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Chapter 18. The Micro/Macro Connection Chapter 18. The Micro/Macro Connection
Heating the air in a hot-air
Topics:
balloon increases the thermal
energy of the air molecules. •  Molecular Speeds and Collisions
This causes the gas to •  Pressure in a Gas
expand, lowering its density and •  Temperature
allowing the balloon to float in •  Thermal Energy and Specific Heat
the cooler surrounding air. •  Thermal Interactions and Heat
Chapter Goal: To understand •  Irreversible Processes and the Second Law
the properties of a macroscopic of Thermodynamics
system in terms of the
microscopic behavior of its
molecules.
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Molecular Speeds and Collisions Molecular Speeds and Collisions

•  A gas consists of a vast number of molecules, each

moving randomly and undergoing millions of
collisions every second.
•  Despite the apparent chaos, averages, such as the
average number of molecules in the speed range
600 to 700 m/s, have precise, predictable values.
•  The micro/macro connection is built on the idea
that the macroscopic properties of a system,
such as temperature or pressure, are related to
the average behavior of the atoms and molecules.

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Molecular Speeds and Collisions Mean Free Path

If a molecule has Ncoll collisions as it travels distance L,

the average distance between collisions, which is called
the mean free path λ (lowercase Greek lambda), is

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The table shows the properties of four gases, each

having the same number of molecules. Rank in
order, from largest to smallest, the mean free paths
of molecules in these gases.
Gas A B C D
Volume V 2V V V
Atomic mass m m 2m m
Atomic radius r r r 2r

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The table shows the properties of four gases, each EXAMPLE 18.1 The mean free path at room
having the same number of molecules. Rank in temperature
order, from largest to smallest, the mean free paths
of molecules in these gases. QUESTION:
Gas A B C D
Volume V 2V V V
Atomic mass m m 2m m
Atomic radius r r r 2r

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EXAMPLE 18.1 The mean free path at room EXAMPLE 18.1 The mean free path at room
temperature temperature

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Pressure and Collisions of Molecules Pressure in a Gas

The pressure on the wall of a container due to all the
molecular collisions is

This expresses the macroscopic pressure in terms of the

microscopic physics. The pressure depends on the density
Impulse momentum theorem gives: of molecules in the container and on how fast, on average,
Favg Δt = Δpx the molecules are moving.
N coll
Favg = 2 mvx
Δt
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Root-mean-square speed
The speed of every molecule in a gas is
suddenly increased by a factor of 4. As a
result, vrms increases by a factor of

A.  2.
vrms = (v ) 2
avg
B.  <4, but not necessarily 2.
C.  4.
vrms = (v 2
x + vy2 + vz2 ) avg
D.  >4 but not necessarily 16.
E.  16.
1 N 2
vrms = ∑ vi
N i =1
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Temperature in a Gas
The speed of every molecule in a gas is
•  The thing we call temperature measures the average
suddenly increased by a factor of 4. As a
translational kinetic energy of molecules in a gas.
result, vrms increases by a factor of •  A higher temperature corresponds to a larger value of єavg
and thus to higher molecular speeds.
A.  2. •  Absolute zero is the temperature at which єavg and all
B.  <4, but not necessarily 2. molecular motion ceases.
C.  4. •  By definition, єavg = ½mvrms2, where vrms is the root mean
D.  >4 but not necessarily 16. squared molecular speed. Using the ideal-gas law, we
E.  16. found єavg = 3/2 kBT.
•  By equating these expressions we find that the rms speed
of molecules in a gas is

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Which system has the largest average Which system has the largest average
translational kinetic energy per translational kinetic energy per
molecule? molecule?

A.  2 mol of He at p = 2 atm, T = 300 K A.  2 mol of He at p = 2 atm, T = 300 K

B.  2 mol of N2 at p = 0.5 atm, T = 450 K B.  2 mol of N2 at p = 0.5 atm, T = 450 K
C.  1 mol of He at p = 1 atm, T = 300 K C.  1 mol of He at p = 1 atm, T = 300 K
D.  1 mol of N2 at p = 0.5 atm, T = 600 K D.  1 mol of N2 at p = 0.5 atm, T = 600 K
E.  1 mol of Ar at p = 0.5 atm, T = 450 K E.  1 mol of Ar at p = 0.5 atm, T = 450 K

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Typical values Thermal Energy for Monatomic Gases

vrms ≈ 500 m/s (nitrogen at room Eth = K micro = N ε avg

temperature)
3 3
Eth = N kBT = nRT
Laser cooling cools molecules to T < 1 µK ⇒ vrms ≈ 1.4 cm/s 2 2
3 3
ΔEth = nRΔT = nCV ΔT ⇒ CV = R = 12.5 J/mol K
2 2
Mean time between collisions: τ coll ≈ 45 ns

1 nanosecond = 1 billionth of a second

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The Equipartition Theorem Thermal Energy for Solids

1 2 1 2 1 2
ε= mvx + mvy + mvz A total of six degrees of
2 2 2 freedom:
• Three degrees of freedom from translational kinetic energy 3 ways they can vibrate
• Rotation and vibration are other modes, or degrees of freedom (they cannot get translated)
3 modes kinetic energy
3 modes potential energy
Eth = 3NkBT = 3nRT
ΔEth = 3nRΔT = nCΔT ⇒ C = 3R = 25.0 J/mol K

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Dulong-Petit and Debye Models Thermal Energy and Diatomic Gases

8 degrees of freedom:
3 translational
3 rotational
2 vibrational (kinetic
Model Dulong-Petit Debye +potential)
Statistics Maxwell- Bose-Einstein
Boltzman
Eth = 4NkBT = 4nRT
Temperatures T>TD All
ΔEth = 4nRΔT = nCV ΔT
CV = 4R = 33.2 J/mol K
Source: http://hyperphysics.phy-astr.gsu.edu/hbase/solids/phonon.html

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Thermal Energy and Diatomic Gases Thermal Energy Summary

At room temperature:

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Thermal Interactions and Heat Thermal Interactions and Heat

•  Consider a rigid, insulated container divided into two
sections by a very thin, stiff membrane. The left side,
which we’ll call system 1, has N1 atoms at an initial
temperature T1i. System 2 on the right has N2 atoms at an
initial temperature T2i.
•  The membrane is so thin that atoms can collide at the
boundary as if the membrane were not there, yet it is a
barrier that prevents atoms from moving from one side to
the other.
•  System 1 and system 2 begin with thermal energies

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Thermal Interactions and Heat Systems A and B are interacting

thermally. At this instant of time,

A.  TA > TB.

B.  TA < TB.
C.  TA = TB.
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Systems A and B are interacting

thermally. At this instant of time,

2nd Law of thermodynamics

A.  TA > TB.

B.  TA < TB.
C.  TA = TB.
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Atomic Level Processes Macroscopic Processes

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Irreversible Processes

•  You cannot see transfer of heat from Cold to

Hot Reversible atomic processes lead to
•  You can easily mix sugar and coffee, irreversible macroscopic processes!
separating them is not spontaneous
•  Shake marbles of different colors to mix them,
if you keep shaking they won’t separate

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Transferring balls At equilibrium, what can say about the

approximate number of balls in each box?
A)  N1≈N2
B)  N1>N2
C)  N1<N2
D)  Any of them is equally likely

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Two identical boxes each contain 1,000,000

molecules. In box A, 750,000 molecules happen
to be in the left half of the box while 250,000 are
in the right half. In box B, 499,900 molecules
Reversible atomic processes lead to happen to be in the left half of the box while
500,100 are in the right half. At this instant of
irreversible macroscopic processes time,
because some macroscopic states are A. the entropy of box A is larger than the
vastly more probable than others. entropy of box B.
B. the entropy of box A is smaller than the
entropy of box B.
C. the entropy of box A is equal to the
entropy of box B.
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Two identical boxes each contain 1,000,000 Order, Disorder, and Entropy
molecules. In box A, 750,000 molecules happen
to be in the left half of the box while 250,000 are •  Scientists and engineers
in the right half. In box B, 499,900 molecules use a state variable called
happen to be in the left half of the box while entropy to measure the
500,100 are in the right half. At this instant of probability that a
time, macroscopic state will
occur spontaneously.
A. the entropy of box A is larger than the •  It is often said that
entropy of box B. entropy measures the
B. the entropy of box A is smaller than the amount of disorder in a
entropy of box B. system.
C. the entropy of box A is equal to the
entropy of box B.
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The Second Law of Thermodynamics

Establishing the “arrow of time” is one of the most profound

implications of the second law of thermodynamics.
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