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PL
Zbadano ekstrakcję jonów chromu (III) w układach dwufazowych typu kwas antranilowy-toluen-woda (H+, Na+, SO2-/4); I=0,5. Określono warunki wydzielania jonów chromu (III) w badanych układach, podano skład kompleksów chromu (III) w fazie organicznej i opisano równaniami równowagi ekstrakcyjne.
EN
It was carried out the extraction of chromium (III) ions in two-phase systems: anthranilic acid-toluene-water (H+, Na+, SO2-/4); I=0,5. The conditions of separation of chromium(III) ions in examined systems were determined. The composition of chromium (III) complexes in organic phase and extraction equilibriums were described.
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Content available remote Specjacja funkcjonalna chromu w glebie i weryfikacja wyników analitycznych
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PL
Wpływ chromu na przebieg reakcji biochemicznych w środowisku zależy między innymi od możliwości jego przechodzenia z gleby do roztworów glebowych. Wykonano 5-etapową ekstrakcję sekwencyjną gleby powierzchniowej z terenu miasta Rzeszowa metodą Tessiera i zbadano rozkład Cr pomiędzy różne frakcje glebowe. Stwierdzono, że Cr występuje przede wszystkim we frakcji organicznej i pozostałości glebowej oraz w niewielkich stężeniach we frakcji wymiennej, węglanowej i tlenkowej. Przeprowadzono weryfikację wyników analitycznych oznaczenia Cr w glebie i wodnych frakcjach glebowych.
EN
Influence of chromium on the course of biochemical reactions in the environment depends among others on possibility of its getting from soil to soil solutions. The 5-stages Tessier's method the sequential extraction of surface soil from the Rzeszów town was performed and Cr distribution among various soil fractions was researched. It was found that Cr occurs first of all in the organic fraction and the soil residue as well as in not larges concentrations in the exchangeable, carbonate and oxide fraction. The verification analytical results Cr determination in soil and waters soils fractions was carried out.
PL
Na podstawie badań własnych i danych literaturowych analizowano zależności stałych podziału Kp i stałych dimeryzacji Kd kwasu 2-chlorobenzoesowego w układach dwufazowych od niektórych parametrów fizykochemicznych alkoholi alifatycznych. Stwierdzono, że wraz ze wzrostem gęstości alkoholu, refrakcji molowej, temperatury topnienia i temperatury wrzenia rośnie wartość stałej dimeryzacji Kd, a maleje wartość stałej podziału Kp kwasu. Zwiększenie natomiast parametru rozpuszczalności Hildebranda oraz stałej dielektrycznej alkoholu wywołuje wzrost wartości stałej podziału Kp i obniżenie wartości stałej dimeryzacji Kd.
EN
The dependences of distribution constants (Kp) and dimerization constants (Kd) of 2-chlorobenzoic acid in the diphasic systems on some physico-chemical properties of the alifatic alcohols on the base on the own and literature date were determined. It was found that the value of the dimerization constant Kd increases with an increase of density of the alkohol, molar refraction, melting point and boiling point, whereas the value of the partition constant Kp of the acid decreases following the same trends of the parameters. In case when Hildebrand solubility parameter and dielectric constant of alcohol increase the value of the partition constant Kp increases, whereas the value of dimerization constant Kd of acid decreases.
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Content available remote Zastosowanie derywatyzacji w metodach chromatograficznych w analizie śladowej
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EN
Derivatization is a modern method used in both organic and inorganic analytical chemistry. Application of derivatization to determine trace quantity of compounds requires very sensitive detection techniques. That combined with separation of analyzed compounds, makes the chromatographic systems like GC (gas chromatography) and HPLC (high performance liquid chromatography) especially useful in the analysis. There are mainly three routes in trace analysis of derivatized compounds. One can obtain derivative before performing a column separation (pre-column technique), which can be done both inside or outside chromatographic apparatus, or after column separation (post-column technique). The third method is based on dcrivatization reaction taking place simultaneously with column separation and requires special column filling which is resistant to derivatization reagents. There are several methods used to obtain derivatized compounds suitable for chromatographic methods. Acylation adapted to determine traces of amphetamine, methamphetamine and their metabolites allows lowering the detection level to 1 ppb. Very important part of derivatization methods in trace analysis is a determination of heavy metals via sodium tetraalkylborate alkylation with AED detection (atomic emission detection). Organometallic traces can be derivatized with tetraborate salts with AAD detection (atomic absorption detection). Less known methods like condensation and esterification are also very useful with suitable detector. For example, determination of ketones and aldehydes via derivatization with pentafluorophenylhydrazine allows to lower detection level down to 10^(-14) mol. Esterification of fatty acids with 9-(2-hydroxyethyl)carbazole performed on HPLC column gives full separation of esters with detection limit being around 45 fmol.
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Content available remote Rozdział i oznaczanie Cr(III) i Cr(VI) w próbkach środowiskowych
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EN
Learning the biochemical properties of Cr(III) and Cr(VI), especially mutagenic activity of Cr(VI) caused quick development of investigation of Cr speciation in environmental samples. Complex composition of matrix, possible course of the redox reaction of Cr and its low concentration often make difficult application of direct methods of determination of Cr(III) and Cr(VI). The investigation of speciation of Cr by preliminary separation of Cr(III) and Cr(VI) and their preconcentration eliminates a series of analytical problems and creates a possibility of Cr detection with various techniques, also in coupled systems. The Cr(III) and Cr(VI) in systems HPLC-ICP-AES, HPLC-ICP-MS, HPLC-AAS, HPLC-FI-AAS, HPLC-UV were separated, preconcetrated and determined. Independently from HPLC also other chromatographic techniques were used. Ion-exchange was applied mainly to separation of Cr(III) and Cr(VI), as well as to separation of Cr(VI) or Cr(III) [58] from other ions. To separation of Cr(III) and Cr(VI) there were applied: sorption, biopolymer coating and bioaccumulation. Separation and preconcentration of Cr(III) and Cr(VI) is possible by applying solvent extraction. To extraction of Cr(III) and Cr(VI) and their separation were applied amines, ammonium salts and non-ammonium salts, amine oxides, carboxylic and hydroxycarboxylic acids and other reagents. To separation and preconcentration of Cr(III) and Cr(VI) there are proposed ion-exchange membrane, electrophoresis, precipitation and co-precipitation and other methods of separation. Determination of Cr(III) and Cr(VI) without preliminary separation is possible in environmental samples, in which at the stage of preparing to analysis or during analysis the redox reactions with participation of Cr do not proceed. For direct determination of Cr(VI) spectrophotometric method (UV) is applied with the use of 1,5-diphenylcarbazide, methylene blue, iodonitrotetrazolium chloride, tetrazolium violet , 5-Br-PADAP, dibenzyl-dithiocarbamate, rhodamine 6G, nitrotetrazolium blue and neotetrazolium chloride, whereas for determination of Cr(III) there were applied: EDTA, triphenylmethane reagents, PAR and PAN. For direct determination of Cr(VI) or Cr(III) polarography and others methods were applied.
EN
The sequential extraction of Cr, Fe, Co and Ni from industrial ashes was studied in order to characterize the following chemical fractions of metals: soluble in water, soluble in acids, oxides, sulfides and residue. It was found that Cr and Fe occur first mostly in the oxide fraction and residue while Co and Ni occur in sulfide fraction and residue. The soluble in water and soluble in acids fractions Cr, Fe, Co and Ni contain: 11.8% (Cr), 1.9% (Fe), 23.9% (Co) and 23.2% (Ni) contents of the total metals in industrial ash.
PL
Badano ekstrakcję sekwencyjną Cr, Fe, Co i Ni z popiołu przemysłowego celem scharakteryzowania frakcji chemicznych metali: rozpuszczalnej w wodzie, rozpuszczalnej w kwasach, tlenkowej, siarczkowej i pozostałości. Stwierdzono, że Cr i Fe występują przede wszystkim we frakcji tlenkowej i pozostałości, natomiast Co i Ni - siarczkowej i pozostałości. Możliwe do wyługowania z popiołu w warunkach środowiskowych frakcje Cr, Fe, Co i Ni, tj. rozpuszczalna w wodzie i rozpuszczalna w kwasach, stanowią odpowiednio: 11,8% (Cr), 1,9% (Fe), 23,9% (Co), 23,2% (Ni) zawartości całkowitej metalu w popiele przemysłowym.
PL
Celem badań było określenie wpływu modyfikacji chemicznej odpadowego lotnego popiołu węglowego (FA) za pomocą roztworów HNO3, CH3COONH4 (AcNH4), NaOH oraz dietyloditiokarbaminianu sodu (NaDDTC) na adsorpcję jonów ołowiu(II) w obecności jonów kadmu(II) w układzie jedno- i dwuskładnikowym. Analizowano modele izoterm adsorpcji w układzie jednoskładnikowym, m.in.: Freundlicha, Langmuira, Redlicha-Petersona, Jovanoviča, Fumkina- Fowlera-Guggenheima, Fowlera-Guggenheima-Jovanoviča-Freundlicha oraz Halseya, a także w układzie dwuskładnikowym za pomocą rozszerzonego modelu Langmuira, Langmuira- Freundlicha oraz Jaina-Snoeyinka. W testach laboratoryjnych badano równowagę oraz kinetykę adsorpcji. Adsorpcję jonów Pb(II) i Cd(II) w układzie jednoskładnikowym za pomocą FA, FA-NaOH i FA-AcNH4 dobrze opisuje model Langmuira oraz Redlicha-Petersona. Najwyższą wartość maksymalnej pojemności adsorpcyjnej uzyskano w przypadku FA-NaOH, która wynosiła 220 mg·g–1 s.m. oraz 55 mg·g–1 s.m. odpowiednio dla jonów Pb(II) i Cd(II). Badania wykazały, że FA-NaOH posiadają większą selektywność względem jonów Pb(II) niż względem jonów Cd(II), co jest związane z wielkością promienia uwodnionego jonu metalu i wartością pierwszej stałej równowagi reakcji hydrolizy. Otrzymane dane kinetyczne adsorpcji zostały dobrze wyrażone za pomocą modelu pseudo-drugiego rzędu (R2 = 0,998), natomiast wykazały bardzo słabe dopasowanie do modelu pseudo-pierwszego rzędu (R2 < 0,8). Przeanalizowano model Elovicha oraz model sorpcji wewnątrzziarnowej, który wykazał, że proces sorpcji jonów Pb(II) i Cd(II) jest kontrolowany przez dyfuzyjną warstwę graniczną oraz dyfuzję wewnątrz porów.
EN
The increasing demand for energy throughout the world has led to an increase in the utilization of coal and, subsequently, in the production of large quantities of fly ash as a waste product. In the light of the increasing quantity of fly ash, with a growing demand for electrical energy and hence for thermal power plants, the main challenges faced by the researchers and planners have been to solve the various environmental problems that arise due to the unused and surplus quantity of fly ash. Fly ash is composed of minerals such as quartz, mullite, subordinately hematite and magnetite, carbon, and a prevalent phase of amorphous aluminosilicate. These oxides are very effective adsorbents. Hence, fly ash can be a promising candidate material for heavy metals removal. The aim of this study was to investigate the chemical modifications of coal fly ash (FA) treated with HNO3, CH3COONH4 (AcNH4), and sodium diethyldithiocarbamate (NaDDTC) as an adsorbent for the removal of lead(II) and cadmium(II) ions in single- and bi-component system. In laboratory tests, the equilibrium and kinetic adsorption were examined. The adsorption isotherm models in single-component system were analysed, among others Freundlich, Langmuir, Redlich-Peterson, Jovanovič, Fumkin-Fowler-Guggenheim, Fowler-Guggenheim-Jovanovič-Freundlich, and Halsey, as well as in bi-component system by means of extended Langmuir, Langmuir-Freundlich, and Jain-Snoeyink models. The maximum Pb(II) and Cd(II) ions adsorption capacity obtained from the Langmuir model can be grouped in the following order: FA-NaOH > FA-AcNH4 > FA > FA-NaDDTC > FA-HNO3. Adsorption of Pb(II) and Cd(II) ions in single-component system, both the Langmuir and Redlich-Peterson models for the FA, FA-NaOH, and FA-AcNH4 could be fitted to experimental data. The maximum monolayer adsorption capacity of the FA-NaOH was found to be 220 mg·g–1 dry mass and 55 mg·g–1 dry mass for Pb(II) and Cd(II) ions respectively. Equilibrium experiments shows that the selectivity of FA-NaOH towards Pb(II) ions is greater than that of Cd(II) ions, which is related to their hydrated ionic radius and first hydrolysis equilibrium constant. The adsorption kinetics data were well fitted by a pseudo-second-order rate model (R2 = 0.998) but showed a very poor fit for the pseudo-first order model (R2 < 0.8). The Elovich and intra-particle model were analysed, also revealed that there are two separate stages in the sorption process, namely, the external diffusion and the inter-particle diffusion. It was found that the chemical enhancement of coal fly ash by NaOH treatment yields an effective and economically feasible material for the treatment of Pb(II) and Cd(II) ions-containing effluents.
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Content available remote Ekstrakcja sekwencyjna metali z próbek środowiskowych
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EN
The metals contribution in food chain: soil - plant- animal - man and influence of metals on the course of biochemical reactions in the environment depends among others on possibility of its transfer from sample to solutions. In practice mobility process of metals is investigated by performance of the sequential extraction of sample. The metals sequential extraction for a given sample depend among others on the type of sample, leaching reagent, conditions of the process, the initial condition of sample (environmental sample, air-dried sample) and chemical forms of metals presents in sample. Most often the studies evaluate the chemical fraction of metals in environmental sample as: exchangeable, carbonate, oxide, organic, sulfide and residue forms. Many procedures of sequential extraction of sample e.g. soil, bottom sediments and fly ash were described, which include group extraction of metals to solution. Applied procedures of sequential extraction concern of group extraction of metals and doesn't selective for individual metals. Therefore, we have attempted to establish optimum conditions for researches of individual chemical fraction of metals in sample by sequential extraction method. Chemical fraction described as mobility in environmental conditions are frequently research in first and second step of sequential extraction. Next researches fractions of metals are mobile in environmental in specific conditions. Among various methods of the sequential extraction, the Tessier, Rudd, BCR, Gatehouse, Kersten and Forstner, Psenner and Sposito procedures are most often used for environmental samples. The procedures sequential extraction of environmental samples, defined metals fraction and list of researches metals in sample are shown in Table 1. Analysis of chemical fraction of metals depends on quantity of steps method, strong of reagents and conditions of researches.
EN
The investigations leading to determination of conditions of Cr(VI) to Cr(III) reduction and coexistence of these species in solutions and soiI eluates with [formula] after the sequential extraction of soil were carried out. Influence of: pH, temperature, mixing time and Cr(VI) concentration on the course of reaction was studied. It was found of influence of the parameters on Cr(VI) reduction. Moreover, it was found that total reduction of Cr(VI) to Cr(III) in soiI eluates after the sequential extraction of soil (0.04 M NH2OH . HCI in 25% CH]COOH, t = 96°C, GCXIn = 6 h, oxides fraction of soil) does proceed.
PL
Wykonano badania prowadzące do określenia warunków redukcji Cr(VI) do Cr(III) i współistnienia form w roztworach i eluatach glebowych z [wzór] po ekstrakcji sekwencyjnej gleby. Badano wpływ pH, temperatury, czasu mieszania oraz stężenia Cr(VI) na przebieg reakcji. Stwierdzono wpływ badanych parametrów na redukcję Cr(VI). Stwierdzono ponadto, że w eluatach glebowych po ekstrakcji sekwencyjnej gleby (0,04 M NH2OH . HCI w 25% CH)COOH, t = 96°C, 9.xln = 6 h, trakcja tlenkowa gleby) zachodzi całkowita redukcja Cr(VI) do Cr(III).
EN
The study investigates chemical modifications of coal fly ash (FA) treated with HCl or NH4 HCO3 or NaOH or Na2 edta, based on the research conducted to examine the behaviour of Cd(II) and Pb(II) ions adsorbed from water solution on treated fly ash. In laboratory tests, the equilibrium and kinetics were examined applying various temperatures (293 - 333 K) and pH (2 - 11) values. The maximum Cd(II) and Pb(II) ions adsorption capacity obtained at 293 K, pH 9 and mixing time 2 h from the Langmuir model can be grouped in the following order: FA-NaOH > FA-NH 4 HCO 3 > FA > NaOH2edta > FA-HCl. The morphology of fly ash grains was examined via small-angle X-ray scattering (SAXS) and images of scanning electron microscope (SEM). The adsorption kinetics data were well fitted by a pseudo-second-order rate model but showed a very poor fit for the pseudo- first order model. The intra-particle model also revealed that there are two separate stages in the sorption process, i.e. the external diffusion and the inter-particle diffusion. Thermodynamics parameters such as free energy, enthalpy and entropy were also determined. A laboratory test demonstrated that the modified coal fly ash worked well for the Cd(II) and Pb(II) ion uptake from polluted waters.
EN
The influence of Cr (III) and Cr (VI) on biochemical reactions in the environment depends in part on the possibility of its getting from soil to soil solutions. The various methods of sequential extraction of Cr from soil were studied (Tessier et al. [1, 2], Rudd [3], BCR [4-7], Gatehouse [8], Kersten and Förstner [9], Psenner [10], Sposito [11]) in order to characterize chemical fractions. It was found that chromium determination depends on the method used and varies from 18.2% (BCR) to 96.5% (Tessier) of chromium detection in soil (34.1 mg·kg⁻¹). Quantitative evaluation of chemical fraction of Cr in soil by methods of sequential extraction was carried out by Tessier [1-2], Kersten and Förstner method [9] and indicated that Cr desorption increases according to the following order: exchangeable fraction
EN
Methods of sequential extraction are used to determine various chemical forms of metals in environmental samples. With the variety of different sequential extraction procedures used in environmental exploration studies, it is difficult to compare results between studies. The attempt of validation of methods of analysis of chemical fraction of Mn in ashes by FAAS method for two procedures of sequential extraction (BCR and Tessier et al.) was perfomed. It was found that both tested procedures give comparable and reproducible results. The optimal conditions of BCR methods were established, which are: parameters of ash sample (grain diameter – 0.06 mm, drying temperature – 110°C for 24 hrs, mass sample – 1.00 g) and parameters of sequential extraction process (time – 6 hrs, relation of mass of sample to the volume of extraction solution – 1:4). The optimum conditions of sequential extraction of Mn from coal fly ash can be applied in the study of chemical fraction of Mn in fly ash in different research laboratories.
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