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Single-Phase Systems Overview

1) This chapter discusses physical properties of single-phase systems including liquids, solids, and ideal gases. Properties like density can be estimated from literature, correlations, or direct measurement. 2) For liquid and solid mixtures, volume relationships can sometimes assume additive volumes but may also involve nonadditive excess volumes, especially near critical conditions or for strongly interacting species. 3) Ideal gases obey the ideal gas law and have a compressibility factor of 1. Real gases are more accurately modeled using equations of state like the virial equation or cubic equations like van der Waals.

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Mduduzi Magiva Mahlangu
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45 views4 pages

Single-Phase Systems Overview

1) This chapter discusses physical properties of single-phase systems including liquids, solids, and ideal gases. Properties like density can be estimated from literature, correlations, or direct measurement. 2) For liquid and solid mixtures, volume relationships can sometimes assume additive volumes but may also involve nonadditive excess volumes, especially near critical conditions or for strongly interacting species. 3) Ideal gases obey the ideal gas law and have a compressibility factor of 1. Real gases are more accurately modeled using equations of state like the virial equation or cubic equations like van der Waals.

Uploaded by

Mduduzi Magiva Mahlangu
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOC, PDF, TXT or read online on Scribd

Chapter 5

Single-Phase Systems
Physical Properties
Sources:

1) literature (handbook, library or web sources)


2) estimation techniques (correlations or theory)
3) measurement (most expensive but sometimes required)

Liquid and Solid Densities


Temperature dependence -- modest but sometimes important
Pressure dependence -- usually negligible (incompressible)
Mixtures -- sometimes additive volumes can be assumed
V

w
1
i

x M
x V
i

(Can you derive the last two from the first?)


Mixtures -- Nonadditive volumes
V

x V
i

V E large:

V E

Excess Volume (per mole)

1) near mixture critical conditions (high T and P)


2) for strongly interacting species (e.g., ethanol + water)

Ideal Gases (sometimes called "perfect gases")


Obey the ideal gas law:

PV nRT
PV RT

Equation of state -- a relationship between P, V , and T -- the equation above is


called the ideal gas equation of state.

Compressibility factor:

PV
RT

z 1
Standard conditions: 1) scientific

definition of z
for ideal gases

0 oC, 1 atm (exact - not 1 sig. fig.)

(to 3 sig. figs.)


1 mol (at std. conditions) 22,400 cm3
1 lbmol 359 ft3
2) natural gas industry

60 oF, 14.7 psia

1 lbmol 379 ft3


Calculations: usually involve converting from one set of conditions to another
P2V2
T
2

T1
PV
1 1

or

P2V2
n T
2 2
PV
n1T1
1 1

Ideal gas mixtures


Partial pressure of component A:

p A Py A

Note: This is used as the definition of "partial pressure", even for


non-ideal gases. It is equal to the pressure that
would be
exerted if A alone occupied the container
only for ideal
gases.
Total pressure = sum of partial pressures:

Py

P yi P (1)

Real Gases (sometimes called imperfect gases)


Equation of state is usually complicated -- compressibility factor not unity.
Virial equation of state -- expansion about ideal gas law:
z

PV
B C
1 2
RT
V V

B, C, ... = 2nd, 3rd, etc., virial coefficients (functions of T)


Cubic equations of state -- all modifications of Van der Waals equation of state:
Van der Waals equation of state

a
P 2 V b RT

V
RT
a
P
2
V b V
PV
V
a
z

RT
V b RTV

cubic in molar volume

Note: As the molar volume becomes large, z 1.


Soave-Redlich-Kwong equation of state
P

a
RT

V b V V b

f (T / TC , )

(see Eqn. 5.3-12, p. 203)

a 0.42747 R T / PC
2

2
C

b 0.08664 RTC / PC

Corresponding states approach for compressibility factors


Simple (two-parameter) corresponding states: All fluids obey the
same equation of state written in reduced form.
T P
z
f
,

zC
TC PC

z r f Tr , Pr

Since zC is nearly a constant for many organic species (about 0.27),


the most often used form is

z f ( Tr , Pr ) see charts on pp. 208-11

They also use the following, which is helpful when the


molar volume is known:
Vr Vrideal

V
RTC
PC

Extended (three-parameter) corresponding states


z f Tr , Pr ,
z z 0 z 1

Note: The Pitzer acentric factor is zero for simple species.


Gas mixtures
Use pseudocritical properties -- Kay's rules

yT
P y P

TC

Ci
Ci

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