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Mihai Dima
Applications of the first two principles
Content
• 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.
𝜕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)
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.
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
1 𝜕U 𝜕V
C p − CV = +p
ν 𝜕V T
𝜕T p
𝜕U
= 0 due to the neglection of the inter-molecular interaction forces, the internal energy does not
𝜕V T
depend on volume
Consequently:
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)
dU = δQ − pdV = δQ − d pV + Vdp
𝛛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
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
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
𝜕V R V
=ν =
𝜕T p
p T
dT dV
+ (n − 1) =0
T V
• The simple transformations of the ideal gas are obtained in particular cases:
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 (- ∞, ∞)
• 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
• 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.
log p1 − log p2
n=
log V2 − log V1
• 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
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 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
• 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
• 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.
• 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
and:
𝐩𝟏
𝐒𝟐 − 𝐒𝟏 =νR ln
𝐩𝟐
𝐕𝟏
𝑺𝟐 − 𝑺𝟏 =νR ln
𝐕𝟐
δQ = dU + pdV => δQ = dU
𝐓𝟐
Q12 = U2 V, T2 − U1 V, T1 = න 𝛎 𝐂𝐕 𝐝𝐓 = 𝐐𝟏𝟐
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
𝜕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
• Thus, even if the internal energy does not change, the temperature
can change due to conversion between kinetic and potential
energy.
• 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
If Cv is constant:
ν2 a
dU = ν CV dT + dV = 0 and
V2
𝜕T νa
η= =− <0
𝜕V U
CV V 2
• 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
o the gas is pushed in the right space, through the hole (at
constant pressures, reaching another equilibrium state (p f, Vf;
pi>pf).
L = න pi dV + න pf dV = −pi Vi + pf Vf
Vi 0
Uf − Ui = −L = pi Vi − pf Vf
Ui + pi Vi = Uf + pf Vf
Hi = Hf
𝜕H 𝜕H 𝜕T 𝜕T
=− = −νCp
𝜕p T
𝜕T p
𝜕p H
𝜕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
𝜕H dH
νCp = = ; dH = νCp dT
𝜕T p dT
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).
In a free expansion of an isolated system, the temperature is constant for an ideal gas, but
decreases for a real one.