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1
1.1.4 Helmholtz Free Energy Change dA
From the definition of Helmholtz free energy
A = U − TS
Differentiating
dA = dU − T dS − SdT
Substituting for dU from Eqn.(1.2)
dA = −P dV − SdT (1.6)
If F = F (x, y, z) then
dF = M dx + N dy + P dz
Exactness Criteria:
µ ¶ µ ¶
∂M ∂N
=
∂y x,z ∂x y,z
µ ¶ µ ¶
∂M ∂P
=
∂z x,y ∂x y,z
µ ¶ µ ¶
∂N ∂P
=
∂z x,y ∂y x,z
2
1.2.3 Other Relations of Importance
µ ¶ µ ¶ µ ¶
∂z ∂z ∂w
=
∂x y ∂w y ∂x y
µ ¶
∂x 1
= ¡ ∂y ¢
∂y z ∂x z
dU = T dS − P dV I
@ µ
¡
dA = −P dV − SdT @ ¡
@ ¡
dG = −SdT + V dP U ¡
@ G
¡ @
dH = V dP + T dS ¡ @
¡ @
Applying exactness criteria of differential equation:
µ ¶ µ ¶ T H V
∂T ∂P
= − PASGVHTU
∂V S ∂S V
µ ¶ µ ¶
∂P ∂S
=
∂T V ∂V T
µ ¶ µ ¶
∂S ∂V
= −
∂P T ∂T P
µ ¶ µ ¶
∂V ∂T
=
∂S P ∂P S
3
Volume expansivity β
µ ¶
1 ∂V
β=
V ∂T P
Isothermal compressibility κ
µ ¶
1 ∂V
κ=−
V ∂P T
Considering U = U (T, V )
· µ ¶ ¸
∂P
dU = CV dT + T − P dV
∂T V
Considering H = H(T, P )
· µ ¶ ¸
∂V
dH = CP dT + V − T dP
∂T P
4
Considering S = S(T, V )
µ ¶
CV ∂P
dS = dT + dV
T ∂T V
V β2
CP − CV = T
κ
Specific heat ratio:
CP (∂P/∂V )S
=
CV (∂P/∂V )T
Specific heat variations:
µ ¶ µ ¶
∂CP ∂ 2V
= −T
∂P T ∂T 2 P
µ ¶ µ 2 ¶
∂CV ∂ P
= T
∂V T ∂T 2 V
5
1.5 Two-phase Systems
Equilibrium in a closed system of constant composition:
Gα = Gβ
where Gα and Gβ are the molar Gibbs free energies of the individual phases.
dGα = dGβ
dP sat ∆S αβ
=
dT ∆V αβ
dP sat ∆H αβ
=
dT T ∆V αβ
µ ¶
P2sat ∆H 1 1
ln = −
P1sat R T1 T2
6
1.6 Gibbs Free Energy as a Generating Function
µ ¶
G 1 G
d = dG − dT
RT RT RT 2
Substituting for dG from fundamental property relation, and from the defi-
nition of G:
µ ¶
G V H
d = dP − dT
RT RT RT 2
This is a dimensionless equation.
· ¸
V ∂(G/RT )
=
RT ∂P T
· ¸
H ∂(G/RT )
= −T
RT ∂T P
M = M ig + M R
where M ig is ideal gas value of the property, and M R is the residual value
of the property.
For example for the extensive property V :
RT
V = V ig + V R = +VR
P
Since V = ZRT /P
RT
VR= (Z − 1)
P
7
For Gibbs free enrgy
µ R¶
G VR HR
d = dP − dT (1.7)
RT RT RT 2
· ¸
VR ∂(GR/RT )
= (1.8)
RT ∂P T
· ¸
HR ∂(GR/RT )
= −T (1.9)
RT ∂T P
SR HR GR
= − (1.10)
R RT RT
At constant T Eqn.(1.7) becomes
µ R¶
G VR
d = dP
RT RT
Integration from zero pressure to the arbitrary pressure P gives
Z P R
GR V
= dP (const. T ) (1.11)
RT 0 RT
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
= (Z − 1) (const. T ) (1.12)
RT 0 P
Differentiating Eqn.(1.12) at with respect to T at constant P
· ¸ Z Pµ ¶
∂(GR/RT ) ∂Z dP
=
∂T P 0 ∂T P P
Z µ ¶
HR P
∂Z dP
= −T (const. T ) (1.13)
RT 0 ∂T P P
Combining Eqn.(1.12) and (1.13) and from Eqn.(1.10)
Z Pµ ¶ Z P
SR ∂Z dP dP
= −T − (Z − 1) (const. T ) (1.14)
R 0 ∂T P P 0 P
8
1.8 Generalized Correlations of Thermodynamic Prop-
erties for Gases
Of the two hinds of data needed for the evaluation of thermodynamic proper-
ties, 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 ,
Z µ ¶
HR Pr
∂Z dPr
= −Tr2 (const. Tr ) (1.15)
RTc 0 ∂Tr Pr Pr
Z µ ¶ Z
SR Pr
∂Z dPr Pr
dPr
= −Tr − (Z − 1) (const. Tr )
R 0 ∂Tr Pr Pr 0 Pr
(1.16)
Z = Z 0 + ωZ 1
HR (H R)0 (H R)1
= +ω
RTc RTc RTc
SR (S R)0 (S R)1
= +ω
R R R
(H R)0 (H R)1 (S R)0 (S R)1
Calculated values of the quantities , , and
RTc RTc R R
are shown by plots of these quantities vs. Pr for various values of Tr .
(H R)0 (S R)0
and used alone provide two-parameter corresponding states
RTc R
correlations that quickly yield coarse estimates of the residual properties.
9
1.8.2 Correlations from Redlich/Kwong Equation of State
µ ¶
1 4.934 h
Z= −
1−h Tr1.5 1+h
where
0.08664Pr
h=
ZTr
and
T
Tr =
Tc
P
Pr =
Pc
(c) Density of saturated liquid and the critical pressure and temperature.
3. State: 1
Fix values for H and S of saturated-liquid at a reference state.
10
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 ∆Hlv
=
dT T (Vv − Vl)
and
∆Hlv
∆Slv =
T
Here Vl shall be measured, and Vv is calculated from the relation ob-
tained in step-2.
From these values of ∆Hvl and ∆Svl obtaine the values of H and S
at state: 2
11
5. State: 3 Follow the constant pressure line.
· µ ¶ ¸
∂V
dH = CP dT + V − T dP
∂T P
µ ¶
dT ∂V
dS = CP − dP
T ∂T P
7. State: 7 The calculations made for state: 2 can de done for the tem-
perature at state: 6.
12
1.10 Thermodynamic Diagrams of Importance
1.10.1 T − S diagram
13
1.10.2 P − H diagram
14
1.10.3 H − S diagram
15
2 Thermodynamics of Flow Processes
2.1 Conservation of Mass
dm
+ ∆(ρuA) = 0 (2.1)
dt
where the symbol ∆ denotes the difference between exit and entrance streams.
For steady flow process
∆(ρuA)fs = 0 (2.2)
16
2.2 Conservation of Energy
d(mU )
+ ∆[(U + 12 u2 + zg)ṁ] = Q̇ − Ẇ (2.4)
dt
d(mU )
+ ∆[(H + 12 u2 + zg)ṁ] = Q̇ − Ẇs (2.6)
dt
For most applications, kinetic- and potential-energy changes are negligi-
ble. Therefore
d(mU )
+ ∆(H ṁ) = Q̇ − Ẇs (2.7)
dt
Energy balances for steady state flow processes:
Bernoulli’s equation:
P u2
+ + gz = 0 (2.9)
ρ 2
∆u2
∆H + =0 (2.10)
2
In differential form
dH = −udu (2.11)
d(uA/V ) = 0 (2.12)
17
or
udV
du = (const. A) (2.13)
V
Substituting this in Eqn.(2.11)
u2 dV
dH = − (2.14)
V
From the fundamental property relations
T dS = dH − V dP
Therefore
u2 dV
T dS = − − V dP (2.15)
V
As gas flows along a pipe in the direction of decreasing pressure, its specific
volume increases, and also the velocity (as ṁ = 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 dP = 0 (const. S)
V
Rearranging
µ ¶
∂P
u2max = −V 2
(2.16)
∂V S
d(uA/V ) = 0
1 dV
(udA + Adu) − uA =0
V V2
18
or
udA + Adu V dV
=
uA V2
From the fundamental property relation for dH and from steady flow energy
equation
−V dP = udu (const. S)
dA du udu
+ =
A d −V 2 (∂P/∂V )S
From the relation for velocity of sound, the above equation becomes
dA du udu
+ =
A u u2sonic
Therefore
µ ¶
dA udu du u2 du
= − = −1
A u2sonic u u2sonic u
The ratio of actual velocity to the velocity of sound is called the Mach Number
M.
dA du
= (M2 − 1) (2.17)
A u
Depending on whether M is greater than unity (supersonic) or less than
unity (subsonic), the cross sectional area increases or decreases with velocity
increase.
includegraphicssupersonic.eps
includegraphicssubsonic.eps
includegraphicsconvergdiverg.eps
2.5 Nozzles
Z " µ ¶(γ−1)/γ#
P2
2γP1 V1 P2
u22 − u21 = −2 V dP = 1− (2.18)
P1 γ−1 P1
19
From the definition of sound velocity
µ ¶
∂P
u2max = −V 2
∂V S
and from the evaluation of the derivative (∂P/∂V )S for the isentropic ex-
pansion of ideal gas with constant heat capacities from the relation P V γ =
const,
u2throat = γP2 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
µ ¶γ/(γ−1)
P2 2
= (2.20)
P1 γ+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
20
and
Ws = −∆H (2.22)
Ws ∆H
η= = (2.24)
Ws(isentropic) (∆H)S
∆H = 0
Joule-Thomson Coefficient:
µ ¶
∂T T (∂V /∂T )P − V
µJ = =
∂P H CP
21
For ideal gases µJ = 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 = φ(P ),
µJ = 0.
Inversion curve: T − P diagram. The points in the curve correspond
to µJ = 0. In the region inside the curve µJ is positive.
2.8 Compression
Z P2
W =− V dP
P1
22
Multistage compression:
µ ¶1/n
P2
Optimum compression ratio per stage =
P1
" µ ¶ γ−1 #
nγP1 VI P2 γn
W = 1−
γ−1 P1
Relation between VD and VI :
" µ ¶1/γ #
P2
VI = VD 1 + C − C
P1
where C = VC /VD For compression in multistages,
" µ ¶ nγ 1
#
P2
VI = VD 1 + C1 − C1
P1
where C1 is the clearance in the first stage.
23
2.9 Ejectors
24