Equations of State

Lecture I

Cubic Equations
Virial Equation Mixing Rules Lecture II Complex Equations Generalized Correlations Learning Objective Use appropriate equations of state to estimate densities of liquid and vapor phases of pure substances and mixtures.

Phase Behavior of Pure Fluids

Pressure 1 4

2
Solid 3 7 10 11 Volume 5 8 6 12

1. 2. 3. 4. 5. 6.

Critical Pressure Liquid Solid Solid/Liquid Liquid/Vapor Gas

7. 8. 9. 10. 11. 12.

Satd Liquid Satd Vapor Vapor Solid/Vapor Critical Volume Critical Temperature

Pressure PC Liquid
Liquid/Vapor

Solid

Lsat

Vsat

GasMay be ideal gas TC Vapor

Solid/Vapor VC Volume

What is the shape of an isotherm in the gas or vapor region? What is an isotherm?

Ideal Gas Equation

All gases approach ideality as P 0

There is no fixed algorithm for identifying the region where the gas behaves ideally, because the behavior of a gas depends on the chemical properties of the molecule
PV = nRT Ideal gases have NO interparticle interactions Real gases HAVE interparticle interactions

Thermodynamic properties (i.e. H, U) of ideal gases are special because of the lack of interparticle interactions.
Residual properties allow us to determine the deviation from ideality by MR = M - MID

Hard Sphere Model Equation of State

Like ideal gas assumption, this model applies at low fluid density and high temperature. All spheres have the same diameter - Compressibility factor A depends on fluid density -

~ N /V

volume V

~ N Is the number of spheres in

Density () is conventionally in terms of the packing fraction packing fraction is the ratio of V of spheres to container V

Hard Sphere Model Equation of State, contd

The packing fraction can be written without the number density term

Vspheres V

~ N 4 ( / 2) 3 3V

NA 6v

v is the specific volume (volume/mole) Because there are voids between spheres, < 1 The maximum packing fraction occurs when spheres form a face-centered cubic lattice

2
m ax

0.74048 ...

Hard Sphere Model Equation of State, contd

This maximum packing is for a solid phase

For a fluid composed of hard spheres

max

0..494...

The compressibility factor can be written in terms of the packing fraction

1 (1

3 3

For < 0.494

In the limit as 0, Z 1 which is for an ideal gas

Real Gases
Simplest representation of real gas is the compressibility factor

PV RT

Walas fig 1.2b

Effects of temperature and pressure on the compressibility of nitrogen at several temperatures. From Walas fig 1.2b.

Figure 1.8 Walas

Corresponding states representations, from Walas fig. 1.8a

Figure 1.8 Walas

Corresponding states representations, from Walas fig. 1.8b

Real gases have non-negligible intermolecular forces

Attractive forces
Repulsive forces

Molecules may be: electrically neutral and symmetrical, usually non-polar electrically neutral and unsymmetrical, polar molecules that associate due to residual valences

Cubic Equations of State

In bringing particles together there is a point where attractive forces begin, then finally there are repulsions at close distances. Coefficients of the virial equation account for the attractive forces between distant molecules. Earliest cubic equation van der Waals (1873) 1. 2. Takes into account the real volume of the particles b ~ volume of a particle Takes into account the real pressure exerted by particles subject to interactions, which are predominantly attractive. Pid = Preal + P0 P0 (1/V)2 P0 is called the inner pressure. V is the specific volume, or 1/

we define the constant a, P0 = a(1/V2)

1 V

a V

RT

Van der Waals Equation of State

a V2

RT

a is called the attraction parameter b is the repulsion parameter b is the effective molecular volume ~4x the volume of the actual molecules Useful forms of the equation: Explicit in pressure:

Volume form:

V3

RT a P V b V2 RT 2 a ab V V P P P

How many roots are there? What do they physically represent?

Cubic equations can represent the continuity of physical states

Diagram of a cubic equation of state in the two-phase region. Shows metastable regions and tie line connecting volumes of liquid and vapor phases in equilibrium. Areas FEDF and DCBD are equal (Maxwells principle). Region EDC is physically impossible for a pure substance

Figure 1.7 in Walas 3 volume roots: highest value is the vapor volume, lowest volume is the liquid volume, third one is physically meaningless

Determination of parameters for cubic equations

At the critical point,

3 C

b
V P

RTC 2 VC PC
0

a VC PC
RTC VC b 2 RTC VC b
2

ab PC
2a VC3 6a VC4

V P2

0
T

Solve these three simultaneously to obtain

Determination of parameters for cubic equations, contd

a 3PCVC2 VC b 3

27R 2TC2 64PC RTC 8PC

If the Law of Corresponding States truly held, ALL gases would have the same ZC.

Solution of three equations yields a third parameter

8 PCVC 3TC
0.375

This value of R is meaningless, however, it enables the calculation of ZC

ZC

Other Cubic Equations

After Van der Waals, the next major improvement in cubic equations was Redlich Kwong (1949).

RT V b

a T V (V

b)

Redlich-Kwong Parameters

0.42748R 2TC2.5 PC
0.0866 RTC PC

Redlich Kwong, contd

RT V b

a T V (V

RK equation has two parameters, a and b

b)

RT T P V b V (V b)

vs.

RT a V b V V

1.) a was found to be dependent on T, so T0.5 has a significance 2.) Increased role of molecular volume.

Redlich (1976): They had no particular theoretical basis for their equation, so it is to be regarded as an arbitrary but inspired empirical modification of its predecessors.

Soave Redlich-Kwong (1972)

RT a V b V (V b)
[1 (0.48508 1.55171

a/T1/2 of RK is replaced with (T, )

0.15613

)(1 Tr0.5 )] 2

a
b

0.42748R 2TC2 PC 0.0866 RTC PC

1.096 e (

The Soave Equation has been designed for hydrocarbon gaseous phases.

is a function of Tr and For hydrogen:

0.15114Tr )

Acentric Factor
Third parameter in equations of state. Acentric factor () was identified by Pitzer Pitzer used the fact that the log of vapor pressure of a pure fluid is approximately linear with the reciprocal of absolute temperature.

d log Prsat d 1 Tr
1.2

The slope of a plot of log Prsat vs 1/Tr For simple fluids (Ar, Kr, Xe), this slope = -2.3
1.4

1/Tr Slope = -2.3 (Ar, Kr, Xe)

log (Prsat)

-1

-2

Tr = 0.7

Find the difference of other fluids with the value of log Prsat at Tr = 0.7
Then = -1-log(Prsat)Tr = 0.7

According to Pitzer, measures the deviation of intermolecular potential functions from that of simple, spherical molecules.

Peng Robinson Equation

RT V b V (V

a (T ) b) b(V
2 2 C

b)
Close for nonpolars

Parameters

a
b

0.45724R T PC

ZC

0.307

0.07780 RTC PC

At temperatures other than the critical temperature

a(T )
0.5

a(TC ) (Tr , ) 1 (1 Tr0.5 )( 0.37464 1.5422 0.26992

2

Peng Robinson Equation, contd

Clear goals for the development of this equation 1) 2) 3) All parameters expressible in terms of PC, TC, and Focus accuracy near the critical point No more than 1 binary interaction parameter for mixing rules and these should be independent of T, P and composition

4)

Applicable to natural gas processes for calculation of all fluid properties

PR equation is more accurate for liquid densities than RK

Example calculation: Finding roots of cubic equation

Methyl chloride Critical properties: TC = 416.3 K PC = 66.8 bar

Using volume form of the Van der Waals equation

RT 2 V P

a V P

ab P

a
b

27 R 2TC2 =7.566e+06 bar cm6/mol2 64PC For initial guesses, use b for the liquid root, and RT/P for the vapor RTC 3 =64.766 cm /mol root. 8PC

See excel calculation, use goal seek

Finding roots of cubic equations, contd

Poling criteria is an algorithm to determine what phase corresponds to the root you have found. Poling Criteria Find =

1 V

V P

What is this called??

T

(V b) 2 V 2 = RTV 3 2a (V b) 2

For Van der Waals equation For Redlich Kwong equation

V (V 2 b 2 ) 2 = RTV 2 (V b) 2 a(2V b)(V b) 2 / T

For liquid root, < 0.005 atm-1 3 Vapor phase 0.9 P P

Virial Equation of State

First described by Thiesen in 1885

PV RT

B C V V2
C
2

...
...
2

Notice that B = B And C = C

1 B

1 B' P C ' P .

B B' ; RT

C B2 C' ( RT ) 2

This equation can be derived from statistical mechanical analysis of the forces between molecules. B is the second virial coefficient describing interactions between pairs of molecules. C is the third virial coefficient describing interactions between triplets of molecules. Virial coefficients are functions only of temperature.

Virial Equation of State, contd

The truncated form of the Virial Equation

PV RT

B BP 1 B' P 1 V RT

Is extremely convenient to use because of its mathematical simplicity. According to Prausnitz (1957) it is often adequate when P < 0.5T(yiPCi)/(yiTCi)

A rough estimate (Smith & Van Ness): B truncated equation up to 5 bar, C truncated equation up to 15 bar The virial equation cannot be used for liquid phases, only gaseous.

Complex Equations of State

Four main categories (see Walas section 1.6) 1. Equations specific for individual substances water, air, CO2. These are required to have great accuracy over a wide range of conditions, which is achieved by the use of many constants.

2.

Equations of a particular form with different constants for use with different substances. Combining rules may extend these to mixtures
Equations with universal parameters evaluated in terms of the readily known properties of individual pure substances. Equations that can be applied to mixtures (from #2 and 3) that incorporate binary interaction parameters.

3. 4.

Some key equations

Several equations were developed from the original virial equation

RT (1 B

...)

One of the first successful complex equations was the Beattie-Bridgeman equation (1927)

RT

B0 RT

A0

Rc T2

B0bRT

A0 a

RB0 c T2

RB0bc T2

With 5 parameters, this equation worked well below the critical point. The Benedict-Webb-Rubin equation was an improvement over the Beattie-Bridgeman equation (1940).

P a

RT
6

B0 RT c T2
3

A0
2

C0 T2 ) exp(

bRT
2

(1

For more details on these equations, including mixing rules and parameters, see Walas, Chapter I.

Complex Equations of State, contd

A number of researchers determined constants for many compounds. Starling modified the BWR equation(1973), referred to commonly as the BWRS equation.

RT a d T

B0 RT
6

A0
3

C0 T2 (1
2

D0 T3

E0 T4
2

d bRT a T

c T2

) exp(

Nishiumi (1980) extended the BWR equation to work for water, polar compounds and heavy hydrocarbons, and calculated (measured) parameters for 92 substances. Their equation had 15 parameters that are functions of the acentric factor. The BWR and BWRS equations have high degree of accuracy - for Tr as low as 0.3 and for r as high as 3 - and are used widely by industry, including for cryogenic systems.

Corresponding States Equations

Correlation of the deviations of PVT properties from those of particular reference substances. The first of these equations was developed by Pitzer (1955 1958) of the compressibility as a polynomial in acentric factor:

Z ( 0)

Z (1)

Z ( 2)

Normally truncated at Z(1) Z(0) is the compressibility of a simple fluid (e.g. argon) and the additional terms account for deviation from simple fluid behavior. Values for Z(0) and Z(1) were tabulated and can also be found in plots. The equation with data for Z(0) and Z(1) in these forms are accurate above reduced temperatures of 0.7. Correlations for Z(0) and Z(1) have also been developed, especially by Lee and Kesler (1975).

Lee Kesler Equation

Z
(r )

Z ( 0)

(r )

Z (r )

Z ( 0)

Z ( 0)

Z (1)

0.3978

Acentric factor for octane, the largest hydrocarbon for which extensive data is available.

Z
B C D

PrVr Tr
b1 c1 d1 b2 Tr c2 Tr

B Vr
b3 Tr2 c3 Tr3

C Vr2
b4 Tr3

D Vr5

c4 Tr3Vr2

2 r

exp

Vr2

Constant b1 b2 b3 b4 c1 c2 c3 c4 d1 x 1 0 4 d2 x 1 0 4

Simple Fluids Reference Fluids 0.1 1 81 1 93 0.202657 9 0.2657 28 0.1 547 9 0.030323 0.02367 44 0.01 86984 0.0 0.0427 24 0.1 55488 0.623689 0.65392 0.0601 67 0.331 51 1 0.027 665 0.203488 0.031 3385 0.050361 8 0.01 6901 0.041 57 7 0.487 36 0.07 40336 1 .226 0.037 54

d2 Tr

Lee Kesler Equation, contd

Strategy to determine Z 1. 2. 3. From equation for Z, at specified Tr and Pr, find Vr(0) and Vr(1) by trial Find Z(0) and Z(1) and solve for Z. Note that Vr is not the reduced volume. Rather, 1/Vr = Pr/ZTr

Check the literature for updates on this equation.

Equations for Liquids

RK, SRK and Lee-Kesler are not very accurate for liquids, especially compressed liquids. Rackett equation (1970)

sat

VC Z

(1 Tr )0.2857 C

To find the molar volume of saturated liquids

Yamada and Gunn (1973) stated the average error of the Rackett eqn. is 2.4%. They developed an equation similar in form:

sat

V'Z

(1 (1 Tr ) 2 / 7 ) C

exp( (1 Tr ' )2 / 7 )

Zc can be calculated in terms of the acentric factor Zc = 0.29056 0.08775 In this equation, V and Tr are corresponding values of the specific volume and the reduced temperature.

Equations for Liquids, contd

For liquid mixtures, a similar equation was developed by Spencer & Dunn (1973) 2/7

V sat

(1 xiTCi / PCi ZC

(1 Tr )

ZC

xi ZCi

To find the liquid volume for compressed liquids, a chart method was developed by XXX and is described in Smith & Van Ness.

V2
Known volume

V1

r1 r2

Read from a chart

Equations for Liquids, contd

Fig. 3.17: Generalized density correlation for liquids.

Calculate the Tr and Pr for the state of your liquid and then read the r off the left axis.

Comparison of Equations
For calculation of volumetric properties and gas phase fugacity calculations, both RK and B-truncated virial equation are useful at Pr < 0.5Tr. PR is more accurate for liquid densities than RK, but generalized correlations by Rackett or Yamada & Dunn are more accurate for liquids. BWR and BWRS are very accurate but difficult to use. BWRS is more accurate above the critical point. As stated easrlier, the BWR and BWRS equations have high degree of accuracy - for Tr as low as 0.3 and for r as high as 3 - and are used widely by industry, including for cryogenic systems. Lee-Kesler equation is claimed to be accurate in the range of 0.3 < Tr < 4 and 0 < Pr < 10, however some difficulties may be encountered between 0.93 < Tr < 1. Recommendation estimate values with simple equations first prior to using more complex equations, because mistakes can be detected using the estimated values.