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fundamental equations of thermodinamics

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FUNDAMENTA

L EQUATIONS

(Q and/or W)

(Q and/or W)

exchange matter with its surroundings,

although it may exchange energy.

dni = 0(i = 1, 2, ..)

(1.1)

boundary.

All energy exchange between a closed

system and its surroundings appears as

heat and work.

The total energy change of the

surroundings equals the net energy

transferred to or from it as heat and

dU TdS PdV

(1.2)

dU TdS PdV

(1.3)

- P dV = dWrev : work done by the system

dU TdS PdV

(1.4)

calculated by integrating eq. (1.2):

S2

V2

U U2 U1 TdS PdV

S1

V1

(1.5)

dUS,V 0

(1.6)

minimum in an actual or irreversible

process in a closed system, and

remains constant in a reversible

process.

ENTHALPY

Definition:

H U PV

(1.

7)

dH dU PdV VdP

(1.3) leads

to

dH TdS VdP

(1.

r a closed system at constant S and P : 8)

(1.

dHS,P 0

9)

the Helmholtz free energy (A) is a

thermodynamic potential that measures

the useful work obtainable from a

closed system at a constant temperature

and volume.

Definition:

A U TS

dA dU TdS SdT

(1.1

0)

(1.3) leads to

TdS SdT

dA TdS PdV

dA SdT PdV

(1.1

1)

dAT,V 0

(1.1

2)

extractable from a thermodynamic

process in which temperature and

volume are held constant.

Under these conditions, it is minimized at

Gibbs free energy (G) is a

thermodynamic potential that measures

the "useful" or process-initiating work

obtainable from a thermodynamic system

at a constant temperature and pressure

(isothermal, isobaric).

The Gibbs free energy is the maximum

amount of non-expansion work that can

be extracted from a closed system; this

maximum can be attained only in a

Definition:

G H TS

(1.1

3)

dG dH TdS SdT

(1.8) leads to

dG TdS VdP TdS SdT

dG VdP SdT

(1.1

a closed system at constant P and T : 4)

dGT,P 0

(1.1

5)

MAXWELL EQUATION

= F(x, y), the total differential of F is:

F

F

dF

dy

dx

x y

y x

dF Mdx Ndy

with

F

x

F

N

(1.1

6)

2F

M

y x xy

x y xy

x

x

dF Mdx Ndy

Hence from equation:

we obtain:

N

M

y x x

(1.1

7)

Resume:

(1.3) dU TdS PdV

(1.

8)

dH TdS VdP

1)

(1.1 dG VdP SdT

4)

T P

V S

S

T V

P S S

S

(1.19)

(1.20)

S V

P T

T

(1.18)

(1.21)

H H T,P

H

H

dH

dT

dP

T P

P T

(1.22)

H

CP

T P

(1.23)

dH TdS VdP

(1.

8)

rentiation with respect of P at constant T yield

H T S V

(1.24)

H V T V

P T

T

(1.25)

V

dH CPdT V T

dP

T P

(1.26)

function of P and T, we may express:

S S T,P

S

S

dS

dT

dP

T P

P T

(1.27)

S V

P T

T

(1.21)

dH TdS VdP

(1.

8)

rentiation with respect of T at constant P yield

H T S

(1.28)

S CP

T P T

(1.29)

dT V

dS CP

dP

T T P

(1.30)

The pressure dependence of the internal

energy is obtained by differentiation of

the equation

U H PV

U H P V V

P T P T P T

H V T V

P T

T

U T V P V

P T

T P P

(1.31)

IDEAL GAS

RT

V

P

Vig

ig

P

P

(1.32)

From eq. (1.26)

ig

V

ig

ig

ig

dP

dH CP dT V T

T P

P

ig

P

dHig CPigdT

ig

(1.33)

Penjelasan:

RT

V

P

R

1

dV dT RT 2 dP

P

P

ig

ig

R

RT

dV dT 2 dP

P

P

ig

2

2

dT PdT P dT P P dT

dVig R

dT P

Vig

P

P

(P konstan)

From eq. (1.31)

ig

dT

ig

ig

dS CP

dP

T T P

dT dP

dS C

R

T

P

ig

ig

P

(1.34)

(T1, P1) ke (T2, P2), maka perubahan entropynya

adalah:

Sig

2

T2

P2

dT

dP

ig

ig

igdS CP T R P

T1

P1

S1

T2

P2

S S S C ln

Rln

T1

P1

ig

ig

2

ig

1

ig

P

Temperature and volume often serve as

more convenient independent variables

than do temperature and pressure.

The most useful property relations are

then for internal energy and entropy.

Required here are the derivatives (U/T)V,

(U/V)T, (S/T)V, and (S/V)T.

dU TdS PdV

At constant V:

U T S

T V T

U

CV

S CV

T V T

(1.35)

At constant V:

U T S P

V T V T

Equation (1.20):

S

U T P P

V T T V

(1.36)

U U T,V

U

U

dU

dT

dV

T V

V T

S S T,V

S

S

dS

dT

dV

T V

V T

equations are given by Eqs. (1.20), (1.35),

(1.36), and the definition of CV.

P

(1.37)

dU CVdT T

P dV

T V

P

dS CVdT

dV

T V

(1.38)

homogeneous fluids of constant composition

given by Eqs. (1.3), (1.8), (1.11), and (1.14)

show that each of the thermodynamic properties

U, H, A, and G is functionally related to a special

pairdG

ofvariables.

VdP SdT In particular

(1.14

)

presses the functional relation:

G G P,T

Thus the special, or canonical variables for the

Gibbs energy are temperature and pressure.

Since these variables can be directly measured

and controlled, the Gibbs energy is a

thermodynamic property of great potential

fundamental property relation, follows

from the mathematical identity:

d G 1 dG G dT

RT2

RT RT

dG VdP SdT

G by Eq. (1.13) gives:

d G 1 VdP SdT H TS dT

RT

RT2

RT

G

V

H

d

dP 2 dT

RT

RT RT

(1.39)

Penjelasan:

d G 1 d G 1

RT R T

1 1

1

dG

G

d

R T

T

1 1

G

dG 2 dT

R T

T

1

G

dG 2 dT

RT

RT

1

1

1

d T 2 dT

T

T

V G RT

RT

P

(1.40)

H

G RT

T

RT

T

(1.41)

P

and P, V/RT and H/RT follow by simple

differentiation. The remaining properties

are given by defining equations. In

S H G

U H PV

particular,

and

R RT RT

RT RT RT

Penjelasan:

d G V dP H dT

RT2

RT RT

d G RT V dP H dT V H dT

2

2

dP

RTdP RT dP RT RT dP

Untuk T konstan, dT = 0

d G RT V

dP

RT

(T konstan)

V d G RT

RT

dP

V G RT

RT

P

(T konstan)

related to its canonical variables, T and P,

i.e., when we are given G/RT = g(T, P), we

can evaluate all other thermodynamic

properties by simple mathematical

operations.

The Gibbs energy when given as a

function of T and P therefore serves

as a generating function for the other

thermodynamic properties, and

implicitly represents complete

property information.

RESIDUAL PROPERTY

No experimental method for the direct

measurement of numerical values of G or

G/RT is known.

However, the concept of the Gibbs energy

as a generating function for other

thermodynamic properties carries over to

a closely related property for which

numerical values are readily obtained.

MR M Mig

(1.42)

where M and Mig are the actual and idealgas properties are at the same

temperature and pressure.

M is the molar value of any extensive

thermodynamic property, e.g., V, U, H, S,

or G.

GR G Gig

(1.43)

ideal-gas values of the Gibbs energy at

the same temperature and pressure.

Other residual properties are defined in

an analogous way. The residual volume,

for example, is:

RT ZRT RT

R

ig

V V V V

P

P

P

RT

V Z 1

P

R

(1.44)

Equation (1.39):

G

V

H

d

dP 2 dT

RT

RT RT

Can be written for the special case of an

ideal gas:

Hig

Gig Vig

d

dP 2 dT

RT

RT RT

HR

GR VR

d

dP 2 dT

RT

RT RT

(1.45)

Penjelasan:

G

V

H

d

dP 2 dT

RT

RT RT

Hig

Gig Vig

d

dP 2 dT

RT

RT RT

()

H Hig

G Gig V Vig

d

dP

dT

2

RT

RT

RT

GR VR

HR

d

dP 2 dT

RT

RT RT

residual properties applies to fluids of

constant composition. Useful restricted

forms are:

VR GR RT

RT

P

R

(1.46)

T

G

T

H

RT

RT

T

(1.47)

energy:

G H TS

For the special case of an ideal gas:

Gig Hig TSig

by difference:

GR HR TSR

R

S H G

R RT RT

(1.48)

generating function for the other residual

properties, and here a direct link with

experiment does exist.

It is provided by Eq. (1.46), written:

R

d G

V

RT

RT

dP

R

GR VR

d

dP

RT RT

(constant T)

(constant T)

arbitrary pressure P yields:

GR P VR

dP

RT 0 RT

(constant T)

(1.49)

zero because the zero-pressure state is

an ideal-gas state.

Penjelasan:

R

R

G

V

d

dP

RT RT

GR

(constant T)

V

G

R d RT RTdP(constant T)

0

Gig

R

igR

P R

G G

V

dP (constant T)

RT RT 0 RT

GR P VR

dP

RT 0 RT

(constant T)

GR G Gig

ig R

Gig Gig 0

RT

V Z 1

P

R

GR P 1 RT

Z 1 dP (constant T)

RT 0 RT P

GR P

dP

Z 1

RT 0

P

(constant T)

(1.50)

obtained by differentiating Eq. (1.50)

with respect to temperature.

HR

GR RT

T

(1.47)

RT

T P

P

HR

Z dP

RT

0 T P P

(const T)

(1.51)

combination of Eqs. (1.48), (1.50), and

(1.51):

P

P

SR

Z

dP

T

Z 1 dP (const T)

(1.52)

RT

0 T P P

0

BP

Z 1

RT

BP

Z 1

RT

GR P B

dP

RT 0 RT

We get:

GR BP

RT RT

(constant T)

(1.53)

(1.53)

(1.54)

(1.54

)

(1.51)

(1.55)

(1.53)

(1.55)

(1.52)

(1.56)

(1.53) (1.55)

(1.56)

(1.57)

(1.58)

(1.58)

(1.50)

(1.59)

(1.59)

(1.60)

(1.60)

(1.61)

(1.56)

(1.62)

Residual enthalpy:

Residual entropy:

(1.63)

(1.64)

EOS

vdW

RK

1

RK

0

1

0

0

SRK

SRK

PR

PR

1 2

RK Tr

1+

2

27/64

1/8

0,42748 0,0866

4

0

0,42748 0,0866

4

1 - 2 0,45724 0,0777

9

SRK 1 0,48508

1,55171

0,15613

2

0,5 2

PR 1 0,37464

1,54226

0,2699

1 Tr

2

1 Tr0,5

GR

V b

a

Z 1 lnZ ln

RT

V RTV

(1.65)

HR

a

Z 1

RT

RTV

(1.66)

SR

V b

lnZ ln

R

V

(1.67)

GR

V b

a V

Z 1 lnZ ln

ln

RT

V bRT V b

(1.68)

H

a

V

Z 1

T

ln

RT

bRT

T P V b

(1.69)

SR

V b

a

V

lnZ ln

ln

R

V bR T P V b

(1.70)

PR EOS

GR

V b

a

V 0.4142

b

Z 1 lnZ ln

ln

RT

bRT V 2.4142

b

V 2.8284

(1.71)

HR

a

V 0.4142

b

Z 1

T

ln

RT

2,8284

bRT

b

T P V 2.4142

(1.72)

S

V b

a

V 0.4142

b

lnZ ln

ln

R

bR T P V 2.4142

b

V 2.8284

(1.73)

R

RK EOS

1 2

r

RK T

Tc

12

0.5

0.5 c

1.5

T P

T

SRK EOS

1 f 1 T

0,5

r

1 f 1 T0,5 0.5 f 1

r

T P

TcT

0.5

TUGAS 1

Soal nomor

6.14(a)

6.15(a)

6.16(a)

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