Richard Thomas - FK4005 “Thermodynamik” - Solutions to ...

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 1
• 1.9: What is the volume of one mole of air, at room temperature and 1 atm pressure.
From the ideal gas law, we have PV = nRT. Therefore:
V
= nRT
P
V ≈ 0.025 m 3 ≈ 25 L
=
(1 mol)(8.31 J/mol/K)(300 K)
(10 5 N/m 2 )
• 1.10: Estimate the number of air molecules in an average-sized room.
Consider that an average room is about 4 metres squared and 3 metres high. The number
of air molecules (at the standard room temperature and pressure) is
which is about 2000 moles.
N =
PV
k B T = (105 N/m 2 )(4 × 4 × 3 m 3 )
(1.38 × 10 −23 J/K)(300 K)
N = 1.2 × 10 27 ≈ ×10 27
• 1.11: Rooms A and B are the same size, and are connected by an open door. Room A,
however, is warmer (perhaps because its windows face the sun). Which room contains the
greater mass of air? Explain carefully.
Pressure is the same in both because they are connected by an open doorway; if the pressure
were different then a wind would blow from one room to the other. The volume of both rooms
is also the same. Therefore P A V A = P B V B and, given the ideal gas law, N A kT A = N B kT B
as well. Thus the cooler temperature room has the higher number of molecules, and thus
the greater mass.
• 1.12: Calculate the average volume per molecule for an ideal gas at room temperature and
atmospheric pressure. Then take the cube root to get an estimate of the average distance
between molecules. How does this distance compare to the size of a small molecule like N 2
or H 2 O?
The volume per molecule for an ideal gas at room temperature and atmospheric pressure is:
V
N
= k BT
P = (1.38 × 10−23 J/K)(300 K)
10 5 N/m 2
V
N = 4.1 × 10−26 m 3 ≈ 41 nm 3
The average distance between molecules can be estimated as
( V
N
) 1/3
≈ 3.5 nm 3
The diameter of a molecule like N 2 or O 2 is only a few Angstroms, approximately 10×
smaller than this average distance.
• 1.13: A mole is approximately the number of protons in a gram of protons. The mass of a
neutron is about the same as the mass of a proton, while the mass of an electron is usually
negligible in comparison, so if you know the total number of protons and neutrons in in a
molecule (i.e. its “atomic mass”), you know the approximate mass (in grams) of a mole

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 2
of these molecules. Referring to the periodic table, find the mass of each of the following:
water, molecular nitrogen, lead, and quartz (SiO 2 )
H 2 O = 2(1) + 1(16) = 18 grams/mol
N 2 = 2(14) = 28 grams/mol
Lead = Pb = 207 grams/mol
SiO 2 = 1(28.08) + 2(16) = 60 grams/mol
• 1.14: Calculate the mass of a mole of dry air, which is a mixture of N 2 (78% by volume),
O 2 (21%) and Ar (1%).
Use weighted average to calculate the mass of air:
f =
∑
i w i f i
∑ wi
(w i = weights)
m = 0.78m N 2
+ 0.21m O2 + 0.01m Ar
0.78 + 0, 21 + 0, 01
From the periodic table, m N2 = 28.014 g/mol, m O2 = 32.00 g/mol, and m Ar = 39.95 g/mol
Therefore, the mass of a mole of dry air:
m = 0.78(28.014) + 0.21(32) + 0.01(39)
m = 28.92 g/mol
• 1.15: Estimate the average temperature of the air in a hot air balloon (see Fig. 1.1 in book).
Assume that the total mass of the unfilled balloon and payload is 500 kg. What is the mass
of the air inside the balloon?
The upward buoyant force on the balloon is equal to the weight of the air displaced. Assuming
that this force is approximately in balance with gravity, we can write:
ρ 0 V g = (M + ρV )g or ρ 0 − ρ = M/V
where ρ 0 is the density of the surrounding air, V is the volume of the balloon, M is the
mass of the unfilled balloon and payload, and ρ is the density of the air inside the balloon.
According to the ideal gas law, the density of air is:
ρ = mn
V = mP
RT
where m is the mass of one mole of air (≈29 g). This formula applies either inside or outside
the balloon, with the same pressure in both places but different temperatures. Therefore,
teh balance of forces implies:
mP
− mP
RT 0 RT = M V
where T and T 0 are the temperature inside and outside the balloon, respectively. Rearranging
yields:
1
T = − 1 − M P
T 0 m RV

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 3
Assume an outside air temperature of 290 K and atmospheric pressure. The volume of the
balloon can be estimated from the figure. Comparing the heights of the people standing
beneath, a reasonable estimate for the diameter of the balloon in the foreground is ≈15
metres. This gives a volume, assuming a spherical balloon ( 3 3 πr3 ), of about 1770 m 3 . The
mass of the unfilled balloon and payload is assumed to be 500 kg, so the previous expression
evaluates to:
1
T = − 1 (500 kg) (8.31 J/K)
−
(290 K) (0.029 kg) (10 5 N/m 2 )(1770 m 3 )
1
T = − 1
(290 K) − 1
(1235 K) = 1
(379 K)
Thus, the temperature inside the balloon must be about 379 K or just over 100 ◦ C. Assuming
this temperature, the mass of the air inside the balloon should be roughly:
M air = mn = mPV
RT
M air = (0.029 kg)(105 N/m 2 )(1770 m 3 )
(8.31 J/K)(379 K)
= 1600 kg
which s more than three times the mass of the unfilled ballon and payload.
• 1.16: The Exponential atmosphere.
a) Consider a horizontal slab of air whose thickness (height) is dz. If this slab is at rest,
the pressure holding it up from below must balance both the pressure from above and the
weight of the slab. Use this fact to find an expression for dP/dz, the variation of pressure
with altitude, in terms of the density of air.
This diagram shows the forces on the slab of air. P(z) is the atmospheric pressure as a
function of height z, and M is the total mass of the slab.
Because the slab of air is at rest, the net force on the slab must be zero. Thus
P(z + dz)A + Mg − P(z)A = 0 ⇒ [P(z + dz) − P(z)]A = −Mg ⇒ P(z + dz) − P(z) = −Mg
A
Now the volume of the slab is Adz, so if the density of air is ρ(z), then M = ρ(z)Adz, and
so
P(z + dz) − P(z) = − ρ(z)Agdz = −ρ(z)gdz
A
P(z + dz) − P(z)
⇒ = −ρ(z)g
dz

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 4
If dz is very small, then the left hand side is the definition of the derivative dP/dz. Thus,
dP
dz = −ρ(z)g
b. Use the ideal gas law to write the density of air in terms of pressure, temperature, and
the average mass m of the air molecules. Show, then, that the pressure obeys the differential
equation:
called the barometric equation.
dP
dz = −mg kT P,
We can derive this from part a by finding an expression for ρ(z). The density of the slab is
equal to the mass of the slab, M divided by its volume, V . The mass, in turn, is equal to
the mass per molecule, m, times the number of molecules, N. Thus:
ρ = mN
V
The ideal gas law says that PV = NkT, so that N/V = P/kT. Thus ρ = mP/kT, and
dP
dz = −mP kT g = −mg kT P(z)
c. Assuming that the temperature of the atmosphere is independent of height, solve the
barometric equation to obtain the pressure as a function of height: P(z) = P(0)e −mgz/kT .
Show also that the density obeys a similar equation.
For convenience, let’s write α = mg/kT, so that
dP
dz = −αP(z)
This is one of the most basic differential equations, but if you’ve never seen it before, we
can solve it by separation of variables: put the pressure on one side, and the altitude z on
the other:
dP
= −αP(z)
dz
dP
= −αd(z)
P
∫ P(z) ∫
dP z
= − αd(z)
P(0) P 0
ln P(z) − ln P(0) = −αz
( ) P(z)
ln = −αz
P(0)
P(z)
= e −αz
P(0)
P(z) = P(0)e −αz
Substituting in the definition for α gives us P(z) = P(0)e −mgz/kT as expected.

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 5
We showed in part b that ρ = mP/kT , so
ρ(z) = m kT P(0)e−αz ,
we could also write mP(0)/kT as ρ(0), the density at z = 0. Note that the constant α has
units of m −1 ; the constant z 0 = 1/α is the length scale over which the pressure and density
vary.
d. Estimate the pressure, in atmospheres, at Mt. Everest. (Assume that the pressure at sea
level is 1 atm.)
We can write:
P(z) = P(0)e −z/z 0
where z0 = kT/mg and it is convenient to calculate this quantity first. Assume that T =
280K. Air is 80% N 2 , which has an atomic mass of 28, and 20% O 2 which has an atomic
mass of 32. An atomic mass unit is 1.67 × 10 −27 kg (roughly the mass of a proton), so the
average mass per molecule is:
m = 80%(28)(1.67 × 10 −27 kg) + 20%(32)(1.67 × 10 −27 kg) = 4.8 × 10 −26 kg
and so
z 0 = (1.38 × 10−23 J/K)(280K)
(4.8 × 10 −26 kg)(9.8 m/s 2 )
= 8200 m = 8.2 km
(Because this is so large, pressure and density does not vary appreciably inside a room).
Now P(0) is the pressure at sea level, thus 1 atm, and so P(z) = (1atm)e z/8200m , and thus
Mt. Everest = 8850m, pressure = 0.34 atm
• 1.18: Calculate the rms speed of a nitrogen molecule at room temperature.
We know:
v rms =
√
3kT
m
One nitrogen atom has mass 14.00 u. 1.66×10−27 kg
1 u
= 2.3 × 10 −26 kg, so a nitrogen molecule
has (approximately) twice that mass, or m = 4.6 × 10 −26 kg. Thus
v rms =
√
3(1.38 × 10
−23
J/K)(300K)
4.6 × 10 −26 kg
= 5200 m/s
• 1.19: Suppose you have a gas containing hydrogen and oxygen molecules, in thermal equilibrium.
Which molecules are moving faster, on average? By what factor?
√
The rms speed of the molecules in an ideal gas is v rms = 3kT
. The ratio of the speeds of
m
hydrogen and oxygen at the same temperature is:
√
v H mO
=
v O m H
Now oxygen molecules are sixteen times more massive than hydrogen molecules, so v H /v O =
√
16 = 4. So hydrogen molecules will be moving four times faster than oxygen molecules.

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 6
• 1.21: During a hailstorm, hailstones with an average mass of 2 g and a speed of 15 m/s
strike a windowpane at a 45 ◦ angle. The area of the window is 0.5 m 2 and the hailstones hit
it at a rate of 30 /s. What average pressure do they exert on the window? How does this
compare to the pressure of the atmosphere?
The hailstones strike the window at intervals of 1/30 s on average. During this time period,
the average force exerted by the window on the hailstone must be:
→
F x= m ∆v x
∆t
where ∆v x is the change in the component of the hailstone’s velocity perpendicular to the
window. Assuming elastic collisions and a velocity of 15m/s at 45 ◦ , this change in velocity
is 2vcos(45 ◦ ) = 21m/s. The average pressure is then
→
P=
→
F
A = m∆v x
A∆t
=
(0.002 kg)(21 m/s)
(0.5 m 2 )(0.033 s)
= 2.5 N/m 2 = 2.5 Pa
This is smaller than atmospheric pressure by a factor of 40,000. (However, the instantaneous
pressure during a collision is much higher, as the force is localized in time and space; this is
what might cause the window to break.)
• 1.22: If you poke a hole in a container full of gas, the gas will start leaking out. In this
problem you will make a rough estimate of the rate at which gas escapes through a hole.
a. Consider a small portion (area A) of the inside wall of a container full of gas. Show that
the number of molecules colliding with this surface in a time interval ∆t is PA∆t/(2m → v x ),
where P is the pressure, m the average molecular mass, and → v x is the average x velocity of
those molecules that collide with the wall.
As in Eq. 1.9, Newton’s Laws imply that each molecule colliding with the surface exerts an
average pressure of:
→
P= − m∆v x
A∆t
For an elastic collision, ∆v x = −2v x . If there are N molecules, the total pressure is the sum
of N terms of this form, one for each molecule; the sum over v x values can be written as N
times the average, or N → v x . Therefore
P = m(2N → v x )
A∆t
⇒ N = PA∆t
2m → v x
b. It’s not easy to calculate → v x , but a good enough approximation if (vx) 2 0.5 ,
√
where the bar
now represents an average over all molecules in the gas. Show that (vx) 2 0.5 = kT/m.
√
This result follows directly from Eq. 1.15: kT = mvx 2 ⇒ vx 2 = kT/m
c. If we now take away this small part of the wall, the molecules that would have collided
with it will instead escape through the hole. Assuming that nothing enters through the hole,
show that the number N of molecules inside the container as a function of time is governed
by the differential equation:
dN
dt = − A
√
kT
2V m N

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 7
Solve this equation (assuming constant T) to obtain a formula of the form N(t) = N(0)e −t/τ
where τ is the “characteristic time” for N (and P) to drop by a factor of e.
What we called N above is now −∆N, the change in the number of molecules in the
container. Substituting this into part (a), and bringing in part (b), gives us:
−∆N = PA∆t √ m
2m kT
Now use the ideal gas law to eliminate P, and divide through by ∆t, taking the limit ∆t → 0
to get the derivative:
√
(NkT/V )A∆t m ∆N
−δN = = −N kTA √ m dN
2m kT δt 2mV kT dt = − A
√
kT
2V m N = −1 τ N
√
where τ = (2V/A) m/kT. Thus N(t) is a function whose derivative is equal to −1/τ times
itself, which makes it an exponential:
N(t) = N 0 e −t/τ
d. Calculate the characteristic time for air at room temperature to escape from a 1-litre
container punctured by a 1mm 2 hole.
√ √
To calculate τ we start with the quantity kT/m = RT/M, where M is the molar mass
of the gas (that is, the mass of a mole of air). Assuming the gas is near room temperature:
√ √ √√√ RT
M = (8.3 J/mol/K)(300 K)
0.029 kg/mol
= 293 m/s ≈ 300 m/s
A one liter bottle has volume 10 −3 m 3 , and 1 mm 2 = 10 −6 m 2 , so
2V
τ = √
A RT/M = 2(0.001 m 3 )
(10 −6 m 2 )(300 m/s) = 7 s
e. The tire “going flat” I assume to mean that e t/τ ≈ 0 in the shortest time. For example,
e −3 ≈ .05, which is close to 0. That means:
− t √ m
τ − 3 → t = 3τt = 3τ = 32V A k B T = 6V A (3.42 × 10−3 )
Again, I assume V = 1 L and 1 hour = 3600 s.
Calculate the area A;
3600s = 6(10−3 m 3 )
(3.42 × 10 −3 s/m
A
A = 5.7 × 10 −9 m 2 = 5.7 × 10 −3 mm 2
f. Assuming that in time ∆t, all particles within the half sphere of radius v x ∆t surrounding
the hole escape, since v x is on the order of several hundreds of meters per second on average
it seems unlikely that the travelers could toss the corpse out the window in a short enough
time for an insignificant number of particles to escape. Of course, this hinges on the the
definition of significant- if the space ship was very large, the percentage of air compared to
the total volume of the ship would be very small and perhaps termed “insignificant.”

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 8
• 1.26: A battery is connected in series to a resistor, which is immersed in water (to prepare a
nice hot cup of tea). Would you classify the flow of energy from the battery to the resistor
as “heat” or “work”? What about the flow of energy from the resistor to the wire?
Energy flowing from the battery to the resistor should be classified as work, since it is a
process that would not happen spontaneously. The flow of energy from the resistor to the
water is heat, since it is a spontaneous process.
• 1.27: Give an example of a process in which no heat is added to a system but its temperature
increases. Then give an example of the opposite: a process in which heat is added to a system
but its temperature does not change.
An example of a process in which no heat is added to a system but the temperature increases
is pumping a tire full of air. A process in which heat is added to a system but its temperature
remains constant is a phase change, melting a piece of ice for example.
• 1.28: Estimate how long it would take to bring a cup of water to boiling temperature in
a typical 600-watt microwave oven, assuming that all the energy ends up in the water.
(Assume any reasonable initial temperature for the water). Explain why no heat is involved
in this process.
There are a few ways to approach this problem. ∆U = Q + W where, for this problem,
Q = 0 so ∆U = W. Looking at the change in thermal energy (eqn 1.23) for a system of N
molecules with f degrees of freedom:
∆U = Nf 1 2 k∆T
Assuming that the water is at 20 ◦ C at the start and it boils at 100 ◦ C, then ∆T = (100 -
20) =80 ◦ C. H 2 O = 2H + O ⇒ 2 g/mol + 16 g/mol ⇒ 18 g/mol. A typical cup of water is
about 200g, and so:
N =
(200 g) (6.02 × 10 23 molecules)
(18 g/mol) (1 mol)
N = 6.7 × 10 24 molecules
The number of degrees of freedom, f, is not so clearly defined in the problem. There are
certainly 3 translational degrees of freedom and there are 3 rotational. We do not know if
the vibrational degrees of freedom are frozen out, but if we assume that they are then f = 6.
∆U ≈ 6.7 × 10 24 6 2 1.38 × 10−23 73 J∆U ≈ 2.02 × 10 4 J
For a 600 W oven, the “heating” rate is 600 J/s, so:
∆t ≈
∆U
600 J/s ≈ 34 s
Alternatively, we can look at the definition of a calorie. 1 calorie = 4.186 J is the amount
of energy required to raise the temperature of 1 g of water by 1 ◦ C. So, for 200 g of water
we need:
U = (4.186 J/g/ ◦ C)(200 g)(80 ◦ C)
U = 6.11 × 10 4 J

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 9
So,
∆t ≈
6.11 × 104
600
≈ 102 s
Clearly, f = 6 is not correct for liquid water and there must be a larger number of degrees
of freedom.
Remember that flow of heat is a spontaneous process from higher T to lower T. The
microwave overn is an example of electro-magnetic work.
• 1.31: Imagine some helium in a cylinder with an initial volume of 1 litre and an initial
pressure of 1 atm. Somehow the helium is made to expand to a final volume of 3 litres, in
such a way that the pressure rises in direct proportion to its volume. (a) Sketch a graph of
pressure vs volume for this process.
(b) Calculate the work done on the gas during this process, assuming that there are no
“other” types of work being done.
The work done is just minus the area under the graph shown in (a). The easiest way to
compute the area is to note that the average pressure during this process is 2 atm and:
W = −P∆V = −(2 atm)(2 l)
W = −(2 × 10 5 Pa)(2 × 10 −3 m 3 )
W = −400 J
The minus sign indicates that 400 J of work is done by the gas on its surroundings.
(c) Calculate the change in the helium’s energy content during this process
Each helium atom has three degrees of freedom, so at any point the thermal energy of the
helium is U = 3NkT = P . The change in energy during this process is:
2 V
∆U = 3 2 [P fV f − P i V i ]
∆U = 3 [(3 atm)(3 l) − (1 atm)(1 l)]
2
∆U = 12 atm l = 1200J

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 10
(d) Calculate the amount of heat added to or removed from the helium during this process.
By the first law,
This amount of heat enters the gas.
Q = ∆U − W
Q = 1200 − (−400) = 1600 J
(e) Describe what you might do to cause the pressure to rise as the helium expands?
To cause such an increase in pressure (and temperature) as the gas expands, you must
provide heat, for example, by holding a flame under the cylinder and letting the piston out
slowly enough to allow the pressure to rise as desired.
• 1.33: An ideal gas is made to undergo the cyclic process shown in the figure. For each of the
steps A, B, and C, determine whether each of the following is positive, negative, or zero: (a)
the work done on the gas, (b) the change in the energy content of the gas, and (c) the heat
added to the gas. Then determine the sign of each of these three quantities for the whole
cycle. What does this process accomplish (in real-world terms)?
The work done on the gas depends entirely on the change in volume; decreasing volume
means that work is positive, while increasing volume means that work is negative. The
thermal energy of the gas is directly proportional to the temperature, which is in turn
proportional to PV . The heat must then be accounted for via the equation ∆U = W + Q.
For branch A, the volume increases, so W < 0. PV increases as well, so the thermal energy
is increasing. Since the energy increases but work flows out, there must be a flow of heat
inward to compensate, and Q > 0.
For branch B, there is no change in volume so W = 0. PV increases, so ∆U > 0. Because
the energy is increasing, there must be a flow of heat inward.
For branch C, volume and pressure are both decreasing, so W > 0 and ∆U < 0. Because
work flows in and the energy still decreases, there must be a net flow of heat outward, so
Q < 0. To summarize:
Branch energy W Q
A increases negative positive
B increases zero positive
C decreases positive negative
During one complete cycle, PV comes back to its original value, so the thermal energy does
not change. The work done on this system is positive (because branch C has a greater area

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 11
under it than branch A, and thus has more work flowing). Because the system’s energy
doesn’t change, Q must be negative: heat flows out of the system.
In short, this cycle transforms work into heat; it could, for instance, be some sort of space
heater. If we note, however, that this system both absorbs heat (in steps A and B) and emits
heat, we can think of a more sophisticated use: in particular, we can absorb heat from one
room and emit it into the other. Similar cycles can act as refrigerators, but this particular
cycle would not make a practical refrigerator because the heat absorption stages are not at
a lower temperature than the emission stages.
• 1.34: An ideal diatomic gas, in a cylinder with a movable piston, undergoes the rectangular
cyclic process shown in the figure below. Assume that the temperature is always such that
the rotational degrees of freedom are active but that the vibrational modes are “frozen
out.” Also assume that the only type of work done on the gas is quasidiabatic compressionexpansion
work.
(a) For each of the four steps A through D, compute the work done om the gas, the heat
added to the gas, and the change in the energy content of the gas. Express all answers in
terms of P 1 , P 2 , V 1 and V 2 )Hint: compute ∆U before Q using the ideal gas law and the
equipartition theorem.)
For an ideal diatomic gas at room temperature, U = 5 2 Nk BT = 5 2 PV (since PV = Nk BT)
Step A:
Step B:
∆U A = 5 2 V ∆P = 5 2 V 1(P 2 − P 1 )
W A = 0
∆U B = 5 2 P∆V = 5 2 P 2(V 2 − V 1 )
Q A = ∆U A − W A = 5 2 V 1(P 2 − P 1 )

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 12
W B
∫ V2
= − PdV = −P 2 (V 2 − V 1 ) = P 2 (V 1 − V 2 )
V 1
Q B = ∆U B − W B = 5 2 P 2(V 2 − V 1 ) + P 2 (V 1 − V 2 ) = 7 2 P 2(V 2 − V 1 )
Step C:
∆U C = 5 2 V ∆P = 5 2 V 2(P 1 − P 2 ) = − 5 2 V 2(P 2 − P 1 )
W C = 0
Q C = ∆U C − W C = − 5 2 V 2(P 2 − P 1 )
Step D:
∆U D = 5 2 P∆V = −5 2 P 1(V 2 − V 1 )
W D
∫ V1
= − PdV = −P 1 (V 1 − V 2 ) = P 1 (V 2 − V 1 )
V 2
Q D = ∆U D − W D = − 5 2 P 1(V 2 − V 1 ) − P 2 (V 2 − V 1 ) = − 7 2 P 1(V 2 − V 1 )
(b) Describe in words what is physically being done during each of the four steps; for example,
during Step A, heat is added to the gas (from an external flame or something) while the
piston is held fixed.
In step A, the volume is held constant at V 1 , and heat is added to the gas in the cylinder,
thus raising its temperature and pressure. In step B, the piston is moved out to increase
the volume from V 1 to V 2 , and, at the same time, heat is added so as to maintain constant
pressure at P 2 . In step C, the volume is held constant at V 2 , and heat is removed from the
cylinder to lower the pressure from P 2 to P 1 . Finally, in step D, the gas is compressed from
V 2 to V 1 , while continuing to remove heat, so that the pressure is maintained at P 1 .
(c) Compute the net work done on the gas, the net heat added to the gas, and the net change
in the energy of the gas during the entire cycle. Are the results as you expected? Explain
briefly.
For the cyclical process, we have:
∆U cycle
= ∆U A + ∆U B + ∆U C + ∆U D
∆U D = 5 2 V 1(P 2 − P 1 ) + 7 2 P 2(V 2 − V 1 ) + − 5 2 V 2(P 2 − P 1 ) + − 7 2 P 1(V 2 − V 1 )
∆U cycle = 0
Similarly,
W cycle = −P 2 (V 2 − V 1 ) + P 1 (V 2 − V 1 )
W cycle = −(P 2 − P 1 )(V 2 − V 1 )
and
Q cycle = 5 2 V 1(P 2 − P 1 ) + 7 2 P 2(V 2 − V 1 ) − 5 2 V 2(P 2 − P 1 ) − 7 2 P 1(V 2 − V 1 )
Q cycle = 5 2 (P 2 − P 1 )(V 1 − V 2 ) + 7 2 (P 2 − P 1 )(V 2 − V 1 )
Q cycle = (P 2 − P 1 )(V 2 − V 1 )

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 13
Yes, the results are as expected. For a complete cycle, the net change in the internal energy
U should be zero, since U is a function of state. Furthermore, from the first law, we have
∆U = Q + W ⇒ Q = −W if ∆U = 0.
• 1.38: Two identical bubbles of gas form at the bottom of a lake, then rise to the surface.
Because the pressure is much lower at the surface than at the bottom, both bubbles expand
as they rise. However, bubble A rises very quickly so that no heat is exchanged between it
and the water. Meanwhile, bubble B rises slowly (impeded by a tangle of seaweed), so that
it always remains in thermal equilibrium with the water (which has the same temperature
everywhere). Which of the two bubbles is larger by the time they reach the surface? Explain
your reasoning fully.
Both bubbles are identical to begin with, so both have the same number of air molecules N
inside. The pressure inside each bubble must be more-or-less equal to the pressure of the
water (we ignore the effects of surface tension here), so both bubbles end up at the same
pressure as well. Therefore the volume of each bubble, V = NkT/P, depends entirely on
temperature: the warmer bubble will be bigger. That also means that the larger bubble will
have the larger thermal energy. Now both bubbles do work on the surrounding water as they
expand (W < 0) Because bubble A does not exchange heat with its environment, it loses
energy and so cools down. Bubble B, on the other hand, remains at a constant temperature.
Therefore, by our reasoning above, bubble B, the one that absorbs heat, will be larger.
• 1.40: In problem 1.16 you calculated the pressure of the earth’s atmosphere as a function
of altitude, assuming constant temperature. Ordinarily, however, the temperature of the
bottommost 10-15 km of the atmosphere (called the troposphere) decreases with increasing
altitude, due to heating from the ground (which is warmed by sunlight). If the temperature
gradient |dT/dz| exceeds a certain critical value, convection will occur: Warm, low-density
air will rise while cool, high-density air sinks. The decrease of pressure with altitude causes
a rising air mass to expand adiabatically and thus to cool. The condition for convection to
occur is that the rising air mass must remain warmer than the surrounding air despite this
adiabatic cooling. (a) Show that when an ideal gas expands adiabatically, the temperature
and pressure are related by the differential equation:
From the book:
Using these and solving for V gives:
dT
dP = 2
f + 2
T
P
PV γ = const.
V T f/2 = const.
V = 1 P T (f+2)/2 = const.
This can be written in terms of natural logarithms as follows:
ln T (f+2)/2 − ln P = const.
f + 2
ln T − ln P = const.
2

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 14
Now if we take a derivative:
( ) f + 2 dT
T − dP P = 0
Simplifying this gives the desired differential equation
2
dT
dP = 2
f + 2
(b)Assume that dT/dz is just at the critical value fro convection to begin, so that the
vertical forces on a convecting air mass are always approximately in balance. Use the result
of problem 1.16(b) to find a formula for dT/dz in this case. This result should be a constant,
independent of temperature and pressure, which evaluates to approximately -10 ◦ /km. This
fundamental meteorological constant is known as the dry adiabatic lapse rate.
From Problem 1.16 (b):
T
P
dP
dz = − mg
k B T
From the answer in part (a), dT/dP can be decomposed into the product
and therefore
dT
dz
dT
dP = dT dz
dz dP
dz
dP = 2
T
f + 2 P
Substituting in the expression for dP/dz:
dT
dz
(
− k )
BT 1
mg P = 2 T
f + 2 P
The Ts and Ps cancel, and we are left with (after solving for dT/dz)
dT
dz = mg ( ) 2
k B f + 2
Using the mass of air, m air = 4.84 × 10 −26 kg/molecule. Substituting in all the numbers:
dT
dz
dT
dz
= (4.84 × 10−26 kg/molecule)(9.8 m/s 2 )
1.38 × 10 −23 J/K
= .0098 K m ≈ .01 K m
2
5 + 2
To change to K/km we just have to mutliply by 1000 m/km, and we get
Which was to be shown.
dT
dz = 10 K
km

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 15
• 2.1: Suppose you flip four fair coins.
(a) Make a list of all the possible outcomes, as in Table 2.1.
The number of outcomes is 2 4 = 16.
TTTT THTT HTTT HHTT
TTTH THTH HTTH HHTH
TTHT THHT HTHT HHHT
TTHH THHH HTHH HHHH
(b) Make a list of all the different “macrostates” and their probabilities.
0 Heads Ω = 1 P = 1/16
1 Heads Ω = 4 P = 4/16
2 Heads Ω = 6 P = 5/16
3 Heads Ω = 4 P = 4/16
4 Heads Ω = 1 P = 1/16
(c) Compute the multiplicity of each macrostate using the combinatorial formula (2.6), and
check that these results agree with what you got by brute force counting.
Ω(0, 4) = 4! Note : 0! = 1 So, Ω = 1, P=1/16.
0! 4!
Ω(1, 4) = 4! So, Ω = 24, P=4/16.
1! 3! 6
Ω(2, 4) = 4! So, Ω = 24 , P=6/16.
2! 2! 4
Ω(3, 4) = 4! So, Ω = 24, P=4/16.
3! 1! 6
Ω(4, 4) = 4! So, Ω = 1, P=1/16.
4! 0!
• 2.2: Suppose you flip 20 coins. (a) How many possible outcomes “macrostates” are there?
For only 2 possible states ⇒ 2 20 microstates. 2 20 = 1,048,576. Note that this is Ω(all) or
Ω(total)
(b) What is the probability of getting the sequence HTHHTTTHTHHHTHHHHTHT (in
exactly that order)?
Simply, this is only one macrostate out of 2 20 . Since each state is equally probable, the
possibility of getting this particular one is 1/2 20 ⇒ less than one in a million.
(c) What is the probability of getting 12 heads and 8 tails (in any order)=
This is another macrostate:
P =
Ω(20, 12)
Ω(all)
So, the probability is about 12%
• 2.3: Suppose you flip 50 coins.
=
20!
12! (20−12)!
1048576
(a) How many possible outcomes (microstates) are there?
= 125970
1048576 = 0.12
There are two outcomes for each coin, so total number of macrostates: Ω(all) = 2 50 =
1.13 × 10 15
(b) How many ways are there of getting exactly 25 heads and 25 tails?

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 16
To get exactly 25 heads:
Ω(25, 50) =
N!
Ω(q, N) =
(N − q)! q!
50!
= 1.26 × 1014
(50 − 25)! 25!
(c) What is the probability of getting exactly 25 heads and 25 tails?
So, not so large.
P(25) =
P(25) =
Ω(25, 50)
Ω(all)
1.26 × 1014
2 50 = 0.112
(d) What is the probability of getting exactly 30 heads and 20 tails?
Ω(30, 50)
P(30) =
Ω(all)
P(30) = 1 50!
2 50 30! 20! = 0.042
(e) What is the probability of getting exactly 40 heads and 10 tails?
Ω(40, 50)
P(40) =
Ω(all)
P(40) = 1 50!
= 0.0000091 = 9.1 ×
2 50 10−6
40! 10!
(f) What is the probability of getting exactly 50 heads and 0 tails?
P(50) = 1
Ω(all)
= 8.9 × 10−16
(g) Plot a graph of the probability of getting n heads as a function of n
• 2.4: Calculate the number of possible five-card poker hands, dealt from a deck of 52 cards.
(The order of cards in a hand does not matter.) A royal flush consists of the five highestranking
cards (ace, king, queen, jack, 10) of any one of the four suits. What is the probability
of being dealt a royal flush (on the first deal)?
The number of hands:
The probability of getting a royal flush:
N = 52!
5! 47! = 2598960
P = 4!
5! 47! = 2598960

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 17
• 2.5: For an Einstein solid with each of the following values of N and q, list all of the possible
microstates, count them, and verify formula 2.9
(a) N = 3, q = 4 : Ω(N, q) = (q+N−1)! = 15
q! (N−1)!
Oscillator Oscillator
1 2 3 1 2 3
4 0 0 0 1 3
0 4 0 2 2 0
0 0 4 2 0 2
3 1 0 2 1 1
15 states.
3 0 1 0 2 2
1 3 0 1 2 1
0 3 1 1 1 2
1 0 3
(b) N = 3, q = 5 : Ω(N, q) = (q+N−1)! = 21
q! (N−1)!
Oscillator Oscillator
1 2 3 1 2 3
5 0 0 3 1 1
0 5 0 2 3 0
0 0 5 0 3 2
4 1 0 1 3 1
4 0 1 2 0 3 21 states.
1 4 0 0 2 3
0 4 1 1 1 3
1 0 4 2 2 1
0 1 4 2 1 2
3 2 0 1 2 2
3 0 2

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 18
(c) N = 3, q = 6 : Ω(N, q) = (q+N−1)! = 28
q! (N−1)!
Oscillator Oscillator
1 2 3 1 2 3
6 0 0 1 4 1
0 6 0 2 0 4
0 0 6 0 2 4
5 1 0 1 1 4
5 0 1 3 3 0
1 5 0 3 0 3
0 5 1 3 2 1
28 states.
1 0 5 3 1 2
0 3 5 3 3 0
4 2 0 0 3 3
4 0 2 2 3 1
4 1 1 1 3 2
2 4 0 2 1 3
0 4 2 1 2 3
(d) N = 4, q = 2 : Ω(N, q) = (q+N−1)! = 10
q! (N−1)!
Oscillator
1 2 3 4
2 0 0 0
0 2 0 0
0 0 2 0
0 0 0 2
1 1 0 0
10 states.
1 0 1 0
1 0 0 1
0 1 1 0
0 1 0 1
0 0 1 1
(e) N = 4, q = 3 : Ω(N, q) = (q+N−1)! = 20
q! (N−1)!
Oscillator Oscillator
1 2 3 4 1 2 3 4
3 0 0 0 1 0 2 0
0 3 0 0 0 1 2 0
0 0 3 0 0 0 2 1
0 0 0 3 1 0 0 2
2 1 0 0 0 1 0 2
20 states.
2 0 1 0 0 0 1 2
2 0 0 1 1 1 1 0
1 2 0 0 1 1 0 1
0 2 1 0 1 0 1 1
0 2 0 1 0 1 1 1
(f) N = 1, q = anything
Ω(N, q) = (q+N−1)!
q! (N−1)!
= q Oscillator 1: q

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 19
(g) N = anything, q = 1
Ω(N, q) = (q+N−1)!
q! (N−1)!
= N
• 2.6: Calculate the multiplicity of an Einstein solid with 30 oscillators and 30 units of energy.
(Do not attempt to list all the microstates)
Ω(30, 30) = (q+N−1)!
q! (N−1)!
= 59!
30! 29!
= 5.91 × 1016
• 2.7: For an Einstein solid with four oscillators and two units of energy, represent each possible
microstate as a series of dots and lines, as used in the text to prove equation 2.9
N = 4, q = 2, Ω(N, q) = (q+N−1)!
q! (N−1)!
= 10
Oscillator Dots and lines
1 2 3 4 1 2 3 4
2 0 0 0 ··
0 2 0 0 ··
0 0 2 0 ··
0 0 0 2 ··
1 1 0 0 · ·
1 0 1 0 · ·
1 0 0 1 · ·
0 1 1 0 · ·
0 1 0 1 · ·
0 0 1 1 · ·
10 states.
• 2.8: Consider a system of two Einstein solids, A and B, each containing 10 oscillators, sharing
a total of 20 units of energy. Assume that the solids are weakly coupled, and that the total
energy is fixed.
(a) How many different macrostates are available to this system?
Solid A can have anywhere between 0 and 20 units of energy. Therefore, 21 different
macrostates are available to the system of weakly coupled A and B solids sharing 20 units
of energy.
(b) How many different microstates are available to this system?
The combined system has 20 oscillators and 20 units of energy. Therefore,
Ω(N, q) =
(q + N − 1)!
q!(N − 1)!
= 39! = 6.89 × 1010
20! 19!
(c) Assuming that this system is in thermal equilibrium, what is the probability of finding
all of the energy in solid A?
For the macrostate with all energy in solid A:
Ω = Ω A Ω B = Ω A (10, 20)Ω B (10, 0) = 29!
20! 9! = 1 × 107
The probability of this macrostate is:
P = 1 × 107 = 1.45 × 10−4
6.89 × 10
10
(d) What is the probability of finding exactly half the energy in solid A?

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 20
For the macrostate with exactly half the energy in solid A:
Ω = Ω A Ω B = Ω A (10, 10)Ω B (10, 10) = 19!
10! 9!
8.53 × 109
P = = 0.124
6.89 × 10
10
= 8.53 × 109
(e) Under what circumstances would this system exhibit irreversible behaviour?
If the energy was initially all in A, the system would evolve toward half energy in A and
half energy in B, and this distribution of energy would be irreversible. In other words, once
the energy is evenly distributed, it is highly unlikely that the system would find itself with
all the energy back in A.
• 2.16: Suppose you flip 1000 coins. (a) What is the probability of getting exactly 500 heads
and 500 tails? (Hint: First write down a formula for the total number of possible outcomes.
Then, to determine the “multiplicity” of the 500-500 “macrostate”, use Sterling’s approximation.
If you have a fancy calculator that makes Stirling’s approximation unnecessary,
multiply all the numbers in this problem by a sufficient factor that you have to manually
make this approximation.
First, note that the number of possible outcomes (microstates) is 2 1000 . The probability of
getting 500 heads and 500 tails is (from Sterling’s approximation):
( )
1000
Ω(500) = = 1000!
500 (500!) 2
Ω(500) ≈ 10001000 e −1000√ 2π 1000
(
500
500
e −500√ 2π 500 ) 2 = 21000
√
500π
The probability is Ω(500)/Ω(all) :
Ω(500) =
2 1000
2 √ 1000 500π = 1
√ = 0.025 500π
So the chance of getting exactly 500 heads is about 2.5%, or 1 in 40.
(b)What is the probability of getting exactly 600 heads and 400 tails?
From Sterling’s approximation:
( )
1000
Ω(600) = = 1000!
600 600! 400!
Ω(600) ≈
The probability is Ω(600)/Ω(all) :
1000 1000 e −1000√ 2π 1000
600 600 e −600√ 2π 600 400 400 e −400√ 2π 400 = 1000 1000
600 600 400 400 √ 480π
Ω(600) =
Ω(600) =
1000 1000
2 1000 600 600 400 √ 400 480π = 500 1000
600 600 400 √ 400 480π = 500 600 500 400
600 600 400 √ 400 480π
( ) 5 600 ( ) 5 400 1
√
6 4 480π
So the chance of getting exactly 600 heads is 4.6 × 10 −11 , much smaller than P(500)

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 21
• 2.21: Use a computer to plot formula 2.22 directly, as follows. Define z = q a /q such that
(1 − z) = q b /q. Then, aside from a few constants that can be ignored, the multiplicity
function is [4z(1 − z] N , where z ranges from 0 to 1 and the factor 4 ensures that the height
of the peak is equal to 1 for any N. Plot this function for N=1, 10, 100, 1000, and 10,000.
Observe how the width of the peak decreases as N increases.
• 2.23: Consider a two-state paramagnet with 10 23 elementary dipoles, with half the total
energy fixed at zero so that exactly half the dipole point up and half point down.
(a) How many microstates are “accessible” to this system?
With N dipoles of which exactly N/2 point up, the multiplicity of the paramagnet is:
( )
N N!
Ω = N ⇒ ( ) ( ) N
2
2 ! N
2 !
So, taking the Sterling approximation:
Ω =
[ (N
2
N N e −N√ √
2πN 2
) N/2 √ ] 2
= 2 N
e
−N/2
πN
πN
For N = 10 23 , then, the multiplicity is roughly: 2 1023 /4 × 10 11 Since the denominator is
merely “large,” we could just as well neglect it and say that Ω = 2 1023 , which is the number
of microstates if we allow any number of dipoles to be pointing up.
(b)Suppose that the microstate of this system changes a billion times per second. How many
microstates will it explore in ten billion years (the age of the universe)?
A year is about 3 × 10 7 s, so 10 billion years is about 3 × 10 1 7 s, or 3 × 10 2 6 ns. If the
microstate of the system changes once every nanosecond, this is how many microstates the
system will explore in the age of the universe. But this is a tiny fraction of the total number
of microstates. In fact, the fraction is so small that the ratio of states not explored to states
explored is 2 1023 .

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 22
(c) Is it correct to say that, if you wait long enough, a system will eventually be found in
ev ery “accessible” microstate? Explain your answer, and discuss the meaning of the word
“accessible.”
Even if we wait for the age of the universe, the fraction of all “accessible” microstates that
are actually explored by this system is so tiny that it might be more accurate to say that the
system explores none of its “accessible” microstates. When we call a microstate “accessible,”
therefore, we should not think that the system will ever actually be in that microstate. So
what do we mean? One of the best interpretations is in terms of our ignorance of which
microstates the system will actually explore in the future. Forallweknow, the system might
soon be found in any of its “accessible” microstates, even though the probability of its being
found in any of them is vanishingly small.
• 2.24: For a single large two-state paramagnet, the multiplicty function is very sharply peaked
about N ↑ = N/2 (a) Use Sterling’s approximation to estimate the height of the peak in the
multiplicity function.
If N = N ↑ , then N ↑ = N ↓ = N 2
and the multiplicity is:
Ω max =
N!
N ↑ ! N ↓ ! = N! ( N
2 !) 2
Ω max
≈
[ (N
2
N N e −N√ √
2πN 2
) ] N/2 2
= 2
e
−N/2√
N 2π N π N
2
Using Sterling’s approximation:
Ω =
N!
N ↑ ! N ↓ ! ≈
N N ↑
↑ e −N ↑
N N e −N√ 2πN
√
2πN↑ N N ↓
↓ e −N ↓
√
2πN↓
=
N N ↑
↑
N N
N N ↓
↓
√
N
2πN ↑ N ↓
(b) Use the methods discussed in the lectures to derive a formula for the multiplicity function
in the vicinity of the peak, in terms of x ≡ N ↑ − (N/2). Check that your formula agrees
with your answer to part (a) when x = 0
Using x ≡ N ↑ − (N/2), we can rearrange for N ↑ :
and solve for N ↓ :
N ↑ = N 2 + x
N ↓ = N − N ↑
⇒ N ↓ = N − N 2 − x ⇒ N ↓ = N 2 − x
Using the equation obtained from Sterlings approximation:
N N √
N
Ω =
2πN ↑ N ↓
N N ↑
↑
N N ↓
↓
setting N ↑ = (N/2) + x and N ↓ = (N/2) − x:
Ω =
N N
( N
2 + x) N/2+x ( N
2 − x) N/2−x
√
N
2π ( N
2 + x) ( N
2 − x)

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 23
Rearranging ...
Ω =
[ (N
2
N
N
) ] 2 N/2 (N
− x
2
+ 2 x) x ( [
N
− 2 x) −x √ (N ) ] 2
2π
2 − x
2
Apply the logarithmic approximation to this equation:
) 2
− x 2 ]
lnΩ ≈ N lnN − N [ (N
2 ln 2
√
N
2π − 1 [ (N ) 2
]
2 ln − x 2
2
+ ln
( ) ( )
N N
− x ln
2 + x + x ln
2 − x
Nothing yet has been assumed about the size of x relative to N but if x ≪ N, the logarithms
containing two terms can be expanded:
ln
[ (N
2
) 2
− x 2 ]
( ) N
ln
2 ± x
Using these expressions, we get:
( ) N 2
[
= ln + ln 1 −
2
( ) [ N
= ln + ln
2
1 ± 2x
N
( ) 2x 2
]
N
] ( ) N
≈ ln
2
( ) N
≈ 2 ln −
2
± 2x
N
( ) 2x 2
N
lnΩ = N ln N − N ln N 2 + 2x2
N − x ln N 2 − 2x2
N + x ln N 2 − 2x2
√ N
N
2π − ln N 2 + 2x2
+ ln
N 2
√
lnΩ = N ln 2 − 2x2 2
N + ln πN − 2x2
N 2
The last term is clearly negligible and can be neglected. Taking the exponential:
e ln Ω ≈ e N +ln√ ln2−2x2 2
N πN
√
2
Ω = 2 N /N
for x ≪ N
πN e−2x2
This is a Gaussian function, peaked at x = 0. Clearly, when x = 0:
Ω = 2 N √
2
πN
which is the same result obtained in part (a).
(c) How wide is the peak in the multiplicity function?
The Gaussian function falls off to 1/e of its peak value when:
2x 2
N = 1 ⇒ x = √
N
2
But the width of the peak will be 2x so: width = √ 2N

Richard Thomas - FK4005 “Thermodynamik” - Solutions to Räknövningar 24
(d) If you flip one million coins. Would you be surprised to obtain 501,000 heads and 499,999
tails? Would you be surprised to obtain 510,000 heads and 490,000 tails? Explain.
Here, N = 10 6 x = N 2 + 103 . The half-width of the peak in the multiplicity function would
be √ 500000 ≈ 700. So an excess of 1000 heads is only a little beyond the point where the
Gaussian has fallen off to 1/e of its maximum value. It would nit be too surprising to obtain
approximately this many heads, though it would be surprising to obtain an excess of exactly
1000. Conversely, an excess of 10,000 heads lies fay outside the peak in the multiplicity
function. At this point the Gaussian has fallen off to e 200 ≈ 10 −87 of its maximum value. If
a result close to this was achieved, it’s likely that there is a problem with the coins!