Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas

Detalhes bibliográficos
Autor(a) principal: Bonifacio, Viviane Gomes
Data de Publicação: 2008
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/6094
Resumo: In this work, five procedures were developed for determination of anions (chloride, sulphate, phosphate and fluoride), with spectrophotometric detection, being four employing a 100-cm optical length flow-cell and one of them employing a cell whith 1 cm optical length. The first procedure employing flow injection analysis with long pathlenght for chloride determination in natural waters was based in the spectrophotometric procedure described in Standard Methods130 in which the reaction between mercury(II) thiocianate and chloride displace the thiocianate ions yielding a reddish complex with iron(III), that was spectrophotometrically monitored at 455 nm. The analytical curve obtained was linear in the chloride concentration range of 1.0 to 50 mg L-1 (r = 0.9989) with a detection limit of 0.2 mg L-1 (3óblank / slope) and a quantification limit of 0.7 mg L-1 (10óblank / slope), RSD < 1.0% (n = 20) and a sampling rate of 72 h-1. The second procedure for chloride determination employed a solid-phase reactor containing silver chloranilate immobilized coupled to the FIA system. The chloride determination is based on the reaction between chloride and silver chloranilate yielding silver chloride, displacing chloranilate ions which were spectrophotometrically detected at 530 nm and the absorbance signals proportional to the chloride concentration. The analytical curve showed a good linearity in the chloride concentration range of 0.5 to 100 mg L-1 (r = 0.9997) with a detection limit of 0.3 mg L-1 (3óblank / slope) and a quantification limit of 0.5 mg L-1 (10óblank / slope), RSD of 1.05% (n = 20) and a sampling rate of 80 h-1. The flow procedure for sulphate determination in natural waters employed a solid-phase reactor containing barium chloranilate immobilized. The determination is based on the reaction between sulphate ions and barium chloranilate yielding barium sulphate, displacing the chloranilate ions that were spectrophotometrically detected at 530 nm. The analytical curve obtained was linear in the sulphate concentration range of 2.5 to 40 mg L-1 ( r = 0.9994) a detection limit of 0.1 mg L-1 (3óblank / slope) and a quantification limit of 0.3 mg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 50 h-1. The proposed procedure for phosphate determination in natural waters employing flow injection analysis with long pathlenght spectrophotometry is based on the colorless reaction of iron(III) thiocianate and phosphate ions. Iron(III) reacts with thiocianate yielding FeSCN2+, a reddish complex with maximum absorbance in 468 nm. The phosphate ions in contact with FeSCN2+ yield a colorless complex between iron(III) and phosphate, with non-defined stoichiometry. The decrease of the absorbance signals is proportional to the phosphate concentration in the samples. The analytical curve obtained was linear in the phosphate concentration range of 10 to 100 µg L-1 (r = 0.9996) a detection limit of 4.5 µg L-1 (3óblank / slope) and a quantification limit of 15.6 µg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 55 h-1. The procedure for fluoride determination in mineral waters employing a 1-cm optical flow-cell was based on the same procedure for phosphate determination. The reaction between fluoride ions and FeSCN2+ yield the colorless FeF6 3-complex causing an absorbance decrease, proportional to the fluoride concentration in the samples. The analytical curve showed a good linearity for the fluoride concentration range of 0.02 to 5.33 mg L-1 (r = 0.9997) with a detection limit of 5.3 µg L-1 (3óblank / slope) and a quantification limit of 17.6 µg L-1 (10óblank / slope), RSD of 1.9% (n = 20) and a sampling rate of 110 h-1. Results obtained with the proposed procedures were compared with those obtained with the official methods from Standard Methods showing a good agreement at the 95% confidence level.
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spelling Bonifacio, Viviane GomesFatibello Filho, OrlandoÚltima atualização do currículo em 14/03/2011http://lattes.cnpq.br/5797977305592896c8939503-6e3b-4eac-bef9-bf14b89e0d3b2016-06-02T20:34:07Z2008-08-212016-06-02T20:34:07Z2008-02-22BONIFACIO, Viviane Gomes. Development of flow procedures involving conventional spectrophotometry and long pathlenght for determination of anions in waters. 2008. 151 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2008.https://repositorio.ufscar.br/handle/ufscar/6094In this work, five procedures were developed for determination of anions (chloride, sulphate, phosphate and fluoride), with spectrophotometric detection, being four employing a 100-cm optical length flow-cell and one of them employing a cell whith 1 cm optical length. The first procedure employing flow injection analysis with long pathlenght for chloride determination in natural waters was based in the spectrophotometric procedure described in Standard Methods130 in which the reaction between mercury(II) thiocianate and chloride displace the thiocianate ions yielding a reddish complex with iron(III), that was spectrophotometrically monitored at 455 nm. The analytical curve obtained was linear in the chloride concentration range of 1.0 to 50 mg L-1 (r = 0.9989) with a detection limit of 0.2 mg L-1 (3óblank / slope) and a quantification limit of 0.7 mg L-1 (10óblank / slope), RSD < 1.0% (n = 20) and a sampling rate of 72 h-1. The second procedure for chloride determination employed a solid-phase reactor containing silver chloranilate immobilized coupled to the FIA system. The chloride determination is based on the reaction between chloride and silver chloranilate yielding silver chloride, displacing chloranilate ions which were spectrophotometrically detected at 530 nm and the absorbance signals proportional to the chloride concentration. The analytical curve showed a good linearity in the chloride concentration range of 0.5 to 100 mg L-1 (r = 0.9997) with a detection limit of 0.3 mg L-1 (3óblank / slope) and a quantification limit of 0.5 mg L-1 (10óblank / slope), RSD of 1.05% (n = 20) and a sampling rate of 80 h-1. The flow procedure for sulphate determination in natural waters employed a solid-phase reactor containing barium chloranilate immobilized. The determination is based on the reaction between sulphate ions and barium chloranilate yielding barium sulphate, displacing the chloranilate ions that were spectrophotometrically detected at 530 nm. The analytical curve obtained was linear in the sulphate concentration range of 2.5 to 40 mg L-1 ( r = 0.9994) a detection limit of 0.1 mg L-1 (3óblank / slope) and a quantification limit of 0.3 mg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 50 h-1. The proposed procedure for phosphate determination in natural waters employing flow injection analysis with long pathlenght spectrophotometry is based on the colorless reaction of iron(III) thiocianate and phosphate ions. Iron(III) reacts with thiocianate yielding FeSCN2+, a reddish complex with maximum absorbance in 468 nm. The phosphate ions in contact with FeSCN2+ yield a colorless complex between iron(III) and phosphate, with non-defined stoichiometry. The decrease of the absorbance signals is proportional to the phosphate concentration in the samples. The analytical curve obtained was linear in the phosphate concentration range of 10 to 100 µg L-1 (r = 0.9996) a detection limit of 4.5 µg L-1 (3óblank / slope) and a quantification limit of 15.6 µg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 55 h-1. The procedure for fluoride determination in mineral waters employing a 1-cm optical flow-cell was based on the same procedure for phosphate determination. The reaction between fluoride ions and FeSCN2+ yield the colorless FeF6 3-complex causing an absorbance decrease, proportional to the fluoride concentration in the samples. The analytical curve showed a good linearity for the fluoride concentration range of 0.02 to 5.33 mg L-1 (r = 0.9997) with a detection limit of 5.3 µg L-1 (3óblank / slope) and a quantification limit of 17.6 µg L-1 (10óblank / slope), RSD of 1.9% (n = 20) and a sampling rate of 110 h-1. Results obtained with the proposed procedures were compared with those obtained with the official methods from Standard Methods showing a good agreement at the 95% confidence level.Neste trabalho, cinco procedimentos foram desenvolvidos para a determinação de ânions (cloreto, sulfato, fosfato e fluoreto), com detecção espectrofotométrica, sendo quatro empregando célula de 100 cm de caminho óptico e um empregando célula de 1 cm de caminho óptico. O primeiro procedimento utilizando análise por injeção em fluxo com longo caminho óptico para a determinação de cloreto em águas naturais baseou-se no método espectrofotométrico descrito no Standard Methods130 onde a reação entre tiocianato de mercúrio(II) e cloreto leva ao deslocamento dos íons tiocianato e à formação de um complexo de coloração vermelho intenso com Fe(III), que foi monitorado em 455 nm. A curva analítica obtida foi linear para o intervalo de concentrações de 1,0 a 50 mg L-1 de cloreto (r = 0,9989), com um limite de detecção de 0,2 mg L-1 (3óbranco / inclinação), um limite de quantificação de 0,7 mg L-1 (10óbranco / inclinação), RSD menor que 1,0 % (n = 20) e uma freqüência de amostragem de 72 h-1. O segundo procedimento utilizando análise por injeção em fluxo com longo caminho óptico para a determinação de cloreto em águas naturais empregou um reator em fase sólida contendo cloranilato de prata imobilizado. A determinação é baseada na reação entre o cloreto e o cloranilato de prata, formando cloreto de prata que fica retido no reator, deslocando os íons cloranilato que foram detectados espectrofotometricamente em 530 nm, sendo os sinais de absorbância proporcionais à concentração de cloreto. A curva analítica obtida apresentou linearidade no intervalo de concentrações de 0,5 a 100 mg L-1 de cloreto (r = 0,9997), um limite de detecção de 0,3 mg L-1 (3óbranco / inclinação), um limite de quantificação de 0,5 mg L-1 (10óbranco / inclinação), RSD de 1,05 % (n = 20) e uma freqüência de amostragem de 80 h-1. O procedimento para a determinação de sulfato em águas naturais empregou um reator em fase sólida contendo cloranilato de bário imobilizado. O princípio da determinação é baseado na reação entre o sulfato e o cloranilato de bário, formando sulfato de bário que fica retido no reator, deslocando os íons cloranilato que foram detectados espectrofotometricamente em 530 nm. A curva analítica obtida foi linear paro o intervalo de concentração de sulfato de 2,5 a 40 mg L-1 (r= 9994), com limite de detecção de 0,1 mg L-1 (3óbranco / inclinação), limite de quantificação de 0,3 mg L-1 (10óbranco / inclinação), RSD menor que 1,0 % (n = 10) e uma freqüência de amostragem de 50 h-1. O procedimento proposto para a determinação de fosfato em águas naturais utilizando análise por injeção em fluxo com longo caminho óptico, baseia-se na reação de descoloração do tiocianato de ferro (III) pelo fosfato. O nitrato de ferro (III) reage com o tiocianato de sódio formando o tiocianato de ferro (III), um composto de coloração avermelhada que possui absorção máxima em 468 nm. Quando os íons fosfato entram em contato com o complexo FeSCN2+, forma-se o complexo entre o fosfato e o ferro(III), de estequiometria não definida, que é incolor O decréscimo da absorbância, é proporcional à concentração de fosfato na amostra. A curva analítica foi linear par o intervalo de concentrações de 10 a 100 µg L-1 de fosfato (r = 0,9996), com limite de detecção de 4,5 µg L-1 (3óbranco / inclinação), limite de quantificação de 15,6 µg L-1 (10óbranco / inclinação), RSD de 0,5 % (n = 10) e freqüência de amostragem de 55 h-1. O procedimento para determinação de fluoreto em amostras de água mineral, empregando uma célula de 1 cm de caminho óptico, baseia-se no método empregado para a determinação de fosfato, sendo que quando os íons fluoreto entram em contato com o complexo FeSCN2+, forma-se o complexo FeF6 3-entre o fluoreto e o ferro, que é incolor, ocasionando um decréscimo da absorbância que é proporcional à concentração de fluoreto na amostra. A curva analítica apresentou boa linearidade para o intervalo de concentração de 0,02 a 5,33 mg L-1 de fluoreto (r = 9997), limite de detecção de 5,3 µg L-1 (3óbranco / inclinação), limite de quantificação de 17,6 µg L-1 (10óbranco / inclinação), RSD de 1,9 % (n = 20) com freqüência de amostragem de 110 h-1. Os valores obtidos com os procedimentos propostos foram comparados com aqueles obtidos pelo método oficial do Standard Methods, e os resultados estão em concordância a um nível de confiança de 95%.Universidade Federal de Minas Geraisapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarBRInstrumentaçãoAnálise por injeçao de fluxoEspectrofotometriaReator em fase sólidaCIENCIAS EXATAS E DA TERRA::QUIMICADesenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águasDevelopment of flow procedures involving conventional spectrophotometry and long pathlenght for determination of anions in watersinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-17a1dec22-4b2d-4dba-8971-ab07f55c7d54info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL1949.pdfapplication/pdf1264259https://repositorio.ufscar.br/bitstream/ufscar/6094/1/1949.pdf668e8da6a5c7afa14551b12ccd924b26MD51THUMBNAIL1949.pdf.jpg1949.pdf.jpgIM Thumbnailimage/jpeg8859https://repositorio.ufscar.br/bitstream/ufscar/6094/2/1949.pdf.jpg947370c22cb151c21e3281a4e5fc16dfMD52ufscar/60942023-09-18 18:31:10.811oai:repositorio.ufscar.br:ufscar/6094Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:10Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
dc.title.alternative.eng.fl_str_mv Development of flow procedures involving conventional spectrophotometry and long pathlenght for determination of anions in waters
title Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
spellingShingle Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
Bonifacio, Viviane Gomes
Instrumentação
Análise por injeçao de fluxo
Espectrofotometria
Reator em fase sólida
CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
title_full Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
title_fullStr Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
title_full_unstemmed Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
title_sort Desenvolvimento de procedimentos em fluxo envolvendo espectrofotometria convencional e com longo caminho óptico para determinação de ânions em águas
author Bonifacio, Viviane Gomes
author_facet Bonifacio, Viviane Gomes
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/5797977305592896
dc.contributor.author.fl_str_mv Bonifacio, Viviane Gomes
dc.contributor.advisor1.fl_str_mv Fatibello Filho, Orlando
dc.contributor.advisor1Lattes.fl_str_mv Última atualização do currículo em 14/03/2011
dc.contributor.authorID.fl_str_mv c8939503-6e3b-4eac-bef9-bf14b89e0d3b
contributor_str_mv Fatibello Filho, Orlando
dc.subject.por.fl_str_mv Instrumentação
Análise por injeçao de fluxo
Espectrofotometria
Reator em fase sólida
topic Instrumentação
Análise por injeçao de fluxo
Espectrofotometria
Reator em fase sólida
CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
description In this work, five procedures were developed for determination of anions (chloride, sulphate, phosphate and fluoride), with spectrophotometric detection, being four employing a 100-cm optical length flow-cell and one of them employing a cell whith 1 cm optical length. The first procedure employing flow injection analysis with long pathlenght for chloride determination in natural waters was based in the spectrophotometric procedure described in Standard Methods130 in which the reaction between mercury(II) thiocianate and chloride displace the thiocianate ions yielding a reddish complex with iron(III), that was spectrophotometrically monitored at 455 nm. The analytical curve obtained was linear in the chloride concentration range of 1.0 to 50 mg L-1 (r = 0.9989) with a detection limit of 0.2 mg L-1 (3óblank / slope) and a quantification limit of 0.7 mg L-1 (10óblank / slope), RSD < 1.0% (n = 20) and a sampling rate of 72 h-1. The second procedure for chloride determination employed a solid-phase reactor containing silver chloranilate immobilized coupled to the FIA system. The chloride determination is based on the reaction between chloride and silver chloranilate yielding silver chloride, displacing chloranilate ions which were spectrophotometrically detected at 530 nm and the absorbance signals proportional to the chloride concentration. The analytical curve showed a good linearity in the chloride concentration range of 0.5 to 100 mg L-1 (r = 0.9997) with a detection limit of 0.3 mg L-1 (3óblank / slope) and a quantification limit of 0.5 mg L-1 (10óblank / slope), RSD of 1.05% (n = 20) and a sampling rate of 80 h-1. The flow procedure for sulphate determination in natural waters employed a solid-phase reactor containing barium chloranilate immobilized. The determination is based on the reaction between sulphate ions and barium chloranilate yielding barium sulphate, displacing the chloranilate ions that were spectrophotometrically detected at 530 nm. The analytical curve obtained was linear in the sulphate concentration range of 2.5 to 40 mg L-1 ( r = 0.9994) a detection limit of 0.1 mg L-1 (3óblank / slope) and a quantification limit of 0.3 mg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 50 h-1. The proposed procedure for phosphate determination in natural waters employing flow injection analysis with long pathlenght spectrophotometry is based on the colorless reaction of iron(III) thiocianate and phosphate ions. Iron(III) reacts with thiocianate yielding FeSCN2+, a reddish complex with maximum absorbance in 468 nm. The phosphate ions in contact with FeSCN2+ yield a colorless complex between iron(III) and phosphate, with non-defined stoichiometry. The decrease of the absorbance signals is proportional to the phosphate concentration in the samples. The analytical curve obtained was linear in the phosphate concentration range of 10 to 100 µg L-1 (r = 0.9996) a detection limit of 4.5 µg L-1 (3óblank / slope) and a quantification limit of 15.6 µg L-1 (10óblank / slope), RSD < 1.0% (n = 10) and a sampling rate of 55 h-1. The procedure for fluoride determination in mineral waters employing a 1-cm optical flow-cell was based on the same procedure for phosphate determination. The reaction between fluoride ions and FeSCN2+ yield the colorless FeF6 3-complex causing an absorbance decrease, proportional to the fluoride concentration in the samples. The analytical curve showed a good linearity for the fluoride concentration range of 0.02 to 5.33 mg L-1 (r = 0.9997) with a detection limit of 5.3 µg L-1 (3óblank / slope) and a quantification limit of 17.6 µg L-1 (10óblank / slope), RSD of 1.9% (n = 20) and a sampling rate of 110 h-1. Results obtained with the proposed procedures were compared with those obtained with the official methods from Standard Methods showing a good agreement at the 95% confidence level.
publishDate 2008
dc.date.available.fl_str_mv 2008-08-21
2016-06-02T20:34:07Z
dc.date.issued.fl_str_mv 2008-02-22
dc.date.accessioned.fl_str_mv 2016-06-02T20:34:07Z
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dc.identifier.citation.fl_str_mv BONIFACIO, Viviane Gomes. Development of flow procedures involving conventional spectrophotometry and long pathlenght for determination of anions in waters. 2008. 151 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2008.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/6094
identifier_str_mv BONIFACIO, Viviane Gomes. Development of flow procedures involving conventional spectrophotometry and long pathlenght for determination of anions in waters. 2008. 151 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2008.
url https://repositorio.ufscar.br/handle/ufscar/6094
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