Thesis(PhD)--Stellenbosch University, 2008. / ENGLISH ABSTRACT: Aminopolycarboxylic acids (APCAs) are chelating agents widely used to inactivate
various metal ions by complex formation in industrial and household applications.
Ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA)
are the widely used agents. Their use is under scrutiny due to their persistence in the
environment because they cannot readily biodegrade. This led to the introduction of
readily biodegradable agents namely ethylenediaminedisuccinic acid (EDDS) and
iminodisuccinic acid (IDS) as alternatives especially to EDTA. Therefore, there was an
interest to study the separation of EDDS, IDS and other APCAs using a simple, quick and
accurate method.
Capillary electrophoresis was used to determine the separation and speciation of
iminodisuccinic acid with various metal ions at various pH levels. Speciation modelling
was also utilized to compare and validate the presence and distribution of metal-ligand
species. The obtained CE results were compared with speciation profiles and a reasonable
agreement was obtained.
The degradation studies at various time intervals for the metal-ligand (ML) complexes of
DTPA, S,S-EDDS, IDS and R,S-IDS with various metal ions (Cd2+, Cr3+, Cu2+, Fe3+,
Mn2+, Pb2+ and Zn2+) at pH 7 and 9 was evaluated using CE. New peaks were observed in
some ML complexes when the pH was changed from pH 9 to 7. Sharp peaks were seen
for CuL (L = DTPA, S,S-EDDS, IDS and R,S-IDS), FeDTPA and FeEDDS at both pH s.
While small broad peaks were observed for FeIDS, CrL and MnL complexes. CuDTPA
and CuEDDS complexes showed a greater stability over some considerable time as
compared to CuIDS, CuR,S-IDS and other metal complexes at pH 9.
This work also investigated the effect of various cationic electroosmotic flow (EOF)
modifiers and counter anions on the CE separation of EDTA, EDDS and IDS as Cu(II)
complexes. The performance of the modifiers was evaluated in terms of migration times,
resolution and plate numbers. The best results were observed when Tetradecyltrimethylammonium bromide (TTAB) and Cetyltrimethylammonium bromide
(CTAB) was used as modifiers in order to reverse the EOF in the fused silica capillary.
This resulted in short analysis time and better peak shapes. The effect of different
counteranions attached to EOF modifiers on the separation was also shown. It was also
found that the counter anions of EOF modifiers used influences the separation of the
complexes. The EOF modifiers namely Cetyltrimethylammonium chloride (CTAC) and
Tetradecyltrimethylammonium chloride (TTAC) were further utilized for the
determination of EDTA in South African river waters and industrial effluents.
A method for the simultaneous separation of Fe (III) complexed with EDTA, S,S -EDDS
and IDS was developed by CE and high-performance liquid chromatography (HPLC).
The recalcitrant EDTA is used in combination with readily biodegradable analogues like
EDDS and IDS in many commercial products. The methodology performance was
evaluated in terms of linearity, limit of detection (LOD), limit of quantitation (LOQ) and
reproducibility for both CE and HPLC methods. The LOD values obtained from HPLC
were low when compared with CE. The applicability of both methods was demonstrated
for the analysis of cosmetic products such as foam bath and shower cream. The results
obtained by both CE and HPLC were found to be comparable and are in good agreement. / AFRIKAANSE OPSOMMING: Aminopolikarboksiel sure (APCAs) is komplekseer middels wat algemeen gebruik word
om verskillende metaal ione te deaktifeer deur kompleks vorming in industriële en
huishoudige toepassings. Etileendiamientetraasynsuur (EDTA) en
dietileentriamienpentaasyn suur (DTPA) is die mees algemene APCA s. Hul gebruik
word deesdae noukerig ondersoek as gevolg van hul volharding in die omgewing. Daar
is n intense soektog na bio-afbreekbare agente soos etieleendiamiendisuksien suur
(EDDS) and iminodisuksien suur (IDS) wat as plaasvervangers kan dien vir nieafbreekbare
EDTA. Daar is dus n behoefte om te kyk na eenvoudige, vinnige en
noukeurige metodes vir die bepaling van EDTA, EDTA , IDS en ander APCA s.
Kapillere elektroforese (CE) was gebruik vir die skeiding en spesiering van
iminodisuksien suur met verskillende metale by verskillende pH s. Spesiasie modellering
was ook gebruik om die teenwoordigheid en verspreiding van metaal- spesies te vergelyk.
Die CE uitslae was met die spesiasie profiele vergelyk en n redelike ooreenkoms was
gevind.
Die degraderings studies as n funksie van tyd was met CE bestudeer vir verskillende
metal-ligand (ML) samestellings van DTPA, S,S-EDDS, IDS en R,S-IDS met
verskillende metal ione (Cd2+, Cr3+, Cu2+, Fe3+, Mn2+, Pb2+ en Zn2+) by pH 7 en 9. Nuwe
pieke was opgemerk in sommige ML samestellings wanneer die pH van pH 9 na 7
verander. Hoë pieke was vir CuL (L = DTPA, S,S-EDDS, IDS and R,S-IDS), FeEDTA
en FeEDDS by alle pH s gevind. Lae, breë pieke was vir FeIDS, CrL en MnL komplekse
gevind. CuDTPA en CuEDDS komplekse het n goeie stabiliteit gewys oor ʼn redelike tyd
as dit met CuIDS, CuR,S-IDS en ander metal komplekses by pH 9 vergelyk word.
In hierdie werk was die effek van verskillende kationiese elektro-osmotiese stroom (EOF)
modifiseerders ook ondersoek. Veral die effek wat teen ioone op die CE skeidings het
van EDTA, EDDS en IDS asook Cu(II) komplekse was ondersoek. Die effek van die
modifiseerders was ondersoek en ge-evalueer in terme van migrasie tye, resolusie en plaat getalle. Die beste skeidingskondisies was bereik wanneer
tetradesieltrimetielammonium bromied (TTAB) and setieltrimetielammonium bromied
(CTAB) as modifiseerders gebruik word. Hierdie kondisies het ook aanleiding gegee tot
korter ondersoek tye en beter piekvorme. Die effek van verskillende teen ioone wat aan
die EOF modifiseerders gekoppel was het ook interresante resultate opgelewer. Die EOF
modifiseerders setieltrimetielammonium chloried (CTAC) en
tetradesieltrimetielammonium chloried (TTAC) was ook gebruik vir die bepaling van
EDTA in Suid Afrikaanse rivier waters en industrieel afloop.
ʼn Metode vir die gelyktydige skeiding van Fe(III) met EDTA, S,S’-EDDS en IDS was
met behulp van CE en hoedruk vloeistof chromatography (HPLC) ontwikkel. Die
metodologie was ondersoek ingevolge lineariteit, limiet van deteksie (LOD), limiet van
kwantifisering (LOQ) en die herhaalbaarheid van CE en die HPLC metodes. Die LOD
waardes verkry vanaf HPLC was swakker vergeleke met die verkry deur CE. Die
toepaslikheid van al die metodes was vir die ontleding van kosmetiese produkte soos bad
skuim en stortbad room getoets. Die uitslae deur CE en HPLC was vergelykbaar en ʼn
goeie ooreenkoms was gevind.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:sun/oai:scholar.sun.ac.za:10019.1/19537 |
| Date | 03 1900 |
| Creators | Katata, Lebogang Maureen |
| Contributors | Crouch, Andrew M., Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science. |
| Publisher | Stellenbosch : Stellenbosch University |
| Source Sets | South African National ETD Portal |
| Language | en_ZA |
| Detected Language | English |
| Type | Thesis |
| Format | xvii, 151 leaves : ill. |
| Rights | Stellenbosch University |
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