Molecular Physics

Mihai Dima
 Applications of the first two principles
Content

 The caloric equation of state – U=U(T,V)

 The caloric equation of state – H=H(T,p)

 The politropic process

 The adiabatic process

 The isobaric process

 The isothermal process

 The isochoric process

 The Joule experiment

 The Joule-Thomson experiment

 The caloric equation of state – U=U(T,V)

• The caloric equation of state expresses the internal energy (or the enthalpy) as a function of the state
variables.

• In the case of the simple systems, with only one external parameter, there are only two independent parameters.

• 1. T and V as independent parameters

U = U(T, V) - caloric equation of state

𝜕U 𝜕U
dU = dT + dV - the caloric equation of state in diferential form
𝜕T V 𝜕V T

• Similarly with the case of the thermal equation of state, if the caloric equation of state is determined theoreticaly,
𝜕U 𝜕U
then one could determine and (based on the two equations above).
𝜕T V 𝜕V T

𝜕U 𝜕U
• Viceversa, if and are determined experimentally, then one can derived the caloric equation of state
𝜕T V 𝜕V T

based on its differential form, using also the information that U is an exact total differential (as a function of state).
 The caloric equation of state – U=U(T,V)

• From the principle 1 applied to an infinitesimal reversible transformation:

δQ = dU + pdV

and from the differential form of the caloric equation of state (shown above) one obtains:

𝜕U 𝜕U
δQ = dT + + p dV
𝜕T V 𝜕V T

where δQ is the heat exchanged by the system in an infinitesimal reversible transformation, in which T varies
with dT and V changes with dV.

• In an isochoric tranformation (V=const.), dV=0, and the above equation becomes:

𝜕U
δQ = dT
𝜕T V

• Therefore, the molar heat at constant voulme is:

1 𝜕Q 1 𝜕U
CV = =
ν 𝜕T V ν 𝜕T V

𝜕U
• As CV can be easily determined experimentally, can be also determined.
𝜕T V
 The caloric equation of state – U=U(T,V)
𝜕U 𝜕U
• From the definition of Cp and from the relation: δQ = dT + + p dV (shown before)
𝜕T V 𝜕V T

1 𝜕Q 1 𝜕U 1 𝜕U 𝜕V
Cp = = + +p
ν 𝜕T p ν 𝜕T V ν 𝜕V T 𝜕T p

and from the second previous relation, one obtains:

1 𝜕U 𝜕V
C p − CV = +p
ν 𝜕V T
𝜕T p

• For the ideal gas:

𝜕V νR
pV = νRT so that = and from the relation above:
𝜕T p p

𝜕U
= 0 due to the neglection of the inter-molecular interaction forces, the internal energy does not
𝜕V T
depend on volume
Consequently:

𝐔 = 𝛎𝐂𝐕 𝐓 + 𝐔𝟎 - the caloric equation of state for the ideal gas

𝐂𝐩 − 𝐂𝐕 = R - the Robert-Meyer relation for the ideal gas

• For the van der Waals gas:

ν2 a 𝛎𝟐 𝐚
(p + 2 )(V − νb) = νRT 𝐔 = 𝛎𝐂𝐕 𝐓 − + 𝐔𝟎 - the caloric equation of state for the van der Waals gas
V 𝐕

𝐑
𝐂𝐩 − 𝐂𝐕 = 𝟐𝛎𝐚(𝐯−𝛎𝐛)𝟑
- the Robert-Meyer relation for the van der Waals gas
𝟏−
𝐑𝐓𝐕 𝟑
 The caloric equation of state – H=H(T,p)

• 2. T and p as independent parameters

dU = δQ − pdV = δQ − d pV + Vdp

d U + pV = dH = δQ + Vdp or dQ = δH − Vdp in which H is enthalpy

The caloric equation of state is:

H = H(T, p) - the caloric equation of state formulated based on enthalpy

𝛛𝐇 𝛛𝐇
𝐝𝐇 = 𝐝𝐓 + 𝐝𝐩 - the differential form of the caloric equation of state, based on enthalpy
𝛛𝐓 𝐩 𝛛𝐩 𝐓

𝜕H 𝜕H
dQ = dH − Vdp = dT + − V dp
𝜕T p
𝜕p T

1 𝜕Q 1 𝜕H
Cp = =
ν 𝜕T p
ν 𝜕T p

1 𝜕Q 1 𝜕H 1 𝜕H 𝜕p
CV = = + −V
ν 𝜕T V
ν 𝜕T p
ν 𝜕p T
𝜕T V

1 𝜕H 𝜕p
C v − C𝑝 = −V
ν 𝜕p T
𝜕T V

For the ideal gas: H = U+pV = ν CpT + H0, where U = νCV T + U0 and the equation of state were also used;
𝜕H 𝜕p νR
= 0; = and Cp − CV = R
𝜕p T 𝜕T V V
 The equation of the politropic process
• The politropic process is that in which the molar heat is constant. For such a process:

δQ = νCdT

• Combining the equation above with two relations demonstrated before (and shown again below):

𝜕U 𝜕U
δQ = dT + + p dV
𝜕T V 𝜕V T

1 𝜕U 𝜕V
Cp − CV = +p
ν 𝜕V T
𝜕T p

one obtains the equation of the politropic process:

𝐝𝐕 Cp −C
𝐝𝐓 + (𝐧 − 𝟏) 𝛛𝐕 =𝟎 where n= is the politropic index
CV −C
𝛛𝐓 𝐩

Cp −C Cp
• If C=0, then δQ=0 and n = is the adiabatic exponent γ = ; C, CV, Cp – molar heats
CV −C CV

• The equation of the adiabatic process is:

𝐝𝐕
𝐝𝐓 + (𝛄 − 𝟏) =𝟎
𝛛𝐕
𝛛𝐓 𝐩
 The equation of the politropic process for the ideal gas
𝜕V
• In order to be able to integrate the equation of the politropic process, one has to know (therefore, the
𝜕T p

thermal equation of state). For the ideal gas:

𝜕V R V
=ν =
𝜕T p
p T

and the equation of the politropic process becomes:

dT dV
+ (n − 1) =0
T V

Through integration of the above equation:

TV n−1 = const. and pV n = const. (after using TES)

• The simple transformations of the ideal gas are obtained in particular cases:

 n=γ, C=0 - adiabatic transformation

 n=0, C=Cp, p=const. - isobaric transformation

 n=1, C=∞, T=const. - isothermal transformation

 n=∞, C=Cv, V=const. - isochoric transformation

 Politropic processes (C=const.)
• The equation of the politropic process based on the variables T and V (shown before), is:

𝐝𝐕 Cp −C
𝐝𝐓 + (𝐧 − 𝟏) 𝛛𝐕 =𝟎 where n= is the politropic index
CV −C
𝛛𝐓 𝐩

• In order to express it also based on the variables p and V, one combines the above equation with the relation:

𝜕T 𝜕T
dT = dp + dV
𝜕p V
𝜕V p

obtaining:

𝜕T 𝜕T
dp + n dV = 0
𝜕p V
𝜕V p

• As it was shown before, for the ideal gas, the equation of the politropic process is:

pV n = const. with n є (- ∞, ∞)

• In a politropic transformation the system can release or receive heat.

• It is used mainly to study the processes of expansion and compression in engines with gas, in which the
transformations are neither adiabatic, neither isothermal.
 Politropic processes (C=const.)
• The mechanical work performed in a politropic transformation is:
2
L12 = න pdV
1
p1 Vn p1 V1 V1 n−1
• As: p= 1
=> L12 = 1−
Vn n−1 V2

• For the ideal gas:

n−1
νRT1 V1 p1 V1 − p2 V2 p1 V1 T2 𝛎𝐑(𝐓𝟏 −𝐓𝟐 )
L12 = 1− = = 1− = = 𝐋𝟏𝟐
n−1 V2 n−1 n−1 T1 𝐧−𝟏

• The change of internal energy in a politropic transformation is determined based on the first principle:
𝜕U 𝜕U
dU = dT + dV
𝜕T V
𝜕V T
2 V2
𝜕p
U2 − U1 = න CV dT + න T − p CV dT
1 V1 𝜕T V
𝜕p
• For the ideal gas, if the equation of state is used to express , then the term between square brackets above is
𝜕T V
zero and the change in internal energy becomes:
𝟐
𝐔𝟐 − 𝐔𝟏 = ν න 𝐂𝐕 𝐝𝐓 = ν 𝐂𝐕 (𝐓𝟐 −𝐓𝟏 )
𝟏
• Consequently, from the first principle, the heat exchanged in a politropic process is:
𝛎𝐑(𝐓𝟏 −𝐓𝟐 )
𝐐𝟏𝟐 = Δ𝐔 + 𝐋𝟏𝟐 = ν 𝐂𝐕 𝐓𝟐 −𝐓𝟏 +
𝐧−𝟏
 Politropic processes (C=const.)
• From principle 2, the change of entropy can be expressed as:
2
δQ
S2 − S1 = න
1 T
• In the politropic process: δQ = νCdT, implying that:
T2
νC
S2 − S1 = න dT
T1 T
• For C=const., the above equation becomes:
𝐓𝟐
𝐝𝐓 𝐓𝟐
𝐒𝟐 − 𝐒𝟏 = 𝛎𝐂 න = 𝛎𝐂 𝐥𝐧
𝐓𝟏 𝐓 𝐓𝟏
so that the change of entropy depends logaritmically on
temperature.

• In order to determined the value of the politropic exponent in a

transformation of a gas, one needs to measure temperature and
pressure and to use the relation derived from the politropic
equation for the ideal gas (pV n = const.):

log p1 − log p2
n=
log V2 − log V1

• n is the slope of the line constructed experimentally in a (log p, log

V) representation of a politropic transformation.
 Adiabatic processes (δQ=0)
• Adiabatic process – a thermodynamics transformation in which the system does not exchange heat wih the outside
world.

• According to the second principle, in a reversible transformation dQ=TdS. If the process is also adiabatic,
then dS=0. Therefore, and adiabatic reversible transformation is isentropic.

• An adiabatic process can be also irreversible, as it is the the flow with friction of a gas through a tube
adiabatically isolated. In such a case some heat is dissipated during the flow. As the process is irreversible
and the entropy grows: dQ=0 and dS>0. The transformation is not isentropic.

• Therefore, any isentropic transformation of an isolated system is adiabatic, but the reciprocal statement is
not valid.

• Let consider the equation of the first principle for and adiabatic reversible (isentropic) process (δQ=0):
δQ = dU + pdV => dU=-pdV

δQ = dH − Vdp => dH=Vdp

so that:
𝜕U 𝜕H 𝛛𝐇 𝐕 𝛛𝐩
= −p =V =− - the differential equation of the isentropic process
𝜕V S 𝜕p S 𝛛𝐔 𝐒 𝐩 𝛛𝐕 𝐒
 Adiabatic processes (δQ=0)
• Let define:
𝜕H
k= - the exponent of the isentropic transformation
𝜕U S

• The equation of the isentropic process becomes:

V 𝜕p 𝜕lnp
− =k => = k => dlnp = −kdlnV
p 𝜕V S 𝜕lnV S

• By integrating the last equation:

𝑝2 𝑉2 𝑝2 𝑉1
ln = −k n => ln = k ln
𝑝1 𝑉1 𝑝1 𝑉2

• If the isentropic exponent is constant during the transformation, then:

𝑝2 𝑉2𝑘
ln = ln => p1 V1k = p2 V2k => 𝐩𝐕 𝐤 =const. - the Poisson equation (the equation of the adiabatic process)
𝑝1 𝑉1𝑘

• The equation of the isentropic process is valid for gases, liquids and solids.

• For water, at 0oC, k=3602000, whereas at 100oC, k=23000. for gases, k∼1.5
Cp
• For the ideal gas: k = γ =
CV

• γ is practically independent of temperature

• During an isentropic expansion (adiabatic and reversible process) the system cools. This type of transformation
is efficent in cooling the gases.
 Adiabatic processes (δQ=0)
• From principle 1, the mechanical work in an adiabatic (reversible or irreversible) expansion is:

δL=pdV=-dU L12 = −(U2 − U1 )

• Similarly with the case of the politropic process, the mechanical work in an adiabatic transformation is:
𝐤−𝟏
𝟐
𝐕𝟏𝐤 𝐩𝟏 𝐕𝟏 𝐕𝟏
𝐋𝟏𝟐 = න 𝐩𝟏 𝐤 𝐝𝐕 = 𝟏−
𝟏 𝐕 𝐤−𝟏 𝐕𝟐

• For an ideal gas:

𝟐 𝐩𝟏 𝐕𝟏 −𝐩𝟐 𝐕𝟐
𝐋𝟏𝟐 = 𝛎 ‫ 𝟐𝐓( 𝐕𝐂 𝛎 = 𝐓𝐝 𝐕𝐂 𝟏׬‬−𝐓𝟏 ) or 𝐋𝟏𝟐 =
𝐧−𝟏

• In an isentropic processes the change of entropy and of the molar heat are zero.
 Isothermal processes (T=const.)
• For the ideal gas the isothermal transformation is described by the Boyle-Mariotte law: pV=const.

• In (p,V) coordinates, for the ideal gas, the isotherm is a hyperbole. For real gases it can have different shapes.

• The compresibility coefficient is always positive and therefore an increase of pressure along an isotherm results in a
decrease of volume.

• The mechanical work in an isothermal process is:

𝒑 𝐕𝟐
𝐋𝟏𝟐 = ‫𝐕𝐝𝐩 𝟐 𝒑׬‬ and for the ideal gas: 𝐋𝟏𝟐 = 𝛎𝐑𝐓 𝐥𝐧
𝟏 𝐕𝟏

• The heat exchanged in an isothermal transformation is:

TdS = δQ => 𝐐𝟏𝟐 =T(𝐒𝟐 −𝐒𝟏 )

• For the ideal gas, the first principle implies that the mechanical work performed by the gas in an isothermal
transformation equals the received heat: L = Q

• The entropy variation in an isothermal transformation is:

p2
𝜕S
S2 (p2 , T) − S1 (p1 , T) = න dp
p1 𝜕p T
• If one uses one of the Maxwell relations, the previous equation becomes:
p2
𝜕V
S2 − S1 = න dp
p1 𝜕T p
 Isothermal processes (T=const.)
• Alternatively, the change of entropy in an isothermal process can be expressed as a function of V and T:
p2
𝜕S
S2 (V2 , T) − S1 (V1 , T) = න dV
p1 𝜕V T
• If one uses one of the Maxwell relations, the previous equation becomes:
p2
𝜕p
S2 − S1 = න dV
p1 𝜕T p

• For the ideal gas:

𝜕p νR 𝜕V νR
= =
𝜕T V V 𝜕T V p

and:
𝐩𝟏
𝐒𝟐 − 𝐒𝟏 =νR ln
𝐩𝟐
𝐕𝟏
𝑺𝟐 − 𝑺𝟏 =νR ln
𝐕𝟐

• In an isothermal transformation the molar heat tends to infinite (CT -> ∞)

 Isobaric processes (p=const.)
• For an isobaric process:
V2 V1
=
T2 T1
• For gases, as temperature increases, the volume also grows. For real gases, liquids and solids, the warming is
associated with a thermal expansions along the isobaric process.

• The mechanical work performed in an isobaric transformation is:

𝒑 𝐕𝟐
𝐋𝟏𝟐 = ‫𝐕𝐝𝐩 𝟐 𝒑׬‬ and for the ideal gas: 𝐋𝟏𝟐 = 𝛎𝐑𝐓 𝐥𝐧
𝟏 𝐕𝟏

• The heat exchanged in an isobaric transformation is determined as follows:

δQ = dU + pdV => δQ = dH − Vdp

T2 T2
𝜕H
Q12 = H2 p, T2 − H1 p, T1 = න dT = න ν Cp dT = Q12
T1 𝜕T p T1

• If Cp is independent on temperature, then:

𝐐𝟏𝟐 = 𝛎 𝐂𝐩 (𝐓𝟐 −𝐓𝟏 )
• The change of entropy in isobaric transformation is:
T2 T2 ν Cp
𝜕S
S2 p, T2 − S1 p, T1 = න dT = න dT
T1 𝜕T p T1 T
• If the molar heat does not depend on temperature, then:
𝐓𝟐
𝐒𝟐 𝐩, 𝐓𝟐 − 𝐒𝟏 𝐩, 𝐓𝟏 = 𝛎𝐂𝐩 𝐥𝐧
𝐓𝟏
 Isochoric processes (V=const.)
• The increase of temperature at constant volume always generates an increase of pressure.

• The mechanical work performed in an isochoric transformation is zero.

𝟐
𝐋𝟏𝟐 = න 𝐩𝐝𝐕 = 𝟎
𝟏

• The heat exchanged in an isochoric transformation is determined as follows:

δQ = dU + pdV => δQ = dU
𝐓𝟐
Q12 = U2 V, T2 − U1 V, T1 = න 𝛎 𝐂𝐕 𝐝𝐓 = 𝐐𝟏𝟐
𝐓𝟏

• If CV is independent of temperature, then:

Q12 = 𝛎 𝐂𝐕 (T2 −T1 )

• The change of entropy in an isochoric transformation is (using also a relation shown before):
T2 T2
𝜕S ν CV
S2 V, T2 − S1 V, T1 = න dT = න dT
T1 𝜕T V T1 T
• If the molar heat does not depend on temperature, then:
𝐓𝟐
𝐒𝟐 𝐕, 𝐓𝟐 − 𝐒𝟏 𝐕, 𝐓𝟏 = 𝛎𝐂𝐕 𝐥𝐧
𝐓𝟏
 The Joule experiment
• The caloric equation of state, U=U(T,V), can be written in
differential form, for U=const.:
𝜕U 𝜕U
dU = dT + dV therefore
𝜕T V 𝜕V T

𝜕U 𝜕U 𝜕T 𝜕T
=− = ν CV
𝜕V T
𝜕T V
𝜕V U
𝜕V U

• Therefore, assuming that Cv is known, in order to determine

𝜕U 𝜕T
one must know .
𝜕V T 𝜕V U

𝜕T
• The dependence can be determined experimentally.
𝜕V T

• Let assume that in an initial state, a veesel (the left one in the
figure) contains gas at Pi, Vi and Ti, whereas the right vessel
contains vacuum and that both of them are adiabatically isolated
from the external environment. Initially, the two vesells are totally
isolated from each other through a wall. Then, the wall is
removed so that the gas in the left vessel can expand in the right
one.
 The Joule experiment

• The internal energy is the sum of thermal kinetic energy

(associated with molecular motion) and thermal potential energy
(associated with inter-molecular interactions).

• Temperature is a measure of thermal kinetic energy. Therefore, a

change in temperature indicates a change in thermal kinetic
energy.

• Thus, even if the internal energy does not change, the temperature
can change due to conversion between kinetic and potential
energy.

• This is what happens in a free expansion and typically produces a

decrease in temperature as the fluid expands.
 The Joule experiment
• In this tranformation, L=0 (expansion in vacuum) and Q=0
(adiabatic transformation), so that, according to principle 1:
Uf=Ui.

• For a rarefied (ideal) gas, the experiment shows that Tf=Ti, so that:
𝜕T
= 0 which implies (according to a previous relation) that:
𝜕V U

𝜕U
=0
𝜕V T

• Therefore, the internal energy of the ideal gas does not depend on
𝜕U
volume, but only on temperature, so that is an exact total
𝜕T V

differential:
𝜕U dU
νCV = = ; dU = νCV dT which, by integration:
𝜕T V dT

U T
න dU = U − U0 = න ν CV dT
U0 T0

U0 – the internal energy at a given temperature, T0.

If Cv is constant:

𝐔 = 𝛎 𝐂𝐕 (𝐓 − 𝐓𝟎) + 𝐔𝟎– the caloric equation of state

 The Joule experiment
• In general, one defines the Joule coefficient:
𝜕T
η=
𝜕V U

which, in general is different from zero.

• For the van der Waals gas:

ν2 a
dU = ν CV dT + dV = 0 and
V2

𝜕T νa
η= =− <0
𝜕V U
CV V 2

• Therefore, any real gas is cooling as a result of an adiabatic

expansion in vacuum.

• One notes that for a ideal gas, in which the intermolecular forces
are not considered (therefore can not have a mutual
transformations between internl kinetic and potential energy), its
free expansion does not generate a change of temperature.

• For a real gas (e.g. van der Waals), during the expansion, some
internal kinetic energy is transformed in internal potential energy.
As temperature is linked to the internal kinetic energy, its
decrease results in cooling during a free expansion.
 The Joule-Thomson experiment

• The design of the Joule-Thomson experiment:

o in an adiabatically isolated cyclinder are placed two pistons

separated by a wall having a hole, which allows the gas
transfer between them;

o initially, in the left space (between piston and wall) there is

gas in thermodynamic equilibrium (pi, Vi);

o the gas is pushed in the right space, through the hole (at
constant pressures, reaching another equilibrium state (p f, Vf;
pi>pf).

• The process in which a gas or liquid at pressure p1 flows into a

region of lower pressure p2, without significant change in kinetic
energy, is called the Joule–Thomson expansion.
 The Joule-Thomson experiment

• The mechanical work performed by the gas during this

irreversible process is:
0 Vf

L = න pi dV + න pf dV = −pi Vi + pf Vf
Vi 0

• From principle 1, considering also that Q=0 (adiabatic process):

Uf − Ui = −L = pi Vi − pf Vf

Ui + pi Vi = Uf + pf Vf

Hi = Hf

• Therefore, in the Joule-Thompson experiment, the initial enthalpy

is equal with the final one. One could not say that during this
process the enthalpy is constant, because the intermediate stages
are not equilibrium states.
 The Joule-Thomson experiment
• The caloric equation of state could be expressed based on
enthalpy, assuming that H=const.:
𝜕H 𝜕H
dH = dT + dp = 0 or
𝜕T p 𝜕p T

𝜕H 𝜕H 𝜕T 𝜕T
=− = −νCp
𝜕p T
𝜕T p
𝜕p H
𝜕p H

• Assuming that Cp is determined experimentally, we want to

𝜕T
determine also the value of .
𝜕p H

• For and ideal gas, there is no change of the internal energy and
therefore temperature remains constant. Consequently:
𝜕T 𝜕H
= 0 and = 0 (from the relation above)
𝜕p H 𝜕p T

• Therefore, the enthalpy does not depend on pressure, but only on

𝜕H
temperature and is an exact total differential:
𝜕T 𝑝

𝜕H dH
νCp = = ; dH = νCp dT
𝜕T p dT

𝐇 = 𝛎𝐂𝐩 (𝐓 − 𝐓𝟎 ) + 𝐇𝟎 – the caloric equation of state

 Some key ideas

 In practical applications, if temperature is measured easily than volume, then the caloric
equation of state expressing H=H(T,p) is more useful than that expressing U=U(T,V).

 An isentropic transformation (S=const.) of an isolated system is adiabatic, but the reciprocal is

not true.

 In a free expansion of an isolated system, the temperature is constant for an ideal gas, but
decreases for a real one.