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[[File:UNIQUACRegressionChloroformMethanol.png|thumb|UNIQUAC [[Regression analysis|Regression]] of Activity Coefficients ([[Chloroform]]/[[Methanol]] Mixture)]]
'''UNIQUAC''' (short for ''UNI''versal ''QUA''si''C''hemical) is an [[activity coefficient]] model used in description of phase equilibria.<ref>Abrams D.S., Prausnitz J.M., “Statistical
Thermodynamics of Liquid Mixtures: A New Expression for the Excess Gibbs
Energy of Partly or Completely Miscible Systems”, AIChE J., 21(1), 116–128,
1975</ref> 
The model is a so-called lattice model and has been derived from a first order approximation
of interacting molecule surfaces in statistical thermodynamics. The model is however not fully thermodynamically consistent due to its two liquid mixture approach. In this approach the local concentration around one central molecule is assumed to be independent from the local composition around another type of molecule.

It has been shown that while the local compositions are correlated, ignoring this correlation gives little effect on the correlation of activity coefficients.<ref>McDermott (Fluid Phase Equilibrium 1(1977)33) and Flemr (Coll.Czech.Chem.Comm., 41(1976)3347)</ref>  Today the UNIQUAC model is frequently applied in the description of phase equilibria (i.e. liquid–solid, liquid–liquid or liquid–vapor equilibrium). The UNIQUAC model also serves  as the basis of the development of the group contribution method [[UNIFAC]], where molecules are subdivided in atomic groups. In fact, UNIQUAC is equal to UNIFAC for mixtures of  molecules, which are not subdivided; e.g. the binary systems water-methanol, methanol-acryonitrile and formaldehyde-DMF.

A more thermodynamically consistent form of UNIQUAC  is given by the more recent [[COSMOSPACE]] and the equivalent GEQUAC model.<ref>Egner, K., Gaube, J., and Pfennig, A.: GEQUAC, an excess Gibbs energy model for simultaneous
description of associating and non-associating liquid mixtures. Ber. Buns. Ges. 101(2): 209–218 (1997). Egner, K., Gaube, J., and Pfennig, A.: GEQUAC, an excess Gibbs energy model describing associating
and nonassociating liquid mixtures by a new model concept for functional groups. Fluid Phase Equilibria 158–160: 381–389 (1999)</ref>

== Equations ==

In the UNIQUAC model the activity coefficients of the ''i''<sup>th</sup> component of a two component mixture are described by a combinatorial and a residual contribution.

<math> \ln \gamma_i = \ln \gamma^C_i + \ln \gamma^R_i</math>

The first is an entropic term quantifying the deviation from ideal solubility as a result of differences in molecule shape. The latter is an enthalpic <ref group="nb">Here it is assumed that the enthalpy change upon mixing can be assumed to be equal to the energy upon mixing, since the liquid [[excess molar volume]] is small and Δ ''H''<sup>ex</sup>=Δ''U''<sup>ex</sup>+''V''<sup>ex</sup> Δ''P'' ≈ Δ''U''</ref> correction caused by the change in interacting forces between different molecules upon mixing.

=== Combinatorial contribution ===

The combinatorial contribution accounts for shape differences between molecules and affects the entropy of the mixture and is based on the lattice theory. 
The excess entropy γ<sup>C</sup> is calculated exclusively from the pure chemical parameters, using the relative Van der Waals volumes ''r''<sub>''i''</sub> and surface areas q<sub>i</sub> <ref group="nb">Here it is assumed that all molecules have the same coordination number as the methylene group of an alkane, which is the reference to calculate the relative volume and surface area.</ref> of the pure chemicals.

<math>\ln \gamma_i^C = (1 - V_i + \ln V_i) - \frac{z}{2} q_i \left( 1 - \frac{V_i}{F_i} +
\ln \frac{V_i}{F_i}\right)</math>
<br>
 
With the volume fraction per mixture mole fraction, V<sub>i</sub>, for the i<sup>th</sup>
component given by:
<br>
<math>V_i = \frac{r_i}{\sum_j r_j x_j}</math>
<br>
And the surface area fraction per mixture molar fraction, F<sub>i</sub>, for the
i<sup>th</sup> component given by:
<br>
<math>F_i = \frac{q_i}{\sum_j q_j x_j}</math>
<br>
The first 3 terms on the right hand side of the combinatorial  term form the Flory-Huggins contribution, while the left terms, the Guggenhem-Staverman correction, reduce this because a connecting segments cannot be placed in all direction in space.  This spatial correction shifts the result of the Flory-Huggins term about 5% towards an ideal solution. The coordination number, z, i.e. the number of close interacting molecules around a central molecule, is frequently set to 10. It can be regarded as an average value that lies between cubic (z=6) and hexagonal packing (z=12) of molecules that are simplified by spheres.

In the limit of infinite dilution and a binary mixture the equations for the combinatorial contribution reduces to:

<math>\begin{cases}
\ln \gamma_1^{C, \infty} = 1 - \dfrac{r_1}{r_2} + \ln \dfrac{r_1}{r_2} - \dfrac{z}{2} q_1 \left( 1 - \dfrac{r_1 q_2}{r_2 q_1} +\ln \dfrac{r_1 q_2}{r_2 q_1}\right) \\
\ln \gamma_2^{C,\infty} = 1 - \dfrac{r_2}{r_1} + \ln \dfrac{r_2}{r_1} - \dfrac{z}{2} q_2 \left( 1 - \dfrac{r_2 q_1}{r_1 q_2} +\ln \dfrac{r_2 q_1}{r_1 q_2}\right)
\end{cases}
</math>

This pair of equation shows that molecules of  same shape, i.e. same r and q parameters, have <math> \gamma_1^{C, \infty} = \gamma_2^{C, \infty}= 1 </math>

=== Residual contribution ===

The residual term contains an empirical parameter, <math>\tau_{ij} </math>, which is derived from
experimental or occasionally estimated activity coefficients. The expression for the residual activity coefficient for molecule i is:

<math>\ln \gamma_i^R = q_i \left( 1 - \ln \frac{\sum_j q_j x_j \tau_{ji} }{
	\sum_j q_j x_j} - \sum_j {\frac{q_j x_j \tau_{ij}}{\sum_k q_k x_k \tau_{kj}}}
	\right)</math>

with

<math>\tau_{ij} = e^{-\Delta u_{ij}/{RT}}</math>

Δu<sub>ij</sub> [J/mol] is the binary interaction energy parameter. Theory defines 
Δu<sub>ij</sub> = u<sub>ij</sub> –  u<sub>ii</sub>,  and Δu<sub>ji</sub> = u<sub>ji</sub> –  u<sub>jj</sub>, where u<sub>ij</sub> is the interaction energy between molecules i and j.

Usually Δu<sub>ij</sub> ≠ Δu<sub>ji</sub>, because the energies of evaporation (i.e. u<sub>ii</sub>), are in many cases different, while the energy of interaction between molecule i and j is symmetric, and therefore u<sub>ij</sub>=u<sub>ji</sub>. If the interactions between the j molecules and i molecules is the same as between molecules i and j, than mixing has no excess energy effect upon mixing,  Δu<sub>ij</sub>=Δu<sub>ji</sub>=0. And thus <math> \gamma_i^{R} = 1 </math>

Alternatively, in some process simulation software <math>\tau_{ij} </math> can be expressed as follows :

<math>\ln \tau_{ij}  = A_{ij} + B_{ij}/T + C_{ij} \ln(T)+ D_{ij} T^2 + E_{ij}/T^2 </math> .

The "C", "D", and "E" coefficients are primarily used in fitting liquid–liquid equilibria (with "D" and "E" rarely used at that). The "C" coefficient is useful in vapor-liquid equilibria as well. The use of such an expression ignores the fact that on a molecular level the energy, Δu<sub>ij</sub>, is temperature independent. It is a correction to repair the simplifications, which were applied in the derivation of the model.

== Applications ==
Activity coefficients can be used to predict simple phase equilibria (vapour–liquid, liquid–liquid, solid–liquid), or to estimate other physical properties (e.g. viscosity of mixtures). Models such as UNIQUAC allow chemical engineers to predict the phase behavior of multicomponent chemical mixtures. They are commonly used in [[process simulation]]  programs to calculate the mass balance in and around separation units.

== Parameters ==
UNIQUAC requires two basic underlying parameters:
#Relative surface and volume fractions are chemical constants, which must be known for all chemicals.
#An empirical parameter between components that describes the intermolecular behaviour. This parameter must be known for all binary pairs in the mixture. In a quaternary mixture there are six such parameters (1–2,1–3,1–4,2–3,2–4,3–4) and the number rapidly increases with additional chemical components. The empirical parameters are derived from experimental activity coefficients, or from phase diagrams, from which the activity coefficients themselves can be calculated. An alternative is to obtain activity coefficients with a method such as [[UNIFAC]], and the UNIFAC parameters can then be simplified by fitting to obtain the UNIQUAC parameters. This method allows for the more rapid calculation of activity coefficients, rather than direct usage of the more complex method.

=== Newer developments ===
UNIQUAC has been extended by several research groups. Some selected derivatives are:
*[[UNIFAC]] : A method which permits the volume, surface and in particular,the binary interaction parameters to be estimated. This eliminates the use of experimental data to calculate the UNIQUAC parameters.
*Extensions for the estimation of activity coefficients for electrolytic mixtures.<ref name="NewExtention">Wisniewska-Goclowska B., Malanowski S.K., “A new modification of the UNIQUAC equation including temperature dependent parameters”, Fluid Phase Equilib., 180, 103–113, 2001</ref>
*Extensions for better describing the temperature dependence of activity coefficients<ref name="NewExtention"/>
*Solutions for specific molecular arrangements.<ref>Andreas Klamt, Gerard J. P. Krooshof, Ross Taylor “COSMOSPACE: Alternative to conventional activity-coefficient models”, AIChE J., 48(10), 2332–2349,2004</ref>

== See also ==
*[[Chemical equilibrium]]
*[[Chemical thermodynamics]]
*[[Fugacity]]
*[[MOSCED]], a model for estimating limiting activity coefficients at infinite dilution
*[[Non-Random Two Liquid model|NRTL]], an alternative to UNIQUAC of the same local composition type

== Notes ==
{{reflist|group="nb"}}

== References ==
<references/>

{{DEFAULTSORT:Uniquac}}
[[Category:Thermodynamic models]]