TERMODYNAMICS

Problems for the rst olloquium o 2 De ember 2019

Problem T.1
Prove that if the internal energy U of a simple system does not depend on its total
volume V (only on its temperature T and the numbers of moles of its onstituents), it is
also independent of the pressure. Are ex eptions from this rule possible?
Problem T.2
Knowing that the internal energy is a state fun tion and relying on 2TMDL in the form
d¯Q = T dS show that

∂(T, S)
= 1.
∂(p, V )

Problem T.3
It has been established experimentally that the oe ients: αp of thermal isobari expan-
sion and the one of isothermi ompressibility kT of a simple substan e behave, as fun tions
of its volume and temperature, as follows:
3bT 2
   
1 ∂V 1 ∂V a
αp ≡ = , kT ≡ − = ,
V ∂T p V V ∂p T V

with a and b being some onstants. Write down the equation of state of this substan e.
How the onstants a and b depend on the total number n of its moles if it possessess the
extensivity property?
Problem T.4
By measuring the oe ient of isothermi ompressibility kT and the iso hori thermal
pressure oe ient βV of a simple homogeneous substan e it has been established that
   
∂p ∂p nR
= −nRT f (V ) , = − 2anRT ,
∂V T ∂T V V

where a is a onstant and f (V ) a fun tion of the volume only. Write down the equation
of state of this substan e.
Problem T.5
The oe ients: αp of thermal isobari expansion and the one of isothermi ompressibi-
lity kT of a simple body depend on the temperature T and pressure p as follows:
aT 2 bT 3
   
1 ∂V 1 ∂V
αV ≡ = , kT ≡ − = ,
V ∂T p p V ∂p T p2

where a and b are some onstants. Write down the equation of state of this substan e.
Are the onstants a and b related?
Problem T.6

2
Compute the molar heat apa ity of the perfe t gas (whose equation of state is p v = RT
and whose molar heat apa ity at onstant volume cv is independent of temperature) in
the reversible hange in whi h
pv a+1 = const.

In other words, nd the oe ient of the dierential dT in the (molar) heat one-form
dq proje ted onto the urve determined by the above equation in the spa e of the gas
equilibrium states.
Problem T.7
Two metalli pistons en lose from opposite sides a ylinder of the ross se tion A onta-
ining perfe t gas. The pistons attra t one another owing to a battery holding the potential
dieren e ϕ between them.1 Give the equation of the hange (analogous to the Boyle equ-
ation pV = onst. orresponding to the isothermal expansion of su h a gas) the gas is
undergoing when its volume hanges (due to reversibly displa ing one of the two pistons
by applying to it an external for e) if in the pro ess it takes heat form the surrounding
(via the diathermal side wall of the ylinder). Find the gas heat apa ity in this hange
expressing it through either Cp or CV (its prin ipal heat apa ities) whi h are assumed
to be onstant.
Problem T.8
Show that the dieren e of the prin ipal heat apa ities Cp and CV of a simple system
an be written in the form
  "  #
∂V ∂U
Cp − CV = p+ .
∂T p ∂V p

Problem T.9
let us introdu e the new state fun tion, the enthalpy H dened by H = U + p V . Justiy
the formula
 
∂H
Cp = .
∂T p

Using enthalpy show that

       
∂p ∂V ∂U
Cp − CV = − p + .
∂T V ∂p T ∂p T

Problem T.10
Relying on 1TMDL only but assuming that the internal energy of a gas, whose equation
of state is pV = nRT , does not depend on the volume V , that is, that U = U(T, n),
1 Weassume that the ross se tion A of the ylinder is large enough and therefore the ele tri eld
between the pistons an be treated as onstant in the whole ylinder volume.

3
nd the relation2 between its two prin ipal heat apa ities Cp i CV (and therefore also
between its molar prin ipal heat apa ities cp i cv ).
Problem T.11
Relying on 1TMDL alone (i.e. not appealing to entropy), prove the relation kad =
(cv /cp )kT linking the oe ients of adiathermal and isothermal ompressibilities of a
simple body with its (molar) prin ipal heat apa ities.
Hint: Start by equating to zero the (molar) heat one-form dq .

Problem T.A
Write down the dierential equation whi h determines on the plane (v, p) the urve orre-
sponding to the (quasistati ) hange of a simple substan e in whi h a quantity x (a given
fun tion of the variables p and v , e.g. x = p5 v 3 , or something of this sort) expressing this
equation through the molar heat apa ities cx i cv , derivatives whi h an be omputed
knowing the equation of state and the dependen e of the internal energy on the volume.
Apply the obtained equation to the perfe t gas, assuming that the gas internal energy
does not depend on the volume. Solve the equation assuming that the perfe t gas prin i-
pal heat apa ities and cx are onstant. Simplify also the obtained general equation using
2TMDL.
Problem T.12
Relying on 1TMDL alone (that is, without appealing to entropy) and starting from the
state fun tion h = u + pv - the molar enthalpy - prove the relation (holding for simple
substan es)
    
∂cp ∂ kT
= v αp − (cp − cv ) .
∂p T ∂T αp p

Problem T.13
Relying on 1TMDL alone prove the relation (obtained for the rst time by
Plan k)

∂2T
       
∂cp ∂T ∂cv ∂T
(cp − cv ) + − = 1,
∂p∂v ∂p v ∂v p ∂v p ∂p v

linking the properties of a simple substan e.

Hint: Expres the derivative (∂u/∂p)v through cv , and the derivative (∂u/∂v)p
through cp and equate to one another mixed se ond derivatives of the (molar)
internal energy u omputed in two dierent ways.
2 Itis impossible to nd this relation using 1TMDL alone; adding the information that the internal
energy does not depend on the volume is ne essary. Only if 2TMDL is used, it is possible to determine
the dependen e of U (and of CV ) on the volume, that is to prove (mathemati ally and not by using
heuristi physi al reasonings) that U independent of V is onsistent with the perfe t gas equations of
state.

4
Problem T.14
Exploiting the hara teristi s of the air (treated as perfe t gas) at NTP, that
is at normal temperature and pressure: T = 273.15 K and p = 1.013 × 105 N/m2 :
ρ = 1.29 kg/m3 , c̃p = 238 al·kg−1 ·K−1 , γ ≡ cp /cv ≡ c̃p /c̃v = 1.41 and v =
22.4 × 10−3 m3 /mol, and expresssing the gas onstant R in two dierent ways,
determine the ratio (1 al/1 J). In other words, determine the work equivalent
of heat.

Problem T.15
Exploiting the hara teristi s of the air (treated as perfe t gas) at NTP: T =
5 2 3 −1 −1
273.15 K, p = 1.013 × 10 N/m : ρ = 1.29 kg/m , c̃p = 238 J·kg ·K and γ ≡
cp /cv ≡ c̃p /c̃v = 1.41, ompute the heat needed to raise temperature from 0o C
to 20o C of the air having initially the volume V = 27 m3 , in two dierent
situations:
a) the air is heated at onstant volume (therefore its pressure hanges as it
absorbs heat),
b) the air is heated at onstant volume and pressure be ause the ontainer
en losing it has a hole as a result of whi h the pressure inside is equal to the
pressure outside poutside = 1.013 × 105 N/m2 .

Problem T.16
Prove that the measurable oe ients βV , kT , αp hara terizing a simple ther-
modynami al system are not independent (it su es to measure two of them,
to know the third one). Express through these oe ients the equality orre-
lating the hanges dp, dT and dV of pressure, temperature and volume when
the system passes from one equilibrium state to another equilibrium state
innitesimally lose to the rst one.

Problem T.
Show that the so- alled Grüneisen oe ient Γ whi h an be obtained by me-
(t)
asuring the heat apa ity CV (referred to the unit of an empiri al temperature
t) and the oe ients αp = (1/V )(∂V /∂t)p (of isobari thermal expansion) and
kt = −(1/V )(∂V /∂p)t (of isothermi ompressibility), dened as

V αp
Γ= ,
CV kt
ontains information about the dependen e of a uid (or any simple system
hara terized by the parameters V and p) internal energy U on its pressure.
Furthermore, knowing that in some range of parameters this oe ient is
nearly onstant, give the most general form of the dependen e (valid in this
range) of the system's internal energy U on pressure and volume.

Problem T.17
Compute the oe ients αp , k T and βV of a gas whose equation of state is the

5
Dieteri i equation
 an 
pV = nRT exp − .
TV
Che k dire tly that the omputed oe ients satisfy the relation found in the
pre eding Problem.

Problem T.18
Knowing that 77% of the air mass are N2 mole ules and the remaining 23%
- mole ules of O2 ompute the air molar heat. The spe i heats (per unit
(N2 ) (O2 )
mass) of these two gases are c̃v = 176 al·kg−1 ·K−1 and c̃v = 158 al·kg−1 ·K−1 ,
respe tively. Treat air as a mixture of two idel gases not intera ting with one
another.

Problem T.19
Assuming that sound waves propagating in air are its adiathermal ompres-
sions and de ompressions (i.e. are adiathermal hanges of the air pressure p
and density ρ) one nds for the sound speed csound the following simple formula:
p
csound = (∂p/∂ρ)ad .

Express this speed through the air oe ient kad and ompute the sound speed
in air at NTP, approximating air by the perfe t gas having onstant molar
heat apa ity and internal energy independent of the volume and treating air
ompressions and de ompressions as a reversible hanges.
Show also that the spe i internal energy (per unit mass) ũ and spe i
enthalpy h̃ of a perfe t gas whose internal energy is independent of the volume
and the fa tor γ ≡ cp /cv is onstant, an be expresses by the formulae

c2sound c2sound
ũ = + const., h̃ = + const.,
γ(γ − 1) γ−1

Problem T.
Starting from the denition of heat as the work defe t determine heat absor-
bed by the perfe t gas (equation of state pV = nRT , n is the number of moles)
in the pro ess of transition from one equilibrium state hara terized by the
volume V1 and pressure p1 to another equilibrium state having volume V2 and
pressure p2 (assuming V2 < V1 and p2 > p1 ). The gas has been rst heated by a
Bunsen ame keeping its volume xed and then isothermally (T = onst) and
γ γ
reversibly ompressed. It is also known that p1 V1 = p2 V2 where γ = 5/3, that
is that the initial and nal states are onne ted by an adiabat (saying this is
equivalent to taking onstant its molar heat apa ity: cv = onst.).
Problem T.20

6
Taking for granted that the internal energy of a perfe t gas (molar equation of
state pv = RT ) does not depend on the volume and its molar heat apa ities cp
i cv are onstant, ompute the dieren e cp − cv onsidering the sequen e of the
following three hanges of the gas: a) adiathermal free expansion from volume
V1 and pressure p1 to volume V2 and pressure p2 (simply the wall losing the
gas in the subvolume V1 of the bigger, adiathermally isolated ylinder of total
volume V2 gets suddenly removed) b) the gas is quasistati ally and reversibly
ompressed at onstant pressure p2 (so no longer adiathermally) from V2 to V1 ,
and nally, ) reversibly and quasistati ally heated (by bringing it su essively
into thermal onta t with a sequen e of heat baths having higher and higher
temperatures) at onstant volume V1 untill it rea hes the initial pressure p1 .
Problem T.24
A perfe t gas whose internal energy is given by the formula U = CV T + onst.
with onstant CV an be taken from the state 1 hara terized by the values
(p1 , V1 , T1 ) of its pressure, volume and temperature to the state 2 hara terized
by (p2 , V2 , T2 ) as a result of three dierent reversible pro esses: i) by iso hori
ooling it until it rea hes the state A with pressure pA = p2 and subsequently
expanding it at onstant pressure to V2 , ii) rst expanding it isothermally to
the volume V2 (state B) and then ooling it down to pressure p2 , keeping its
volume onstant, and iii) expanding it adiathermally and reversibly to the
state C in whi h it has volume V2 and then ooling it iso hori ally down to
pressure p2 . Make the budget of work Wi and heat Qi absorbed by the gas
in ea h of these three pre esses. Show dire tly that in ea h of them the sum
Wi + Qi is equal to the hange ∆U of the gas internal energy.

Problem T.25
Compute the heat apa ity C of an innitely high olumn of ross se tion A,
ontaining a perfe t gas (molar equation of state pv = RT ) whose total mass
M is xed and molar heat apa ity cv is temperature independent (that is
u(T ) = cv T + onst.). The gas is in thermal and me hani al equilibrium in the
onstant gravitational eld g (that is, we negle t hanges of the gravitational
eld with the height).
Hint: The gas is not a homogeneous system; however sin e the temperature
of the gas is uniform (thermal equilibrium!) one an divide it into small
sli es and apply to ea h sli e (whi h already an be treated as homogeneous)
equilibrium thermodynami s. (The problem is not very realisti - it should
be treated as an exer ise in mathemati s.)

Problem T.28
Eploiting the Hess law (i.e. 1TMDL) al ulate the heat released in the hange
of diamond into graphite using as the data the heats released in burning these
two substan es (in the same external onditions)

Cdiament + O2 −→ CO2 + Q̄1 ,

7
 Cgrafit + O2 −→ CO2 + Q̄2 .

Q̄1 = 395.40 kJ·mol−1 , Q̄2 = 393.50 kJ·mol−1 . In the room temperature the
(phase) transition of diamond into graphite o urs very slowly whi h makes
dire t measument of the heat released in it unfeasible.

Problem T.29
Eploiting the Hess law (i.e. 1TMDL) al ulate the heat released in the heat
Q̄ released in the rea tion

Cgrafit + 2 H2 −→ CH4 + Q̄ ,

knowing the heats released in the following two hemi al rea tions

1
H2 + O2 −→ H2 O + Q̄1 ,
2
Cgrafit + O2 −→ CO2 + Q̄2 .
CH4 + 2 O2 −→ CO2 + 2 H2 O + Q̄3 ,

in whi h Q̄1 = 285.80 kJ, Q̄2 = 393.50 kJ i Q̄3 = 890, 40 kJ.

Problem T.30
On the basis of: a) Clausius inequality, b) 2TMDL as formulated by Kelvin
that if as a result of an isothermal reversible hange (pro ess) a system re-
turns to the initial state then the heat it absorbed in this hange from the
surrounding must be zero (and, by 1TMDL also the work done by the system
must be zero).

Problem T.31
Show that the e ien y of a y le (not ne essarily a reversible one) at dierent
stages of whi h the working substan e takes heat from a number of reservoirs
of temperatures not grater than Tmax and not lover than Tmin is bounded by

Tmin
ηmax = 1 − .
Tmax

Problem T.32 (K1.II.E2)

Show, exploiting 2TMDL in the form dS = (dU + p dV )/T , that if the equation
of state of a simple system has the form

p = T f (V ) ,

the internal energy U of this sustem does not depend on its volume. (An
example of su h a system is the elebrated perfe t gas.)

Problem T.33

8
Exploiting 2TMDL, that is the existen e of entropy as a state fun tion, express
the oe ients
   
∂T ∂T
αS−1 ≡V , βS−1 ≡p ,
∂V S ∂p S

hra terizing hanges of the body's temperature resulting form an adiathermal

and reversible (adiabati , in short) hange of its volume or pressure through
the quantities whi h an be omputed knowing the body's equation of state
and one of its heat apa ities. Express by the oe ients αS−1 and βS−1 the
hanges of the body's entropy resulting from the reversible volume hanges
at onstant pressure and reversible pressure hanges at onstant volume.3

Problem T.34
Prove the relation kad = (Cv /Cp )kT linking the ompressibility oe ients of a
body with its prin ipal heat apa ities, using 2TMDL.4

Problem T.35
Express the dieren e Cp − CV of the prin ipal heat apa ities of a simple
body through the measurable oe ients αp of isobari thermal expansion, kT
of isothermi ompressibility and/or βV -iso hori thermal pressure oe ient
(all of whi h an be omputed from the equation of state f (T, V, p) = 0).
Problem T.36
Using 2TMDL show that

  "  #
∂cp ∂αp
= −T v αp2 + .
∂p T ∂T p

Problem T.37
Using 2TMDL in the form Q̄ = T dS derive the formulae for the dependen e
on pressure p of the enthalpy H = U + p V ,
entropy S and the heat apa ity
Cp (that is, express the derivatives of these three quantities with respe t to
p through quantities whi h an be obtained from the equation of state) of a
simple body (a gas or a liquid). Treat the number of moles as xed. Do this
twi e: in the enthalpy and in the entropy representations. Using the results
give a method of re onstru ting the state fun tions U(T, p) and S(T, p) from
the data on the heat apa ity Cp (T, p0 ) (known at one parti ular value p0 of the
pressure) and the equation of state f (T, V, p) = 0.

Problem T.
3 Reversibility must be se ured by the ex hange of heat with a sequen e of heat reservoirs having
temperatures adjusted to the a tual temperature of the body.
4 Proof of this relation was already the ontent of Problem T.11; the point here is to appre iate hw
using entropy fa ilitates the task.

9
Express the dierentials dU
dH of the internal energy enthalpy of a simple
and
body through the dierentials dV and dp, the variables V and p, mesurable
heat apa ities Cp , CV and the oe ients αp (of isobari thermal expansion)
and kT (of isothermal ompressibility) of this body.

Problem T.38
Show that the heat apa ity CV (measured at xed volume V of a gas whose
parameters are related by the Van der Waals equation of state does not depend
on the volume V. Assuming that CV is known as a fun tion of temperature T,
determine the heat apa ity Cp (measured at xed pressure p) of this gas.

Problem T.40
Determine the dependen e of the internal energy u(T ) per unit volume of a
simple system, knowing that its pressure p depends only on the temperature
T and is related to u(T ) by 3p = u(T ). What this system an be?

Problem T.41
At temperature T = 25oC the volume of one mole of water is given by the
empiri al formula
  p 2 
p
v = 10.066 − 0.000715 + 0.000000046 cm3 .
1 atm 1 atm

It is also known, that for pressures between 1 and 1000 atm,

 
∂v h p i 3 −1
= 0.0045 + 0.0000014 cm ·K .
∂T p 1 atm

Compute the work ne essary to ompress isothermally from 1 atm to 1000 atm
two moles of water whi h remains in thermal onta t with a heat reservoir at
temperature T = 25o C, the heat absobed in this por ess by the wated and the
orresponding hange ∆U of these two moles of water.

Problem T.42
Give the formulae whi h determine as fun tions of the variables T and v the
internal energy u and entropy s of one mole of a gas, whose parameters satisfy
the VdW equation
 a
p+ (v − b) = RT ,
v2
assuming that the molar heat apa ity cv of the gas is known as a fun tion of
temperature at one value v0 of the molar volume. Give also the expli it form
of entropy S depenen e on the internal energy u volume v and the number of
moles n, valid in the range of temperatures in whi h the molar heat apa ity of
the gas is independent of temperature. Obtain this result on e by expressing

10
in the formula for S(T, v) the temperature as an expli it fun tion T = T (u, v)
and the se ond time by integrating dire tly the one-form

1 p
ds = du + dv .
T T

Problem T.
The tension K of a rubber band is, at xed its length L, a linear fun tion of
temperature: K = T A(L). Show that internal energy of su h a rubber band
is independent of its length and that in the range of lengths, in whi h the
tension K is positive, the rubber band entropy de reases with its stret hing
(elongation). Show also, that in the same range of lengths the temperature of
the band rises when it is stret hed adiabati ally (adiathermally and reversibly)
and (appealing to the obvious thermodynami stability ondition whi h states
that teh rubber band does not stret h spontaneously, that is, that (∂K/∂L)T >
0) that it shrinks when heated at onstant tension K.
Problem T.43
It follows from experien e that when a rubber band is stret hed adiabati ally
(adiathermally and reversibly), its temperature raises. Using this fa t, show
that the thermal expansion oe ient of the rubber band, (∂L/∂T )K , where L
is the rubber band length and K its tension, is negative, whi h implies that
the rubber will shrink with the in rease of its temperature.
Hint: Exploit the thermodynami stability onditions expressed by the ine-
qualities CL > 0 (CL is the rubber band heat apa ity at onstant length L)
and (∂K/∂L)T > 0 (whi h is the rubber band analog of the stability ondition
(∂p/∂V )T < 0 for uids).
Problem T.44
The heat apa ity of a rubber band measured in the onditions in whi h its
length was held xed, L = L0 , hanges linearly with temperature. Pojemno±¢
ieplna ta±my gumowej zmierzona w warunka h, It has also been found that
in some range of temperatures the tension K of the dependen e of the band
tension K on its length and temperaure is given by the formula

L2
 
L
K(T, L) = aT − 02 ,
L0 L

in whi h L0 an be taken for onstant (independent of temperature). Deter-

mine the band internal energy U and entropy S. Give also the formula for its
heat apa ity CK (at onstant tension).

Problem T.45
Two rubber bands as in the pre eding Problem but with dierent oe ients
(1) (2)
in their linearly depndent on temperature heat apa ities CL i CL at xed

11
length and dierent oe ients a(1) i a(2) in the formulae giving dependen es of
their tensions on temperatur and length have initially dietent temperatures
T1 and T2 . The bands have been joined side by side (allowing their thermal
onta t) but keeping un hanged the length of ea h. What will be their nal
temperature when they attain thermal equilibrium? Compute also the hange
of entropy and show that it is positive.

Problem T.47
It has been found experimentally, that the for e K with whi h two ends of a
rubber rod must be stret hed to keep it in the me hani al equilibrium at the
length L is given by the formula

L20 (T )
 
L
K = aT − ,
L0 (T ) L2
in whi h a is a onstant and dL0 (T )/dT = α = onst. Compute the heat released
(transferred to the surrounding) if the rod is stret hed from L1 = L0 to L2 = 2L0
if the stret hing is done isothermally (and reversibly - the rod remains in
thermal onta t with the surrounding).

Problem T.
Prove that if the internal energy U of a simple uid does not depend on its
volume V then:

• its heat apa ity CV (at onstant volume) also annot depend on the
volume

• its equation of state must have the form V = f (p/T ), in whi h f (·) is some
fun tion of a single variable,

• Cp − CV is also a fun tion of the ratio p/T only.

Problem T.
Show that in isobari expansion of a simple body, that is, in a pro ess in
whi h its volume hanges by δV at onstant pressure, its entropy S in reases
or de reases, depending on the sign of the oe ient αp ≡ (1/V )(∂V /∂T )p of
thermal expansion of this body.

Problem T.
Compute the nal temperature T and the hange ∆s of the entropy of one mole
of a gas whi h from the equilibrium state hara terized by the parameters v0
and T0 has adiathermally (that is being thermally isolated) expanded into the
va uum till the nal molar volume v. Parameters T, v i p of this gas satisfy
the Berthelot equation of state

RT a
p= − 2 .
v−b v T

12
It is also known that when v → ∞, its molar heat apa ity be omes equal to
the molar heaat apa ity of one-atomi perfe t gas.

Problem T.
Prove that the temperature drop of any gas resulting from its adiabati (adia-
thermal, reversible) de ompression from the pressure p to the pressure p − dp
is greater (i.e. the nal temperature is lower) than in its transition from the
same initial state to the nal pressure p − δp in the Joule'a-Thomson pro ess.
Hint: Compare the appropriate derivatives relevant to ea h of these pro esses.

Problem T.
By dire t al ulation show that the e ien y of the Carnot y lebeing a om-
plished by n moles of the Van der Waals gas equals η = 1 − T− /T+ , where T±
are temperatures of the hoter and older reservoirs.

Problem T.
By dire t al ulation show that the in rease of entropy of a perfe t gas (of
onstant molar heat apa ity cv ) as a result of a pro ess whi h aused also
in rease of its temperature from T1 to T2 > T1 at onstant presssure (e.g.
stirring or ele tri ally heating the gas lling a baloon - its pressure is then
equal to the atmospheri one) is γ = cp /cv times greater than the entropy
in rease as a result of a pro ess in whi h the gas temperature has also hanged
from T1 to T2 > T1 but at onstant volume (when the gas is en losed in a rigid
ontainer). How this ratio (of the entropy hanges in the two pro esses) would
look like if the gas heat apa ity dependend on temperature?

Problem T.
It has been established experimentally that the produ t pV of the volume and
pressure of a uid is onstant at onstant empiri al temperture t, that is, that
p V = f (t). It is also known that the internal energy of this uid is a fun tion
of t only. Show that f (t) has the meaning of the absolute temperature.
Hint: Write down the heat form of the uid in the variables t, V and seek its
integrating fa tor; then show that in a Carnot y le with this uid as a working
substan e the ratio of heats Q1 and Q2 taken by the uid in the isothermal
parts of the y le at temperatures t1 and t2 is equal to the appropriate ratio
of the integrating fa tors.

Problem T.
The dependen e of the thermal expansivity oe ient αp of a solid on the
volume and hydrostati pressure is, in some range of the pressure and at xed
temperature T0 , given by the empiri al formula
a + b p + c p2
αp = ,
V
in whi h a, b and c are some onstants (of appropriate physi al dimensions).
What will be the entropy hange of this body, if the hydrostati pressure to

13
whi h it is subje ted, will in reas from p1 to p2 at onstant temperature T = T0
of the environement with whi h the solid is at the beginning and at the end
in equilibrium?

Problem T.
Compute the hanges ∆S of the entropy, ∆F of the free Helmholtza energy
and ∆G of the Gibbs fun tion (free enthalpy) resultting from the isothermal
ompression of 2 moled of a perfe t gas from p1 = 1 atm to p2 = 100 atm at
20o C.
Problem T.
Give the formula for the molar free Helmholtz energy of the perfe t gas as-
suming that the equation of state p v = RT and the molar heat apa ity cv
of this gas as a fun tion of the temperature are given. Show that the two
formulae: one obtained dire tly from the denition f = u − T s and the se ond
one, obtained by integrating up the (exa t) dierential form df = −s dT − p dv ,
although look diernetly at rst sight, are in fa t equivalent.

Problem T.
A simple, one omponent substan e has the following properties: i) n of its
moles expanding reversibly from V0
V at onstant temperature T0 does
to the
work W̄ = nRT0 ln(V /V0 ), ii) entropy of n its moles is given by the formula
 a
V0 T
S = nR ,
V T0

in whi h a is some onstant exponent. Find the free Helmholz energy of this
substan e, its equation of state and work it (teh substan e, not the equation
of state!) does expnding reversibly from V0 to V1 at an arbitrary onstant
tempetature T.
Problem T.
Show that the oe ients of adiathermal (adiabati ) and of isothermal om-
pressibility, kS and kT , of a simple body, dened by the formulae
   
1 ∂V 1 ∂V
kS = − , kT = − ,
V ∂p S V ∂p T

are related by
"  #2
T ∂V αp2
kS = kT − = kT − V T .
V Cp ∂T p Cp

Problem T.

14
What minimal work is required to produ e in the environment of tempera-
ture T25 = 25o C 103 kg of i e out of water having (initially) the same tem-
perature as the envirinment? The molar heat apa ity of water is cH 2 O =
−1 −1
18.05 al·mol ·K and the latent heat of the i e-water phase transition is
qice→water = 1436.3 al·mol−1. Assume that the ooling of water o urs at (pra -
ti ally) onstant volume (so the molar heat apa ity given here is to be inter-
preted as the one at onstant volume). On the other handm the solidi ation
of water is a ompanied by the in rease of volume (so the given latent heat is
to be interpreted as pertaining to xed pressure and temperature). Compute
the minimal work (negle ting the ee t of the volume in rease) realizing di-
re tly an appropriate pro ess. Compare the resulult of su h al ulation with
the one obtained using the general formula Wmin = ∆(U − T0 S + p0 V ) for the
minimal work required to realize the transition of the thermodnami system
from one equilibrium state to another one.

Problem
Compute the maximal work that an be obtained from ooling of n moles of
a perfe t gas (of onstant molar heat apa ity cv ) from the initial tempera-
ture T and pressure p doen to the temperature T0 of the environment with
simultaneous de ompressing down to the environment pressure p0 .

Problem
A diathermal umovable wall divides an isolated ontainer into two parts of
volumes V1 and V2 . Ea h of them ontains n moles of the same perfe t gas
of onstant molar heat apa ity cv . The pemeratures of the two parts of the
ontainer are equal (the wall is diathermal). What would be the hange ∆S
of entropy of the whole system if the wall were removed? What maximal
work ould be obtained bringing the gas to a nal state orresponding to the
absen e of the wall?

15