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Solutions homework 1

Statistical Thermodynamics (Cornell University)

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AEP 4230 Set 1 Solutions

By Your Wonderful TAs
September 5, 2018

Problem 1
(a)
A graphical trick one can use with P V Rdiagrams is that Rthe area within the closed curve is equal to the
work. This is intuitively understood as: Pupper (V )dV − Plower (V )dV the area represents the work done
by the system minus the work done on the system.
Hence, for the first problem, the area within the rectangular contour is:

W = (P2 − P1 )(V2 − V1 ) = −Q.

(b)
For an isothermal process in an ideal gas we have that P V = N kT where T is constant, hence
N kT
P (V ) = .
V
We have again have two isochoric processes, so the area under the curve is
Z V2  
N kT2 N kT1
W =− − dV
V1 V V
Z V2
dV
= −N k(T2 − T1 )
V1 V
 
V2
= −N k(T2 − T1 ) log
V1
= −Q.

Problem 2
(a)
For the heat engine, the first law gives us

δQ1 + δQ2 = W

where δQ1 and δQ2 are the heat gotten from the reservoirs, with

δQ1 = Cp (T1 − Tf ), δQ2 = Cp (T2 − Tf )

So
W = Cp (−2Tf + T1 + T2 )

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(b)
The second law of thermodynamics tell us that

∆S1 + ∆S2 + ∆Sengine ≥ 0

where the equal sign applies for reversible procedures. Note that in order to calculate the change of entropy,
we need to choose a ‘reversible’ procedure with the same initial and final states. For the reservoirs, this
means a reversible isothermal procedure, so
Z Tf
Cp dT Tf
∆Sreservoiri = = Cp ln( )
Ti T Ti

and the state of the heat engine does not change, so

∆Sengine = 0

Collecting things together, we will get

Tf2 Tf2 Tf2

Cp ln( ) ≥ 0, ln( ) ≥ 0, ≥1
T1 T2 T1 T2 T1 T2
So p
Tf ≥ T1 T2

(c)
Due to Carnot’s theorem, we get the maximal amount of work when the whole procedure is reversible, which
means that we get
∆S1 + ∆S2 + ∆Sengine = 0
and p
Tf = T1 T2
So putting this expression back into the expression for work, we get
p
W = Cp (−2 T1 T2 + T1 + T2 )

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Problem 3
We are asked to find the final temperature of the van der Waal gas after adiabatic expansion into free space.
The key here is to realize that, in addition to no heat flowing, there is also no work done as the gas is released
into a vacuum. Hence,
U (T 1, V 1) = U (T 2, V 2)
Thus, we can solve for T2 :

3 C C
2 N kT2 − = 32 N kT1 −
V2 V1
 
1 C C
T2 = T1 + 3 −
2Nk
V2 V1
 
2C V2 − V 1
T2 = T1 −
3N k V1 V2

Note that in the limit, C → 0, T2 → T1 , for an ideal gas the temperature does not change. In the case
of the van der Waal, the temperature changes because there is attractive potential between molecules, and
separating the mean spacing costs energy.

Problem 4

(a)
Piston does negative work, so according to the first law, and the fact that the system is insulated(∆Q = 0),
the internal energy decreases. As
3
∆U = kB ∆T
2
We know that the temperature also decrease.

(b)
As this procedure is not quasi-static, it cannot be reversible, so the second law tells us that

∆S > 0

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(c)
(The problem is not clearly stated if the heat capacity is for one molecule or for the whole N particles, so if
your answer is differ by some N in front of CV it is still correct).
As the system is insulated, ∆Q = 0, so the first law tells us that,

∆U = Won

(Note that our sign convention applies to work done ‘on’ the system)

V 0 − V1
N Cv (T1 − T0 ) = mg
A
Then we combine ideal gas equation and mechanical equilibrium condition
mg N k B T1 A
P 1 V 1 = N k B T 1 , P1 = , V1 =
A mg
So
mg N k B T1 A
N Cv (T1 − T0 ) = (V0 − )
A mg
Cv T0 + mgV
NA
0

T1 =
Cv + kB

Problem 5

(a)
The information at the beginning of this problem indicates that this gas behaves like an ideal gas, of the
kind with U = 23 N kT .
The first mechanism stated is a constant pressure volume change, followed by a constant volume pressure
change.
The work done by the gas in the isobaric process is PA (VB − VA ). The heat added during this process is

∆Q = ∆U − ∆W
= 32 N k∆T + PA (VB − VA )
= 32 PA (VB − VA ) + PA (VB − VA )
= 25 PA (VB − VA )

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In the second step the work done is zero. The heat released is:

∆Q = ∆U
= 23 N k∆T
= −(PA − PB )VB

Hence the total work done is PA (VB − VA ), and the net heat absorbed is 52 PA (VB − VA ) − (PA − PB )VB .

(b)
The work done is
Z VB
W = P dV
VA
PB − PA
where P = (V − VA ) + PA
VB − VA
⇒ W = 21 (PA + PB )(VB − VA ).

The heat added is

∆Q = ∆U − ∆W
= 32 N k∆T + 21 (PA + PB )(VB − VA )
= 32 (PB VB − PA VA ) + 21 (PA + PB )(VB − VA )
= 12 (VB (PA + 4PB ) − VA (4PA + PB ))

Problem 6
This is basically an experimental problem, the only quantitative thing you shall understand is that in the
second situation, the system almost goes back to its initial state, which tells you that this is an reversible
adiabatic procedure. On the other hand, the first one clearly differs pretty much from the initial state and
it’s an adiabatic irreversible procedure.
For the reversible one, we will be able to analyze the details of the procedure in our next problem set.
(and also when we have canonical ensemble in the future).

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