2/3/2009

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3.1 PVT Behavior of Pure Substances

Phase diagram (PT diagram)

ITK 226 Termodinamika Teknik Kimia

Fliq = ?

3.0 Volumetric Properties of Pure Fluids

Fliq = 2 (divariant)

Author: Dr. Ir. Buana Girisuta

Ftp = ? Ftp = 0 (invariant)

Fvap. curve = ? Fvap. curve = 1 (univariant)

Liquid if vaporization results from P reduction at constant T Gas if condensation results from T reduction at constant P The region where T > Tc is termed supercritical fluid
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Contents
PVT Behavior of Pure Substances Virial Equations of State The Ideal Gas Application of the Virial Equations Cubic Equations of State Generalized Correlations for Gases Generalized Correlations for Liquids

3.1 PVT Behavior of Pure Substances

In a PV diagram, the phase boundaries becomes areas/regions

Triple point

T1 and T2 are subcritical temperatures consist of three segments Line BC single-phase (saturated) liquids at boiling temperature CD single-phase (saturate) vapor at condensation temperature
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3.1 PVT Behavior of Pure Substances

Single-phase region
A relation connecting P, V, and T for any pure homogeneous fluid in equilibrium states may be expressed through an equation of state: f (P V T) = 0 (P, V, The simplest equation is for an ideal gas, PV = RT For example, if V = V (T, P), then: dV = V dT + V dP T P P T 1 V Volume expansivity: V T P
1 V V P T Combining these equations yield: dV = dT dP V The isotherms for liquid phase in PV diagram are very steep due to the low values and . For incompressible fluid and are zero.

3.2 Virial Equations of State

Ideal-gas temperatures
Homework: read this topic in the textbook.

Universal gas constant (R)

Isothermal compressibility:

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3.2 Virial Equations of State

PVT behavior of a pure substance is complex by an equation. difficult to describe

3.2 Virial Equations of State

By defining the compressibility factor:
Z PV RT

The virial equation can be rewritten in two forms as follow:

Pressure function: Z = 1 + B' P + C ' P 2 + D' P 3 + K Volume function: Z = 1 +
B C D + + +K V V2 V3

However, f the gas region alone relatively simple equations often H for th i l l ti l i l ti ft suffice. For example: PV = a(1 + B' P + C ' P 2 + D' P 3 + K)
Where a, B, C, etc., are constants for a given temperature and a given chemical species.
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The parameters are called virial coefficients B and B are second virial coefficients, C and C are third virial coefficients, etc. The two sets of coefficients are related as follow: B D 3BC + 2B 3 C B2 B' = D' = C' = RT (RT )2 (RT )3

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3.3 The Ideal Gas

The term B/V arises on account of interactions between pairs of molecules; the C/V2 term, on account of three-body interactions.
As the pressure of real gas is reduced at constant temperature V increases and th contribution of th terms B/V C/V2, etc., d i d the t ib ti f the t B/V, t decrease. As P approaches zero, V becomes infinite, then Z approaches unity: (ideal gas) Z = 1 or PV = RT

3.3 The Ideal Gas

Equations for process calculations:
For a unit mass or a mole of ideal gas in any mechanically reversible closed-system process:
dQ + dW = CV dT

dW = PdV

dQ = CV dT + PdV

Internal energy of a real gas is a function of P and T

P dependency is the result of forces between the molecules. If such forces did not exist (ideal gas behavior) the internal energy of a gas d depends on t d temperature only! t l ! (ideal gas) U = U (T )
P=

RT V dV V

V=

RT P dP P dP P

T=

PV R

dQ = CV dT + RT dW = RT dV V

dQ = CP dT RT

dQ =

C CV VdP + P PdV R R

dW = RdT + RT

dW = PdV

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3.3 The Ideal Gas

Implied property relations for an ideal gas:
Heat capacity at constant V (CV) is a function of temperature only dU U dU = CV dT U = CV dT CV = CV (T ) = T V dT Enthalpy (H) is a function of temperature only H U + PV = U (T ) + RT = H (T ) Heat capacity at constant P (CP) is a function of temperature only dH H dH = CP dT H = CP dT CP = CP (T ) = T P dT Relation between CP and CV dH dU CP = = + R = CV + R dT dT
This equation does not imply that CP and CV are themselves constant for an ideal gas, but only that they vary with temperature in such a way that their difference is equal to R.
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3.3 The Ideal Gas

Isothermal process: U = H = 0
Q = W = RT ln P V2 = RT ln 2 P1 V1 H = CP dT W = R (T2 T1 )

Isobaric process:

U = CV dT Q = H = CP dT

Isochoric process:

U = CV dT
Q = U = CV dT

H = CP dT
W =0

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3.3 The Ideal Gas

Adiabatic process (constant heat capacities):
TV TP
1

Exercise 3-1
One kmol of an ideal gas is taken through a four-step cyclic process:
A to B: the gas is subjected to an isothermal expansion at 600 K from 5 to 4 bar. B t C an adiabatic expansion t 3 b to C: di b ti i to bar. C to D: a constant-pressure cooling. D to A: a constant-volume heating.
CP CV

= constant = constant

(1 )

PV = constant W = U = CV dT = CV T

W =

RT2 RT2 P2V2 P1V1 = 1 1

( 1)

P V P W = 1 1 2 1 P1

RT P ( 1) 1 2 1 1 = 1 P1

All processes are assumed reversible. For these processes, it is reasonable to assume CP is constant and equal to 30 kJ kmol-1 K-1. Calculate Q, W, U, and H for each step and for the entire process.

The process should be mechanically reversible! How about for irreversible process?

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3.3 The Ideal Gas

Irreversible process
Those equations that relate changes in state functions only are valid for reversible and irreversible ideal gases regardless of the process processes in both open and closed system system. On the other hand, Q and W is specific to the process considered in its derivation.

Homework
Please read and redo the following examples from the textbook:
Smith, J.M., Van Ness, H.C., and Abbot M. M. Introduction to Chemical Engineering Thermodynamics, 6th ed., McGraw Hill, 2001. E Examples 3 2 3 6 on pp. 78 87 l 3.2 3.6 78-87.

Calculation of work for an irreversible process:

1st step: determine W for a mechanically reversible process that accomplishes the same change of state as the actual irreversible p process maximum work obtained or minimum work required. q 2nd step: Multiply or divide this result by an efficiency to give the actual multiply by an efficiency if the process produces work and work divide by an efficiency if the process required work.

Derive the equations to calculate Q, W, U, and H for an ideal gas that goes trough an adiabatic process.

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3.4 Application of the Virial Equations

General virial equations are infinite series
Z = 1 + B ' P + C ' P + D' P + K
2 3

Exercise 3-2
Reported values for the virial coefficients of isopropanol vapor at 200 C are: C = -26000 cm6 mol-2 B = -388 cm3 mol-1 Calculate V and Z for isopropanol at 200 C and 10 bar by:
The ideal-gas equation Truncated virial equation to two terms Truncated virial equation to three terms

B C D Z = 1+ + 2 + 3 + K V V V

For engineering purposes two or three terms are sufficient! (for gases and vapors at low to moderate pressures)
Z = 1+ B' P

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3.4 Application of the Virial Equations

Truncated virial equations:
Two terms
Z= PV BP = 1+ RT RT
PV B C = 1+ + 2 RT V V

3.5 Cubic Equations of State

The van der Waals EOS
Proposed by Johannes Diderik van der Waals (1837 1923)
P= RT a V b V2

PVT behavior of vapors at subcritical T and P < 5 bar.

Three terms
Z=

Suitable for 5 bar < P < Pcrit

Extended virial equations

2 Benedict/Webb/R bin eq ation P = RT + B0RT A0 C0 T + bRT a Benedict/Webb/Rubin equation: V3 V V2 a c + 6 + 3 2 1 + 2 exp 2 V V T V V

Used in the petroleum and natural-gas industries for light hydrocarbons and a few other commonly encountered gases.
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3.5 Cubic Equations of State

Determination of EOS parameters
Suitable estimates of EOS parameters are usually found from values for critical isotherm exhibits a horizontal the critical constants Tc and Pc inflection at the critical point! 2P P =0 = V Tc V 2 T c More straightforward procedure p. 94 from the textbook! Estimates for the van der Waals EOS: 3 RTc 1 RTc 27 R 2Tc2 Vc = b= a= 8 Pc 8 Pc 64 Pc Substitution of Vc into the vdW EOS gives: PV 3 Zc c c = RTc 8 Unfortunately, each chemical species has its own value of Zc! Table B.1 of App. B from the textbook.
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3.5 Cubic Equations of State

Theorem of corresponding states
All fluids, when compared at the same reduced temperature (Tr) and reduced pressure (Pr), have approximately the same compressibility factor, and all deviate from the ideal-gas behavior to about the same degree. ideal gas

Tr

T Tc

Pr

P Pc

This theorem is very nearly exact for the simple fluids (Ar, Kr, Xe). However, systematic deviations are observed for more complex fluids. Therefore an acentric factor () is introduced as follow:

1.0 log(Prsat )T =0.7

r

see

Th value of can b d t The l f be determined f any fl id f i d for fluid from Tc, Pc, and a single d i l vapor-pressure measurement made at Tr = 0.7. App. B lists the values of and the critical constants Tc, Pc, and Vc for a number of fluids.

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3.5 Cubic Equations of State

Generic Cubic EOS
RT a(T ) P= V b (V + b )(V + b )

3.5 Cubic Equations of State

Vapor and vapor-like roots of the generic cubic EOS Z Z = 1 + q (Z + )(Z + )
Iterative solution starts with the value of Z = 1.

Constants and are pure numbers, the same for all substances. Constants a(T) and b are substance dependent. The temperature dependence of a(T) is specific to each EOS.

Parameter estimates (Tr )R 2Tc2

a(T ) = Pc

b=

RTc Pc

Liquid and liquid-like roots of the generic cubic EOS 1+ Z Z = + (Z + )(Z + ) q Iterative solution starts with the value of Z = . For both equations, the following equations apply: P (Tr ) q= = r
Tr Tr

Constants and are pure numbers determined for a particular EOS from the values assigned to and . Function (Tr) is an empirical expression specific to a particular EOS

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3.5 Cubic Equations of State

Parameter assignments for EOS
EOS

3.6 Generalized Correlations for Gases

Pitzer correlations for the second virial coefficient:
Z = 1+ B0 Pr P + B 1 r Tr Tr

(Tr)
1
Tr1 2

0 1 1
1+ 2

0 0 0
1 2

1/8

27/64

Zc

vdW (1873) RK (1949) SRK (1972) PR (1976)

3/8 1/3 1/3

Z = Z 0 + Z 1 B 0 = 0.083 0.422 Tr1.6 B1 = 0.139 0.172 Tr4.2

0.08664 0.42748 0.08664 0.42748

SRK(Tr; ) PR(Tr;
)

0.07779 0.42748 0.30740

2

SRK (Tr ; ) = [1 + (0.480 + 1.574 0.176 2 )(1 Tr1 2 )]

PR (Tr ; ) = [1 + (0.37464 + 1.54226 0.26992 2 )(1 Tr1 2 )]

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3.6 Generalized Correlations for Gases

Pitzer correlations for the compressibility factor: Z = Z 0 + Z 1
Z0 and Z1 are functions of both Tr and Pr. The commonly used Pitzer-type correlation was developed by Lee and Kesler, which is given in table form in App. E. The Lee/Kesler correlation provides reliable results for gases which are nonpolar or slightly polar (errors of no more than 2 or 3%).

Exercise 3-3
Determine the molar volume of n-butane at 510 K and 25 bar by each the following:
The ideal-gas equation The generalized compressibility-factor correlation The generalized virial-coefficient correlation

The correlation for quantum gases (H2, He, Ne) is accommodated by use of temperature-dependent effective critical parameters.
F hydrogen: For h d
Tc (K ) = 43.6 21.8 1+ 2.016T Pc (bar ) = 20.5 44.2 1+ 2.016T Vc cm3 mol -1 =

51.5 9.91 1 2.016T

T is absolute temperature in kelvins.

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3.7 Generalized Correlations for Liquids

The simplest generalized equation for the estimation of molar volume of saturated liquids, proposed by Rackett:
( V sat = Vc Zc1Tr )
0.2857

Lydersen, Greenkorn, and Hougen developed a two-parameter corresponding-states correlation for estimation of liquid volumes: Vc r = V2 = V1 r 1 c V r 2 r1 reduced density c density at the critical point
V2 required volume V1 known volume r1 , r2 reduced densities read from Fig. 3.17(p. 109)

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Thank you Questions or comments?

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