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**1.1 Relations for Energy Properties
**

1.1.1 Internal Energy Change dU

From ﬁrst law of thermodynamics

dU = dQ+dW (1.1)

For a reversible process

dW = −PdV

From second law of thermodynamics for a reversible process

dQ = TdS

Therefore Eqn.(1.1) becomes

dU = TdS −PdV (1.2)

1.1.2 Enthapy Change dH

From the deﬁnition of enthalpy

H = U +PV (1.3)

Diﬀerentiating

dH = dU +PdV +V dP

Substituting for dU from Eqn.(1.2)

dH = V dP +TdS (1.4)

1.1.3 Gibbs Free Energy Change dG

From the deﬁnition of Gibbs free energy

G = H −TS

Diﬀerentiating

dG = dH −TdS −SdT

Substituting for dH from Eqn.(1.4)

dG = V dP −SdT (1.5)

1

1.1.4 Helmholtz Free Energy Change dA

From the deﬁnition of Helmholtz free energy

A = U −TS

Diﬀerentiating

dA = dU −TdS −SdT

Substituting for dU from Eqn.(1.2)

dA = −PdV −SdT (1.6)

1.2 Mathamatical Concepts

1.2.1 Exact Diﬀerential Equations

If F = F(x, y) then

dF = Mdx +Ndy

Exactness Criteria:

∂M

∂y

x

=

∂N

∂x

y

If F = F(x, y, z) then

dF = Mdx +Ndy +Pdz

Exactness Criteria:

∂M

∂y

x,z

=

∂N

∂x

y,z

∂M

∂z

x,y

=

∂P

∂x

y,z

∂N

∂z

x,y

=

∂P

∂y

x,z

1.2.2 Cyclic Relation Rule

For the function in the variables x, y & z

∂x

∂y

z

∂y

∂z

x

∂z

∂x

y

= −1

2

1.2.3 Other Relations of Importance

∂z

∂x

y

=

∂z

∂w

y

∂w

∂x

y

∂x

∂y

z

=

1

∂y

∂x

z

1.3 Maxwell Relations

For the fundamental property relations:

dU = TdS −PdV

dA = −PdV −SdT

dG = −SdT +V dP

dH = V dP +TdS

Applying exactness criteria of diﬀerential equation:

T V

P S

U G

H

A

d

d

d

d

d

d

ds

PASGVHTU

∂T

∂V

S

= −

∂P

∂S

V

∂P

∂T

V

=

∂S

∂V

T

∂S

∂P

T

= −

∂V

∂T

P

∂V

∂S

P

=

∂T

∂P

S

1.4 Relations for Thermodynamic Properties in terms

of PV T and Speciﬁc heats

1.4.1 Deﬁnitions

∂U

∂T

V

= C

V

∂H

∂T

P

= C

P

3

Volume expansivity β

β =

1

V

∂V

∂T

P

Isothermal compressibility κ

κ = −

1

V

∂V

∂P

T

1.4.2 Relations for dU

∂U

∂V

T

= T

∂P

∂T

V

−P

Considering U = U(T, V )

dU = C

V

dT +

¸

T

∂P

∂T

V

−P

dV

For van der Waals gas,

dU = C

V

dT +

a

V

2

dV

1.4.3 Relations for dH

∂H

∂P

T

= V −T

∂V

∂T

P

Considering H = H(T, P)

dH = C

P

dT +

¸

V −T

∂V

∂T

P

dP

1.4.4 Relations for dS

∂S

∂T

V

=

C

V

T

∂S

∂T

P

=

C

P

T

4

Considering S = S(T, V )

dS =

C

V

T

dT +

∂P

∂T

V

dV

For van der Waals gas,

dS =

C

V

T

dT −

R

V −b

dV

Considering S = S(T, P)

dS =

C

P

T

dT −

∂V

∂T

P

dP

1.4.5 Relations for Speciﬁc heats

C

P

= T

∂P

∂T

S

∂V

∂T

P

C

V

= −T

∂P

∂T

V

∂V

∂T

S

Speciﬁc heat diﬀerences:

C

P

−C

V

= −T

∂P

∂V

T

∂V

∂T

2

P

For van der Waals gas,

C

P

−C

V

= T

V β

2

κ

Speciﬁc heat ratio:

C

P

C

V

=

(∂P/∂V )

S

(∂P/∂V )

T

Speciﬁc heat variations:

∂C

P

∂P

T

= −T

∂

2

V

∂T

2

P

∂C

V

∂V

T

= T

∂

2

P

∂T

2

V

5

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 = 0, dG = 0.

For two phases α and β of a pure species coexisting at equilibrium:

G

α

= G

β

where G

α

and G

β

are the molar Gibbs free energies of the individual phases.

dG

α

= dG

β

dP

sat

dT

=

∆S

αβ

∆V

αβ

1.5.1 Clapeyon equation

dP

sat

dT

=

∆H

αβ

T∆V

αβ

1.5.2 Clausius-Clapeyron equation

ln

P

sat

2

P

sat

1

=

∆H

R

1

T

1

−

1

T

2

**1.5.3 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

d

G

RT

=

1

RT

dG−

G

RT

2

dT

Substituting for dG from fundamental property relation, and from the deﬁ-

nition of G:

d

G

RT

=

V

RT

dP −

H

RT

2

dT

This is a dimensionless equation.

V

RT

=

¸

∂(G/RT)

∂P

T

H

RT

= −T

¸

∂(G/RT)

∂T

P

When G/RT is known as a function of T and P, V/RT and H/RT fol-

low by simple diﬀerentiation. The remaining properties are given by deﬁning

equations.

S

R

=

H

RT

−

G

RT

U

RT

=

H

RT

−

PV

RT

1.7 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

+V

R

Since V = ZRT/P

V

R

=

RT

P

(Z −1)

7

For Gibbs free enrgy

d

G

R

RT

=

V

R

RT

dP −

H

R

RT

2

dT (1.7)

V

R

RT

=

¸

∂(G

R

/RT)

∂P

T

(1.8)

H

R

RT

= −T

¸

∂(G

R

/RT)

∂T

P

(1.9)

From the deﬁnition of G:

G

R

= H

R

−TS

R

S

R

R

=

H

R

RT

−

G

R

RT

(1.10)

At constant T Eqn.(1.7) becomes

d

G

R

RT

=

V

R

RT

dP

Integration from zero pressure to the arbitrary pressure P gives

G

R

RT

=

P

0

V

R

RT

dP (const. T) (1.11)

where at the lower limit, we have set G

R

/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

G

R

RT

=

P

0

(Z −1)

dP

P

(const. T) (1.12)

Diﬀerentiating Eqn.(1.12) at with respect to T at constant P

¸

∂(G

R

/RT)

∂T

P

=

P

0

∂Z

∂T

P

dP

P

H

R

RT

= −T

P

0

∂Z

∂T

P

dP

P

(const. T) (1.13)

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

S

R

R

= −T

P

0

∂Z

∂T

P

dP

P

−

P

0

(Z −1)

dP

P

(const. T) (1.14)

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 PV 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 = P

c

P

r

and T = T

c

T

r

,

dP = P

c

dP

r

and dT = T

c

dT

r

H

R

RT

c

= −T

2

r

Pr

0

∂Z

∂T

r

Pr

dP

r

P

r

(const. T

r

) (1.15)

S

R

R

= −T

r

Pr

0

∂Z

∂T

r

Pr

dP

r

P

r

−

Pr

0

(Z −1)

dP

r

P

r

(const. T

r

)

(1.16)

1.8.1 Three Parameter Models

From three-parameter corresponding states principle developed by Pitzer

Z = Z

0

+ωZ

1

Similar equations for H

R

and S

R

are:

H

R

RT

c

=

(H

R

)

0

RT

c

+ω

(H

R

)

1

RT

c

S

R

R

=

(S

R

)

0

R

+ω

(S

R

)

1

R

Calculated values of the quantities

(H

R

)

0

RT

c

,

(H

R

)

1

RT

c

,

(S

R

)

0

R

and

(S

R

)

1

R

are shown by plots of these quantities vs. P

r

for various values of T

r

.

(H

R

)

0

RT

c

and

(S

R

)

0

R

used alone provide two-parameter corresponding states

correlations that quickly yield coarse estimates of the residual properties.

9

1.8.2 Correlations from Redlich/Kwong Equation of State

Z =

1

1 −h

−

4.934

T

1.5

r

h

1 +h

where

h =

0.08664P

r

ZT

r

and

T

r

=

T

T

c

P

r

=

P

P

c

1.9 Developing Tables of Thermodynamic Properties

from Experimental Data

Experimental Data:

(a) Vapor pressure data.

(b) Pressure, speciﬁc volume, temperature (PV T) data in the vapor re-

gion.

(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 PV 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

=

∆H

lv

T(V

v

−V

l

)

and

∆S

lv

=

∆H

lv

T

Here V

l

shall be measured, and V

v

is calculated from the relation ob-

tained in step-2.

From these values of ∆H

vl

and ∆S

vl

obtaine the values of H and S

at state: 2

11

5. State: 3 Follow the constant pressure line.

dH = C

P

dT +

¸

V −T

∂V

∂T

P

dP

dS = C

P

dT

T

−

∂V

∂T

P

dP

Here for the speciﬁc heat of vapor corresponding to the pressure at

state: 2 is obtained from the relation:

∂C

P

∂P

T

= −T

∂

2

V

∂T

2

**and from the zero pressure speciﬁc heat data.
**

With the value of C

P

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 con-

stant temperature lineand the values at states 4, 5 and 6 can be ob-

tained.

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

dt

+ ∆(ρuA) = 0 (2.1)

where the symbol ∆denotes the diﬀerence between exit and entrance streams.

For steady ﬂow process

∆(ρuA)

fs

= 0 (2.2)

Since speciﬁc volume is the reciprocal of density,

˙ m =

uA

V

= constant. (2.3)

This is the equation of continuity.

16

2.2 Conservation of Energy

d(mU)

dt

+ ∆[(U +

1

2

u

2

+zg) ˙ m] =

˙

Q−

˙

W (2.4)

W = W

s

+ ∆[(PV ) ˙ m] (2.5)

d(mU)

dt

+ ∆[(H +

1

2

u

2

+zg) ˙ m] =

˙

Q−

˙

W

s

(2.6)

For most applications, kinetic- and potential-energy changes are negligi-

ble. Therefore

d(mU)

dt

+ ∆(H ˙ m) =

˙

Q−

˙

W

s

(2.7)

Energy balances for steady state ﬂow processes:

∆[(H +

1

2

u

2

+zg) ˙ m] =

˙

Q−

˙

W

s

(2.8)

Bernoulli’s equation:

P

ρ

+

u

2

2

+gz = 0 (2.9)

2.3 Flow in Pipes of Constant Cross-section

∆H +

∆u

2

2

= 0 (2.10)

In diﬀerential form

dH = −udu (2.11)

Equation of continuity in diﬀerential form:

d(uA/V ) = 0 (2.12)

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

du

V

−

udV

V

2

= 0

17

or

du =

udV

V

(const. A) (2.13)

Substituting this in Eqn.(2.11)

dH = −

u

2

dV

V

(2.14)

From the fundamental property relations

TdS = dH −V dP

Therefore

TdS = −

u

2

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.

u

2

max

dV

V

+V dP = 0 (const. S)

Rearranging

u

2

max

= −V

2

∂P

∂V

S

(2.16)

This is the speed of sound in ﬂuid.

2.4 General Relationship between Velocity and Cross-

sectional Area

d(uA/V ) = 0

1

V

(udA+Adu) −uA

dV

V

2

= 0

18

or

udA+Adu

uA

=

V dV

V

2

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

d

=

udu

−V

2

(∂P/∂V )

S

From the relation for velocity of sound, the above equation becomes

dA

A

+

du

u

=

udu

u

2

sonic

Therefore

dA

A

=

udu

u

2

sonic

−

du

u

=

u

2

u

2

sonic

−1

du

u

The ratio of actual velocity to the velocity of sound is called the Mach Number

M.

dA

A

= (M

2

−1)

du

u

(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

u

2

2

−u

2

1

= −2

P

2

P

1

V dP =

2γP

1

V

1

γ −1

¸

1 −

P

2

P

1

(γ−1)/γ

¸

(2.18)

19

From the deﬁnition of sound velocity

u

2

max

= −V

2

∂P

∂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 PV

γ

=

const,

u

2

throat

= γP

2

V

2

(2.19)

Substituting this value of the throat velocity for u

2

in Eqn.(2.18) and solving

for the pressure ratio with u

1

= 0 gives

P

2

P

1

=

2

γ + 1

γ/(γ−1)

(2.20)

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 P

2

/P

1

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

= − ˙ m∆H (2.21)

20

and

W

s

= −∆H (2.22)

W

s

(isentropic) = −(∆H)

S

(2.23)

η =

W

s

W

s

(isentropic)

=

∆H

(∆H)

S

(2.24)

2.7 Throttling Processes

∆H = 0

Joule-Thomson Coeﬃcient:

µ

J

=

∂T

∂P

H

=

T(∂V/∂T)

P

−V

C

P

21

For ideal gases µ

J

= 0. For a real gas u

J

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),

µ

J

= 0.

Inversion curve: T −P diagram. The points in the curve correspond

to µ

J

= 0. In the region inside the curve µ

J

is positive.

2.8 Compression

W = −

P

2

P

1

V dP

For reversible-adiabatic compression

W =

γP

1

V

1

γ −1

¸

1 −

P

2

P

1

γ−1

γ

¸

Eﬀect of clearance on work of compression:

W =

γP

1

V

I

γ −1

¸

1 −

P

2

P

1

γ−1

γ

¸

22

Multistage compression:

Optimum compression ratio per stage =

P

2

P

1

1/n

W =

nγP

1

V

I

γ −1

¸

1 −

P

2

P

1

γ−1

γn

¸

Relation between V

D

and V

I

:

V

I

= V

D

¸

1 +C −C

P

2

P

1

1/γ

¸

where C = V

C

/V

D

For compression in multistages,

V

I

= V

D

¸

1 +C

1

−C

1

P

2

P

1

1

nγ

¸

where C

1

is the clearance in the ﬁrst stage.

23

2.9 Ejectors

24

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