Documente Academic
Documente Profesional
Documente Cultură
PROPERTIES OF PURE
SUBSTANCES
1
EQUATION OF STATES (EOS)
An Equation of State (EOS) is an equation that relates
the pressure, temperature, and the molar volume
(PVT) of a substance.
Types of EOS
i. Ideal Gas (gas)
ii. Virial EOS (gas)
iii. Van der Waals EOS (gas & liquid)
Cubic EOS
iv. Redlich-Kwong EOS (gas & liquid)
Ideal Gas EOS
The simplest and best-known equation of state for
substances in the gas phase is the ideal-gas equation of
state. This equation predicts the P-v-T behavior of a
gas quite accurately within some properly selected
region.
Ideal gas equation of state
For ideal gas in any closed-system process;(dQ dW) or (dQ + dW) = dU = CvdT
Adiabatic, 0
(T/T) = (V/V)^ R/Cv = Cp/Cv Cp = Cv
= Cv/Cv + R/Cv
= [(mRT/P)*(P/mRT)]^ R/Cv
= 1 + R/Cv
= (TP/TP)^R/Cv = (T/T)^R/Cv * (P/P)^R/Cv
R = (-1)Cv
(T/T)^(1+ R/Cv) = (P/P)^R/Cv
(T/T)^(Cv/Cv+ R/Cv) = (P/P)^R/Cv
(T/T)^(Cp/Cv) = (P/P)^R/Cv
(T/T) = (P/P)^[(R/Cv)*(Cv/Cp)] (T/T) = (P/P)^ (-1)Cv/Cv
(T/T) = (P/P)^ R/Cp = (P/P)^ (-1)/
T(P)^-(-1)/ = T(P)^-(-1)/
T(P)^(1-)/ = constant
Example; 3.2 (J.M Smith Book)
1 mol of air is compressed from an initial state of 1 bar and 25oC
to a final state of 5 bar and 25oC by three different
mechanically reversible processes in a closed s 25oC system;
From Ideal gas law, find v1 and v3, v1 = v2 = 0.02479 m3/mol & v3 =0.004958m3/mol
b) Isothermal compression
Q = 0-1663+1495 = -168J
W = 998 + 665 1495 = 168J
U = 998-998+ 0 = 0
H = 1663-1663 +0 = 0
ii- Show the processes on a Pv diagram.
Virial EOS
For real gases, 0<Z<1 ; Z>1
Virial
expansions
~ RT BP
V [1 ]
P RT
~ RT
V B
P
~ (83.1483.14cm3 bar / mol.K)(473.15 K )
V ( 388cm3 / mol )
10 bar
~
V 3546cm3 / mol
~ RT B C
V 1 ~ ~2
P V V
PV (10)(3488)
Z 0.8867
RT (83.14)(473.15)
Cubic Equations of State (EOS)
isotherm
saturation pressure
saturated liquid
saturated vapor
25
where a & b are (+ve) substance dependent constant
27 2 1
= ; = and; = Critical Temperature
64 8 Appendix B
Table B.1
= Critical pressure
a
The term is Van der Waals forces which account for the attractive
V2
forces between molecules
Table B.1 : Characteristic Properties of Pure Species
Redlich-Kwong (pg 94)
Modification of Van der Waals equation
It incorporates the temperature dependence of Van der Waal's
forces
Where;
( )2 2
= ;b = Tc & Pc Appendix B, Table B.1
T P
Tr , Pr
Tc Pc
= +
+ (+)
=
Related parameters available in Table 3.1 (pg. 98)
Example 3.9[J.M Smith pg 98]
0 1
Z Z Z
Z 0 , Z 1 can be found in Appendix E, Table E1- E4
/Compressibility Chart
can be found in Appendix B, table B1
The compressibility chart Appendix B ; Table B1
where
B B 0
B 1
0 0.422 1 0.172
B 0.083 1.6
, B 0.139
Tr Tr4.2
3) Pitzer Correlation for the Third Virial Coefficient
where C C0 C1
0 0.02432 0.00313
C 0.01407 10.5
,
Tr Tr
1 0.05539 0.00242
C 0.02676
Tr2.7 Tr10.5
Example 3.10[J.M Smith]
2. Analyze the molar volume of vapor of ethane at 55 oC, 8 bar using Van der
Waals equation.
3. Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the
molar volumes of (a) Saturated-vapor n-butane (b) Saturated-liquid n-
butane at these conditions as given by the van der Waals(vdW) and Peng
Robinson (PR).
4. Analyze the molar volume of n-pentane in cm3/g at 237 oC and 25 bar, using
the generalized Pitzer correlation for third virial coefficient method.
END
THANK YOU..
44