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Thermodynamics Short Notes
Thermodynamics Short Notes
1.1
1.1.1
Thermodynamic Relations
Relations for Energy Properties
Internal Energy Change dU
(1.1)
(1.2)
Enthapy Change dH
(1.3)
Differentiating
dH = dU + P dV + V dP
Substituting for dU from Eqn.(1.2)
dH = V dP + T dS
1.1.3
(1.4)
(1.5)
1.1.4
1.2
1.2.1
Mathamatical Concepts
Exact Differential Equations
If F = F (x, y) then
dF = M dx + N dy
Exactness Criteria:
=
x
N
x
If F = F (x, y, z) then
dF = M dx + N dy + P dz
Exactness Criteria:
y x,z
M
z x,y
N
z
1.2.2
x y,z
x y,z
x,y
x,z
x
y
z
y
= 1
y
(1.6)
1.2.3
x
y
1.3
1
= y
x z
Maxwell Relations
=
=
=
=
T dS P dV
P dV SdT
SdT + V dP
V dP + T dS
P
T
=
V S
S V
P
S
=
T V
V T
S
V
=
P T
T P
V
T
=
S P
P S
1.4
1.4.1
I
@
@
@
T V
H
T
= CV
= CP
G
@
H
PASGVHTU
Volume expansivity
=
1
V
V
T
Isothermal compressibility
=
1.4.2
1
V
V
P
Relations for dU
=T
Considering U = U (T, V )
P
dU = CV dT + T
P dV
T V
For van der Waals gas,
dU = CV dT +
1.4.3
a
V2
dV
Relations for dH
=V T
V
T
Considering H = H(T, P )
dH = CP dT + V T
1.4.4
V
T
Relations for dS
T V
S
T
CV
T
CP
T
dP
P
Considering S = S(T, V )
dS =
CV
T
dT +
dV
CV
T
dT
R
V b
dV
Considering S = S(T, P )
dS =
1.4.5
CP
T
dT
dP
CP = T
CV
= T
T S T P
V
P
T
CP CV = T
V 2
CP
(P/V )S
(P/V )T
P T
CV
V
2V
= T
T 2
2
P
= T
T 2 V
5
2
P
1.5
Two-phase Systems
dT
H
T V
Clausius-Clapeyron equation
ln
1.5.3
Clapeyon equation
dP sat
1.5.2
P2sat
P1sat
1
T1
T2
B
T
B
T +C
The values of the constants A, B and C are readily available for many
species.
6
1.6
RT
1
RT
dG
RT 2
dT
Substituting for dG from fundamental property relation, and from the definition of G:
G
V
H
d
=
dP
dT
RT
RT
RT 2
This is a dimensionless equation.
V
RT
H
RT
(G/RT )
= T
P
T
(G/RT )
T
When G/RT is known as a function of T and P , V /RT and H/RT follow by simple differentiation. The remaining properties are given by defining
equations.
S
R
U
RT
1.7
=
=
H
RT
H
RT
G
RT
PV
RT
Residual Properties
RT
P
+VR
Since V = ZRT /P
VR=
RT
P
7
(Z 1)
VR
RT
HR
(GR/RT )
= T
RT
(1.7)
P
T
(GR/RT )
T
(1.8)
(1.9)
HR
GR
(1.10)
R
RT
RT
At constant T Eqn.(1.7) becomes
R
G
VR
d
=
dP
RT
RT
Integration from zero pressure to the arbitrary pressure P gives
Z P R
V
GR
=
dP
(const. T )
RT
0 RT
(1.11)
where at the lower limit, we have set GR/RT equal to zero on the basis that
the zero-pressure state is an ideal-gas state. (V R = 0)
Since V R = (RT /P )(Z 1) Eqn.(1.11) becomes
Z P
GR
dP
=
(const. T )
(1.12)
(Z 1)
RT
P
0
Differentiating Eqn.(1.12) at with respect to T at constant P
Z P
(GR/RT )
Z
dP
=
T
T P P
0
P
HR
RT
Z
= T
Z
T
dP
P
(const. T )
(1.13)
Z P
Z P
SR
dP
Z
dP
= T
(const. T ) (1.14)
(Z 1)
R
T P P
P
0
0
8
1.8
Of the two hinds of data needed for the evaluation of thermodynamic properties, heat capacities and P V T data, the latter are most frequently missing.
Fortunately, the generalized methods developed for compressibility factor Z
are also applicable to residual properties.
Substituting for P = PcPr and T = TcTr ,
dP = PcdPr and dT = TcdTr
HR
RTc
SR
R
=
Z
= Tr
Tr2
Pr
Pr
Tr
Tr
Pr
(const. Tr )
Pr
Pr
dPr
Pr
dPr
Pr
(Z 1)
dPr
Pr
(1.15)
(const. Tr )
(1.16)
1.8.1
=
=
(H R)0
RTc
(S R)0
R
+
+
(H R)1
RTc
(S R)1
R
(S R)1
(H R)0 (H R)1 (S R)0
and
,
,
Calculated values of the quantities
RTc
RTc
R
R
are shown by plots of these quantities vs. Pr for various values of Tr .
(S R)0
(H R)0
used alone provide two-parameter corresponding states
and
RTc
R
correlations that quickly yield coarse estimates of the residual properties.
1.8.2
1
1h
4.934
Tr1.5
1+h
where
h=
0.08664Pr
ZTr
and
Tr =
Pr =
1.9
T
Tc
P
Pc
Experimental Data:
(a) Vapor pressure data.
(b) Pressure, specific volume, temperature (P V T ) data in the vapor region.
(c) Density of saturated liquid and the critical pressure and temperature.
(d) Zero pressure specific heat data for the vapor.
From these data, a complete set of thermodynamic tables for the saturated
liquid, saturated vapor, and super-heated vapor can be calculated as per the
steps below:
1. Relation for ln P sat vs. T such as
ln P sat = A
B
T +C
4. State: 2
Enthalpy and entropy changes during vaporization are calculated from
Clapeyron equation using the ln P sat vs. T data as:
dP sat
dT
Hlv
T (Vv Vl)
and
Slv =
Hlv
T
Here Vl shall be measured, and Vv is calculated from the relation obtained in step-2.
From these values of Hvl and Svl obtaine the values of H and S
at state: 2
11
V
dH = CP dT + V T
dP
T P
V
dT
dP
dS = CP
T
T P
Here for the specific heat of vapor corresponding to the pressure at
state: 2 is obtained from the relation:
2
CP
V
= T
P T
T 2
and from the zero pressure specific heat data.
With the value of CP for this state as calculated above, S and H
values at state: 3 are calculated.
6. State: 4, 5 & 6 The above calculation can be done along constant temperature lineand the values at states 4, 5 and 6 can be obtained.
7. State: 7 The calculations made for state: 2 can de done for the temperature at state: 6.
12
1.10
1.10.1
T S diagram
13
1.10.2
P H diagram
14
1.10.3
H S diagram
15
2.1
Conservation of Mass
dm
dt
+ (uA) = 0
(2.1)
where the symbol denotes the difference between exit and entrance streams.
For steady flow process
(uA)fs = 0
(2.2)
uA
V
= constant.
16
(2.3)
2.2
Conservation of Energy
d(mU )
dt
+ [(U + 12 u2 + zg)m]
= Q W
W = Ws + [(P V )m]
d(mU )
dt
+ [(H + 12 u2 + zg)m]
= Q W s
(2.4)
(2.5)
(2.6)
For most applications, kinetic- and potential-energy changes are negligible. Therefore
d(mU )
+ (H m)
= Q W s
dt
(2.7)
(2.8)
Bernoullis equation:
P
2.3
u2
2
+ gz = 0
(2.9)
u2
=0
(2.10)
In differential form
dH = udu
(2.11)
udV
V2
17
=0
(2.12)
or
du =
udV
(const. A)
(2.13)
u2 dV
(2.14)
u2 dV
V
V dP
(2.15)
As gas flows along a pipe in the direction of decreasing pressure, its specific
volume increases, and also the velocity (as m
= uA/V ). Thus in the
direction of increasing velocity, dP is negative, dV is positive, and the two
terms of Eqn.(2.15) contribute in opposite directions to the entropy change.
According to second law dS 0.
u2max dV
V
+ V dP = 0 (const. S)
Rearranging
u2max
= V
P
V
(2.16)
S
2.4
(udA + Adu) uA
18
dV
V2
=0
or
udA + Adu
uA
V dV
V2
From the fundamental property relation for dH and from steady flow energy
equation
V dP = udu (const. S)
i.e., V = udu/dP at constant S. Therefore
dA
A
du
udu
V 2 (P/V )S
From the relation for velocity of sound, the above equation becomes
dA
A
du
u
udu
u2sonic
Therefore
dA
A
udu
u2sonic
du
u
u2
u2sonic
du
1
u
The ratio of actual velocity to the velocity of sound is called the Mach Number
M.
dA
A
du
= (M2 1)
(2.17)
2.5
Nozzles
u22 u21 = 2
P2
V dP =
P1
2P1 V1
1
19
"
P2
P1
(1)/#
(2.18)
= V
P
V
and from the evaluation of the derivative (P/V )S for the isentropic expansion of ideal gas with constant heat capacities from the relation P V =
const,
u2throat = P2 V2
(2.19)
Substituting this value of the throat velocity for u2 in Eqn.(2.18) and solving
for the pressure ratio with u1 = 0 gives
/(1)
2
P2
=
(2.20)
P1
+1
The speed of sound is attained at the throat of a conerging/diverging nozzle
only when the pressure at the throat is low enough that the critical value
of P2 /P1 is reached. If insufficient pressure drop is available in the nozzle
for the velocity to become sonic, the diverging section of the nozzle acts as
a diffuser.
2.6
Turbines
W s = mH
20
(2.21)
and
Ws = H
(2.22)
Ws(isentropic) = (H)S
(2.23)
2.7
Ws
Ws(isentropic)
H
(H)S
Throttling Processes
H = 0
Joule-Thomson Coefficient:
T
T (V /T )P V
=
J =
P H
CP
21
(2.24)
For ideal gases J = 0. For a real gas uJ can be positive, zero or negative.
Any gas for which volume is linear with temperature along an isobar will
have a zero Joule-Thomson coefficient. i.e., if V /T = constant = (P ),
J = 0.
Inversion curve: T P diagram. The points in the curve correspond
to J = 0. In the region inside the curve J is positive.
2.8
Compression
Z
W =
For reversible-adiabatic compression
W =
P1 V1
1
P2
V dP
P1
"
P2
#
1
P1
Multistage compression:
W =
nP1 VI
1
"
P2
P1
VI = VD 1 + C C
#
1
n
P2
1/ #
P1
23
P2
P1
1/n
2.9
Ejectors
24