Authors:R. Illés, Cs. Kassai, G. Pokol, E. Fogassy, and D. Kozma
The enantioselectivity of the diastereomeric supramolecular compound (SMC) formation between O,O'-dibenzoyl-(2R,3R)-tartaric
acid (DBTA) and chiral secondary alcohols was investigated. On the basis of TG measurements the DBTA:chiral alcohol molar
ratio in the SMC-s is nearly 1:1. Among the investigated complexes the most stable SMC is trans-2-iodo-cyclohexanol-DBTA. The SMC forming capability and the enantioselectivity depends on the space filling of the alcohol
side chain or ring. In the case of trans-2-halogen-cyclohexanols a relationship can be observed between the thermal stability of the SMC-s and the enantioselectivity
of SMC forming.
Authors:J. Madarász, M. Krunks, L. Niinistö, and G. Pokol
Identification and monitoring of gaseous species released during thermal decomposition of the title compound 1, Zn(tu)2Cl2, (tu=thiourea, (NH2)2C=S) have been carried out in flowing air atmosphere up to 800°C by both online coupled TG-EGA-FTIR and simultaneous TG/DTA-EGA-MS.
The first gaseous products of 1, between 200 and 240°C, are carbon disulfide (CS2) and ammonia (NH3). At 240°C, an exothermic oxidation of CS2 vapors occurs resulting in a sudden release of sulphur dioxide (SO2) and carbonyl sulphide (COS). An intense evolution of hydrogen cyanide (HCN) and beginning of the evolution of cyanamide
(H2NCN) and isothiocyanic acid (HNCS) are also observed just above 240°C. Probably because of condensation and/or polymerization
of cyanamide vapors on the windows and mirrors of the FTIR gas cell optics, some strange baseline shape changes are also occurring
above 330°C. Above 500°C the oxidation process of organic residues appears to accelerate which is indicated by the increasing
concentration of CO2, while above 600°C zinc sulfide starts to oxidize resulting in the evolution of SO2. All species identified by FTIR gas cell were also confirmed by mass spectrometry, except for HNCS.
Authors:M. Zaharescu, A. Jitianu, A. Braileanu, J. Madarász, and G. Pokol
It is well known that SiO2 -based inorganic-organic hybrid materials present significant differences due to the organic moieties bound to the inorganic
network and to the preparation conditions.
In the present work the ageing effect on the thermal stability of the SiO2 -based inorganic-organic hybrid materials prepared using tetraethoxysilan (TEOS), triethoxymethylsilan (MTEOS), triethoxyvinylsilan
(VTEOS), tetramethoxysilan (TMOS), trimethoxymethylsilan (MTMOS) and trimethoxyvinylsilan (VTMOS) was studied.
TG/DTA-MS was used to study the decomposition process of the materials. The structural modifications of the materials during
ageing were studied using spectral methods.
The gels obtained starting with more reactive alkoxides, of methoxy-type, present more complex structures and are less stable
Authors:Laura Bereczki, Katalin Marthi, P. Huszthy, and G. Pokol
Thermochemical properties of crown ether complexes have been studied by simultaneous TG-DTA (thermogravimetric analysis-differential
thermal analysis) coupled with a mass spectrometer, DSC (differential scanning calorimetry) and hot stage microscopy (HSM).
The examined complexes contain benzylammonium- [BA], (R)-(+)-a-phenylethylammonium- [(R)-PEA], (R)-(+)- and (S)-(-)-a-(1-naphthyl)ethylammonium perchlorate [(R)-NEA and (S)-NEA] salts as guests. In the cases of BA and (R)-PEA an achiral pyridono-18-crown-6 ligand [P18C6], and in the case of (R)-NEA and (S)-NEA a chiral (R,R)-dimethylphenazino-18-crown-6 ligand [(R,R)-DMPh18C6] was used as host molecule to obtain four different crown ether complexes. In all cases, the melting points of
the complexes were higher than those of both the host and the guest compounds. The decomposition of the complexes begins immediately
after their melting is completed, while the BA and (R)-PEA salts and the crown ether ligands are thermally stable by 50 to 100 K above their melting points. During the decomposition
of the salts and the four complexes strongly exothermic processes can be observed which are due to oxidative reactions of
the perchlorate anion. Ammonium perchlorate crystals were identified among the decomposition residues of the salts. P18C6
was observed to crystallize with two molecules of water. The studied complexes of P18C6 did not contain any solvate. BA was
observed to exhibit a reversible solid-solid phase transition upon heating. The heterochiral complex consisting of (S)-NEA and (R,R)-DMPh18C6 shows a solid-solid phase transition followed by two melting points. HSM observations identified three crystal
modifications, two of them simultaneously co-existing.
Authors:D. Kozma, L. Poszáváca, Mária Ács, G. Pokol, and E. Fogassy
The diastereoisomeric salt pair formed between α-phenyl-ethyl-amine and R-1-phenylethylsuccinamic acid were investigated by
physico-chemical methods. Melting and solubility phase diagrams were determined, the coincidence of the eutectic points of
the two phase diagrams were demonstrated. The large difference in physico-chemical properties of the salt pair explains the
efficient enantiomer separation.
Authors:J. Madarász, T. Leskelä, G. Pokol, and L. Niinistö
Cesium hexachlorocerate(IV), Cs2CeCl6 (I) and sodium pentakis(carbonato)cerate(IV), Na6Ce(CO3)5·12H2O (II) have been investigated in air by simultaneous TG/DTA, FTIR and XRD in order to follow the oxidation state of cerium during their thermal treatment. The thermal decomposition of the hexachloro compound (I) is accompanied by a double change in the oxidation state of cerium. First, in an inner reduction-oxidation reaction, chlorine is evolved and a Cs2CeCl5 phase is obtained. The immediately starting oxidation of this Ce(III) species caused various phase transitions in the CeCl3-CsCl system formed. The presence of Cs3CeCl6 above 400°C can also be assumed and finally this phase also oxidizes into CeO2 with the formation of CsCl as by-product. In the case of the pentacarbonato complex (II), no Ce(III) species were detected. The final products of its decomposition were CeO2 and Na2CO3.
Authors:V. Leovac, R. Petković, A. Kovács, G. Pokol, and Katalin Szécsényi
Factors determining the complex formation reaction of copper(II), nickel(II) and cobalt(II) chloride and copper(II) bromide
with 3,5-dimethyl-1-(hydroxymethyl)-pyrazole (HL) has been studied. Depending on experimental conditions, complexes with different
composition were obtained: [CuCl2(dmp)]2 (I), [CuCl2(dmp)2]2 (II), [CoCl2(dmp)2] (III) (dmp=3,5-dimethylpyrazole), [CuBr(L)]2 (IV), [CoCl(L)(EtOH)]4 (V) and [NiCl(L)(EtOH)]4 (VI). The compounds were characterized by FTIR spectroscopy, solution conductivity and magnetic measurements. The crystal structure
of [CoCl(L)(EtOH)]4 has been determined by single crystal X-ray diffraction. The thermal decomposition of the compounds was studied and found
to be continuous for all of the compounds. The desolvation mechanism of [MCl(L)(EtOH)]4 (M=Co(II), Ni(II)) is explained on the basis of the route of complex formation of CoCl2 with HL.
Authors:J. Madarász, G. Pokol, C. Novák, H. Moselhy, and S. Gál
Residual differences after model fitting were investigated in both isothermal and non-isothermal kinetics in order to make
numerical comparisons between several models and various parameter-estimating methods. Data from two independent experimental
series were evaluated.
A large data set, collected earlier under isothermal conditions from decompositions and hydrothermal reactions of aluminium
hydroxides and oxides, was processed first. It showed that mechanical activation of the starting gibbsite affected reactivity
of samples in several subsequent reactions for all model equations tried. The relative residual deviation concept is introduced,
and statistics were applied to find a model that fits a certain reaction in most of the cases.
In the second study, the sulphate decomposition step of aluminium sulphate octadecahydrate was investigated. TG curves were
measured using a constant heating rate. Dynamic models were fitted by three mathematical methods, including a new general
purpose one. Fitting ability of the methods with various complexity were compared on the basis of residual deviations obtained
after integration of the model equations. As well as evaluating the best fit, this new parameter-estimating method provides
a statistical analysis of the reliability of the whole model fitting process.
Authors:J. Madarász, E. Beregi, J. Sztatisz, I. Földvári, and G. Pokol
Sintering processes in the Y2O3–Al2O3–B2 O3 system and its subsystems (Y2O3–B2O3 and Al2 O3–B2O3) have been investigated by using combined DTA and XRD measurements to get a better understanding of solid state chemical
changes resulting in the formation of yttrium aluminum borate (YAl3(BO3)4, YAB) phase and to study the possible role and contribution of various simple borates formed also in the former processes.
Two new exothermic heat effects of YBO3 formation have been detected by DTA in the Y2O3–B2O3 system between 720 and 980C. In the Al2O3–B2O3 system a new experimental XRD profile of Al4B2O9 was observed. Formation of these borates seems to promote the nucleation of double borate YAB below 1000C. Conversion of
Al4B2O9 to Al18B4 O33 was observed after a long term (10 h) sintering at 1050C. Similarly, an increased formation of YAB has been observed as
a product of the sintering reaction between YBO3 and Al18B4O33 at 1150C. The two latter single borates are found to be identical with the high temperature decomposition products of YAB.
Authors:D. Janke, J. Madarász, S. Lukács, and G. Pokol
Differential scanning calorimetric (DSC) measurements have been carried out on Bi-Sn based amalgam precursors to be used in
compact fluorescent lamps (CFLs) to study the changes in melting and solidifying behaviour caused by In dopant. The phase
and elemental compositions of the samples have been characterized by using X-ray diffraction (XRD) and scanning electron microscopy-energy
dispersive X-ray analysis (SEM-EDX), respectively. One of the endothermic peaks of the liquid amalgam formation shifted from
121°C to 112 and 105°C, with increasing content of 2.5 and 4.8 mass% In of samples, respectively.