Applicability of glass fiber as a support material for generation of gaseous standard mixtures using thermal decomposition of the surface compound. Calibration of analytical equipment

The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds.     

Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.     

Thermal decomposition of immobilized compounds for the generation of gaseous standard mixtures containing ammonia and amines

The thermal decomposition of phthalamic acid derivatives chemically bonded to the surface of silica gel was examined and utilized for the generation of single-component gaseous standard mixtures of ammonia, methylamine, diethylamine and triethylamine. The conditions of the thermal decomposition (temperature, time, diluent gas flow rate) were optimized to ensure complete liberation and rapid elution of the compounds from the bed of modified silica gel. The total amounts of these four compounds that can be released from unit mass of the modified silica gel are in the range of several mg.     

Adsorption from binary solvent mixtures onto silica gel by HPLC frontal analysis

Summary The chromatographic technique of frontal analysis is applied to measuring adsorption from binary liquid mixtures by silica gel. The complete adsorption isotherm of a solvent mixture is obtained by measuring the break-through curves for a series of small concentration steps of the mobile phase. This method offers a direct way to determine the composition of the stationary phase in liquid-solid chromatography with mixed mobile phases. The surface excess isotherms of all binary systems formed by benzene, cyclohexane, and 1,2-dichloroethane, at the solution-silica gel interface at 25 °C are presented. The data of the three systems are shown to be thermodynamically mutually consistent.     

Thermal decomposition of silica based surface compounds as a source of volatile standards. A new approach to the generation of gaseous calibration mixtures

A new approach to the preparation of standard gaseous mixtures based on thermal decomposition of surface compounds, has been reviewed. The method is used to prepare standard mixtures containing volatile analytes such as thiols, isothiocyanates, carbon monoxide, carbon dioxide, ammonia, amines, ethylene and methyl chloride. The method enables the preparation of the standard immediately before a calibration step. It is specially useful for the generation of standard mixtures containing volatile, malodorous, unstable and toxic compounds. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

DFT and direct ab-initio MD study on hyperfine coupling constants of methyl radicals adsorbed on model surface of silica gel

Methyl radicals interacting with silica gel surfaces have been investigated by means of DFT and direct ab-initio molecular dynamics (MD) methods using cluster models. Four typical binding sites of CH₃ on the cluster models were found in the geometry optimization from several initial geometries of CH₃ around the silica gel clusters. These were two silanol Si–OH sites and two siloxane Si–O–Si sites. In both sites, magnitude of hyperfine coupling constants of the methyl radical (a_H) was smaller than that of free CH₃ (a_H = 23.04 G). Temperature effects on a_H of the methyl radical were investigated by means of the direct ab-initio MD method. The hyperfine coupling constant of CH₃ interacting with the SiOH group decreased with increasing temperature. The methyl radical interacting with alkali metal supported silica gel was also investigated for comparison. The electronic states of methyl radicals on silica gel were discussed on the basis of theoretical results.     

On some aspects of the silica surface modification with hexamethylcyclotrisilazane,hexamethyldisilazane and their mixtures

Summary The paper is concerned with the structure of an organic layer bonded to the silica surface modified with silazanes. The changes of the retention volumes of hydrocarbons is studied for the silicas modified with hexamethylcyclotrisilazane, hexamethyldisilazane and their mixtures. It is shown that most of the carbon in the layer after hexamethylcyclotrisilazane modification is bonded to the surface by Si−O−Si bonds. This fact supports the assumption of a fragmentation of the cyclosilane used for modification.     

Functionalization of silica gel by ultrasound-assisted surface Suzuki coupling

Mesoporous silica gel was functionalized by various organic functional groups using thiol-ene coupling of surface thiol groups with 4-vinylphenylboronic acid followed by Suzuki coupling with aromatic halides. For better performance, the synthesis was conducted under sonication. The presence of surface functional groups was confirmed by thermoanalysis, FT-IR spectroscopy and characteristic reactions of these groups. Solid-phase conditions of the synthesis eliminate the risk of side reactions of boronic acids.     

NIR studies of the surface modification in silica fillers

Methods of estimating the degree of condensation of the surface silanol groups of silica due to its modification by silane coupling agents are reported.Also, a procedure for estimating the surface silanol groups for the pre- and post-modified silicas for the NIR 7326 cm^–1 band is given.Using electron microscope studies and heats of immersion of silica surfaces, the silane effect on agglomeration of silica particles and, thus, on the physicochemical properties of its surface has been demonstrated.     

Multilayer adsorption of alcohols from benzene/n-heptane mixtures on silica gel

An equation for multilayer adsorption from multicomponent liquid mixtures on solid surfaces¹ has been examined. For this purpose experimental adsorption data for four alcohols from benzene/n-heptane mixture on silica gel have been measured. Average number of the adsorbed layers, heterogeneity parameter and capacity of the surface phase have been evaluated by using the equation mentioned above.

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Mehrschichten-Adsorption von Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel

Zusammenfassung Eine Gleichung für Mehrschichten-Adsorption an festen Oberflächen¹ aus Mehrkomponentenlösungen wurde getestet. Zu diesem Zweck wurden experimentelle Daten für die Adsorption von vier Alkoholen aus Benzol/n-Heptan-Mischung an Silica Gel herangezogen. Der Mittelwert für die Anzahl der Adsorptionsschichten, der Heterogenitätsparameter und die Kapazität der Oberflächenphase wurde aus dieser Gleichung berechnet.

     

Permeation devices for the preparation of standard gaseous mixtures

Summary Two new permeation devices for generation of standard gaseous mixtures in wide concentration range have been designer. Teflon membranes and tubing have been utilized as the permeation barriers. The devices enable generation of multi-component mixtures.     

硅胶的表面硅烷化处理及其吸附性能研究

为研究改性硅胶对挥发性有机废气的吸附性能,分别采用十六烷基三甲氧基硅烷、辛基三乙氧基硅烷、苯基三甲氧基硅烷、一甲基三乙氧基硅烷对硅胶进行气相改性处理,试验研究了不同改性剂、改性时间对硅胶饱和吸附率的影响,考察了改性硅胶对甲苯、水二组分体系的吸附选择性.结果表明,硅胶对甲苯的吸附主要为物理吸附,长链的硅烷改性剂在60℃、...     

Efficient and solvent-free synthesis of bis-indolylmethanes using silica gel supported aluminium chloride as a reusable catalyst

Stable and non-hygroscopic silica gel supported aluminium chloride（SiO₂-AlCl₃）,which is prepared easily from cheap and commercially available compounds was found to be an environmentally friendly heterogeneous catalyst for the condensation of indole with aldehydes and ketones to afford bis-indolylmethanes at room temperature under solvent-free conditions.The catalyst can be reused up to five times after simple washing with ether.     

Continuous dynamic-gravimetric preparation of calibration gas mixtures for air pollution measurements

 The preparation of calibration gas mixtures for air pollution measurements by the dynamic-gravimetric method was investigated using sulphur dioxide in nitrogen as a model. The target mole fraction was 200×10^–9 mol/mol, with the option of also getting smaller mole fractions. Thermal mass flow meters calibrated with reference mass flows were used to measure the dilution gas flow (nitrogen). The relative standard uncertainty of the dilution gas flows between 10 mg/s (approx. 500 ml/min) and 40 mg/s (approx. 2000 ml/min) was 0.15%. The mass flow of the target component measured as the permeation rate was determined via the quasi-continuous observation of the loss in the permeation tube mass during the measuring time. A magnetic coupling system and an adapted microbalance were used for this purpose. The results presented show permeation rates measured over the lifetime of a tubular permeation source. The measurement cycles took between 3 days and 7 h at least. The relative standard uncertainty of the mixture composition did not exceed 2%. First comparisons with gas mixtures prepared by the static-gravimetric method show compatibility. The applicability of the system is not restricted to the SO₂/N₂ mixture. It can also be used for preparing other gas mixtures in this field of application. Received: 26 April 2000 / Accepted: 12 September 2000     

An efficient synthesis of propargylamines using a silica gel anchored copper chloride catalyst in an aqueous medium

The design and development of a silica gel anchored copper chloride heterogeneous catalyst for the synthesis of propargylamines using an amine, an aldehyde, and an alkyne through C-H activation in water is described. Both aliphatic and aromatic aldehydes and amines are used for the reaction. The catalyst was recovered quantitatively by simple filtration and reused several times.     

Synthesis of bis(indolyl)methanes using silica gel as an efficient and recyclable surface

Here we describe a simple, clean, and efficient solvent-free protocol for the synthesis of bis(indolyl)methanes promoted by silica gel. The products were obtained in good to excellent yields through the reaction of indoles with cyclohexanone and a range of aldehydes. The silica gel was easily recovered and utilized for further reactions without loss of activity.     

Sorption equilibrium of methanol on new composite sorbents “CaCl<Subscript>2</Subscript>/silica gel”

This paper presents experimental data on methanol sorption on new composite sorbents which consist of mesoporous silica gels and calcium chloride confined to their pores. Sorption isobars and XRD analysis showed the formation of a solid crystalline solvate CaCl₂⋅2MeOH at low methanol uptake, while at higher uptake the formation of the CaCl₂–methanol solution occurred. The solution confined to the silica pores showed the sorption properties similar to those of the CaCl₂–methanol bulk solution. Calorimetric and isosteric analyses showed that the heat of methanol sorption depends on the methanol uptake, ranging from 38±2 kJ/mol for the solution to 81±4 kJ/mol for the solid crystalline phase CaCl₂⋅2MeOH. The above mentioned characterizations allowed the evaluation of the methanol sorption and the energy storage capacities, clearly showing that the optimal applications of these new composite sorbents are the methanol removal from gaseous mixtures, heat storage and sorption cooling driven by low temperature heat.     

In situ preparation and surface modification of magnesium hydroxide nanoparticles

Hydrophobic magnesium hydroxide (Mg(OH)₂) nanoparticles were successfully synthesized via a one-step solution precipitation method with octadecyl dihydrogen phosphate (n-C₁₈H₃₇OPO₃H₂, ODP) as a surface modifier. The ODP was used to control the growth of crystal in the c direction (direction perpendicular to the layers) and to modify the surface property of the Mg(OH)₂ particles produced from the precipitation. Measurements of relative contact angle and active ratio indicated that Mg(OH)₂ samples were hydrophobic. The samples were characterized by using field emission scanning electron microscope (SEM), X-ray diffraction (XRD), infrared analysis (IR). The mechanism of influence of ODP on the surface property and morphology of Mg(OH)₂ was discussed. Furthermore, from the results of the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) tests, it was confirmed that small amount of magnesium alkyl phosphate on the surface of Mg(OH)₂ particles enhanced the thermal stability of the low density polyethylene(LDPE)/Mg(OH)₂.     

Synthesis and characterisation of morin-functionalised silica gel for the enrichment of some precious metal ions

Silica gel was firstly functionalised with aminopropyltrimethoxysilane obtaining the aminopropylsilica gel (APSG). The APSG was reacted subsequently with morin yielding morin-bonded silica gel (morin-APSG). The structure was investigated and confirmed by elemental and thermogravimetric analyses, IR and (13)C NMR spectral studies. Morin-APSG was found to be highly stable in common organic solvents, acidic medium (<2molL(-1) HCl, HNO(3)) or alkaline medium up to pH 8. The separation and preconcentration of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) from aqueous medium using morin-APSG was studied. The optimum pH values for the separation of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) on the sorbent are 5.7, 2.2, 3.7, 3.7 and 6.8, giving rise to separation efficiencies of 43.9, 85.9, 97.7, 60.9 and 91.0%, respectively, where the activity was found to be >90% in the presence of acetate ion. The ion sorption capacity of morin-APSG towards Cu(II) at pH 5.5 was found to be 0.249mmolg(-1) where the sorption capacities of Ag(I) and Pd(II) were 0.087 and 0.121mmolg(-1) and 0.222 and 0.241mmolg(-1) at pH 2.2 and 5.7, respectively. This indicates a 1:1 and 1:2 morin/metal ratios at pH 2.2 and 5.7, respectively. Complete elution of the sorbed metal ions was carried out using 10mL (0.5molL(-1) HCl+0.01molL(-1) thiourea) in case of Au(III), Pd(II), Pt(II) and Rh(III) and 10mL 0.5molL(-1) HNO(3) in case of Ag(I). Morin-APSG was successfully employed in the separation and preconcentration of the investigated precious metal ions from some spiking water samples yielding 100-folds concentration factor. The relative standard deviation (R.S.D.) and the T-test (|t|(1)) were calculated.     

Aspects of surface modification, structure characterization, thermal stability and metal selectivity properties of silica gel phases-immobilized-amine derivatives

Four silica gel phases-bound-amine derivatives (I-IV) were prepared based on chemical immobilization technique. The surface modification was identified by determination of the coverage values in mmol g⁻¹ via thermal desorption method (1.463-1.807) and elemental analysis of nitrogen and carbon contents (1.089-2.456). Structure characterization related to immobilization of the amine derivatives was accomplished and evaluated by means of infrared (IR) and secondary ion mass spectrometric (SIMS) technique. The modified silica gel phases (I-IV) along with their interaction products with copper(II) were also examined by electron impact mass spectrometric analysis (EI-MS) as a method for evaluation of their thermal stability and structure elucidation. Potentiometric titration as a method of characterization was applied for the modified silica gel phases (II-IV) and their copper(II)-adduct. A series of bi- and trivalent metal ions were selected to focus more aspects of the selectivity properties incorporated into the modified silica gel phases for binding and interaction with these metals based on determination of the distribution coefficient and separation factor. The results of these evaluation processes were found to prove higher selectivity and preference of these four phases for binding with lead(II) and cadmium(II) compared to other metal ions.