pressure volume tempertue
TRANSCRIPT
Pressure-Volume-Temperature Relationship Of Pure Gases
Scope:
The volumetric behavior of pure gases as functions of temperature and pressure is covered
in this assignment. The basis for the correlations is the thermodynamic fact that each substance
there exist a unique relation among Pressure, Temperature, and specific Volume for any single
phase.
General Considerations:
Methods of correlating the P-V-T behavior of pure gases can be conveniently, but somewhat
arbitrarily, divided in three groups.
First there are methods which are classified under the general term corresponding states and are
based on dimensional similitude considerations. The compressibility factor reduced property
correlation is a good example of this treatment.
Second there is the more theoretical approach employing a virial expansion of P-V-T equations
with the constants directly related to the intermolecular potential energy distance relationship
applicable to the substance in question.
Third and finally, many analytical equations of state have been proposed.
Introduction to volumetric properties: The volumetric properties of a pure fluid in a given state are commonly expressed with the
compressibility factor Z, which can be written as a function of T and P or of T and V.
Z ≡ = fp (T, P)
= fv (T, V) where V is the molar volume, P is the absolute pressure, T is the absolute temperature, and R is
called the universal gas constant. The value of R depends upon the units of the variables used. Z
is unity for ideal gases. Z approaches unity at low pressures for all gases and may be greater or
less than unity at higher pressures if the temperature is above the so-called Boyle temperature, Z
will always be greater than unity, but if the temperature is below the Boyle temperature, Z is less
than unity at low pressures and greater than unity at high pressures. Since the compressibility
factor is dimensionless, it is often represented by a function of dimensionless (reduced)
temperature, Tr = T/T*, and dimensionless (reduced) pressure, Pr = P/P*, where T*, and P* are
characteristic properties for the substance, such as the component’s vapor-liquid critical, Tc , and
Pc. It could also be given as a function of Tr and reduced volume, Vr = V/V*, where V* could be
chosen as Vc or RTc /Pc or another quantity with units of volume. Then Z is considered a
function of dimensionless variables:
Z = ƒPr (Tr , Pr)
=ƒVr (Tr , Vr )
The reasons why Z deviates from unity are:
1) Shape factors and Intermolecular Forces. Molecules are not point masses and have many diverse shapes. Even simple spherical atoms
attracts or repel other atoms, depending upon the separation distance, in addition, at high
pressures, the volume fractions occupied by the atoms themselves may be significant Molecules
behave in the similar manner. The fact that real gases have interacting forces and finite molecular
volumes is usually the most important reason that why Z deviates.
2) Electrical Forces: Electrical forces of permanent kind are usually important in polar molecules. Nonpermanent
electrical forces, such as electric moments arising during collisions are included in above and are
present in all real systems. The forces are included in the potential energy relationships between
molecules. So Z deviates from ideality.
3) Hydrogen bonding: Hydrogen bonding between molecules usually occurs in systems of polar nature. Suchj forces are
considered in same category as electrical forces.
4) Quantum Effects: Quantum effects are considered in those molecules where the translational energy modes must be
quantized.
These four effects must be considered when methods are proposed to describe the
variation of P-V-T behavior of a real gas from that of an ideal gas.
Corresponding State Correlations: The basis of the corresponding state correlations is the observation that the graphs of P vs V,
with isotherms, are quantitatively similar for all gases.
The variations in Z is small compared with possible variations in P, V, T. to show the P-V-T
behavior of a particular gas, Z is plotted against pressure, with curves representing isotherms and
isometrics. To show the behavior of Z in a general way i.e for all gases, recourse is usually had
to the principle of corresponding states. The principle has been stated in many ways, but it is best
visualized by applying dimensional analysis to the important system parameters. The set of
dimensionless groups which are obtained may then be utilized to define the system. The
equations of Z, graphs and the Equations of State are all formulations of a general principle of
dimensionless functions and dimensionless variables called the corresponding states principle
(CSP) or sometimes the “Law of Corresponding States.” It asserts that suitably dimensionless
properties of all substances will follow universal variations of suitably dimensionless variables of
state and other dimensionless quantities. Its general and specific forms can be derived from
molecular theory by Hakala.
For very high pressures and temperatures, Breedveld and Prausnitz have generated more accurate
extensions of graphs between these variables.
Many versions of these graphs have been published. All differ somewhat, as each reflects the
choice of experimental data and how they are smoothed. Those shown are as accurate as any
two-parameter plots published, and they have the added advantage that V can be found directly
from the lines of V =V/ (RTc /Pc).
Equations of state (EoS) are mathematical representations of graphical information such as
shown in these graphs.
Two-Parameter CSP: Pitzer and Guggenheim describe the molecular conditions for this lowest level CSP when only
two characteristic properties, such as Tc and Pc, are used to make the state conditions
dimensionless, and the dimensionless function may be Z. Thus, these graphs and Equations are
examples of this two parameter form of CSP where the characteristics are Tc and Pc or Tc and Vc.
Only the monatomic substances Ar, Kr, Xe, or “simple fluids” follow this behavior accurately;
all others show some deviation. For example, two parameter CSP requires that all substances
have the same critical compressibility factor, Zc = PcVc / RTc. Simple transformations of EoS
models show that all those with only two substance-specific constant parameters such as the
original van der Waals EoS (1890), also predict the same Zc for all compounds. Analysis shows
that popular two-parameter cubic EoS models yield values greater than 0.3. This behavior
suggests that more than two dimensionless characteristics must be used both in concept and in
modeling.
Three-Parameter CSP: In general, successful EoS has included one or more dimensionless characteristic parameters
into the function expressed by Equations especially to obtain good agreement for liquid
properties. The first step in accomplishing this is to introduce a third parameter; usually it is
related to the vapor pressure, Pvp , or to a volumetric property at or near the critical point. This
improves accuracy for many substances. Molecular theory by Hakala, suggests that effects of
non polar non sphericity and of “globularity” (the range and sharpness of non polar repulsive
forces) should require separate CSP parameters, but in practice, only a single characteristic
accounts for both. Several different third parameters were introduced at about the same time but
the most popular have been Zc and the acentric factor, ,.Lydersen, and a later revision by
Hougan, tabulated Z at increments of T/Tc and P/Pc for different values of Zc.
For example, the compressibility factor was given as:
Z =Z(0) (
T/Tc , P/Pc) + Z(1)
(T/Tc , P/Pc )
where Z
(0) and Z
(1) are generalized functions of reduced temperature and pressure with Z
(0)
obtained from the monatomic species and Z(1)
by averaging (Z - Z(0)
) / for different substances.
It was expected that would describe only “normal fluids,” not strongly polar or
associating species such as via hydrogen-bonding, and limited to smaller values of . Pitzer
focused on the surface tension as being the most sensitive property to indicate when the
molecular forces were more complex than those for “normal” substances. These ideas can be
coalesced into a single equation for surface tension, , made dimensionless with critical
properties.
Pitzer states that if a substance deviates more than 5% from above Equation it appears to indicate
significant abnormality. Otherwise, the substance is expected to be normal and three-parameter
CSP should be reliable.
Higher Parameter and Alternative CSP Approaches: One method to extend CSP to substances more complex than normal fluids is to use more
terms in above equation with new characteristic parameters to add in the effects of polarity and
association on the properties.
Alternative expansions have also appeared. Rather than use simple fluids as a single reference,
multiple reference fluids can be used. For example, Lee and Kesler and Teja developed CSP
treatments for normal fluids that give excellent accuracy. The concept is to write Z in two terms
with two reference substances having acentric factors (R1)
and (R2)
, Z(R1)
(Tr , Pr, (R1)
)and
Z(R2)
(Tr, Pr, (R2)
). The expression is:
For “quantum fluids,” H2, He, Ne, Gunn, showed how to obtain useful values for CSP over wide
ranges of conditions. The equations are
where M is the molecular weight, T
cl, P
cl and V
cl are “classical” critical constants found
empirically. The “classical” acentric factor for these substances is defined as zero.
EQUATIONS OF STATE: An equation of state (EoS) is an algebraic relation between P, V, and T. This section discusses
what behavior of Nature must be described by EoS models. First, the virial equation, which can
be derived from molecular theory, but is limited in its range of applicability. It is a polynomial in
P or 1/V (or density) which, when truncated at the Second or Third Order term, can represent
modest deviations from ideal gas behavior, but not liquid properties.
Two Constant Equations Of State: There are four two constant equation of state which have been widely used,
Van der waals:
Berthelot:
Dieterici:
Redlich-Kwong:
The first three are discussed by Hirschfelder, Curtiss, and Bird, and the last is considered
to be the best of the four by Gambill. Only Dieterici’s equation gives a reasonable value
of Zc, and none predicts the second virial coefficient curvature as would be obtained from
theory by using the Lennard-Jones potential.
Three Constant Equations Of State:
Gambill discusses the generalized Wohl equation as a three constant equation of state.
Wohl Equation:
Where
a1= 6PcVc2
a2= 4PcVc2
b =Vc/4
This equation is not much, if any, more accurate than any of the two constant equations
and it is restricted to regions not near the saturation curve; nor should it be considered
valid at reduced densities greater than unity.
Four Constant Equations Of State:
The most useful four constant equation of state is McLeod equation.
McLeod equation:
(P + /V2)(V-b) = RT
Where
b = A – Bπ + Cπ2
π = P + /V2
The relationship of the four constants , A, B, C to critical properties has been studied
by Rush and Gamson and by Kobe and Murti.
Five Constant Equations Of State:
By far the most accurate and best known of the five constant equations is Beattie-
Bridgman.
Beattie Bridgman equation:
Where
Multi Constant Equations of State:
A number of very complex but highly accurate equations of state have been proposed.
The eight constant Benedict-Webb-Rubin equation is accurate for light hydrocarbons.
There are two quite accurate but somewhat cumbersome generalized equations of state
which have been widely used when machine computation was possible. They are given
below.
1) Hirschfelder, Buehler, McGee, and Sutton Equation Of State.
2) Martin and Hou Equation Of State.
For values of Vr = 1 / r > 1, the Martin and Hou equation appears somewhat more accurate, and
errors in estimating the pressure should not exceed 1 per cent.
For values of Vr < 1, the Hirschfelder equations were considered more accurate than the original
Martin Hou equation.
Virial Equation Of State:
The virial equation of state is a polynomial series in pressure or in inverse volume whose
coefficients are functions only of T for a pure fluid. The consistent forms for the initial terms are
Z = 1 + B( ) + (C – B2) ( )
2 + . . . . . .
= 1 + + + . . . . . . . . . . . . . . . ..
where the coefficients B, C, . . . are called the second, third, . . . virial coefficients. Except at high
temperatures, B is negative and, except at very low T where they are of little importance, C and
higher coefficients are positive.
Because 1) the virial expansion is not rigorous at higher pressures, 2) higher order molecular
force relations are intractable, and 3) alternative EoS forms are more accurate for dense fluids
and liquids, the virial equation is usually truncated at the second or third term and applied only to
single-phase gas systems.
The general ranges of state for applying these equations are given in Table 4-4; they were
obtained by comparing very accurately correlated Z values of Setzmann and Wagner with those
computed with their highly accurate virial coefficients over the entire range of conditions that
methane is described. When only B is used, the equations are equivalent at the lowest densities.
2nd
Equation in density is more accurate to somewhat higher densities but if it is used at higher
pressures, it can yield negative Z values. Thus, it is common to use 1st equation in pressure if
only the second virial, B, is known. If the term in C is included, 2nd
equation in density is much
more accurate than 1st equation.
Estimation of Second Virial Coefficients:
Unlike for empirical EoS, there is direct theoretical justification for extending simple CSP for B
to complex substances by merely adding terms to those for simple substances. Thus, essentially
all of the methods referenced above can be written in the form:
where V* is a characteristic volume, such as Vc or Pc /RTc, the ai are strength parameters for
various intermolecular forces, and the ƒ(i)
are sets of universal functions of reduced temperature,
T/T*, with T* typically being Tc. Then, ƒ(0)
is for simple substances with a0 being unity, ƒ(1)
corrects for non spherical shape and globularity of normal substances with a1 commonly being,
, ƒ(2)
takes account of polarity with a2 being a function of the dipole moment, and ƒ(3)
takes
account of association with a3 an empirical parameter.
Estimation of Third Virial Coefficients:
The trio intermolecular potential includes significant contributions that cannot be determined
from the pair potentials that describe second virial coefficients. Thus, CSP is also used for C,
though the range of substances considered has been much more limited.
The principal techniques for C are the CSP methods of Chueh and Prausnitz, De Santis and
Grande and Orbey and Vera. All use T* = Tc in the equation:
Analytical Equations Of States:
An EoS used to describe both gases and liquids requires the form Z in terms of V and it must be
at least cubic in V. The term analytical equation of state implies that the function ƒV (T, V) has
powers of V no higher than quartic. Then, when T and P are specified, V can be found
analytically rather than only numerically.
It is possible to formulate all possible cubic EoS in a single general form with a total of five
parameters. If one incorporates the incompressibility of liquids to have P go to infinity as V
approaches a particular parameter b, the general cubic form for P is:
where, depending upon the model, the parameters , b , , and η may be constants, including
zero, or they may vary with T and/or composition.
Above equation in terms of Z is:
When it is rewritten as the form to be solved when T and P are specified and Z is to be found
analytically, it is :
where the dimensionless parameters are defined as:
When a value of Z is found by solving from above equation for given T, P and parameter values,
V is found from V = ZRT/P. V must always be greater than b.
Non Analytic Equations Of State:
The complexity of property behavior cannot be described with high accuracy with the cubic or
quartic EoS that can be solved analytically for the volume, given T and P. So five approaches
that are available for pure components. Two are strictly empirical: BWR/MBWR models and
Wagner formulations. Two are semi empirical formulations based on theory: perturbation
methods and chemical association models. The last method attempts to account for the
fundamentally different behavior of the near-critical region by using Crossover expressions.
BWR and MBWR Models:
The BWR expressions are based on the pioneering work of Benedict, Webb and Rubin who
combined polynomials in temperature with power series and exponentials of density into an
eight-parameter form. Additional terms and parameters were later introduced by others to
formulate modified Benedict-Webb-Rubin (MBWR) EoS.
The general form of BWR/MBWR correlations is:
this equation form was standard for IUPAC and NIST compilations of pure component fluid
volumetric and thermodynamic properties. Kedge and Trebble have investigated an expression
similar to above equation with 16 parameters that provides high accuracy. However, other
formulations described below have become more prevalent in use.
Wagner Models:
Setzmann and Wagner describe a computer-intensive optimization strategy for establishing
highly accurate EoS models by a formulation for the residual Helmholtz energy.
where Ao(T, V) is the ideal gas Helmholtz energy at T and V. The compressibility factor
equation is found as using a thermodynamic partial derivative:
There are actually a few additional terms in the expression of Setzmann and Wagner. Equations
in this form can describe all measured properties of a pure substance with an accuracy that
probably exceeds that of the measurements. It gives excellent agreement with the second virial
coefficient where B/Vc is all terms in the sums of above equation when = 0. It can predict the
properties of fluids at hyper pressures and hyper temperatures.
Perturbation Models:
The technique of perturbation modeling uses reference values for systems that are similar
enough to the system of interest that good estimates of desired values can be made with small
corrections to the reference values. For EoS models, this means that the residual Helmholtz
energy of above equation is written as:
where the form of the perturbation terms [Ar (T, V) /RT](i)
can be obtained from a rigorous or
approximate theory, from a Taylor’s expansion or from intuition.
Chemical Theory EoS:
The interactions between the molecules are quite strong due to charge-transfer and hydrogen
bonding. This occurs in pure components such as alcohols, carboxylic acids, water and HF and
leads to quite different behavior of vapors of these substances. For example, Twu, show that Z
for the saturated vapor of acetic acid increases with temperature up to more than 450 K as
increased numbers of molecules appear due to a shift in the dimerization equilibrium. However,
the liquid Z behaves like most other polar substances. Also, the apparent second virial
coefficients of such components species are much more negative than suggested by
corresponding states and other correlations based on intermolecular forces and the temperature
dependence is much stronger.
Instead of using parameters of a model from only non polar and polar forces, one approach has
been to consider the interactions so strong that new “chemical species” are formed. Then the
thermodynamic treatment assumes that the properties deviate from an ideal gas mainly due to the
“speciation” plus some physical effects. It is assumed that all of the species are in reaction
equilibrium. Thus, their concentrations can be determined from equilibrium constants having
parameters such as enthalpies and entropies of reaction in addition to the usual parameters for
their physical interactions.
An example is the formation of dimers (D) from two monomers (M)
2M = D
The equilibrium constant for this reaction can be exactly related to the equation:
KD = yD / y2M P = - B / RT
The model of Hayden and O’Connell explicitly includes such contributions so that it can also
predict the properties of strongly interacting substances. Anderko notes that there are two general
methods for analyzing systems with speciation. The first, exemplified by the work of Gmehling
is to postulate the species to be found, such as dimers, and then obtain characteristic parameters
of each species such as critical properties from those of the monomers along with the enthalpy
and Gibbs energy of each reaction. The alternative approach was first developed by Heidemann
and Prausnitz and extended by Ikonomu and Donohue Anderko, Twu, and Visco and Kofke.
This approach builds the species from linear polymers whose characteristics and reaction
equilibrium constants can be predicted for all degrees of association from very few parameters.
EoS Models for the Near-Critical Region: Considerable work has been done to develop EoS models that will suitably bridge the two
regimes. The first is to use a “switching function” that decreases the contribution to the pressure
of the classical EoS and increases that from a non classical term. The advantage of this method is
that no iterative calculations are needed. Another approach is to “renormalize” Tc and Pc from
the erroneous values that a suitable EoS for the classical region gives to the correct ones.
Examples of this method include Fox, Pitzer and Schreiber, Chou and Prausnitz, Vine and
Wormald, Solimando, Lue and Prausnitz and Fornasiero.
The final approach to including non classical behavior has been the more rigorous approach via
crossover functions of Sengers and coworkers. The original method was to develop an EoS
model that was accurate from the critical point to well into the classical region, but did not cover
all conditions. Anisimov, and Tang show results for several substances.
Recent efforts with this method have led to EoS models applicable to all ranges. Though not
applied extensively yet, indications are that it should be broadly applicable with accuracies
similar to the scaling methods. In addition, theoretical analyses of this group have considered the
differences among approaches to the critical point of different kinds of systems such as
electrolytes, micelles and other aggregating substances, and polymers where the range of the non
classical region is smaller than molecular fluids and the transition from classical to non classical
can be sharper and even non universal.