A range of ion-selective electrodes (ISEs) for the determination of nitrate has been
produced based upon rubbery membranes having covalently bound betaine salt sensor
molecules. The best performing electrode contained N,N,N-triallyl leucine betaine (6.5 %
m/m) covalently bound to polystyrene-block-polybutadiene-block-polystyrene (SBS)
(43.5% m/m), with 2-nitrophenyIoctyl ether (2-NPOE) as solvent mediator (40 % m/m)
and dicumyl peroxide (DCP) as free radical initiator (10% m/m). The Nemstian slope was
-59.1 mV per decade over a linear range of 1 x 10'^-5 x 10"^ mol dm'^ nitrate, a limit of
detection of 0.34 pmol dm'^ nitrate and a selectivity coefiBcient for nitrate against chloride
( ^ ° N 0 3 . , CI-) of 3.4 X IQ"^. The speed of response was less than 1 minute over the linear
Nerastian range. The lifetime in the laboratory exceeded 5 months with no potentiometric
drift over the linear Nemstian range. Temperafure dependency (0-25°C), pH range (2-12)
and a selection of interfering anions (F', CI", B r , T, SCN, CIO4", HCO3", NO2", S04^
phthalate) were studied.
A field evaluation by continuous immersion in both agricultural drainage weirs and a river
were undertaken. The nitrate results obtained with the ISEs compared very favourably
(R^=0.99) with those obtained with a segmented-flow instmment in a concentration range
0.47-16 ppm nitrate-N. The electrodes perfonned continuously for over 5 months in mnoff
water from a field and over 2 months in river water. The ISEs did not require recalibration
and no deterioration in performance or fouling of the membrane surface was
observed.
A preliminary investigation of a phosphate ionophore based upon a heterocyclic
macrocycle was also undertaken. This work, based on previous literature, resulted in a
dibasic phosphate electrode having a linear Nemstian range from 3 x lO"'' to 1 x 10"^ mol
dm'^, a slope of -27 mV per activity decade and a Umit of detection of 1 x 10"^ mol dm"^
HP04^".
Date of Award | 2000 |
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Original language | English |
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Awarding Institution | |
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DEVELOPMENT OF NOVEL SENSORS FOR ANIONS OF ENVIRONMENTAL INTEREST
Le Goff, T. (Author). 2000
Student thesis: PhD