Estudo do comportamento ácido-base da 4,4'-ditiodipiridina

Despite the importance of the 4,4'-dithiodipyridine as an electrode modifier on the protein electrochemical studies and as a remarkable bridged-ligand on conducting electronic density in binuclear mixed valence complexes, there is no data available in the literature concerning acid-base behavior of this compound. Aiming to afford such information we undertook the ionization equilibrium study of this ligand. Although two acid species, DTDPH+ and DTDPH2+ have been detected in solution, only the diacid-form was possible to be isolated as a perclorate salt DTDPH2(ClO4)2. The ionization constants for the two step equilibrium processes (pKa1=2.70 and pKa2=4.80) were determined by using the spectrophotometric technique and aqueous solutions of CF3COONa, mu=0,1 mol.L-1 .

O pKa de indicadores ácido-base e os efeitos coloidais

An experiment is proposed that can be included in undergraduate courses of chemistry. The subject is the acidity of organic compounds, which are employed as pH indicators, particularly in acid-base titrations. The indicators used are methyl orange, bromophenol blue and bromocresol green in aqueous medium. The influence of colloidal systems on the equilibrium is evaluated by the pKa. The colloids employed are surfactants like sodium dodecyl sulfate, cetyl-trimethylammonium bromide and a polymeric non-ionic F127 (pluronics). The effect of stabilization promoted by the system on the acidic or basic structureof the indicator establishes the action mechanism of the colloid on the pKa values.

Dificuldades conceituais no aprendizado de equilíbrios químicos envolvendo reações ácido-base

Common student misunderstandings regarding chemical equilibrium are reported taking into account the response of freshman students to some typical questions involving acid-base reactions. Language has been shown to be one of the main issues associated with students' difficulties on this subject, such as in the case of concentration and amount of substance (mol). Another usual problem was observed in questions involving buffer solutions after addition of a reagent. A number of recommendations have emerged from the results presented in this work as an attempt to enhance the learning of this topic in general chemistry courses given to first-year students.

Desempenho e estado ácido-base sanguíneo em corredores de 10 km submetidos a corridas em diferentes intensidades contantes

Universidade Estadual de Campinas. Faculdade de Educação Física

Auxiliar Informático Para o Diagnóstico e Terapêutica de Alterações do Equilíbrio Ácido-Base e Hidro-Electrolítico

Para encarar a detecção crescente de distúrbios do equilíbrio ácido-base e hidro-electrolítico nos nossos serviços hospitalares, descrevemos e exemplificamos um programa informático auxiliar no diagnóstico e terapêutica destes distúrbios. Partindo dos resultados dum ionograma e dos gases no sangue são apontados os síndromas presentes, e na sequência de um curto diálogo máquina/utilizador os diagnósticos etiológicos mais prováveis. 0 programa propõe também uma terapêutica concreta para esse doente e fornece referências bibliográficas. São discutidas criticamente as possíveis aplicações deste trabalho na clínica e no ensino médico.

Preliminary evaluation of acid mine drainage in Minas Gerais State, Brazil

Mining in the State of Minas Gerais-Brazil is one of the activities with the strongest impact on the environment, in spite of its economical importance. Amongst mining activities, acid drainage poses a serious environmental problem due to its widespread practice in gold-extracting areas. It originates from metal-sulfide oxidation, which causes water acidification, increasing the risk of toxic element mobilization and water resource pollution. This research aimed to evaluate the acid drainage problem in Minas Gerais State. The study began with a bibliographic survey at FEAM (Environment Foundation of Minas Gerais State) to identify mining sites where sulfides occur. Substrate samples were collected from these sites to determine AP (acidity potential) and NP (neutralization potential). The AP was evaluated by the procedure of the total sulfide content and by oxygen peroxide oxidation, followed by acidity titration. The NP was evaluated by the calcium carbonate equivalent. Petrographic thin sections were also mounted and described with a special view to sulfides and carbonates. Based on the chemical analysis, the acid-base accounting (ABA) was determined by the difference of AP and NP, and the acid drainage potential obtained by the ABA value and the total volume of material at each site. Results allowed the identification of substrates with potential to generate acid drainage in Minas Gerais state. Altogether these activities represent a potential to produce between 3.1 to 10.4 billions of m³ of water at pH 2 or 31.4 to 103.7 billions of m³ of water at pH 3. This, in turn, would imply in costs of US$ 7.8 to 25.9 millions to neutralize the acidity with commercial limestone. These figures are probably underestimated because some mines were not surveyed, whereas, in other cases, surface samples may not represent reality. A more reliable state-wide evaluation of the acid drainage potential would require further studies, including a larger number of samples. Such investigations should consider other mining operations beyond the scope of this study as well as the kinetics of the acid generation by simulated weathering procedures.

Pyridyyliryhmän sisältävien erotusmateriaalien ominaisuudet ja soveltaminen hydrometallurgiassa

Diplomityössä tutkittiin silikarunkoisen, pyridyyliryhmän sisältävän erotusmateriaalin kykyä erottaa selektiivisesti kuparia, nikkeliä, kobolttia ja kadmiumia sinkkisulfaattiliuoksista. Erotuskykyä verrattiin kolonnikokein toiseen kaupalliseen polystyreenidivinyylibentseenirunkoiseen (PS-DVB) erotusmate-riaaliin, jonka funktionaalinen ryhmä on samantyyppinen. Silikarunkoisen erotusmateriaalin happo-emäsominaisuuksia selvitettiin titrauksin. Metallien sitoutumisen kinetiikkaa ja eluointia verrattiin PS-DVB-runkoisen erotus-materiaalin kirjallisuudessa esitettyihin tuloksiin. Lisäksi määritettiin kummankin erotusmateriaalin partikkelikokojakaumat. Silikarunkoisen materiaalin havaittiin turpoavan noin 4 % muutettaessa se vapaastaemäsmuodosta happomuotoon. Turpoaminen oli huomattavasti vähäisempää kuin PS-DVB-runkoisella materiaalilla. Silikarunkoisen erotus-materiaalin titrauksen tuloksena voitiin todeta, että se oli heikosti emäksinen. Titrauskäyrä muistutti PS-DVB-runkoisen erotusmateriaalin titrauskäyrää, vaikka erotusmateriaalien protonoitumisalueet olivat hieman erilaiset. Tämä johtuu siitä, että silikarunkoisen materiaalin funktionaaliset ryhmät poikkeavat rakenteeltaan hieman PS-DVB-runkoisesta materiaalista. Tasapainokokeet osoittivat, että silikarunkoinen erotusmateriaali adsorboi tutkituista metalleista eniten kuparia ja nikkeliä ja vähiten sinkkiä. Kaikkien tutkittujen metallien eluointi silikarunkoisesta erotusmateriaalista onnistui rikkihapolla toisin kuin PS-DVB-runkoisesta erotusmateriaalista, jonka regenerointiin tarvitaan rikkihappoa tai ammoniumhydroksidia riippuen siitä, mitä metalleja siihen on ladattu.

Epäpuhtauksien poistaminen sinkkisulfaattiliuoksista käyttäen selektiivisiä ioninvaihtimia

Diplomityössä on tutkittu kuparin, koboltin, nikkelin ja kadmiumin poistamista sinkkisulfaattiliuoksista käyttäen uusia silikarunkoisia kelatoivia erotusmateriaaleja. Vertailukohteena on käytetty perinteisiä kaupallisia polymeerirunkoisia kelatoivia ioninvaihtohartseja. Laboratoriokokeissa selvitettiin erotusmateriaalien adsorptio- ja ioninvaihto-ominaisuuksia tasapaino- ja kolonnikokeilla. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittiin olosuhteissa, jotka vastaavat prosessisyklin eri vaiheita. Metallien adsorptiomekanismien selvittämiseksi erotusmateriaaleille tehtiin happo-emäs ja sulfaattititraukset. Tasapainokokeet osoittivat, että silikarunkoisilla erotusmateriaaleilla saatiin kupari erotettua väkevistä sinkkisulfaattiliuoksista polymeerirunkoisia kelatoivia ioninvaihtohartseja paremmin. Tutkituilla erotusmateriaaleilla ja ioninvaihtohartseilla ei havaittu merkittävää selektiivisyyttä koboltille, nikkelille tai kadmiumille sinkin ja kuparin läsnä ollessa. Kolonnikokeilla yritettiin löytää paras esikäsittely-lataus-eluointisykli kuparin talteenottoon väkevistä sinkkisulfaattiliuoksista silikarunkoisilla erotusmateriaaleilla. Kolonnikokeissa esikäsittely tehtiin laimealla NaOH:lla, jonka jälkeen petiin syötettiin hapanta sinkkisulfaattiliuosta. Eluointi onnistui hyvin laimealla rikkihapolla. Kolonnikokeiden tulokset osoittivat, että kupari on mahdollista erottaa väkevistä sinkkisulfaattiliuoksista. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittaessa havaittiin materiaalien kestävän hyvin happoja ja 60 oC:en lämpötilaa. Sitä vastoin alkaalisissa olosuhteissa tapahtui silikan liukenemista. Tutkituilla erotusmateriaaleilla havaittiin kuparin sitoutumista sekä ioninvaihtomekanismin avulla että sitoutuneena neutraalina suolana.

Caracterização ácido-base da superfície de espécies mistas da alga Spirulina através de titulação potenciométrica e modelo de distribuição de sítios discretos

Acid base properties of mixed species of the microalgae Spirulina were studied by potentiometric titration in medium of 0.01 and 0.10 mols L-1 NaNO3 at 25.0±0.10 C using modified Gran functions or nonlinear regression techniques for data fitting. The discrete site distribution model was used, permitting the characterization of five classes of ionizable sites in both ionic media. This fact suggests that the chemical heterogeneity of the ionizable sites on the cell surface plays a major role on the acid-base properties of the suspension in comparison to electrostatic effects due to charge-charge interactions. The total of ionizable sites were 1.75±0.10 and 1.86±0.20 mmolsg-1 in ionic media of 0.01 and 0.10 mols L-1 NaNO3, respectively. A major contribution of carboxylic groups was observed with an average 34 and 22% of ionizable sites being titrated with conditional pcKa of 4.0 and 5.4, respectively. The remaining 44% of ionizable sites were divided in three classes with averaged conditional pcKa of 6.9, 8.7 and 10.12, which may be assigned respectively to imidazolic, aminic, and phenolic functionalities.

O ensino de aspectos históricos e filosóficos da Química e as teorias ácido-base do século XX

In this paper, an overview about philosophy of science, the concept of "theory" and some characteristics of a"good"theory (1- ordination and explanation of the facts, 2- proposal of problems, and 3- simplicity and funcionality) are initialy introduced. Following, some historical landmarks of acidity and basicity and a summary of the main acid-base theories of the XX century (Arrhenius, solvent systems, protonic, electronic, Lux, Usanovich and ionotropic) are presented. Historical and conceptual relations between these theories are discussed and the three characteristics of a "good" theory are applied. The results showed that the protonic and eletronic theories are the "best". Some discussion of the implications to chemical education are presented too.

Titulações espectrofotométricas de sistemas ácido-base utilizando extrato de flores contendo antocianinas

Considering the attraction of the students' attention by the changes in the colors of vegetable crude extracts caused by the variation of the pH of the medium, the use of these different colors in order to demonstrate principles of spectrophotometric acid-base titrations using the crude extracts as indicators is proposed. The experimental setup consisted of a simple spectrophotometer, a homemade flow cell and a pump to propel the fluids along the system. Students should be stimulated to choose the best wavelength to monitor the changes in color during the titration. Since the pH of the equivalence point depends on the system titrated, the wavelength must be properly chosen to follow these changes, demonstrating the importance of the correct choice of the indicator. When compared with the potentiometric results, errors as low as 2% could be found using Rhododendron simsii (azalea) or Tibouchina granulosa (Glory tree, quaresmeira) as sources of the crude extracts.

Uso das técnicas de infravermelho e de ressonância magnética nuclear na caracterização da reação ácido-base de um cimento odontológico experimental

Glass ionomer cements (GICs) are products of the acid-base setting reaction between an finely fluoro-alumino silicate glass powder and poly(acrylic acid) in aqueous solution. The sol gel method is an adequate route of preparation of the glasses used to obtain the GICs. The objective of this paper was to compare two powders: a commercial and an experimental and to investigate the structural changes during hardening of the cements by FTIR and Al MAS NMR. These analyses showed that the experimental glass powder reacted with organic acid to form the GICs and it is a promising material to manufacture dental cements.

Aplicação de um corante tiazolilazo como indicador ácido-base e determinação das suas constantes de ionização ácida

The pKa values of the 6-[2´-(6´-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid (Me-BDBD) have been determined at 25 °C, in 0.10 mol L-1 NaCl medium by spectrophotometric method. The SQUAD computer program was used to process experimental data in pH range 1.78 - 11.54 and 290 - 720 nm. The pKa values obtained were 4.60 ± 0.04 and 9.48 ± 0.02. The Me-BDBD reagent was applied as indicator in titration of acid-base. The results were compared with phenolphthalein and bromocresol green indicators. Statistical t and F tests indicated that there were no statistically significant differences between the results for indicators with good agreement.

Antocianinas em extratos vegetais: aplicação em titulação ácido-base e identificação via cromatografia líquida/espectrometria de massas

Anthocyanins extracted from picao, quaresmeira, petunia, flamboyant, purple ipe, lobeira, pata de vaca, jaboticaba, purple cabbage and jambul were evaluated as natural acid-base indicators. Anthocyanins in extracts were identified using HPLC/MS. Clear, rapid change in color at final-point titration was observed for extracts but only picao showed strong change in pH. Indirect determination of carbonate in limestone using a natural indicator was performed and results compared with phenolphthalein indicator and potentiometer titration. Optimal results were obtained with picao but other extracts showed good accuracy and precision.

Reações ácido-base: conceito, representação e generalização a partir das energias envolvidas nas transformações

Undergraduate students on the first year of Chemistry Courses are unfamiliar with the representation of acid-base reactions using the ionic equation H+ + OH- → H2O. A chemistry class was proposed about acid-base reactions using theory and experimental evaluation of neutralization heat to discuss the energy involved when water is formed from H+ and OH- ions. The experiment is suggested using different strong acids and strong base pairs. The presentation of the theme within a chemistry class for high school teachers increased the number of individuals that saw the acid-base reaction from this perspective.