(in lungs) (expanded cloud)
P1 = ? P2 = 1 atm
V1 = 6 L V2 = ?
T1 = 310 K T2 = 77 K
n1=n2 n1=n2
Topic 7 extra example: Superman 1
Superman’s adiabatic breath
Superman routinely freezes villains by blowing on them. The idea behind this is adiabatic
gas expansion: when a process happens very quickly, it becomes approximately adiabatic
because there isn’t time for heat transfer between the system and its surroundings, so a
rapidly-expanding gas may be treated as approximately adiabatic even though there’s no
insulation between it and the surrounding gas. (A real-world example is when you let air
rapidly out of a car’s tire: it will get cold, and sometimes even frost up, around the valve
where the air is rushing out.) Here are some calculations about adiabatic gas expansion,
using this situation as a starting point.
Exhale (reversible)
First, consider the case where we approximate the expansion as adiabatic and reversible.
(This isn’t realistic: a rapid exhalation is definitely not a reversible process! But it gives us
an excuse to practice with the reversible adiabatic expansion equations.) We want to find
what the pressure in the lungs would need to be in order to have liquid-nitrogen temperatures
upon expansion: (P1 =?, V1 = 6 L, T1 = 310 K) → (P2 = 1 atm, V2 =?, T2 = 77 K). We know
! "1−γ
T2 V2
=
T1 V1
Turn this into a dependence on P , since that’s what we want to know, using the ideal
gas law:
V2 T2 P1
= ·
V1 T1 P2
! "1−γ ! "1−γ ! "1−γ ! "1−γ
T2 V2 T2 P1 T2 P1
= = · =
T1 V1 T1 P2 T1 P2
! "γ ! "1−γ
T2 P1
=
T1 P2
! " 1−γ γ
T2 P1
=
T1 P2
! " 1−γ γ
T2
P1 = P2
T1
Treating air as a diatomic ideal gas, C¯P = 27 R and C¯V = 25 R, so the heat capacity ratio
is γ = (7R/2) / (5R/2) = 7/5 = 1.4. So γ/(1 − γ) = −3.5, and
! "−3.5
77 K
P1 = (1 atm) # 130 atm
310 K
Then we can find V2 just from the ideal gas law
Topic 7 extra example: Superman 2
V2 T2 P1 77 K 130 atm
= · = · # 32
V1 T1 P2 310 K 1 atm
V2 = 32V1 # 190 L
Note that to achieve this high a pressure in the lungs, Superman must have inhaled a lot
of gas molecules (the inhalation wasn’t a constant-n process):
PV (130 atm)(6 L)
n1 = = # 30 mol
RT (.08206 L · atm/mol/K)(310 K)
(at standard temperature and pressure, 1 mole of an ideal gas occupies somewhere around
24 L, so the inhalation has packed a lot of extra molecules into the 6 L lung volume)
Inhale (reversible)
However, consider what happens during the inhale, when room-temp air is compressed up
to 130 atm, in preparation for blowing onto the villain: (P1 = 1 atm, V1 =?, T1 = 300 K) →
(P2 = 30 atm, V2 = 6 L, T2 =?). What temperature is the air after this inhalation, assuming
adiabatic, reversible compression?
! "γ ! "1−γ
T2 P1
=
T1 P2
! " 1−γ
P1 γ
T2 = T1
P2
! "−0.286
1 atm
= (310 K) # 1250 K
130 atm
So the process of compressing the air during the inhalation would raise its temperature
far above room temperature! In fact, if we did a reversible inhale followed by a reversible
exhale, this time using an initial temperature of T1 = 1250 K for the expansion, we would
find that the gas heats up on the inhale, then cools back down exactly to room temperature
on the exhale, with no net heating or cooling. This is because of the reversible nature of
the compression and expansion we’re using; the temperature would not return exactly to its
initial value for irreversible compression/expansion.
Exhale (irreversible)
The whole justification for treating this process as adiabatic was its speed, but by assuming
reversibility we’ve been considering a process of expansion (or compression) that must be
infinitely slow to preserve near-equilibirum at all times! It’s much more realistic to consider
an irreversible process wherein the gas expands rapidly against a constant external pressure.
Let’s consider the case where the gas is at the initial pressure we found for the reversible
expansion (where it originally yielded a final temperature of 77 K), and ask what the final
Topic 7 extra example: Superman 3
temperature will be if we instead have it expand irreversibly against a constant external
pressure of 1 atm: (P1 = 130 atm, V1 = 6 L, T1 = 300 K) → (P2 = 1 atm, V2 =?, T2 =?).
Since q = 0, for adiabatic processes (only!) we have ∆U = q + w = w. We can combine
two different expressions for ∆U to find the final temperature: one from the work done in
the constant-external-pressure expansion, and one from the expression U = 25 nRT = CV T
for a diatomic ideal gas (we’re continuing to treat air that way):
∆U = w = −Pext (V2 − V1 ) = CV (T2 − T1 )
Convert those volumes to pressures/temperatures using the ideal gas law, since those are
the things we either know or wish to know:
! "
nRT2 nRT1 5
−Pext − = CV (T2 − T1 ) = nR(T2 − T1 )
P2 P1 2
! " ! "
Pext Pext 5
T1 − T2 = (T2 − T1 )
P1 P2 2
Rearrange this to solve for T2 :
#P 5
$
P1
ext
+ 2
T2 = T1 Pext 5
P2
+ 2
Substitute Pext = P2 = 1 atm and P1 = 130 atm:
1
+ 52
! "
130
T2 = T1
1 + 25
# 0.716T1 # 220 K = −53 ◦ C
This is chilly, but significantly warmer than the reversible expansion, as we should have
expected: the reversible expansion does the maximum possible work, which means it lowers
the internal energy of the gas by the maximum possible amount, and thus cools the gas
most. Any irreversible expansion does less work and thus cools the gas less.
Related question (you might want to try this for yourself before reading on ...): What
initial pressure would we need to make T2 = 77 K in the irreversible expansion case?
Ready? The equation(s) relating T1 and T2 already contain everything we need, so we
just need to rearrange to solve for P1 :
Topic 7 extra example: Superman 4
! " ! "
Pext Pext 5
T1 − T2 = (T2 − T1 )
P1 P2 2
! "
Pext 5 5
T1 − T2 (1) = T2 − T1
P1 2 2
! "
Pext 7 5
T1 = T2 − T1
P1 2 2
Pext 7 T2 5
= −
P1 2 T1 2
7 77 K 5
= −
2 310 K 2
= −1.63
Wait, what? This is giving the nonsensical result that P1 would need to be negative?
This surprised me, but rather than cutting it out, let’s work through that surprise together.
It actually makes sense, when we look at the equations again. Take a look at the expression
for T2 :
#P 5
$ # 1 atm 5 $
ext
+ +2
T2 = T1 P1 5 2 = T1 P1
7
1+ 2 2
It turns out that there’s a limit to how much the irreversible process can possibly lower
the temperature: if we let P1 → ∞ in that expression, (1/P1 ) → 0, and we end up with
0 + 52
! "
5
T2 = T1 7 = T1 # 220 K
2
7
Another way of saying the same thing is that we need the ratio of the external pressure
to the initial pressure to be positive, and we can figure out the range of final temperatures
for which that will be true:
Pext 7 T2 5
= − >0
P1 2 T1 2
7 T2 5
>
2 T1 2
7T2 > 5T1
5
T2 > T1
7
That’s the same result we got, above. So 220 K is the lowest final temperature that an
irreversible expansion is capable of reaching, given our constraints on initial temperature
and volume: there’s a maximum to the amount of work that the gas can do under these
conditions, which in turn places a limit on the temperature drop that can be achieved.
Topic 7 extra example: Superman 5
Cooling the villain
How much is this whole cold-breath thing really going to cool down something the size of a
human body, anyway? I have some bad news for the comics, on that front ...
Let’s take the most favourable possible case, where the breath’s expansion is (implausibly)
reversible and it cools down to T2 = 77 K. And tell you what, I’ll even throw in a phase
change for free: let’s assume that since 77 K is the boiling point of liquid nitrogen, we can
assume that the breath liquified and the villain was hit with 30 moles of liquid N2 . If the
villain undergoes a constant-pressure cooling process (since he’s at 1 atm the whole time),
we can work out the heat transfer out of his body by figuring out the enthalphy change
involved in turning that LN2 (liquid nitrogen) back into a gas, then warming it back up
to 310 K (body temperature). That involves two contributions to change in enthalpy: the
phase change; and the constant-pressure heating.
∆H = ∆H(l → g)[at 77 K] + ∆H[warming f rom 77 to 310 K]
Online tables give me the phase transition enthalpy for nitrogen as 200 kJ/kg, or (200000 J/1000 g)·
(28 g/mol) = 5600 J/mol. If we continue to treat N2 as a diatomic ideal gas, its constant-
pressure heat capacity is CP = 72 nR, and we can treat that as constant, so the enthalpy
change from warming is CP ∆T :
7
∆H = (30 mol) (5600 J/mol) + (30 mol) (8.315 J/K/mol) (310 − 77 K)
2
= 168, 000 J + 203, 400 J
= 371, 000 J
Assuming that all the heat transfer (∆H = qP ) for this phase-change+warming process
comes directly out of the villain, they will be losing the same number of Joules (qP =
−371, 000 J). To work out the temperature change, we need to know the villain’s heat
capacity. Villains, of course, are made of a wide range of materials (metal, clay, alien
symbiotes, ...), but let’s assume a human-ish opponent with a mass of around 100 kg. The
human body is mostly water, so as a first approximation let’s assume that we’re cooling
off a 100 kg bag of water. Liquid water has a specific constant-pressure heat capacity of
4.81 J/g/K, so the villain has a rough heat capacity of CP = (100, 000 g)(4.81 J/g/K) =
481, 000 J/K.
The temperature change, then, is
∆H = qP = CP ∆T
qP
∆T =
CP
−371, 000 J
=
481, 000 J/K
= −0.77 K
Topic 7 extra example: Superman 6
After going to all the trouble of breathing on this villain, Superman has only cooled their
body down by less than a degree!
Believe it or not, there’s something unrealistic being depicted in the comic about the guy
who can fly, lift battleships, and shoot beams out of his eyes ...