THERMODYNAMICS - TDS-02/03

SECOND LAW OF THERMODYNAMICS AND ENTROPY

For a mass "m":
For a unit mass:
TdS = dQ + dLw,tot
TdS = dQ + dLw,tot
TdS = dQ + dLw + dLw' = cdT
TdS = dQ + dLw + dLw' = CdT
Where
"S" is the entropy of the total mass "m", and "S" is the entropy of the unit mass
"Lw,tot" is the total of energy losses of the fluid system with mass "m", and "Lw,tot" is the total of energy
losses of the unit mass of the fluid system
"Lw" are the fluid-dynamic losses of the fluid system with mass "m", and "Lw" are the fluid-dynamic
losses per unit mass of the fluid system
"Lw' " are all the energy losses of different kind, for the fluid system with mass "m", and "L w' " are all the
energy losses of different kind, for the unit mass fluid system. They are commonly considered zero, in
the case of fluid machines.
Thanks to the first law of thermodynamics the second law can be written as:
TdS = dQ + dLw = mcdT = CdT = dU + pdV = dH Vdp
for the total mass "m"
TdS = dQ + dLw = cdT = dU + pdv = dh vdp
for the unit mass
Moreover, owing to the perfect gas law and to the following definitions
dU = mcvdT = CvdT ; dH = mcpdT = CpdT ; dU = cvdT ; dh = cpdT
the second law of thermodynamics can be written as
T dS C dT Cv dT m R T dv v Cp dT m R T dp p

T dS c dT c v dT R T dv v cp dT R T dp p

Therefore, the entropy change can be obtained as

dS C dT T Cv dT T m R dV V Cp dT T m R dp p
dS c dT T c v dT T R dv v cp dT T R dp p

And the entropy finite difference can be calculated through a proper integration
dS C dT T Cv dT T m R dV V Cp dT T m R dp p

dS C dT T C v dT T R dV V

Cp dT T R dp p

T
T
V
T
p
S SB SA C ln B C v ln B m R ln B Cp ln B m R ln B
TA
TA
VA
TA
pA

and also:
dS c dT T c v dT T R dv v cp dT T R dp p

dS c dT T c v dT T R dv v

c p dT T R dp p
A

T
T
v
T
p
S SB SA c ln B c v ln B R ln B cp ln B R ln B
TA
TA
vA
TA
pA

THERMODYNAMICS - TDS-02/03

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Relationship between the generic specific heat "c" and the polytropic power index ""
c dT T c v dT T R dv v cp dT T R dp p

pv R T
p v constant p v v 1 R T v 1 =>

T v 1 constant

d T v 1 0 v 1 dT T 1 v 2 dv

=>

dT T 1 dv v 0

dv
1 dT

v
1 T

c dT T c v dT T
c cv

R
dT T
1

R cv
k 1
R
c v 1

c v 1
1
1

Therefore:
c cv

k
1

cp c
cv c

*****
NOTES
For an unsteady flow process with constant pressure (over time):
U + Le = ... = H
For a steady flow process wrapped by still walls (even if the pressure changes point to point):
U + Le = H + Li = H
Therefore, generally speaking:
a steady-state flow process (also combustion) at constant pressure can be handled with the same
equations of an unsteady-state flow process which is in contact with fixed walls (that is without moving
parts of a machine).
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THERMODYNAMICS - TDS-02/03

THERMODINAMIC DIAGRAMS FOR GAS AND VAPOUR

Diagrams "p-v", "T-S", "h-S", "p-V" , "p-h" etc.
.- "pressure vs volume per unit mass":
useful for gaseous fluids; areas in this plane correspond to energy quantities per unit mass
.- "absolute temperature vs entropy per unit mass":
useful for gaseous fluids (and vapour, too); areas in this plane correspond to energy quantities per unit
mass
.- "enthalpy per unit mass vs entropy per unit mass":
useful for vapour (e.g. the Molliers diagram for water vapour); vertical segments on this plane
correspond to energy quantities per unit mass
.- "pressure vs volume":
useful for volumetric machines because takes into account both the thermodynamic characteristics of the
fluid (pressure) and the design and operating characteristics of the machine (volume); areas in this plane
correspond to energy quantities.
.- "pressure vs enthalpy per unit mass":
useful for refrigeration and heating systems (e.g. heat pumps); horizontal segments on this plane
correspond to energy quantities per unit mass
*****
Gas
Main thermodinamic processes or transformations
Isobar : "p" constant ; = 0 ; c = cp ; TB/TA = vB/vA
Isochoric : "v" const ; = ; c = cv ; TB/TA = pB/pA
Isotherm : "T" const ; = 1 ; c = ; pB/pA = vA/vB
Isentropic : "S" const ; = k = cp/cv ; c = 0
Areas of the "p-v" plane where > 0;< 0 and areas of the "p-v" plane where c > 0;< 0
Areas of the "T-S" plane where > 0;< 0 and areas of the "T-S" plane where c > 0;< 0
"cp" and "cv" can be seen as sub-tangents of the isobar and the isochoric, respectively
Group of isobars as pressure increases
Group of isochorics as volume per unit mass increases
An energetic term (heat, work, enthalpy, "pdv" and " vdp" integrals, internal energy ) can be seen as
an area in the "T-S" plane
Particular case: h = cpT = area underlying the isobar ; U = cvT = area underlying the isochoric
Adiabatic work "Li" (with Q = 0), in the case of E = 0 : Li = h ; Lw = area underlying the
transformation curve (e.g. a polytropic)
Vapour
Mollirs diagram ("h-S") and numeric tables of limit-conditions
.- lower limit conditions (LLC) or saturated liquid conditions (SLC)
.- upper limit conditions (ULC) or saturated vapour conditions (SVC)
On a "h vs S" diagram, energy contributions (enthalpy, heat, work, "pdv" and " vdp" integrals, internal
energy ) can be seen as vertical segments (heat, work, "pdv" and " vdp" integrals, internal energy,
etc., as "equivalent" enthalpy differences)
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THERMODYNAMICS - TDS-02/03

ISENTROPIC EFFICIENCY (is) and POLYTROPIC (or hydraulic) EFFICIENCY (y)

For a gas, with Q = 0 and E = 0
Steady state ADIABATIC COMPRESSION from "1" to "2"
Thermal counter-recovery along a steady state compression process

Basic relationships:

2
DEF = |Lic| Lwc = gHc = A + C
|Lic| = |Lis,c| + Lwc + CR = A + B + C
Definitions
Lis,c
A
is,c

Lic
A BC

2is

1T

DEF Lic L wc
AC

Lic
Lic
ABC

yc

= |Lis,c| = A
= |Lwc| = B
= CR = C

is, c

Lis, c
Lic

S
Therefore:

yc > is,c

h is
L L wc
A
; y c ic

h
A B CR
L ic

v dp
1

L ic L wc
L ic

A CR
A B CR

is, c yc

"Downstream" energy of the fluid (DEF), corresponding to the "operating head" H12 = DEF/g = Hc
DEF = gHc = |Lic| Lwc = yc|Lic|
The thermal counter-recovery of the compression is
CR = |Lic| (|Lis,c| + Lwc ) = DEF |Lis,c|
Therefore:
|Lic| = DEF + Lwc = |Lis,c| + (Lwc + CR)
Putting c = p2/p1 one can obtain:

R T2 T1

c p T2 T1 c
1
k 1
1
is,c
k 1 k
; yc

c p T2is T1 c
c p T2 T1
1 k
1
Upstream, at the starting point of the process (1), the fluid contains the "gross" energy "|Lic|" (per unit
mass), which is the incoming mechanical work (from the external driving motor).
Downstream, at the ending point of the process (2), the fluid contains the "net" energy "|Lic| Lwc" (per
unit mass), because it must consume the "Lwc" amout through the machine, to overcome the viscous
resistance to the motion (that is, the internal drag of the actual fluid).
"Upstream the PGM" means: "at the inlet, before the fluid will operate on the machine".
"Downstream the PAM" means: "at the outlet, after the fluid was operated by the machine".
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THERMODYNAMICS - TDS-02/03

ISENTROPIC EFFICIENCY (is) and POLYTROPIC (or hydraulic) EFFICIENCY (y)

For a gas, with Q = 0 and E = 0
Steady state ADIABATIC EXPANSION from "3" to "4"
Thermal recovery along a steady state expansion process

Basic relationships:
Lis,t = A + B
Lwt = B + C
UEF = Lit + Lwt = gHt = A + B + C
Lit + Lwt = Lis,t + RC = A + B + C

4T

4
4is

Definitions
is,t

= Lit = A
= Lis,t Lit = B
= RC = C
is, t

yt

Lit
A

Lis,t A B

Lit
Lit
A

UEF Lit L wt A B C

Therefore:
yt < is,t

L
L it
Lit
h
A
; y t it

UEF Lit L wt
Lis, t h is A B

v dp

A
A B RC

is, t yt

"Upstream" energy of the fluid (UEF), corresponding to the "head" H34 = UEF/g = Ht
UEF = gHt = Lit + Lwt = Lit/yt
The thermal recovery of the expansion is
RC = (Lit + Lwt) Lis,t = UEF Lis,t
Therefore :
Lit = UEF Lwt = Lis,t (Lwt RC)
Putting t = p3/p4 one can obtain:
c p T3 T4 1 t 1
c p T3 T4
1 k
is,t

; yt

k 1 k

c p T3 T4is 1 t
k 1
R T3 T4
1
Upstream, at the starting point of the process (3), the fluid contains the "gross" energy "Lit + Lwt" (per
unit mass).
Downstream, at the ending point of the process (4), the fluid contains the "net" energy per unit mass "L it"
(per unit mass), which is the outgoing mechanical work (available for the external utilizer), because it
must consume the "Lwt" amout through the machine, to overcome the viscous resistance to the motion
(that is, the internal drag of the actual fluid).
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