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Acentric Factor

The acentric factor, is often a third parameter in corresponding states correlations. Figure 23-2 tabulates it for pure hydrocarbons. The acentric factor
is a function of Pvp, Pc, and Tc.
It is arbitrarily defined as
H= -log(Pvp/Pc)Tr=0.7-1.0 Eq 23-17
This definition requires knowledge of the critical (pseudocritical) temperature, vapor pressure, and critical (pseudocritical)
pressure. For a hydrocarbon mixture of known composition that contains similar components, a reasonably good estimate for the acentric factor is the
molar average of the individual pure component acentric factors:
W= Yi*WiEq 23-18
If the vapor pressure is not known, can be estimated38 for pure hydrocarbons or for fractions with boiling point ranges of
50°F or less using:

EJEMPLO DEL FACTOR ACENTRICO:

A narrow-boiling petroleum fraction has a VABP of 418°F, an ASTM slope of 0.75 and an API gravity of 41°. Estimate its acentric factor. To use Eq
23-19 we need the average boiling point (MeABP); the pseudo-critical temperature (a function of MABP); and the pseudo-critical ressure (a function
of Me- ABP).
From Fig. 23-18, the correction to VABP for mean average is –3°F; the correction for MABP is –5°F. Note that for narrowboiling fractions, all
boiling points approach the volumetric average.
Then, MeABP = 415°F and MABP is 413°F.
From Eq. 23-15, the pseudo-critical pressure is:
T = 415 + 460 = 875 °R
S for 41° API = 141.5/(131.5 + 41) = 0.871
Ppc = 3.12281(109) (875)-2.3125(0.871)2.3201 = 356 psia
From Eq 23-16, the pseudo-critical temperature is:

ENTHALPY BEHAVIOR
The change of enthalpy with temperature and pressure is complex. Predicting the enthalpy for a pure component or mixture is multi-step procedure
that requires information that can only be obtained by experimental measurement. For pure components, use of a P-H diagram like those shown in
Figs. 24-22 to 24-35 is recommended.
The enthalpy behavior of mixtures can be predicted through thermodynamic correlations. Use of a good contemporary equation of state is
ecommended for mixture enthalpy predictions. Fig. 24-2 shows graphically the change in enthalpy of three gas streams and two liquid streams as
pressure is changed at constant temperature. Values for the plot were calculated by the Soave 10 version of the Redlich-Kwong equation
of state11. The curves in Fig. 24-2 are for no phase change and show typical behavior of gas phase enthalpy decreasing and liquid phase enthalpy
increasing with increasing pressure. Enthalpies for mixtures of real gases and liquids can be predicted by hand calculation methods. The ones
recommended for use are based on an extension of the principle of corresponding states and are shown graphically in Fig. 24-6 and 24-7.
Ideal Gas State Enthalpies
Enthalpies for pure component gases are readily correlated as a power series of temperature for a wide range of components including all of those
that occur in natural gas streams.
Typical values for natural gas components are plotted in Figs. 24-3 and 24-4 for temperatures from -200 to 900°F. Enthalpies for gas mixtures can be
obtained as the mole fraction average if molar enthalpies are used, or the weight fraction average if mass enthalpies are used.
Many natural gas streams contain undefined, or pseudo, components. Ideal gas enthalpies for pseudo components are shown in Fig. 24-5. To use Fig.
24-5 the specific gravity, molecular weight and temperature (relative density, molecular mass and temperature) must be known. Fig. 24-5 is for
paraffinic mixtures and should not be used for pseudo components derived form aromatic crude oils. The enthalpy datum chosen is zero enthalpy at
zero absolute pressure and zero absolute temperature, the same datum as used in API Project 44. 1 The choice of datum is arbitrary and a matter of
convenience. Enthalpy differences, the values of interest, are not affected by the datum chosen. However, the same enthalpy datum should be used
for all components in any one calculation.
CHANGE OF ENTHALPY WITH PRESSURE
For purposes of correlation and calculation, the ideal and real gas behaviors are treated separately. The mixture ideal gas enthalpy at a specified
temperature is calculated; the enthalpy change of the real gas mixture is calculated from a correlation prepared from experimental enthalpy
easurements on a variety of mixtures. This relation can be expressed as:
La entalpía ideal a una temperatura dada, que se calcula a partir de una correlación elaborada a partir de mediciones
experimentales de una variedad de mezclas de gas. Esta correlación puede ser expresada de la siguiente manera:

Donde:

la entalpía ideal esta dada a la temperatura deseada T y tiene unidades de BTU/mol.


el cambio de la entalpía con la presión, a partir de la diferencia entre la entalpía del gas ideal y la entalpía a
la temperatura deseada.

es cero a la temperatura absoluta, de tal forma que la ecuación se puede describir como:

Los valores del cambio de la entalpía real de gas o líquido pueden ser obtenidos a partir del principio de estados
correspondientes. La correlación esta diseñada para temperaturas reducidas. La correlación se muestra en las Figuras 24-6 y 24-7 del
GPSA. La segunda carta es la correlación que muestra la desviación de un fluido real a partir del cambio de entalpía con la presión. El

valor de es calculada por:

Donde:

es el cambio de la entalpía de un fluido simple con la presión ( Fig. 24-6, GPSA)

es la desviación para un fluido simple (Fig 24-7 del GPSA)

change for a simple


fluid from Fig. 24-7
Figs. 24-6 and 24-7 can be used for gas and liquid mixtures.
If the mixture is a gas, use the lower chart in each figure. For
liquids read the value from the isotherms at the top of the
chart. The units of (H0 –H) will depend on the units of the
universal gas constant, R, and Tc. For (H0 –H) in Btu/lb mole,
R=1.986 Btu/(lb mole °R) and Tc is in °R.
The reduced temperature and pressure are defined as T r =
T/Tc and Pr = P/Pc, where absolute temperature and pressure
must be used. Values for pure component critical temperature,
pressure and acentric factor are in Section 23 Physical Properties.
Section 23 also contains graphs relating ASTM distillation
temperature, molecular weight, specific gravity
(relative density), critical temperature, and critical pressure
for undefined fractions. The fraction acentric factor can be estimated
from Eq 23-17.
To use Figs. 24-6 and 24-7, the mixture composition must be
known. The mole fraction average (pseudo) critical temperature
and pressure are calculated using Kay’s Rule4 as illustrated
in Fig. 23-3 (TCm = yiTCi and PCm = yiPCi). The mole
fraction average mixture enthalpy is calculated from:
Hm 0 yiHi
0 Eq 24-5
The values of Hi
0 are obtained by multiplying the enthalpy
value from Figs. 24-3 and 24-4 by the molecular weight of the
individual component.
The mole fraction average acentric factor is calculated:
m yi i Eq 24-6
The information necessary to evaluate enthalpies for the
mixture from Figs. 24-3 to 24-7 is now known. Use of the
method will be clearer after study of the following illustrative
calculation.

Edmister (1958) proposed a correlation for estimating the acentric factor T of pure fluids and petroleum fractions. The
equation, widely used in the petroleum industry, requires boiling point, critical temperature, and
critical pressure. The proposed expression is given by the following relationship:

where T acentric factor


pc critical pressure, psia
Tc critical temperature, °R
Tb normal boiling point, °R
If the acentric factor is available from another correlation, the Edmister equation can be rearranged to solve for any of the
three other properties (providing the other two are known).

The acentric factor (w), first proposed by Pitzer (1955); is a measure of a fluid's deviation from the lave of
corresponding states (see the section on compressibility factors). It is defined as:

where p, is the vapor pressure of the fluid at a temperature of 0.7T,, and p, is its critical pressure . As
expected , w is equal to zero for noble gases like argon, and is close to zero for gases like methane.

El factor acéntrico definido por Pitzer (Pitzer, Lippman, Carl y Paterson, 1995) para componentes
puros es:

log ' 110 −r P ; para Tr= 0.7 (36)


donde:

P’r= Presión de vapor reducida, para una temperatura reducida T r = 0.7


= Acéntricidad o no-esfericidad de la molécula; conforme aumenta el peso
molecular de los hidrocarburos, se incrementa. Los valores para Zc,a,b, se
puede observar que son los mismos que los de la ecuación original de Redlich-
Kwong (de Redlich-Kwong, 1949):

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