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CD221: Thermodynamics and Statistical Mechanics

Assignment 1 Work out all the problems

Q1: Consider 1.0L of a monoatomic ideal gas initially at 273.0K and 10.0 atm pressure in a piston. The gas is allowed to expand to a ﬁnal pressure of 1.00 atm by three diﬀerent paths:

 (a) reversible isothermal expansion (b) reversible adiabtic expansion (c) irreversible adiabatic expansion (against constant external pressure P e xt=1 atm)

Calculate the ﬁnal volume V f , temperature T f , and work w performed in each process.

Q2: Consider the quasi-static and cyclic process of an ideal gas (the Carnot cycle) shown in ﬁgure below. The change form 1 to 2 is an isothermal expansion in contact with a heat bath at temperature T 1 , that from 2 to 3 an adiabatic expansion, that from 3 to 4 an isothermal compression in contact with a heat bath at temperature T 2 , and ﬁnally that from 4 to 1 an adiabatic compression. If the heat absorbed from the heat bath at T 1 is Q 1 and the heat absorbed from the heat bath at T 2 is Q 2 , show that Q 1 /T 1 + Q 2 /T 2 = 0. Assume the speciﬁc heat to be constant. Q3: Show that the internal energy of a material whose equation of state has the form P = f (V )T is independent of the volume. Here P is the pressure, T the absolute temperature, and f (V ) is a function of V only.

Q4: Find the three equations of state for a system with the fundamental equation U =

v o θ

R

2

S 3

NV . Corroborate that the equations of state are homogeneous zero order (i.e.,

that T , P , and µ are intensive parameters).

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Q5: An equation of state for a rubber band is either

S =

or

S = L o γ exp(θnU/L o ) L o γ[

L o γ(θU/L o ) 1/2 L o γ[ 1 2 (

L

L

1

o ) 2 + L o

L

2 (

o ) 2 + L o

L

L

L

3 2 ]

3

2

]

where γ, l o and θ are constants, L is the length of the rubber band, U is the internal energy, S is the entropy, n is the number of molecules in the rubber band, and L o = nl o . Which of the two possibilities is acceptable? Why? For the acceptable choice deduce the dependence of the tension, f , upon temperature, T and L/n; that is determine f (T, L/n).

Q6: If C p = T T P,N then prove C p

∂S

∂P

T,N = T 2 V

∂T 2

P,N .

Q7: Consider the two processes of removing the sand from the top of a piston (see ﬁgure below): (a) removing it grain-by-grain in an ideal, inﬁnitely slow manner, or (b) remov- ing it at a ﬁnite rate. Indicate the type of process that each is, and the corresponding change in entropy. Q8: Show that if X and Y are extensive, then X/Y and ∂X/∂Y are intensive.

Q9: Show that (K S /K T ) = C v /C p , where K S =

1

V

T,N are

the adiabatic and isothermal compressibility’s respectively, and C v and C p are the

constant volume and constant pressure heat capacities, respectively. Further prove that for any stable system K S < K T .

∂V

∂P

S,N and K T

1

=

V

∂V

∂P

Q10: Thermodynamicists sometimes refer to the “ﬁrst T dS equation” and the “second T dS equation”;

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 (1) T dS = NC v dT + (T α/κ T )dV (N constant) (2) T dS = NC p dT − T V αdP (N constant)

Derive these equations. Show that the second equation leads directly to the relation

T

T v = C p T vα P

∂s

∂T v .

Q11: Two identical bodies each have heat capacities (at constant volume) of C(T ) = a/T . The initial temperatures are T 10 and T 20 , with T 20 > T 10 . The two bodies are to be brought to thermal equilibrium with each other (maintaining both volumes constant) while delivering as much work as possible to a reversible work source. What is the ﬁnal temperature and what is the maximum work delivered to the reversible work source? Evaluate your answer for T 20 = T 10 and T 20 = 2T 10 . (Answer: W = a ln(9/8) if T 20 = 2T 10 )

Q12: An experimentalist claims to ﬁnd that a particular gaseous material obeys the condi- tions

(∂p/∂v) T < 0

(∂µ/∂v) T < 0

(∂T/∂v) S > 0

(∂p/∂T ) v > 0

 (a) Identify which of these inequalities is guaranteed by stability (b) Identify which pair of inequalities is inconsistent with each other and demonstrate

why they are inconsistent.

Q13: H.B. Callen, problem: 2.8-1

Q14: H.B. Callen, problem: 3.4-10

Q15: H.B. Callen, problem: 4.5-17

Q16: H.B. Callen, problem: 7.4-9

Q17: H.B. Callen, problem: 8.2-1

Q18: H.B. Callen, problem: 8.2-2