Group contribution methods estimate HSP values based on how atoms are arranged in functional groups within a solvent, rather than the specific atomic composition or physical properties. This provides a functional group-scale view that is relatively easy to understand, and does not require knowledge of thermodynamics. The adjustable parameters are determined through regression analysis of HSP data from many solvents, as opposed to modeling a single solvent like in EOS methods. Group contribution methods aim to characterize solvents based on the specific functional groups present.
Group contribution methods estimate HSP values based on how atoms are arranged in functional groups within a solvent, rather than the specific atomic composition or physical properties. This provides a functional group-scale view that is relatively easy to understand, and does not require knowledge of thermodynamics. The adjustable parameters are determined through regression analysis of HSP data from many solvents, as opposed to modeling a single solvent like in EOS methods. Group contribution methods aim to characterize solvents based on the specific functional groups present.
Group contribution methods estimate HSP values based on how atoms are arranged in functional groups within a solvent, rather than the specific atomic composition or physical properties. This provides a functional group-scale view that is relatively easy to understand, and does not require knowledge of thermodynamics. The adjustable parameters are determined through regression analysis of HSP data from many solvents, as opposed to modeling a single solvent like in EOS methods. Group contribution methods aim to characterize solvents based on the specific functional groups present.
Methods Group contribution methods are calculation schemes not based on the specic atomic composition of a solvent or its specic physical properties, but totally on how those atoms are arranged in functional groups.
A. RELATIONSHIP TO OTHER METHODS
By way of comparison:
The model upon which an equation of state (EOS) is
based, as described in Appendix C7, is an attempt to characterize a solvent by the atomic elements of which it composed, and how they are bonded and interact together. This is an atomic-scale view, which can be complicated to understand, but it allows those familiar with this science to test very specic hypotheses about the way in which atoms interact together in a solvent molecule, and how the solvent molecules interact with one another and with soil molecules. Knowledge of thermodynamics is essential. The adjustable parameters (constants) in the methods are found by comparing the model prediction of measurable thermodynamic properties to the actual measurements for each solvent, and adjusting the parameters so that the measured thermodynamic properties are computed for each solvent or polymer or polymer solution. Methods based on correlations, discussed in Appendix C5, are quite different than EOS or group contribution methods because they are based on the totality of the characteristics of a entire solvent molecule, such as acetone (Figure C8-1). Recall that correlation-based methods are a molecular-scale view of a solvent, dont
require knowledge of thermodynamics or
thermodynamic properties, may be partially derived from solubility data, and are relatively easy to understand. Methods based on solubility measurements, related in Appendices C2 through C4, are the original basis for comparing solvents. These methods reect a users view of the solvent, and are very easy to understand. Group contribution methods are an attempt to characterize a solvent by the specic ways in which the atoms of which it is composed are present and interconnected. This is a functional group-scale view that is fairly easy to understand. No knowledge of thermodynamics is required. The adjustable parameters in the methods are found by regression analysis of many data points of the three solubility parameters from many different solventsdnot one specic solvent as is done with an EOS.
These four methods for estimating HSP values dont
share the same history: solubility-based and correlationbased methods evolved chiey in the 1960s through to the millennium, group contribution methods evolved chiey in the 1970sA until now (2012), and EOS methods evolved during the decade of the writing of this book (2002e2012).