Qualitative understanding of partition preferences

Introduction
Cavity model
Rules for partitioning
The cavity model in quantitative terms

Selftest
     1) What does the cavity model say?
           Answer
     2) Main interactions ... ?
           Answer
     3) Size of a solute  molecule ... ?
           Answer
     4) Size of the solvent  molecule ... ?
           Answer
     5) Interpretation of data
           Answer
     6) "Like dissolves like"
           Answer
     7) Concept maps
     8) Functional groups
           Answer
     9) Illustration by given data?
           Answer
     10) Evaluation of the software PcKocWIN
     11) H-bonds between given substances?
     12) Tendency to distribute
           Answer
     13) Gas chromatography
           Answer
     14) Henry's Law constant
           Answer
     15) Quiz
Problems
Intermolecular interactions in every day life
FAQ

12) Tendency to distribute

Question:

Rank the four compounds (I − IV) indicated below in the order of increasing tendency to distribute from (a) air into hexadecane (mimicking an apolar environment), (b) from air to olive oil, and (c) from air to water.

These are the respective volumina for the compounds:
benzene 0.716
chlorobenzene 0.839
benzaldehyde 0.873
phenol 0.775

Answer:

The order of experimental data does not always match the results of qualitative estimates. However, differences in K-values are usually smaller than a factor 3. You cannot expect a qualitative estimation to perform better than that. In addition, please note that a qualitative estimation cannot always be carried out.

air −> hexadecane

 

benzene
I

chlorobenzene
II

benzaldehyde
III

phenol
IV
Kair/C16H34
1.6 × 10-3
2.2 × 10-4
1.0 × 10-4
1.7 × 10-4

The large difference between the partitioning coefficients of benzene and phenol are somewhat unexpected since they have a similar molecular size.

 

air −> olive oil
 

benzene
I

chlorobenzene
II

benzaldehyde
III

phenol
IV
Kair/olive oil
1.5 × 10-3
1.8× 10-4
n.a.
2.3 × 10-5

 

air −> water
 

benzene
I

chlorobenzene
II

benzaldehyde
III

phenol
IV
Kair/olive oil
0.23
0.15
1.1 × 10-3
1.4 × 10-5

 

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