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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           Page 5/5
The cavity model in quantitative terms

Selftest
Problems
Intermolecular interactions in every day life
FAQ

Case IIb

 

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.

 


compound
 / 
solvent
Ksolvent / air

ethanol
/
decane
38
Bipolar compounds
in monopolar phases
or monopolar compounds
in monopolar phases
of opposite polarity

=> H-bonds occur between the
compound i and the bulk phase
but not in the cavity energy.

Partitioning increases
with strength of H-bonds
ethanol
/
cyclohexane
45
ethanol
/
benzene
229
ethanol
isopropylether
470
ethanol
/
heptanedioxane
1920
       
dioxane
/
CCl4
4326
dioxane
/
cyclohexane
1106
dioxane
/
ethyl ether
2436
dioxane
/
chloroform
27366
dioxane
/
CH2Cl2
18712

 

For all remaining cases, i.e. partitioning of mono- and bipolar solutes into mono and bipolar phases we cannot derive any simple rule because here H-bonds occur both in the cavity energy and in the interaction energy between solute and phase so that they partially cancel. It is not always a simple task to predict which ones dominate.

For an extreme case, however, we can still set up an additional, valuable rule (although this cannot be derived here):

6) Almost all organic compounds prefer all organic phases over water due to the strong cavity effect in water. (Exceptions are small polar molecules and ionic organic molecules )

 

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