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Ion-Transfer Current-Scan Polarographic Studies of Metal Extractants with Ascending Water Electrode: Manganese(H)-1,10-Phenanthroline and Related Ligand Systems

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Abstract

The mechanism of transfer of Mn2+ ion from an aqueous to a dichloroethane (DCE) solution of a phenanthroline derivative (Phen); 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-DMP), 4,7-diphenyl-1,10-phenanthroline (4,7-DPP) and 2,9-dimethyl-1,10-phenanthroline (2,9-DMP), was investigated by current scan polarography with the ascending water electrode. The transfer process involves (a) diffusion of Phen to the aqueous/DCE interface, (b) formation of 1:1 Mn2+-Phen complex, whose kinetics are sufficiently slow to influence but not entirely control the polarographic process, (c) transfer of the 1:1 complex from the aqueous into the DCE phase and (d) further reaction of this complex with two additional Phen molecules at the interfacial area in DCE phase. The apparent reaction rates of step (b) were determined in the dimension of the ordinary electrode reaction rate; 8.2×10-2, 5.5×10-2 and 9.3×10-3 dm M-1 s-1 for phen, 4,7-DMP and 4,7-DPP, respectively. The rate for Mn2+-2,9-DMP complex was too slow to be determined.

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Abbreviations

a:

number of ligands involved in a rate-determining step

A:

counter anion

A:

surface area of a drop

b:

number of ligands involved in reactions other than the rate-determining step (=c—a)

c:

total number of ligands bound to a metal ion

C:

complex, MLcAn

d:

thickness of effective reaction layer at interface

D:

diffusion coefficient

E:

electrode potential of a reaction (MLa)i⇄(MLa)oi

E°:

standard electrode potential of a reaction (MLa)⇄(MLa)oi

E 1/2 :

half-wave potential E1/2(app)

f(i):

{(idif-i/(idif-ilim)}a

F:

Faraday constant

g:

(l−c1/2)/(l−c)

i:

subscript denoting interfacial reaction layer on aqueous side

i:

electric current

i dif :

limiting current by diffusion control

i kin :

limiting current by kinetic control

i lim :

limiting current by diffusion and kinetic mixed control

kf, kb:

forward and backward rate constants

K D :

distribution constant

K ex :

extraction constant (=βaKoKDC/kdl

L:

ligand

M:

metal ion

n:

charge of a metal ion

o:

subscript denoting organic phase

oi:

subscript denoting interfacial reaction layer

on:

organic side

P:

=nFAdkf/KaDL

R:

gas constant

s:

= 1 / (dE/ di), slope of a wave at E1/2

S:

=C(n/cD1/2(vtd)2/3

t d :

drop time

T:

temperature

v:

flow rate

β a :

overall stability constant

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Author notes

  1. Hidekazu Doe

    Present address: Osaka City University, Osaka, Japan

Authors and Affiliations

  1. Strategic Metab Recovery Research Facility, Department of Chemistry, University of Arizona, Tucson, AZ, 85721, USA

    Hidekazu Doe & H. Freiser

Authors
  1. Hidekazu Doe
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  2. H. Freiser
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Doe, H., Freiser, H. Ion-Transfer Current-Scan Polarographic Studies of Metal Extractants with Ascending Water Electrode: Manganese(H)-1,10-Phenanthroline and Related Ligand Systems. ANAL. SCI. 7, 303–311 (1991). https://doi.org/10.2116/analsci.7.303

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  • DOI: https://doi.org/10.2116/analsci.7.303

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