Qualitative understanding of partition preferences

Introduction
Cavity model
Rules for partitioning ...
     ...of a given compound
           Recall information ...
           Case Ia
           Case Ib
           Case Ic
           Case IIa
           Case IIb
           Other cases
           Overview
           Furter information
     ...of various compounds
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The cavity model in quantitative terms

Selftest
Problems
Intermolecular interactions in every day life
FAQ

Rules for partitioning ...

...of a given compound into various phases

Partitioning into bulk phases where only vdW-interactions occur

Case Ia
apolar molecules in apolar or monopolar phases

Rule 1(a-c)
Partitioning into different bulk phases differs by less than a factor of three.
Case Ib
monopolar molecules in monopolar phases of the same polarity and in apolar phases

Case Ic
bipolar molecules in apolar phases

Partitioning into bulk phases where also H-bond interactions occur
Case IIa
apolar molecule in bipolar phases
Rule 2
The partitioning of an apolar molecule into various bipolar phases will decrease with the number-density and strength of H-bonds in these phases.
Case IIb
various chemicals in monopolar phases
Rule 3
Partitioning of a compound to a monopolar phase will increase with the strength and number of H-bonds that it can form with this phase.
Other cases IIc
Rule 4
Almost all organic compounds prefer all organic phases over water due to the strong cavity effect in water.

... of various compounds in a given two-phase system

Rule 5
There is a linear trend between the logarithmic partition constants between air and apolar phases, ln Ki air/apolar phase and molecular size for any organic compound.
Rule 6
Organic molecules prefer to stay in any organic phase as compared to the gas phase because they always gain more energy in this phase (even if they only interact by van der Waals forces) than they will loose due to the cavity effect; i.e. Ki org.phase/air values are generally larger than 1.

Rule 7
Logarithmic partition coefficients between air and any kind of organic phase (apolar or polar) increase linearly with molecular size within compound classes (i.e. compounds with identical functional groups).

Rule 8
The increase in partition constants with increasing size of the solute becomes smaller (i.e., the slope becomes shallower) with increasing cohesive energy of the sorbing phase.

Rule 9
Logarithmic water/air partition constants, log Ki water/air, show a slight linear decrease with molecular size for compounds that possess identical functional groups.
Rule 10
Logarithmic organic phase/water partition constants, log Ki org./water, increase linearly with molecular size for compounds that otherwise possess identical functional groups. For bipolar organic phases this increase becomes smaller (i.e., shallower slope) with increasing cohesive energy.

 

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