Acid-base titrations in nonaqueous solvents Analysis of dimethyl sulphate

A nonaqueous titrimetric procedure was developed for the determination of the dimethyl sulphate, methyl hydrogen sulphate and sulphuric acid content of dimethyl sulphate samples. Methyl hydrogen sulphate and sulphuric acid are determined by a differentiating potentiometric titration in pyridine with tributylethylammonium hydroxide. Pyridine converts the dimethyl sulphate into the weakly acidic methylpyridinium methyl sulphate which does not interfere in the titration. Dimethyl sulphate is determined by reacting it with an excess of 2-dimethylaminoethanol and titrating the excess with perchloric acid. Precision and recovery data for commercial samples of dimethyl sulphate are presented.     

Electrodeposition of actinides for alpha-spectrometry

The electrodeposition of the actinides U, Th, Pu, Am, and Cm on stainless steel disks was studied. A sodium hydrogen sulphate — sodium sulphate buffer 0.63M in total sulphate and a ratio sodium hydrogen sulphate to total sulphate ranging from 0.16 (pH 1.8) to 0.48 (pH 1.3) allows the quantitative electrodeposition of the given actinides. No actual pH measurement is needed. Moreover, sodium hydrogen sulphate is an excellent substrate for the wet ashing of organic matter prior to electrodeposition. The method is very robust.     

Determination of inorganic sulphate in plasma by reversed-phase chromatography using ultraviolet detection and its application to plasma samples of patients receiving different types of haemodialysis

The determination of sulphate in plasma is described, making use of reversed-phase high-performance liquid chromatography with ultraviolet detection. The concentration of inorganic sulphate determined in plasma of twenty healthy volunteers was 0.307 +/- 0.092 mmol/l (mean +/- S.D.). In one stable chronic dialysis patient the kinetics of plasma sulphate removal were monitored during and after one single pass dialysis. In addition, plasma sulphate concentrations were determined in three stable chronic dialysis patients during a consecutive scheme of two single pass dialyses, five Redy dialyses and three single pass dialyses. As expected, plasma sulphate accumulates in plasma to a high steady-state level under Redy dialysis, whereas during single pass dialysis sulphate is efficiently removed.     

Differential pulse polarographic study of the hydrolysis of endosulfan and endosulfan sulphate in emulsified medium. Application to the determination of binary mixtures of organochlorine pesticides

Hydrolysis reactions of endosulfan and endosulfan sulphate in the emulsified medium formed with ethyl acetate and a mixture of the two surfactants Hyamine 2389 and Triton X-405 are studied by differential pulse polarography. Besides the heptachlor-endosulfan sulphate pair, whose peak potentials are sufficiently different at pH 8.0 to allow their simultaneous determination, the organochlorine pesticide binary mixtures endosulfan-endosulfan sulphate, dieldrin-endosulfan and dieldrin-endosulfan sulphate can be determined based on their hydrolysis reactions in basic medium and on their different reaction rates. The endosulfan-endosulfan sulphate pair can be determined by allowing the mixture to hydrolyse at pH 11.0 and measuring the endosulfandiol peak for the determination of endosulfan. The analysis of the mixture dieldrin-endosulfan is based on endosulfan hydrolysis at pH 12.0 in which dieldrin is not hydrolysed. Dieldrin and endosulfan sulphate can also be determined simultaneously in a 0.5M sodium hydroxide medium. When determining one pesticide in binary mixtures containing a 5.0 x 10(-6)M concentration of the other pesticide, the lower limits of the calibrations obtained were: endosulfan-endosulfan sulphate mixture, 4.0 x 10(-6) and 1.0 x 10(-6)M respectively; heptachlor-endosulfan sulphate mixture, 2.0 x 10(-6)M for endosulfan sulphate; all other cases, 3.0 x 10(-6)M.     

Potentiometric studies in oxidation-reduction reactions: Reduction with ferrous ethylenediamine sulphate ceric sulphate method

Ferrous ethylenediamine sulphate has been used as a reducing agent to determine indirectly potassium permanganate, ceric sulphate, potassium chlorate, hydrogen peroxide, potassium persulphate, potassium dichromate and potassium bromate by a potentiometric method. An excess of ferrous ethylenediamine sulphate added to each of the substances in acid medium was titrated with a standard solution of ceric sulphate, using platinum foil as an oxidation-reduction electrode coupled with a saturated calomel electrode through an agar-agar potassium chloride bridge.     

Thermogravimetric study of the reduction of basic lead sulphate

In this paper, the results of the study of the reduction of basic lead sulphate with a gas (CO + CO₂) mixture are presented. This is a secondary reaction during the reduction of lead sulphate. The change in the both lead and PbS content in the reaction products, depending on the process temperature and the composition of the gaseous phase, was established. The comparison of the rate of the reduction reaction of lead sulphate and basic lead sulphate shows that the process proceeding with a higher output is the reduction of basic lead sulphate.     

Volumetric studies in oxidation-reduction reactions: Reduction with ferrous ethylenediamine sulphate ceric sulphate method

Ferrous ethylenediamine sulphate has been used as a reducing agent in acid medium for the indirect volumetric estimations of potassium chlorate, potassium bromate, potassium metaperiodate, potassium dichromate, potassium ferricyanide, potassium permanganate, potassium persulphate, hydrogen peroxide and ceric sulphate. The excess of ferrous ethylenediamine sulphate added to each of the substances in acid medium was titrated with standard ceric sulphate solution using ferroin as an indicator.     

Some factors influencing the solubilities of amine sulphates

The relationship between the molecular structures of amines and the solubilities of their sulphates has been examined with the object of finding a better reagent than benzidine for the determination of sulphate. It has been established that the two aromatic rings must have a tendency to be coplanar and collinear, if the sulphate solubility is to be low. With the help of this theory, 4 : 4'-diaminotolane sulphate has been found to be less soluble than bcnzidine sulphate.     

The determination of sulphate in fertilizers by atomic absorption spectrometry

Methods are described for the determination of sulphate in superphosphate fertilizers. Barium sulphate precipitated from an acidified EDTA solution is filtered onto a membrane filter and redissolved in ammoniacal EDTA, and the barium equivalent to the sulphate is determined by atomic absorption spectrometry. Alternatively, after precipitation of calcium as oxalate during sample solution preparation, and by following a similar sulphate precipitation technique, excess of barium is determined in the filtrate. No interferences were encountered when a nitrous oxide—acetylene flame was used with a potassium ionization buffer.     

Liquid chromatographic assay for constituent disaccharides of hyaluronic acid and chondroitin sulphate isomers

An improved high-performance liquid chromatographic (HPLC) method for unsaturated disaccharides prepared from hyaluronic acid and various chondroitin sulphate and dermatan sulphate isomers was developed, which involves an ion-exchange resin prepared from a sulphonated styrene-divinylbenzene copolymer. The retention times of the individual unsaturated disaccharides were unique and reproducible, the disaccharides appearing in the following order: unsaturated non-sulphated disaccharide derived from hyaluronic acid, then unsaturated 6-sulphated, non-sulphated and 4-sulphated disaccharides from chondroitin sulphate isomers. Unsaturated disulphated disaccharide G had a much shorter retention time than the unsaturated non-sulphated disaccharide derived from hyaluronic acid. The contents of these individual unsaturated disaccharides could be determined with similar sensitivities on the basis of their ultraviolet absorbance. Selective and unique retention times and good resolutions were found for various unsaturated disulphated and trisulphated disaccharides. The proposed method can be used to determine various chondroitin sulphate and dermatan sulphate isomers in addition to hyaluronic acid in amounts as small as 100 ng to 8 micrograms. The practicality of this method was verified by its application to the separation and determination of the different types of chondroitin sulphate and dermatan sulphate isomers derived from human arteries in the presence of appreciable amounts of hyaluronic acid.     

A non-enzymic procdure for the quantitative analysis of (3-methoxy-4-sulphoxyphenyl)ethylene glycol(MHPG sulphate) in human urine using stable isotope dilution and gas chromatography-mass spectrometry.

A method is described for the quantitative analysis of (3-methoxy-4-sulphoxyphenyl)-ethylene glycol (MHPG sulphate) in human urine, based on selected ion monitoring gas chromatography--mass spectrometry and using a specifically deuterium-labelled analogue of MHPG sulphate as internal standard. The procedure involves extraction of the urine sample on Amberlite XAD-2, followed by isolation of MHPG sulphate by column chromatography on Sephadex LH-20. Cleavage of the sulphate conjugate and formation of the MHPG tris(trifluoroacetate) derivative are carried out in a one-step reaction, without recourse to enzymic hydrolysis.     

The indirect spectrophotometric determination of the sulphate ion with 2-aminoperimidine

A new spectrophotometric determination of the sulphate ion is described which uses 2-aminoperimidine hydrochloride as a precipitating reagent. The excess of the reagent is measured at 305 nm. The procedure deals with sulphate in the range 4–120 p.p.m., and relies on simple calibration. The relative standard deviation for 50 p.p.m. of sulphate is 3.7%. The interference of 100 p.p.m. of phosphate, fluoride and nitrate is only slight in the determination of 50 p.p.m. of sulphate. The method is recommended for the determination of sulphate in rain and surface waters.     

Improvement of ion chromatography with ultraviolet photometric detection and comparison with conductivity detection for the determination of serum cations

Studies were made of the analytical conditions required for indirect photometric ion chromatography using ultraviolet photometric detection (UV method) for the determination of serum cations following a previously developed serum pre-treatment. The sensitivities of the conductivity detection (CD) and UV methods and the amounts of serum cations determined by both methods were compared. Attempts to improve the sensitivity of the conventional UV method are reported. It was found that the mobile phase previously reported by Small and Miller showed no quantitative response when more than 4 mM copper(II) sulphate pentahydrate was used. As a result, there was no significant difference in the amounts of serum cations shown by the CD and UV methods. However, by adding 0.5-5 mM cobalt(II) sulphate heptahydrate, nickel(II) sulphate hexahydrate, zinc(II) sulphate heptahydrate or cobalt(II) diammonium sulphate hexahydrate to 0.5-1.5 mM copper(II) sulphate pentahydrate, higher sensitivity and a quantitative response were attained.     

Chemiluminescence high-performance liquid chromatography for the determination of hyaluronic acid, chondroitin sulphate and dermatan sulphate.

A sensitive chemiluminescence high-performance liquid chromatographic method has been developed for the determination of hyaluronic acid, chondroitin sulphate and dermatan sulphate as their unsaturated disaccharide-dansylhydrazine derivatives involving an effective sample clean-up system. The dansylhydrazones of the unsaturated disaccharides derived from the hyaluronic acid, chondroitin sulphate and dermatan sulphate by chondroitinase ABC and/or chondroitinase ACII, were separated by reversed-phase chromatography using a mixture of 0.1 M sodium acetate buffer (pH 6.0) and 80% acetonitrile on a column (250 mm x 4.0 mm I.D.) packed with amide-80 silica beads (5 microns diameter). For post-column elution in the chemiluminescence system, 1 mM bis[2-(3,6,9-trioxadecanyloxycarbonyl)-4-nitrophenyl]oxalate and 3mM hydrogen peroxide in acetonitrile were used. The detection limit of each glycosaminoglycan was 100 fmol. The method was applicable to the determination of the levels of hyaluronic acid, chondroitin sulphate and dermatan sulphate in rat peritoneal mast cells.     

High-performance liquid chromatographic analysis of g;ycosaminoglycan-derived oligosaccharides

High-performance liquid chromatography of glycosaminoglycan (GAG)-derived oligosaccharides has been employed for structural analysis and measurement of hyaluronan, chondroitin sulphate, dermatan sulphate, keratan sulphate, herapan sulphate and heparin. Recent developments in the separation and detection of unsaturated dissacharides and oligosaccharides derived from GAGs by enzyme or chemical degradation are reviewed.     

Any x-ray diffraction study on SO2−4-H2O interactions in the presence of nickel and magnesium ions

An x-ray diffraction study was made on solutions of sulphate anion with different cations. In all cases the sulphate ion was found to be hydrated. From at least-squares fitting program we obtained a number of between 7 and 8 water molecules interacting with each sulphate group. The hexa-aquo cations possess a second shell of water molecules.     

Continuous potentiometric determination of sulphate in a differential flow system

Continuous monitoring of sulphate in a differential flow system equipped with two lead ion-selective electrodes is described. All solutions contained 75% methanol and were adjusted to pH 4. In the flow cell, a standard solution of lead(II) is pumped past the first sensing electrode and is mixed with the sample stream containing sulphate in a small mixing chamber; the mixture containing excess of lead(II) and lead sulphate precipitate then flows through the second sensing electrode chamber. The potential difference depends on the sulphate content in the sample. The effects of lead electrode passivation and the interferences of calcium and chloride are discussed. The system is useful for routine sulphate determination in the range 30–400 mg l^-1 with an accuracy of ±5%     

Synthesis,IR, Mössbauer and solid-state NMR studies of 1,1-dimethylguanidinium triphenyltin sulphate

1,1-Dimethylguanidinium triphenyltin sulphate has been synthesised and characterized by infrared, Mössbauer and solid-state NMR spectroscopies. An infinite chain structure with a bidentate sulphate is suggested, the sulphate appearing in a Td symmetry, since the two remaining oxygen atoms are involved in strong H-bonds with the 1,1-dimethylguanidinium, indicating the important influence of the countercation nature on the structure.     

The analytical kinetics of the titanium(III)-perchlorate reaction-I Homogeneous reaction kinetics

A spectrophotometric investigation has been made of the analytically relevant kinetics of the titanium(III)-perchlorate reaction in chloride and sulphate media. Sulphate media give better and more reproducible results. The reaction in sulphate medium is first-order in titanium(III) and hydrogen ion, but of fractional order in perchlorate. The pseudo third-order rate constant k(3)' for the rate equation has a value of 4.22 +/- 0.15 l(2) mol(-2) s(-1) at 49 degrees C. The energy of activation in sulphate medium is 84 +/- 4 kJ mol(-1), and in chloride medium is 80 +/- 12 kJ mol(-1). Small amounts of chloride m a sulphate medium, or of sulphate in a chloride medium, retard the reaction. The basis has been laid for a rate-measurement method for determination of perchlorate at low concentrations.     

Enhanced capacity of chitosan for transition-metal ions in sulphate-sulphuric acid solutions

Batch measurements have shown that the collection yields of chitosan for chromium(III), iron(III), nickel, copper(II), zinc and mercury(II) from sulphuric acid solutions are higher when the solutions contain ammonium sulphate, or when chitosan conditioned in ammonium sulphate is used, particularly at pH 3.0 and 5.0. The contrary is verified for the oxy-anions vanadate, chromate and molybdate. Manganese is never collected. At pH 1.0 no collection occurs. A procedure for recycling chromatographic columns includes fixation of Cu or Ni from a sulphate solution at pH 3-5 on sulphate-conditioned chitosan, and elution with 0.1M sulphuric acid/0.1M ammonium sulphate at pH 1.0; the presence of sulphate in the eluent obviates the detrimental effect of sulphuric acid on the next cycle. Sulphate is the favoured counter-ion of the chelated cations and its action produces shorter chromatographic bands. The interaction of sulphate with chitosan is discussed in terms of crystallinity and steric distribution of the protonated amino-groups in the polymer. Data on the new diethylaminohydroxypropylcellulose are included.