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1

1.1
1.1.1

Thermodynamic Relations
Relations for Energy Properties
Internal Energy Change dU

From first law of thermodynamics


dU = dQ + dW

(1.1)

For a reversible process


dW = P dV
From second law of thermodynamics for a reversible process
dQ = T dS
Therefore Eqn.(1.1) becomes
dU = T dS P dV
1.1.2

(1.2)

Enthapy Change dH

From the definition of enthalpy


H = U + PV

(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)

Gibbs Free Energy Change dG

From the definition of Gibbs free energy


G = H TS
Differentiating
dG = dH T dS SdT
Substituting for dH from Eqn.(1.4)
dG = V dP SdT
1

(1.5)

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

1.2
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

Cyclic Relation Rule

For the function in the variables x, y & z

x
y
z
y

= 1
y

(1.6)

1.2.3

Other Relations of Importance

x
y

1.3

1
= y

x z

Maxwell Relations

For the fundamental property relations:


dU
dA
dG
dH

=
=
=
=

T dS P dV
P dV SdT
SdT + V dP
V dP + T dS

Applying exactness criteria of differential equation:

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

Relations for Thermodynamic Properties in terms


of P V T and Specific heats
Definitions

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

For van der Waals gas,


dS =

CV
T

dT

R
V b

dV

Considering S = S(T, P )
dS =
1.4.5

CP
T

dT

dP

Relations for Specific heats

CP = T
CV

= T

T S T P

V
P
T

Specific heat differences:

CP CV = T

For van der Waals gas,


CP CV = T

V 2

Specific heat ratio:


CP
CV
Specific heat variations:

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

Equilibrium in a closed system of constant composition:


d(nG) = (nV )dP (nS)dT
During phase change T and P remains constant. Therefore, d(nG) = 0.
Since dn 6= 0, dG = 0.
For two phases and of a pure species coexisting at equilibrium:
G = G
where G and G are the molar Gibbs free energies of the individual phases.
dG = dG
dP sat
dT
1.5.1

dT

H
T V

Clausius-Clapeyron equation

ln
1.5.3

Clapeyon equation
dP sat

1.5.2

P2sat
P1sat

1
T1

T2

Vapor Pressure vs. Temperature

From Clausius-Clapeyron equation


ln P sat = A

B
T

A satisfactory relation given by Antoine is of the form


ln P sat = A

B
T +C

The values of the constants A, B and C are readily available for many
species.
6

1.6

Gibbs Free Energy as a Generating Function

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

Any extensive property M is given by:


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 :
V = V ig + V R =

RT
P

+VR

Since V = ZRT /P
VR=

RT
P
7

(Z 1)

For Gibbs free enrgy


R
G
VR
HR
d
=
dP
dT
RT
RT
RT 2

VR

RT
HR

(GR/RT )

= T

RT

(1.7)

P
T

(GR/RT )
T

(1.8)
(1.9)

From the definition of G:


GR = H R T S R
SR

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)

Combining Eqn.(1.12) and (1.13) and from Eqn.(1.10)

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

Generalized Correlations of Thermodynamic Properties for Gases

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

Three Parameter Models

From three-parameter corresponding states principle developed by Pitzer


Z = Z 0 + Z 1
Similar equations for H R and S R are:
HR
RTc
SR
R

=
=

(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

Correlations from Redlich/Kwong Equation of State


Z=

1
1h

4.934

Tr1.5

1+h

where
h=

0.08664Pr
ZTr

and
Tr =
Pr =

1.9

T
Tc
P
Pc

Developing Tables of Thermodynamic Properties


from Experimental Data

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

2. Equation of state for the vapor that accurately represents the P V T


data.
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
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

5. State: 3 Follow the constant pressure line.


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

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

Thermodynamics of Flow Processes

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)

Since specific volume is the reciprocal of density,


m
=

uA
V

= constant.

This is the equation of continuity.

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)

Energy balances for steady state flow processes:


[(H + 12 u2 + zg)m]
= Q W s

(2.8)

Bernoullis equation:
P

2.3

u2
2

+ gz = 0

(2.9)

Flow in Pipes of Constant Cross-section


H +

u2

=0

(2.10)

In differential form
dH = udu

(2.11)

Equation of continuity in differential form:


d(uA/V ) = 0
Since A is a constant, d(u/V ) = 0. Therefore
du
V

udV
V2
17

=0

(2.12)

or
du =

udV

(const. A)

(2.13)

Substituting this in Eqn.(2.11)


dH =

u2 dV

(2.14)

From the fundamental property relations


T dS = dH V dP
Therefore
T dS =

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

This is the speed of sound in fluid.

2.4

General Relationship between Velocity and Crosssectional Area


d(uA/V ) = 0
1
V

(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)

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
u22 u21 = 2

P2

V dP =
P1

2P1 V1
1
19

"

P2
P1

(1)/#
(2.18)

From the definition of sound velocity


u2max

= 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

Effect of clearance on work of compression:


#
"
1
P1 VI
P2
W =
1
1
P1
22

Multistage compression:

Optimum compression ratio per stage =

W =

nP1 VI
1

"

Relation between VD and VI :


"

P2
P1

VI = VD 1 + C C

#
1
n

P2

1/ #

P1

where C = VC /VD For compression in multistages,


"
#
1
n
P2
VI = VD 1 + C1 C1
P1
where C1 is the clearance in the first stage.

23

P2
P1

1/n

2.9

Ejectors

24

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