Thermodynamics Page 1 of 102

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If the state of chemical engineering technology was advanced enough, we could provide one equation to
describe the phase equilibrium of all components and all mixtures of components under all conditions.
Unfortunately, this is not the case and all that is available to us today are "partial" models which apply to specific
classes of components and mixtures. It is our job, as a simulation service, to provide you with the optimum
selection of these models. And your job, as a process engineer, to select the appropriate model when you are
creating the flowsheet.
As you can see from the list above, CHEMCAD provides an extensive array of the most up-to-date methods for
performing heat and material balances. These techniques cover applications ranging from straight hydrocarbon
applications, to chemical models, to a wide variety of special applications involving electrolytes, salt effects,
amines, sour water, to other specialty chemical applications. These methods have been field tested over a
period of years and have been demonstrated to give highly accurate results.
To achieve accurate results, however, it is necessary to select the proper method for a given application. This
section of the manual provides guidelines for making these selections. It should be noted, however, that the
guidelines we will be discussing are for the selection of K-value (phase equilibrium) and enthalpy methods only.
The selection of physical property is not considered important to this discussion. You may refer to the end of this
section for a more complete discussion of properties techniques.
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To understand why a particular equation is preferable in a given application, you must understand some basic
definitions and relationships.
Fugacity
Activity
Equilibrium

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For those users who would like assistance, CHEMCAD provides an advice system for the selection of K-value
and enthalpy methods. Briefly explained, the system works like this:
1. First, it looks at the component list and decides what general type of model is required, i.e., equation-of-state,
activity model, etc.
2. Next, it looks at the temperature and pressure ranges input by the user and decides which equation within a
given category is best at the limits of those ranges.
3. If the method is an activity model, the program then looks at the BIP database to see which model has the
most data sets for the current problem. It then calculates the fractional completeness of the BIP matrix. If that
fraction is greater than the BIP threshold parameter, it uses the chosen activity method; if not, it uses UNIFAC.
The Thermodynamics Wizard is no replacement for engineering judgment. The wizard makes uses an algorithm
based on general rules and may not always be correct. The suggested model may not be the best model for
the system.
Example of how the Thermodynamics Wizard may be incorrect: Choose water, carbon dioxide, and
hydrocarbons as the components in a job. The Thermodynamic Wizard will choose UNIFAC because this is the
best model for a mixture of water, gas and hydrocarbons in certain situations. The wizard did not know that
water is the utility for your heat exchangers and doesnt mix with process streams, or it would have chosen SRK.

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Generally speaking, the primary consideration when selecting a thermodynamic method for your simulation is to
ask yourself what is happening in the liquid phase. We classify liquid solutions into five categories, as discussed
in Types of Solutions.: ideal, regular, polar (highly non-ideal), electrolytes, and special.
The recommendations for specific systems are summarized in the following table:

Hydrocarbons

Soave-Redlich-Kwong (SRK) High - moderate P & T

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Thermodynamics Page 2 of 102

API SRK High - moderate P & T

Peng-Robinson High - moderate P & T

Benedict-Webb-Ruben-Starling High - moderate P & T

Grayson-Streed Moderate P & T

ESSO (Maxwell-Bonnell K- Low pressure, heavy material

charts)

ESD Hydrocarbon-water; hydrocarbon-gases

SAFT Hydrocarbon-water; hydrocarbon-gases

Chemicals

UNIFAC T = 275K - 475K; P = 0-4 atm.; two liquid

phases; non-ideal; group contribution; predictive

Wilson Highly non-ideal

Vapor Pressure Ideal solutions

NRTL Highly non-ideal and 2 liquid phases

UNIQUAC Highly non-ideal and 2 liquid phases

Margules Highly non-ideal and 2 liquid phases. (4 suffix)

T. K. Wilson Highly non-ideal and 2 liquid phases

Hiranuma (HRNM) Highly non-ideal and 2 liquid phases

Regular Solution Moderately non-ideal (predictive)

Van Laar Moderately non-ideal

Modified SRK (4 parameter) Polar compounds in regular solutions

Predictive SRK Polar compounds in non-ideal solutions; better

than UNIFAC at high pressures

Wilson Salt Non-ideal solutions with salts dissolved in them

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Henry's Gas Law Gases dissolved in water

Amine (MEA DEA) Gas sweetening

Sour Water Acid gases and NH3 dissolved in H2O

K Tables User Ks

Polynomial User Ks

User-Added Subroutine User Ks

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Thermodynamics Page 3 of 102

TSRK Methanol system; particularly with light gases

PPAQ General, but electrolyte systems is most

common application

TEG Dehydration of hydrocarbon streams using tri-

ethylene-glycol

FLOR Flory-Huggins method for polymers

UPLM UNIFAC for polymers

ACTX User-specified activity coefficients

ESD Hydrogen bonding; hydrogen bonding at high

pressure

SAFT Hydrogen bonding; hydrogen bonding at high

pressure

For the selection of enthalpy methods, we make the following general recommendations:

K-Value Model Recommended Enthalpy Model

PR PR

BWRS BWRS

SRK, APIS, MSRK, VAP SRK

REGU, SOUR, TEG, TSRK SRK

ESD, SAFT SRK

Grayson-Streed, ESSO Lee-Kesler

NRTL, UNIF, UNIQ, WILS, VANL, LATE

MARG, HRNM, T. K. Wilson, PSRK,
FLOR, UPLM, ACTX

AMIN AMIN

PPAQ SRK or LATE w/HTSL

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Choose the K-value to use for this flowsheet. K-values are the expressions that relate liquid and gas phase
vapor liquid equilibrium (VLE). You can use local K-values on UnitOps to override the global K-value setting.
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Use special binary interaction parameters for ethane/ethylene and propane/propylene systems. This option is
only valid when the SRK or Peng-Robinson method is used for K-values. Typically, the special BIPs will give the
best results near the critical points.

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Thermodynamics Page 4 of 102

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Certain compounds, especially carboxylic acids, have the tendency to dimerize or even polymerize in the vapor
phase. Selecting this option accounts for this vapor phase association. Note that this option will activate the
Poynting correction.
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This method is a correction for pressure of the vapor phase fugacity when using activity coefficient methods. If
this option is selected, the vapor fugacity will be calculated using the SRK equation of state. Typically, it is safe
to ignore this correction at lower operating pressures. This option may only be used with a liquid activity
coefficient method and is recommended when pressure is above 3 atm.
This option also turns on the HF hexamerization when HF is present and activity coefficient models have been
selected.
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For SRK and Peng-Robinson EOS models, you are allowed to choose either the standard alpha function or the
newer Boston-Mathias alpha function. The default is the standard alpha function. Boston-Mathias is
reccomended for temperatures above critical.
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Instructs the program to make all flashes three-phase flashes (LLV) or two-phase flashes (LV). This can only be
used with K-value methods capable of performing three-phase flashes: MARG, NRTL, UNIF, UNIQ, etc.
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Change the immiscibility status of water. Water immiscibility may be invoked for any method, except for liquid
activity coefficient methods; for those options, water is always considered to be miscible. When water is
immiscible for applicable models, the K-value of water will be calculated by a special routine that accounts for
the solubility of water in the hydrocarbons. If the miscible setting is chosen, the global K-value is used for water.
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Account for the effect of dissolved salts on the vapor-liquid equilibrium of the solvents. This option may only be
used with the Wilson equation.
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CHEMCAD allows you to have up to ten (10) sets of BIPs for each activity coefficient method. This gives you the
flexibility of using one set of BIPs in one section of a flowsheet and a different set in another. A typical use of
this would be when you know that two liquid phases exist in the condenser of a distillation column. You can
choose to use NRTL LLE BIPs in the condenser and NRTL VLE for the rest of the column.
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Defines the set to be used globally by the program. Default value is 1. Other sets are treated as local sets.
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If selected, allows you to clear your local K-value options. The entire flowsheet will be reset to use the global K
model.
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If selected, allows you to clear all tray BIPs.
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If selected, upon exiting the K-value screen, the program will go into selection mode and allow you to choose
one or more units from the flowsheet. It will then present you with an input screen where you can define what K-
value model or BIP set is applicable to the particular unit operation.
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If selected, upon exiting the K-value screen, the program will go into selection mode and allow you to choose
one or more distillation towers from the flowsheet. It will then present you with an input screen where you can
enter a range of tray numbers and the BIP set that applies to that range.
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Select which components are to be modeled by Henrys Gas Law K-values. All others will be modeled using the
global K-value method. If checked, a upon exiting the K Value dialog a select Henrys Component dialog
appears. This option applies only when activity models are being used.

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Thermodynamics Page 5 of 102

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Select the enthalpy model for global use on the flowsheet. Separate enthalpy models may be assigned locally to
specific Unit Operations.
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CHEMCAD calculates ideal gas heat capacity, either from a polynomial equation with calculated parameters or
from a DIPPR library equation with empirical parameters. When library parameters exist (within CHEMCAD) for
a component, the polynomial equation is recalculated to reflect the data. The default selection is DIPPR.
The following options may be used in combination with the selected enthalpy model.
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A heat of solution file is an ASCII file which contains heat correction data for compositions of mixtures of
components.
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The electrolytes model contains an enthalpy model to compensate for heat of dissociation. This check box
allows the user to turn off enthalpy effects of dissociation if an electrolytes model is in use. This setting has no
effect on non-electrolytes models.
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The enthalpy of liquids can be adjusted for heats of mixing, based on gamma.
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If selected, allows you to clear your local enthalpy models. All units will be reset to use the global enthalpy
option.
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If selected, prompts you to select units at which you will define a "local" enthalpy model.

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Select the liquid density method used during the simulation from one of four methods: the API method, the
Cavett equation, the Library equation, or the Rackett equation
The Library method is the default. If the Library method coefficients are not available in the database, the
program uses the API method. Since this method requires the specific gravity at 60 F, if the specific gravity
(60/60) is not available, the Cavett equation is used.
API Lu's method is based on Figure 6A2.21, and Procedures 6A2.21 and 6A2.22 of the API databook.
The correlation is based on the relationship C1/d1 = C2/d2 = constant, where d1 and d2 represent two densities
and C1 and C2 represent the corresponding density correlation factors.
Where this relation holds, any density may be expressed as a function of one known density:

where:
d = is the density in units of weight per volume, and
C = represents an empirical density correlation factor (explained below)
C = A(0) + A(1) Tr + A(2)Tr2 + A(3) Tr3
Each coefficient in the above equation is determined by:

where
Tr = reduced temperature
i = 0 --> 3
Pr = reduced pressure
The coefficients are as follows:

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Thermodynamics Page 6 of 102

i B0(i) B1(i) B2(1) B3(i) B4(i)

0 1.6368 -0.04615 2.1138(10-3) -0.7845(10-5) -0.6923(10-6)
1 -1.9693 0.21874 - 8.0082e-3 (10-3) -8.2328(10-5) 5.2604(10-6)
2 2.4638 -0.36461 12.8763(10-3) 14.8059(10-5) -8.6895(10-6)
3 -1.5841 0.25136 -11.3805(10-3) 9.5672(10-5) 2.1812(10-6)
C1 is stored in the database as the specific gravity at 60 F (item 42). d1 equals d at 60o F. d2 is then
determined by evaluating C2 and applying it to the above ratio.
The average error in estimating the density of a pure hydrocarbon is 1 percent. However, errors up to 10
percent can be expected at reduced temperatures greater than 0.95.
The Cavett equation has the form:
liquid volume = Vol Con * (5.7 + 3Tr)
where
liquid volume is in cc/gmole
VolCon is the liquid mole volume constant (item 9 in the databank)
Tr is the reduced temperature
Equation of state predicts liquid density using an equation of state. The default model for liquid density will be
SRK, except where the selected K-value model is one of the following equations of state:
BWRS
PR
PRSV
ESD
SAFT
The Library equation has the following form:

where:
Density is in kgmoles/m3
Temperature is in degrees Kelvin.
A, B, C, D are component specific coefficients stored in the database (items 26 through 29).
The modified Rackett equation, which was developed by Rackett and later modified by Spencer and Danner, is
used to estimate saturated volumes:

ZRA is a unique constant for each compound.

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The primary method for computing liquid viscosities of a pure component is to use the DIPPR equation which
has the following form:

where:
= the liquid viscosity in Pascal seconds
A,B,C,D,E = DIPPR coefficients for liquid viscosities
If the DIPPR data is absent, the following two-term equation is used:

where:
= the liquid viscosity in centipoise
A and B = DIPPR coefficients stored in the database (terms 30 and 31)
If coefficients for methods 1 and 2 are not available, the method of Letsou and Stiel is used.

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Thermodynamics Page 7 of 102

where:

where:
Tc = critical temperature
x = Tc0.166 M -0.5 Pc-0.67
MW = molecular weight
w = the acentric factor
For pseudocomponents, CHEMCAD uses the method of ASME for liquid viscosity estimation.
The following mixing rule is used for the liquid-mixture viscosities:

xi = mole fraction component i

An optional mass-based mixing rule may be selected for liquid mixture viscosities. This rule is sometimes used
for polymer viscosities.

xi = mass fraction component i

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Check this box to activate the liquid viscosity pressure correction model. The high pressure model is based on
API 11A5.1 and 11A5.7.
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The primary method for computing gas viscosities of a pure component is to use the DIPPR equation which has
the form:

where:
g = gas viscosity in Pascal seconds
A,B,C,D = DIPPR coefficients for gas viscosities
For low pressure gas, the Chapman-Enskog relation is used:

where:
M = Molecular weight
R = Gas law constant
T = Temperature
P = Pressure
O = Molecular diameter

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Thermodynamics Page 8 of 102

v = Collision integral
Mp = Dipole moment
For non-polar gases the method of Neufeld is used to evaluate v:

where:
T* = kT/e
A = 1.16145
B = 0.14874
C = 0.52487
D = 0.77320
E = 2.16178
F = 2.43787
For polar compounds, v is evaluated using the method of Brokaw:

where:
v(LJ) = The Leonard-Jones collision integral
d = The polar parameter
T* = kT/e
k = Boltman's constant
e = Th energy potential parameter
If c/K and d are unavailable in the database, an alternative method for evaluating gas viscosity is the method of
Thodos:
For gases:

where:
Tr = Reduced temperature
x = Tc0.166 M-0.5 Pc-0.67
The viscosities of gas mixtures are evaluated using the method of Wilke:

where:
i = The pure component viscosity
Mi = The pure component molecular weight
The method of Dean and Stiel is used for the effect of pressure on the viscosity of gas mixtures.
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Check this box to use the Dean-Stiel correction for high-pressure vapor viscosity.

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Thermodynamics Page 9 of 102

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Select a model from the drop-down list. The library model will not show the mixing effect at low temperatures
which can sometimes occur.
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For thermal conductivity, both for gases and liquids, CHEMCAD uses the DIPPR equation to evaluate pure
component thermal conductivities.
For gases:

where:
lv = the gas thermal conductivity in w/m.K
A, B, C, and D = DIPPR coefficients
T = temperature in Kelvin
The Stiel-Thodos method is used for high-pressure correction.
For liquids:

where:
lL = the liquid thermal conductivity in w/m.K
A, B, C, and D = DIPPR coefficients
T = temperature in Kelvin
For gases where the DIPPR data is absent, CHEMCAD uses the API procedure (12B1.5) to estimate
component thermal gas conductivities.
API procedure 12B4.1 is used for high pressure correction, and API procedure 12B2.1 is used for mixing rules
for gas mixtures.
For liquids where the DIPPR data is absent, the following methods are used:
API procedure 12A1.2 for pressure < 500 psia and TR < 0.8.
API Figure 12A3.1 for hydrocarbon fractions.
API Figure 12A4.1 for high pressure correction.
API procedure 12A1.3 if the methods above do not apply.
API procedure 12A2.1 is used as the mixing rule.
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CHEMCAD normally uses the specific gravity (SG) of the components to calculate the Standard liquid (StdL)
volume rates for a mixture. For a strong electrolyte system, this method uses the poor assumption that molar
volumes (from SG) are additive. A strong dissociating electrolyte is dissolved in water; it does not add its volume
to the mixture.
The Based on actual volume option allows CHEMCAD to calculate actual liquid volume of the mixture at
Standard Conditions.
The Based on components option calculates StdL from the SG of the components. This method was left in
CHEMCAD to prevent existing flowsheets from changing.
Note that if you are defining a feed stream as StdL, CHEMCAD will calculate the mass flow rate of the stream
from your specification.

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It can be shown that

where:

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Thermodynamics Page 10 of 102

G = Gibbs free energy

S = Entropy
T = Temperature
V = Volume
P = Pressure
For a pure component at constant T,

(5-1)
Now let's consider the implications of this for an ideal gas. An ideal gas, you will remember, is a gas made up of
infinitesimally small spheres which are completely elastic in their collisions. Thus, these spheres occupy no
volume and have no intermolecular forces between them. Operating from these assumptions and using the laws
of statistical mechanics, we can derive the following relationship for one mole of gas:

(5-2)
which is the ideal gas law.
Combining 5-1 and 5-2 we get:

(5-3)
This is a useful relationship since we can measure T and P for real gases. However, equation 5-3 is not for real
gases; it is for ideal gases. Therefore, let us define a new quantity, fugacity, which would make Equation 5-3
true for real gases and try to relate fugacity to measurable quantities like P, V, and T. Thus, by definition:

(for a pure component) (5-4)

This is only a partial definition since it only permits us to determine relative values of fugacity. To complete our
definition, let us relate it to an ideal gas. From Equations 5-3 and 5-4, for an ideal gas:

integrating, we get

or

Now define C = 1 to relate fugacity to ideal gas pressures. Since all materials behave like ideal gases as
pressure approaches zero, we have:

(5-5)
A simple analysis for components in solution will yield us the following relations:

(5-6)

(5-7)
We still have to relate fugacity to measurable quantities like P, V, and T. Therefore, let us define two new useful
concepts:
The fugacity coefficient,

(for a pure component) (5-8)

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Thermodynamics Page 11 of 102

(for a component in solution) (5-9)

The compressibility factor, Z

(5-10)
We can combine Equation 5-1 and Equation 5-4 to get:

(5-11)
now

(5-12)

Similarly, for solutions:

(5-13)
Since we have equations-of-state which relate P, V, and T to Z, we can solve for Z and FFi. It merely remains
now to relate FF to phase equilibrium.

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The above approach for computing fugacity is effective only if the equation-of-state we use is adequate for the
computation of i. This may not be true for two reasons. First, the equation may not adequately represent the
compound itself, even in the pure state. Secondly, the mixing rules of the equation may not adequately
represent or quantify what happens to a molecule when it is in solution. This can be for many reasons but
frequently it is due to the failure to adequately model intermolecular forces. In such a case, an alternative
approach is taken.
Define activity, i, as follows:

(5-14)
where

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Thermodynamics Page 12 of 102

= the fugacity of the component in solution

= the fugacity of the component at some arbitrarily defined standard state

Also define the activity coefficient, , so that:

(5-15)
thus

(5-16)
From the Gibbs-Duhem relation, it can be demonstrated that for one mole of solution:

(5-17)
where

The difference between the Gibbs free energy of the component in solution and the Gibbs free energy of the
component in the standard state, called the excess Gibbs free energy. The term 1 is the change in
excess Gibbs free energy for the entire solution.
We can thus approach i, by relating it to the excess Gibbs free energy of solution, !GE. However, since !GE
cannot be directly measured, this is virtually always taken as a theoretical framework or starting point. In the
final analysis, the value of i, must be directly correlated over narrow data ranges. This is done through the use
of binary interaction parameters or BIPs. CHEMCAD provides a BIP database, as well as a data regression
facility through which these BIPs can be directly correlated from phase equilibrium data. Thus, activity
coefficients are a function not only of the component for which they are computed, but also of the nature and
quantity of the other components in the solution. In addition, the activity coefficients themselves are computed
semi-empirically, i.e., the approach has a theoretical basis but the application is dependent on parameters
correlated over specific data ranges.

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At equilibrium, all net driving forces are zero and, thus, all thermodynamic properties such as U (free energy), A
(Hemholtz free energy), G (Gibbs free energy), etc., are minimized. Mathematically, for any quantity, the first
derivative of that quantity equals zero at either a maximum, a minimum, or an inflection point. Since the second
law of thermodynamics tells us that energy always flows downhill, we know we are looking for a minimum, i.e.,
we are seeking to minimize the free energy functions U, A, and G.
(5-18)
Now we have some options:
Since dU = TdS - PdV, if S and T are fixed (i.e., known, measured), we can minimize U. Since dA = -PdV - SdT,
if V and T are fixed, we can minimize A. Since dG = VdP - SdT, if P and T are fixed, we can minimize G. For
our purposes it is best to attempt to minimize G because T and P are easily measured.
For a closed two-phase system,

For any given phase:

Therefore:

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Thermodynamics Page 13 of 102

Conservation of mass requires that dn1 = - dn2. Therefore,

(5-19)
In order for Equation 5-19 to be generally valid, it cannot depend on any particular choice of the dni. Thus the
total Gibbs free energy will be a minimum (dG = 0) for an arbitrary choice of the dni only if

(5-20)
for all components. Thus at equilibrium the partial molar Gibbs free energy of each component must be the
same in each phase present in the system. In other words,

(5-21)
Although developed above for a two-phase system, the above analysis can be equally applied to multi-phase
systems. Thus,

(5-22)
Using previously developed concepts, we can express Equation 5-22 in a variety of ways:

(5-23)
If we assume that phase one is a liquid and phase two is a vapor and we denote the vapor mole fractions with a
yi instead of an xi, we can rearrange Equation 5-23 into its most commonly used forms: namely,

(5-24)
where:
Ki = The vapor-liquid equilibrium constant or K-value.

If we can compute values of ggli, FFvi 2 and 3 we have a method for determining vapor-liquid equilibrium.
In practice, this depends upon two factors:
1. The nature of the molecules under consideration
2. The type of solutions they form

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You will remember that an ideal gas is one composed of infinitesimally small spheres that exert no
intermolecular forces on one another. The farther away from these two assumptions a component gets, the less
accurately the ideal gas law will model the fluid. Therefore, more complex equations-of-state have been
developed to account for deviations from these premises. Some equations, such as the van der Waals' equation
of state:

(5-25)
attempt to explicitly account for these deviations. In the above equation, the term b is meant to account for the
finite size of the molecules and is sometimes referred to as the "molecular volume". Its value depends on the

size and nature of the molecules. The term is a correction which was meant to account for the attractive
forces that exist between molecules.

Other equations-of-state, although attempting to account for the same phenomena, are not so explicit in
assigning physical significance to their parameters. It is generally true, however, that greater levels of

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Thermodynamics Page 14 of 102

complexity are required as we move away from the ideal gas assumptions, i.e., to accurately model behavior,
equations tend to become more complex (add parameters and constants) as follows:
The molecules get bigger.
The molecules get more complex.
The molecules get more polar.
This is true even when discussing the pure component. When evaluating mixtures, these issues become even
more important until attempts to build predictive models break down all together.

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For some systems, the partial molar volume of a component is nearly the same as the molar volume of the pure
component. A mixture of benzene and toluene at ambient temperature and pressure is an example of a liquid
system for which this is true. It is also approximately true for certain gas mixtures even at high pressures. The
treatment of the thermodynamic properties of such systems is greatly simplified, with respect to the general
case, and a pronounced simplification is effected in the solution of phase equilibrium problems. Systems which
exhibit this behavior are called ideal solutions, and the term signified that for such a solution, the partial molar
volume of each component in solution is equal to its pure component volume at the same temperature and
pressure.
We can conclude the following about ideal solutions:
1. They will follow the Lewis-Randall rule:

(5-26)
where fi is the fugacity of the pure component in the same phase and at the same temperature and
pressure as the mixture. Since gaseous mixtures at low to moderate pressures typically obey the Lewis-
Randall rule, it is possible to use Equation 5-26 to evaluate partial fugacities in these systems.
2. Since by definition there is no volume change in these solutions, we can write:

(5-27)
3. An ideal gas will always behave as an ideal solution, but a system need not conform to the ideal gas law to
behave as an ideal solution.
4. If the liquid phases are ideal solutions and the vapor phase is an ideal gas, we can deduce:

(5-28)
where:
Pi = Partial pressure
V*Pi = Vapor pressure at saturation
P = System pressure
This is Raoult's law. The most critical assumption is that the liquid phase is an ideal solution. This is not likely to
be even approximately valid unless the system is made up of species of similar molecular size and chemical
nature as in the case of benzene and toluene or n-hexane and n-heptane.

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The treatment of VLE would be simple if all systems followed Raoult's law because, in this event, no information
about the mixtures which made up the phases would be required. In actual fact, deviations from Raoult's law are
usually observed. Fundamentally, the failure of Raoult's law is due to differences in molecular size and in the
molecular forces of the components. The differences vanish only when the components become identical;
where they are appreciable, the underlying assumptions are invalid. The considerations are usually not
important with respect to a vapor phase at low pressure, where ideal gas behavior is approached. However, in
the liquid phase, the intermolecular distances are small and the molecular interactions, based both on force
fields and on volume differences (packing considerations), determine the departure from ideal solution behavior.
These liquid phase non-idealities are of primary importance and usually must be taken into account. At higher

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Thermodynamics Page 15 of 102

pressures, deviation from ideal gas behavior of the vapor phase must also be considered.
We can speculate that these non-idealities are attributable to either physical or chemical intermolecular forces.
Physical forces would be those due simply to collisions between the molecules. They would be affected
primarily by the size and shape of the molecules. Chemical forces would be electromagnetic type forces at the
molecular level which tend to cause the molecules to group or associate in a non-random fashion. The latter
kind of force tends to be the more difficult to account for and, where it predominates, more empirical approaches
are required.
Where the non-idealities tend to stem predominantly from physical interactions and are in general not too large,
we can define a new class of solutions called regular solutions. The strict definition of a regular solution is one
where the excess entropy of mixing is zero. This most generally occurs in systems where the components are
non-polar and do not differ appreciably in size, shape, and chemical behavior.
Systems of this type can be modeled using modern equations-of-state such as Soave-Redlich-Kwong and
Peng-Robinson. The following considerations are relevant:
1. These equations should be applied to systems with different size molecules but these differences should not
be too large, such as the differences between monomers and polymers. The difference between straight
chained hydrocarbons, such as nC4 and nC12 can be handled by these equations.
2. The equation-of-state selected should be applicable to the components being set up for straight-chained
and ring hydrocarbons. Their accuracy tends to diminish as branch chains are added and other molecules,
such as nitrogen, sulfur, and oxygen, are added. This is especially so if the compound is polar.
Certain extensions have been made to the SRK equation to make it more accurate for branch chained,
polar, and other hydrocarbon chemical compounds. The extension has been incorporated into CHEMCAD
in the form of the MSRK option (MSRK = Modified SRK). This modification extends the three-parameter
SRK equation to a four-parameter equation by dropping the use of the acentric factor and incorporating two
new factors, m and n, which must be correlated against data. In CHEMCAD the m and n are available for
approximately 300 components.
3. The mixing rules of the equations-of-state have a significant bearing on how accurately they handle
mixtures. The mixing rules for the equations-of-state currently available do not account for interactions
between unlike pairs of molecules if they are greatly different from the interactions between like pairs. To
overcome this limitation, a binary interaction parameter, Kij, has been added to the mixing rules of these
equations. Even this, however, has been found to be capable only of improving the accuracy between
molecules of unlike sizes, to quote Peng-Robinson:
"It was found that the optimum binary interaction coefficients were negligibly small for components with
moderate differences in molecular size. However, systems involving components having relatively large
differences in molecular size required the use of a non-trivial interaction coefficient in order to get good
agreement between predicted and experimental bubble point pressures."

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For systems where the non-idealities derive from chemical or intermolecular forces of attraction or repulsion, the
predictive methods described above are generally inadequate. For these situations, it is necessary to use
methods based upon the excess Gibbs free energy, that is, to use activity coefficient methods. For these
methods, the K-value takes the form:

where:
I = Component i liquid activity coefficient

= The standard state fugacity for component i

P = System pressure

= The fugacity coefficient of component i in the vapor mixture

Note the following:

1. In CHEMCAD the standard state fugacity, 4, is defined in one of two ways.

In the default condition, the vapor phase is taken to be ideal and the standard state is the pure component
vapor pressure. In this event, the standard state liquid fugacity equals the vapor pressure of the

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Thermodynamics Page 16 of 102

components, the vapor phase fugacity equals one, and:

An alternate approach assumes the vapor phase is a regular solution and defines the standard state as
follows:

where:
i = The vapor pressure of component i

= The fugacity coefficient of the pure component i at saturation

= The volume of the pure component i at T and VPi

This is the fugacity of the pure component at the temperature and pressure of the system. The fugacity
coefficients in the above equations are calculated using the SRK equation. The vapor phase, therefore, is
not assumed to be ideal, but rather it is assumed to be a non-ideal gas in a regular (non-associating)
solution. Use the Poynting Correction option on the K-value screen to switch back and forth between these
two standard states.
2. The gamma term in the above equation may be calculated using any of the following equations:
UNIFAC
UNIQUAC
NRTL
WILSON, T. K. WILSON, HRNM WILSON, WILSON SALT
VAN LAAR
MARGULES
REGULAR
GMAC
For all of the above, except the UNIFAC and REGULAR equations, system dependent binary interaction
parameters must be supplied in order to produce reliable results. Within CHEMCAD, these BIPs can come
from any of four sources:
They can be correlated or "regressed" from experimental data. This is the preferred and most frequently
used method.
The user can input them directly using the BIP command. This obviously requires obtaining them from
an outside source, such as the literature.
The data can be estimated using the UNIFAC equation and then regressed to produce the required
BIPs. This method is discussed under the UTIL menu and is useful for generating BIPs for secondary
pairs, i.e., pairs not critical to the separation.
The BIPs can be obtained from the CHEMCAD database. CHEMCAD supplies a database of BIPs for
VLE calculations. If the system in question is in the database, these will be automatically retrieved and
used unless overridden by one of the above methods. The user is cautioned that the BIPs in the
database were all regressed from data taken at one atmosphere and, therefore, should be used with
caution at system pressure significantly different from this value.
3. The UNIFAC and REGULAR equations are predictive methods not requiring BIPs. The REGULAR equation
is an old technique which applies only to regular solutions. These are better handled by equations-of-state
these days, so the REGULAR equation is not generally used anymore.
The UNIFAC equation is based upon the group contribution method for estimating activity coefficients. It has
the following advantages and disadvantages:
Parameters almost independent of temperature.
Size and binary interaction parameters available for many functional groups.

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Thermodynamics Page 17 of 102

Temperature range of 275 - 425 K (35-305 F).

Pressures to a few atmospheres.
Extensive comparisons with experimental data.
Not as accurate as Wilson, NRTL, or UNIQUAC methods.
Cannot be used where data on functional groups is not available.
4. The PSRK equation is also a predictive model in the same sense that any equation-of-state is (PSRK
stands for Predictive Soave-Redlich-Kwong). It attempts to combine the best features of the UNIFAC and
SRK methods. The PSRK equation, therefore, can handle non-ideal as well as regular solutions, including
two liquid phases. Its accuracy for non-ideal solutions at low pressure is approximately the same as
UNIFAC but at high pressures it is substantially better.
5. In practice, the number of adjustable constants per binary is typically two or three, but it may be as high as
five (for NRTL). The larger the number of constants, the better the representation of the data but, at the
same time, the larger the number of reliable experimental data points required to determine the constants.
Extensive and highly accurate experimental data are required to justify more than three empirical constants
for a binary mixture at a fixed temperature.
6. For many moderately non-ideal binary mixtures, all equations for GE containing two (or more) binary
parameters give good results; there is little reason to choose one over another except a user may have
more experience with the older ones (Margules, Van Laar). For strongly non-ideal binary mixtures (e.g.,
solutions of alcohols with hydrocarbons), the equation of Wilson is probably the most useful because, unlike
the NRTL equation, it contains only two adjustable parameters and is mathematically simpler than the
UNIQUAC equation. For such mixtures, the Margules equation and the Van Laar equation are likely to
represent the data with significantly less success, especially in the region dilute with respect to alcohol
where the Wilson equation is particularly suitable. The four-suffix (three-parameter) Margules equation has
no significant advantages over the three-parameter NRTL equation.
7. The Wilson equation is not applicable to a mixture which exhibits a miscibility gap; it is inherently unable,
even qualitatively, to account for phase splitting. Nevertheless, Wilson's equation may be useful even for
those mixtures where miscibility is incomplete, provided attention is confined to the one-phase equation.
A number of modifications have been developed to extend the Wilson equation to the liquid-liquid region.
Two of these are included in the program: T. K. Wilson and Hiranuma (HRNM) methods.
8. Unlike Wilson's equation, the NRTL and UNIQUAC equations are applicable to both vapor-liquid and liquid-
liquid equilibria. Therefore, mutual solubility data can be used to determine NRTL or UNIQUAC parameters.
While UNIQUAC is mathematically more complex than NRTL, it has three advantages: (1) it has only two
(rather than three) adjustable parameters, (2) UNIQUAC's parameters often have a smaller dependence on
temperature, and (3) the primary concentration variable is a surface fraction (rather than mole fraction).
UNIQUAC is applicable to solutions containing small or large molecules, including polymers.

6SHFLDO7\SHVRI6ROXWLRQV
The above discussions cover the types of general solutions which CHEMCAD can handle, i.e., ideal, regular,
and polar. There are a wide variety of special systems, however, which CHEMCAD also addresses. These are
discussed briefly below and are described fully later in this chapter.
1. Electrolytes: Electrolyte solutions are mixtures in which one or more of the molecules breaks up into its
constituent atoms or ion radicals. Generally, this occurs with non-hydrocarbon molecules dissolved in water.
They are called electrolytes because such solutions are capable of carrying electrical currents.
CHEMCAD has two generalized models for handling these solutions: The Pitzer method and the MNRTL
method. These are discussed in the Electrolytes Section of this manual. There is, however, an additional,
highly useful technique for handling certain specific situations which are frequently found in petrochemical
plants. These situations have the following characteristics:
There is a single electrolyte component dissolved in water.
This single electrolyte solution is in the presence of other non-electrolyte materials which have limited
solubility in water.
This method is called the PPAQ model and some common examples of its application are columns
absorbing hydrochloric acid and ammonia absorption systems.
The approach PPAQ takes to solve this type of problem is empirical. The user sets up two tables: One
contains data for the partial pressures of the solute and of water over the solution over a range of

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Thermodynamics Page 18 of 102

temperatures and concentrations; the second stores the integral heat of solution as a function of solute
concentration. During the simulation, CHEMCAD interpolates these tables to calculate the K and H values
of the solute and water. Other components are handled either by Henry's Gas Law method, MSRK, or SRK.
The PPAQ method is described in detail later in this section.
2. Dissolved gases: There are two specialty methods for handling non-condensible gases dissolved in some
solute. These are Henry's Gas Law method and the TSRK method. The first is generally used for light gases
dissolved in water and the second is for light gases dissolved in methanol. Both are basically empirical
methods and both are described later in this section.
3. Reactive systems: There are two special methods within CHEMCAD designed to model systems in which
reactions are occurring in the liquid phase. These are the Amine System and the Sour Water System. The
first, AMIN, is for the removal of sour gases from hydrocarbon streams using MEA, MDEA or DEA. The
second, SOUR, is for modeling systems with CO2, NH3, H2S, and other compounds dissolved in water.
Both are empirical systems which model a set of reactions between specific constituents occurring in the
vapor phase. The reaction data is stored in the form of a temperature dependent polynomial. The reaction
equilibrium is computed first, then the vapor-liquid equilibrium constant is calculated.
4. Physical Solvent: A special method for the dehydration of hydrocarbon streams using Tri-Ethylene Glycol
is also available within the program. The method is semi-empirical and is called TEG.
5. Polynomial K-values: You can input the coefficients for a temperature dependent polynomial for the
computation of K and H values if desired.
6. Tabular K-values: You can set up a table of K and H values which the program will interpolate during
simulation.
7. User-Added Subroutines: You can link your own subroutine for the computation of K and/or H values if so
desired.

9DSRU3KDVH6ROXWLRQV
This discussion has thus far focused primarily on the nature and modeling of liquid solutions. The assumption
has been that the vapor phase solution is ideal to moderately regular. Actually, this is not always true. There are
certain vapor phase solutions where some of the molecules associate and, therefore, behave as non-ideal
solutions. This almost always occurs when certain molecules dimerize, trimerize, etc., i.e., when they combine
with other like molecules. Carboxylic acids are the most common example of these types of systems.
In CHEMCAD, the following methods are applicable:
1. If both the vapor and liquid phase form ideal solutions, Raoult's law should be used (the VAP method).
2. If both phases form regular solutions, use an equation of state.
3. If the liquid phase solution is non-ideal and the vapor phase solution is regular, use Poynting's correction.
4. If the liquid phase solution is non-ideal and the vapor phase solution is ideal, do not use Poynting's
correction.
5. If the liquid phase solution is non-ideal and the vapor phase solution is non-ideal, i.e., association occurs in
the vapor phase, use the vapor phase association option.
Invoking the vapor phase association model on the K-value screen changes the way that the vapor phase
fugacity, vi, coefficient and the liquid fugacity coefficient in the standard state, vi, are calculated. Under
vapor phase association, the fugacities of the associating compounds are calculated by actually reacting
them in the equation:

where:
Ca = the compound
Ca2 = the dimer
The solution of this reaction is achieved by solving the equation:

where:

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Thermodynamics Page 19 of 102

The As and Bs for the dimerization of carboxylic acids are included in the program.

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Generally speaking, the primary consideration when selecting a thermodynamic method for your simulation is to
ask yourself what is happening in the liquid phase. We classify liquid solutions into five categories: ideal,
regular, polar (highly non-ideal), electrolytes, and special. For these classifications, we make the following
distinctions and qualifications:
1. Ideal solutions are systems where the vapor phase behaves essentially as an ideal gas (low pressure) and
all the molecules in the liquid phase are of virtually the same size. In addition, no intermolecular forces of
attraction exist. For these systems, you can use the Ideal Vapor Pressure model for K-values and SRK for
enthalpies. Vapor-liquid equilibria will be determined using Raoult's law:

where VPi is calculated using the selected vapor pressure equation.

2. Regular solutions are systems where the non-idealities stem from moderate physical interactions, i.e.,
from differences in the size and shape of the molecules. Intermolecular associations are assumed to be
minimal. These systems are best modeled using equations of state such as Peng-Robinson, SRK, API
SRK, BWRS, CS/GS, and MSRK. It is recommended that you use Peng-Robinson and SRK for all
hydrocarbon systems except for certain wide boiling-range units where CS/GS is advised, and for units
dealing specifically with heavy materials at low pressures where ESSO (really a vapor pressure approach)
is suggested. For chemicals that form regular solutions, such as branch-chained hydrocarbons, halogenated
hydrocarbons, some polar compounds, etc., we recommend the MSRK equation.
In all of these cases, both the vapor and the liquid phases are assumed to form regular (i.e., mildly non-
ideal) solutions, and K-values are calculated as follows:

3. Polar (highly non-ideal) solutions are systems where the liquid phase non-idealities arise predominantly
from molecular associations. These systems must be modeled using activity coefficient methods which
generally require BIPs for accuracy. The vapor phase is taken to be a regular solution, therefore:

where:

The equations that fall into this category are: NRTL, UNIFAC, UNIQUAC, Wilson, T. K. Wilson, Hiranuma,
Van Laar, Margules, and GMAC. Wilson, NRTL, and UNIQUAC are the recommended methods. UNIFAC
may be used where data is absent.
4. Electrolytes are described elsewhere in this Help file.
5. Special systems are provided for the simulation of common applications that do not lend themselves to the
above approaches.

+\GURFDUERQV
Soave-Redlich-Kwong (SRK): High to moderate P & T
API Soave General HC: High to moderate P & T

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Thermodynamics Page 20 of 102

Peng-Robinson: High to moderate P & T

Benedict-Webb-Ruben-Starling: High to moderate P & T
Grayson-Streed: Moderate pressures and temperatures
ESSO (Maxwell-Bonnell K-charts): Low pressure, heavy material
ESD: Hydrocarbon-water; hydrocarbon-gases
SAFT: Hydrocarbon-water; hydrocarbon-gases
&KHPLFDOV
UNIFAC: T = 275K - 475K; P = 0-4 atm.; two liquid phases; non-ideal; group contribution; predictive
Wilson: Highly non-ideal
Vapor Pressure: Ideal solutions
NRTL: Highly non-ideal and 2 liquid phases
UNIQUAC: Highly non-ideal and 2 liquid phases
Margules: Highly non-ideal and 2 liquid phases (four-suffix)
T. K. Wilson: Highly non-ideal and 2 liquid phases
Hiranuma (HRNM): Highly non-ideal and 2 liquid phases
Regular Solution: Moderately non-ideal; predictive
Van Laar: Moderately non-ideal
Modified SRK (four-parameter): Polar compounds in regular solutions
Predictive SRK: Polar compounds in non-ideal solutions; better than UNIFAC at high pressures
Wilson Salt: Non-ideal solutions with salts dissolved in them
6SHFLDO7HFKQLTXHV
Henry's Gas Law: Gases dissolved in water
Amine (MEA DEA): Gas sweetening
Sour Water: Acid gases and NH3 dissolved in H2O
K Table: User Ks
Polynomial K: User Ks
USRK: User Ks
TSRK: Methanol system; particularly with light gases
PPAQ: General, but electrolyte systems is most common application
TEG: Dehydration of hydrocarbon streams using tri-ethylene-glycol
FLOR: Flory-Huggins method for polymers
UPLM: UNIFAC for polymers
ACTX: User specified activity coefficients
ESD: Hydrogen bonding; hydrogen bonding at high pressure
SAFT: Hydrogen bonding; hydrogen bonding at high pressure

For the selection of enthalpy methods, we make the following general recommendations:

If the K-value method is: Use this for enthalpy:

Peng-Robinson (PR) Peng-Robinson (PR)

BWRS BWRS

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Thermodynamics Page 21 of 102

SRK, API SRK, MSRK, Ideal Vapor Pressure, SRK

Regular Solution, Sour Water, TEG Dehydration,
TSRK, ESD, SAFT

Grayson-Streed, ESSO Lee-Kesler

NRTL, UNIF, UNIQ, WILS, VANL, MARG, HRNM, Latent Heat

T.K. Wilson, PSRK, FLOR, UPLM, ACTX

Amine Amine

PPAQ SRK or Latent Heat w/HTSL

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Binary interaction parameters (BIPs) in CHEMCAD can come from a variety of sources:
The built-in CHEMCAD component database includes BIP data for hundreds of component pairs, and more
are added with each CHEMCAD release.
CHEMCAD users can create their own BIPs for pairs of components within a simulation.
Users can also regress experimental VLE (vapor/liquid equilibrium) and LLE (liquid/liquid equilibrium) data
for binary, ternary, and quaternary systems.
BIPs that other users have created or regressed can be made available through shared BIP databases in a
networked CHEMCAD environment.

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For any component pair that has multiple BIPs in the CHEMCAD database, the program must have a way of
determining which BIP will be used by default. If more than one BIP exists between two components,
CHEMCAD chooses which BIP to assign by checking a field called Priority on all available BIPs. The higher the
priority number, the higher the priority CHEMCAD will give that BIP. The standard priority for VLE BIPs in the
CHEMCAD database is 5; the standard priority for LLE BIPs is 4.
Users creating their own BIPs can assign a higher number to give preference to those BIPs. Note that if the
Priority field is left blank at BIP creation, CHEMCAD enters a priority of 0.
Regardless of priority, a user can always elect to use a different BIP than the one that is assigned by default.

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You can create a new BIP or copy an existing BIP.
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You can view or edit detailed parameter data for user-defined BIPs, or view CHEMCAD's built-in BIPs.

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From within a simulation, you can view a listing of all BIPs available for use with a particular component pair
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You can select any available BIP for use with a given component pair.
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In certain situations, CHEMCAD suggests BIPs to add to the current simulation.
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