(#
Carnot's Theorem
• Carnot's Theorem: All Carnot engines operating between the

temperatures Th and Tc have the same efficiency,
Tc
eCarnot = 1−
Th
and no other engine operating between the same two temperatures
can have a greater efficiency.
First Law & Entropy
'1 = '> − '"
3@2'(
'1 = 3?0 '2 +
(
'1 '2 3@'(

= 3?0 +
2 2 (
2 2 22 (2
'1
% = % 'A = 3?0 53 + 3@53
1 2 1 21 (1
22 (2 ' 22 (2
∆A = 3?0 53 + 3@53 = 3 @53 + 3@53
21 (1 2 21 (1
' '
∆A = 0 → ∆1 = 0 ?0 = @ ?3 = ?0 + @ = @ + @
2 2
First Law & Entropy
'1 = '> + &'(
342'(
'1 = 3?0 '2 +
(
'1 '2 34'(

= 3?0 +
2 2 (
2 2 22 (2
'1
% = % 'A = 3?0 53 + 3453
1 2 1 21 (1
22 (2 ' 22 (2
∆A = 3?0 53 + 3453 = 3 453 + 3453
21 (1 2 21 (1
' '
∆A = 0 → ∆1 = 0 ?0 = 4 ?3 = ?0 + 4 = 4 + 4
2 2
2nd law again
∆A ≥ 0
In a reversible process the entropy of an isolated system stays
constant; in an irreversible process the entropy increases.

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Chapter 14 Lecture

© 2016 Pearson Education, Ltd.

• A precise definition of temperature

© 2016 Pearson Education, Ltd.

• One of the most versatile thermometers is the constant-

• The current SI temperature scale is defined using the triple point of

Two points establish the kelvin temperature scale

• Heat is energy being transferred from one object to

• When two substances at different temperatures are

• Conduction is heat transfer through direct physical contact.

© 2016 Pearson Education, Ltd.

• A system is in thermal energy balance when its rate of

A house in thermal-energy balance

d Sun surface temperature: T=?

d Sun surface temperature: T=5778K

d Sun surface temperature: T=5778K

• INTERPRET: This is a problem about energy balance.

• Earth absorbs energy from the Sun at the

© 2016 Pearson Education, Ltd.

• INTERPRET: This is a problem about energy balance.

• ASSESS: Makes sense? This temperature (–18ºC or 0ºF)

© 2016 Pearson Education, Ltd.

• Thermodynamic equilibrium is the state reached when

© 2016 Pearson Education, Ltd.

• To understand ideal gases by

© 2016 Pearson Education, Ltd.

• Experiment shows that a gas of N molecules in a closed

© 2016 Pearson Education, Ltd.

Gas molecules confined to a rectangular box

• Consider the elastic collision shown in the figure:

• The previous slide showed

• However, the molecules are moving randomly so their speeds

• Molecules in a gas exhibit a range of speeds that result

• The thermal speed is

where m is the molecular mass.

• Most substances occur in three phases—solid, liquid, gas.

• The phases of a substance can be displayed on a plot of pressure

• Most materials expand when heated.

• Solids are best characterized by the

• Typical values are

Charles Édouard Guillaume

• The ideal-gas law relates pressure, temperature, and

A pin or pump is NOT allowed!

external work on the system(+) !"

• In a constant-volume process (also called isometric, isochoric,

• Let us now turn our

© 2015 Pearson Education, Ltd. Slide 20-3

© 2015 Pearson Education, Ltd. Slide 20-4

d: degrees of freedom Slide 20-5

© 2015 Pearson Education, Ltd. Slide 20-6

Chapter Goal: Study the causes for the observed

• Now consider a swinging pendulum

© 2015 Pearson Education, Ltd. Slide 20-10

© 2015 Pearson Education, Ltd. Slide 20-11

• Since collisions are

• The graph shows what

© 2015 Pearson Education, Ltd. Slide 20-15

• Suppose now instead of a

© 2015 Pearson Education, Ltd. Slide 20-16

• This situation is the same for the pendulum and three

© 2015 Pearson Education, Ltd. Slide 20-18

© 2015 Pearson Education, Ltd. Slide 20-20

© 2015 Pearson Education, Ltd. Slide 20-21

• Now consider a box containing