Supporting Information

The Journal of Organic Chemistry Manuscript ID: jo2015008303

Micelle Formation in Liquid

Joseph M. Griffin, John H. Atherton and Michael I. Page*

IPOS, The Page Laboratories, Department of Chemical and Biological Sciences, The University of Huddersfield, Queensgate, Huddersfield, HD1 3DH, United Kingdom

Contents Page

1. Ostwald’s dilution law for weak 2

2. Kohlrausch’s law for strong electrolytes 4

3. Observed pseudofirstorder rate constants for the ammonolysis of propargyl benzoate as a function of perfluorononanamide concentration 6

1

1. Ostwald’s dilution law for weak electrolytes:

Attempts were made to fit the liquid ammonia data to Ostwald’s dilution law:

1 1 Λc = ∘ + ∘ Λ Λ (Λ)

Where:

Λ = Molar conductivity (Sm mol )

∘ Λ = Molar conductivity at infinite dilution (Sm mol )

= Acid dissociation constant c = Concentration of (M)

In water a plot cΛm against 1/Λm gives a straight line for a weak electrolyte such as :

1.0E04

8.0E05 3 6.0E05 dm 2

Sm 4.0E05 m Λ c 2.0E05

0.0E+00 0 1000 2000 3000

1/Λ (mol S 1 m2) m

2

But for liquid ammonia, this relationship is not observed for a simple salt, NH 4Cl, and ionic surfactants:

NH 4Cl in liquid ammonia:

5.0E04

4.0E04 3 3.0E04 dm 2 Sm

m m 2.0E04 Λ c

1.0E04

0.0E+00 0 50 100 150 200 250 1/Λ (mol S 1 m2) m

Perfluorooctanoic acid in liquid ammonia:

3.0E04

2.5E04

3 2.0E04 dm 2 1.5E04 Sm m m Λ

c 1.0E04

5.0E05

0.0E+00 0 20 40 60 80 100 120 140 1/Λ (mol S 1 m2) m

3

2. Kohlrausch’s law for strong electrolytes:

Under the assumption that the ionic species in liquid ammonia should behave as strong electrolytes, Kohlrausch’s law unifies the conductance of such species, according to:

∘ ⁄ Λ = Λ −

Where:

Λ = Molar conductivity (Sm mol )

∘ Λ = Molar conductivity at infinite dilution (Sm mol )

= An empirical constant specific to the salt’s stoichiometry c = Concentration of electrolyte (M)

In water, a plot of Λ m against √c for solutions of strong electrolytes g ives a linear relationship. Below is an example for NH 4Cl in water :

0.012

0.01 )

1 0.008 mol 2 0.006 (Sm m

Λ 0.004

0.002

0 0 0.1 0.2 0.3 0.4 0.5 √c (M ½)

4

For liquid ammonia, this relationship is not observed for a simple salt, NH 4Cl, and ionic surfactants:

NH 4Cl in liquid ammonia:

0.02

0.016 )

1 0.012 mol 2 0.008 (Sm m Λ 0.004

0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 √c (M ½)

Perfluorooctanoic acid in liquid ammonia:

0.025

0.02 ) 1 0.015 mol 2

(Sm 0.01 m Λ

0.005

0 0 0.05 0.1 0.15 0.2 √c (M ½)

5

3. Observed pseudofirstorder rate constants for the ammonolysis of propargyl benzoate as a function of perfluorononanamide concentration

The observed pseudofirstorder rate constant for the ammonolysis of propargyl benzoate increases in the presence of perfluorononanamide. Over a range of perfluorononanamide concentrations, the rate increase coincides with concentrations around the cmc obtained from the NMR studies.

16.0

14.0

12.0

-5 10.0 x10

-1 8.0 /s

obs 6.0 k

4.0

2.0

0.0 0 20 40 60 80 100 Concentration of perfluorononanamide M

Figure Observed pseudo firstorder rate constant for the ammonolysis of propargyl benzoate as a function of perfluorononanamide concentration in liquid ammonia at 25 °C.

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