The Study of Influence of Metal Ions on Thermal Decomposition of Humic Acids

Investigations of the influence of the following metal ions: Ca, Mg, Ba, Cr, Mn,Co, Ni, Fe(II), Fe(III), Cu, Zn, Cd, Pb, Hg, Al and Ag on thermal decomposition of humic acids were carried out. Metal-humic compounds were obtained by ion exchange method and by complexing of metal cations on humic acids. For the investigations of thermal decomposition TG and DTA were used. Presence of metal ions in structure of humic acids mostly increases intensity of their thermal decomposition particularly the Hg and Cu ions.They shift this process to lower temperatures 100–300°C. Mass loss of organic matter in this temperature range in humic-mercury compounds are higher by more than 35%, and in humic-copper compounds are higher by more than 20% compared with the mass loss of humic acids itself. Ni and Co ions also increase the intensity of thermal decomposition of humic acids, but Ca, Ba and Mg ions inhibit that process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal degradation behaviour of some metal chelate polymer compounds with bis(bidentate) ligand by TG/DTG/DTA

Seven novel divalent transitional metal chelate polymers compounds (commonly known as chelate compounds or metal coordination complexes or polymer complexes) have been characterized by thermogravimetry (TG), differential thermal gravimetry (DTG) and differential thermal analysis (DTA) methods. Thermal decomposition behaviour of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) polymers with terphthaoyl-bis(p-methoxyphenylcarbamide) has been investigated by thermogravimetric analysis (TGA) at heating rate 10 °C min^?1 under nitrogen atmosphere. TG/DTA of chelate compounds were shown to be a stable compound against thermal decomposition which was measured on the basis of final decomposing temperature, but it is observed in some curves that decomposition takes place at low temperature due to the lattice water, which is always placed at outer coordination sphere of the central metal ion. The presence of both lattice and coordinated water were noteworthy investigated in Co(II), Ni(II) and Cu(II) chelate polymer compounds, whereas lattice water found in Zn(II), Cd(II) and Hg(II). However, Mn(II) showed only coordinated water. Thermal stabilities for release of lattice water, coordinated water and organic moiety that occur in sequential decomposition of chelate compounds are explained on the basis of ionic size effect and electronegativity. The processes of thermal degradation taking place in seven chelate polymers were studied comparatively by TG/DTG/DTA curves which indicating the difference in the thermal decomposition. Coats–Redfern integral method is used to determine the kinetic parameters for the successive steps in the decomposition sequence of TG curves. Scanning electron microscope images of some chelate polymers were shown in previous publication revealed that particle sizes of chelate polymers were found to be of nanomaterial level therefore, resulting chelate compounds might be called as nanomaterial.     

Determination of airborne mercury-203

A method is described for the determination of airborne compounds of²⁰³Hg. The method is based on the sorption of Hg on hopcalite (activated copper oxide/manganese oxide) with subsequent monitoring for the gamma-radiation of²⁰³Hg. Aerosol activity in the air is separated by sucking the air through a filter prior to the absorption tube. The sensitivity of the method permits the assessment of less than one tenth of the maximum permissible concentration in air. It is shown experimentally that the separation procedure used is suitable for the determination of airborne mercuric acetate and its thermal decomposition products.     

用单一非等温DSC曲线确定2,6-二硝基苯酚热分解反应的最可几机理函数和动力学参数

本文用自行设计加工的耐压不锈钢密封池在CDR-1型差动热分析仪上测得的一条DSC曲线, 利用计算非等温动力学的积分方程和微分方程拟合四组实验数据, 逻辑选择确定2,6-二硝基苯酚在分解深度为0.007-0.66范围内的热分解反应的最可几数学模式为F(α)=α。用放热速率方程算得其热分解反应的级数为零, 其表观活化能、指前因子的测量真值分别为134±9 k Jmol~(-1)、10~(9.17±0.77)S~(-1)。积分方程逻辑选择求得的表观活化能和指前因子的测量真值相应为133±8 kJmol~(-1)和10~(9.01±0.79)S~(-1)。微分方程逻辑选择求得的表观活化能和指前因子的测量真值相应为134±8 kJmol~(-1)和10~(9.10±0.63)S~(-1)。三者吻合良好。     

Effect of plasticizer dibutyl phthalate on the thermal decomposition of nitrocellulose

This paper aims to investigate the effects of plasticizer dibutyl phthalate (DBP) on the thermal decomposition of nitrocellulose (NC) by using a series of analytical apparatuses. In the present study, the detailed structures of pure NC (NC-P) and NC with DBP (NC-D) were revealed by scanning electron microscope. It was found that the fibers in NC-D are more closely aligned than those in NC-P, which makes the thermal behaviors of NC-D different from NC-P. The thermal stability of both NC-P and NC-D was examined by means of simultaneous TG-DSC apparatus (STA). Three different kinetic methods (Kissinger–Akahira–Sunose method, Ozawa–Flynn–Wall method, and Friedman method) were applied for determining the activation energy E of these two NC samples. Moreover, the experimental data were compared with sigmoidal models and pre-exponential factor was calculated by compensation effect. Besides, in situ Fourier transform infrared (FTIR) and a TGA instrument coupled with Frontier FTIR spectrometer were employed to investigate the characteristic functional groups of decomposition residues and gaseous products at different temperatures, respectively. The results show that NC-P and NC-D have similar decomposition products and decomposition mechanisms.     

氧气的体积分数对N2O热分解的影响

N2O是大气中不可忽视的污染物.目前,世界上所排放的N2O主要有三个来源:一是硝酸工业等化工生产;二是流化床锅炉等煤燃烧设备;三是汽车发动机.由于N2O会导致温室效应和破坏臭氧层,而近年来大气层中N2O的氧气体积分数逐年上升,N2O排放的控制技术受到越来越多的关注[1～4].……     

迪开石热分解及重结晶的非等温动力学

采用热分析(TG-DTG-DSC)和X射线衍射(XRD)技术研究了福州迪开石在动态空气气氛条件下的热分解及重结晶过程, 利用TG和DSC数据分别对迪开石的热分解和重结晶过程进行动力学分析. 由Friedman法求得热分解过程的表观活化能, 以此为初始值, 通过非线性回归法拟合得到了热分解过程最可能的反应机理和动力学参数; 将迭代的等转化率法和最小偏差法相结合计算得到了高温下迪开石重结晶过程最可能的反应机理和动力学参数. 研究结果表明, 迪开石在450~750 ℃内发生热分解, 脱去2个水分子, 生成无定形的准迪开石, 此过程为两步连串反应, 第一步为随机成核和随后生长机理An, 第二步为自催化反应机理CnC; 在975~1050 ℃内, 准迪开石重结晶转化为莫来石, 此过程对应的反应机理为An.     

Kinetics and mechanism of the non-isothermal decomposition: I. Some divalent cross-linked metal-alginate ionotropic gels

The kinetics of thermal decomposition of Sn(II), Pb(II), Cd(II) and Hg(II) alginate gels have been studied using thermogravimetry (TG) and derivative thermogravimetry (DTG) in static air. The thermal dehydration of each gel complex was found to occur in one step, whereas the decomposition of the dehydrated complexes occurred in two steps. The kinetic parameters were computed by different models and a tentative decomposition mechanism consistent with the kinetic observations is discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermogravimetric analysis of peat decomposition under different oxygen concentrations

Smoldering combustion of peat is of global concern as a natural hazard to consume sequestered carbon and form wide-area haze. It is affected by thermal decomposition kinetics of peat and the diffusion and availability of oxygen. In this work, thermal decomposition behavior of peat was investigated using thermogravimetric analysis under the atmosphere with different oxygen concentrations. The results showed that thermal decomposition process of peat could be divided into three stages: dehydration, oxidative pyrolysis of organic matters into volatiles and char, and oxidation of the generated char. The apparent activation energies of peat decomposition under different oxygen concentrations were calculated by model-free methods of Kissinger, FWO, Starink, Gyulai, and Friedman. A two-step reaction model was proposed to describe thermal decomposition kinetics of peat (excluding dehydration stage) and the effect of oxygen concentration on the kinetic parameters was discussed. These results provide basic data for smoldering modeling of peat.     

An improved speciation method for mercury by GC/CVAFS after aqueous phase ethylation and room temperature precollection

An improvement has been made in previous mercury speciation methods, which omits the use of liquid nitrogen by modifying the GC conditions. In addition, the sometimes observed thermal decomposition of ethylation derivatives in the process of desorbing the compounds to the GC column has been investigated and overcome. The resulting improvements have allowed simultaneous determination of methylmercury (MMHg) and inorganic mercury (Hg(II)). They have also increased the precision of the ethylation reaction and refined the MMHg determination. Optimal conditions for MMHg were confirmed and supplemented, while the parameters for dimethyl mercury (DMHg) and Hg(II) were thoroughly investigated for the first time. The absolute detection limits (DL) for 2sigma of the reagent blanks as Hg and about 0.6, 0.6 and 1.3 pg for DMHg, MMHg and Hg(II), respectively. The improved method is five-fold faster than the original method, allowing up to 80 samples to be analyzed within 8 hr.     

Thermal decomposition of hydrated iron(II) oxalate and manganese(II) oxalate in vacuum

The thermal decomposition of hydrated iron(II) oxalate and manganese(II) oxalate under high vacuum conditions (10^–5 mm Hg) has been studied by differential thermal analysis. The decomposition in vacuum of iron(II) oxalate is exothermic, while that of manganese(II) oxalate is endothermic. An explanation is offered for this behaviour.The financial support by National Bureau of Standards, U.S.A., through a PL-480 scheme is gratefully acknowledged.     

Thermal behavior of Cu(II)-, Cd(II)-, and Hg(II)-exchanged montmorillonite complexedwith cysteine

The thermal behavior of montmorillonite and organically modified montmorillonite, both treated with heavy metal cations [Cu(II), Cd(II) and Hg(II)], was characterized via thermal analyses (TG, DTG and DTA) combined with evolved species gas mass spectrometry (MS-EGA), and X-ray diffraction at in situ controlled temperature (HTXRD). The reactions involving Cu(II)- and Cd(II)-montmorillonite samples are mostly related to H₂O and OH loss, unlike Hg(II)-montmorillonite, where effects associated to Hg(II) loss are also present. Finally reactions related to dehydration, dehydroxylation and to organic matter decomposition can be observed in montmorillonite samples treated with cysteine.     

Thermal and morphological characteristics of solution blended epoxy/NBR compound

Systematic study about the effect of acrylonitrile–butadiene rubber (NBR) concentration on the fracture toughness and thermal behavior of epoxy resin is conducted in this study. NBR is solved in an aromatic hydrocarbon solvent and is added to epoxy resin. We used diethylene-teriamin as the curing agent for epoxy resin. Tensile test results, performed followed by molding procedure, show that the toughness is improved owing to the increase of rubber content. Scanning electron microscopy (SEM) and atomic force microscopy besides thermogravimetric analysis (TG) are used to investigate the epoxy/rubber interface and chemical decomposition of the resultant mixture. The thermal behavior of cured epoxy resin was analyzed via TG instrument at different heating rates. Thermogravimetry curves showed that the thermal decomposition of epoxy system was occurred in only one stage regardless of the rubber content. The apparent activation energies of the rubber/epoxy systems containing 0, 5, and 10 phr of rubber were determined by Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, and Friedman methods. The results prove that the thermal stability of epoxy resin was decreased with enhancing the rubber content. However, the trend of changing activation energy versus conversions is totally different followed by adding the elastomer to the system compared to neat epoxy resin. Moreover, the results obtained via our proposed facile solution blending method are compared to those of resins modified with nano-powdered elastomer.     

Measuring mercury in wood: challenging but important

Mercury (Hg) in tree wood has been overlooked, in part because concentrations are so low as to be below detection limits of some analytical methods, but it is potentially important to forest ecosystem processes and budgets. We tested methods for the preparation and determination of Hg in tree wood by analysing samples of four tree species at the Hubbard Brook Experimental Forest, New Hampshire, USA, using thermal decomposition, catalytic conversion, amalgamation and atomic absorption spectrophotometry (USEPA Method 7473). Samples that were freeze-dried or oven-dried at 65°C were suitable for determination of Hg, whereas oven-drying at 103°C resulted in Hg losses, and air-drying resulted in Hg gains, presumably due to sorption from indoor air. Mean (±SE) concentrations of Hg tree bole wood were 1.75 ± 0.14 ng g^?1 for American beech, 1.48 ± 0.23 ng g^?1 for sugar maple, 3.96 ± 0.19 ng g^?1 for red spruce and 4.59 ± 0.06 ng g^?1 for balsam fir. Based on these concentrations and estimates of wood biomass by species based on stand inventory, we estimated the Hg content of wood in the reference watershed at Hubbard Brook to be 0.32 g ha^?1, twice the size of the foliar Hg pool (0.15 g ha^?1). Mercury in wood deserves more attention and is feasible to measure using appropriate techniques.     

The thermal decomposition of doped ammonium perchlorate

The thermal decomposition of ammonium perchlorate doped with Cu²⁺, Mn²⁺, Co²⁺ and Fe³⁺ (with and without H⁺) was studied using DTA and TG. Small concentrations of these ions inhibit the decomposition by eliminating the first exothermic peak. At higher concentrations, a catalyzed decomposition is observed. Either the influence of the doping ions on the mechanism of the thermal decomposition is different from that of added oxides or a modification of the electron transfer mechanism is needed.     

Influences of product gases on the kinetics of thermal decomposition of synthetic malachite evaluated by controlled rate evolved gas analysis coupled with thermogravimetry

An instrument of controlled rate evolved gas analysis (CREGA) coupled with TG‐DTA was constructed for analyzing the influences of product gases on the kinetics and mechanism of the thermal decomposition of solids that produce more than one gaseous products at the same stage of reaction. The thermal decomposition of synthetic malachite, Cu₂(OH)₂CO₃, was subjected to the measurements of CREGA‐TG under controlled concentrations of H₂O and CO₂ in the reaction atmosphere with taking account of self‐generated H₂O and CO₂ during the course of reaction. By a series of CREGA‐TG measurements carried out under various atmospheric conditions, it was reconfirmed that the reaction is accelerated and decelerated by the effects of atmospheric H₂O and CO₂, respectively. From the kinetic analysis of the CREGA‐TG curves and results of high temperature X‐ray diffraction measurements under various reaction atmospheres, it was revealed that the anomalous effects of atmospheric H₂O on the reactivity and on the reaction rate of the thermal decomposition of synthetic malachite appear at the early stage of the reaction. Usefulness of the CREGA‐TG technique for measuring the kinetic rate data for the thermal decomposition of solids was demonstrated in the present study, by emphasizing the importance of quantitative control of self‐generated reaction atmosphere. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 346–354, 2005     

Thermal studies on palladium alkyl xanthates

Eleven palladium(II) alkylxanthates: Pd(ROCSS)₂ [RMe, Et, nPr, iPr, nBu, iBu, tBu, nAm, iAm, nHex and cyclohex], have been prepared and their thermal properties investigated by thermogravimetric analysis. The complexes, although volatile under vacuum (10^?2 mm Hg), decompose without volatilization at normal atmospheric pressure leaving a residue of palladium metal at 950°C. The intermediate decomposition products were identified mass spectrometrically and a thermal decomposition mechanism is proposed.     

Thermal and electrochemical study of solid-state reaction of mercury with Pt–20% Rh alloy

Thermogravimetry (TG), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface and X-ray diffraction (XRD) have been used to study the reaction of mercury with platinum–rhodium (Pt–Rh) alloy. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt–Rh to form intermetallic compounds each having a different stability, indicated by separate third mass-loss steps. In the first step, between room temperature and 170 °C, only the bulk Hg is removed. From this temperature to about 224 °C, the mass loss can be attributed to decomposition of the intermetallic PtHg₄. The third step, from 224 to 305 °C, can be ascribed to thermal decomposition of solid solution composed of intermetallic species RhHg₂ and PtHg₂. Intermetallic compound such as PtHg₄, PtHg₂, and RhHg₂ was characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of the bulk mercury via thermal desorption.     

Thermoanalytical investigation of 1,2-diimidazoloethane complexes of copper,mercury and cadmium by TG-DTG-DTA techniques in static air atmosphere

The iodide complexes of transition metals with 1,2-diimidazoloethane (DIE) of the general formula MLI₂, (M=Cu(II), Hg(II), Cd(II); L=1,2-diimidazoloethane) were prepared and studied by means of thermogravimetry (TG/DTG) and differential thermal analysis (DTA) techniques. Their compositions were investigated by elemental analysis in order to ensure their purity and structural elucidations were based on conductivity measurements, room temperature magnetic measurements, proton NMR, XRD and IR spectra. Thermal decomposition of these distorted tetrahedral complexes and the ligand took place in two distinct steps upon heating up to 800°C, with the loss of inorganic and organic fragments. The thermal degradation of all the complexes (except for cadmium complex) in static air atmosphere started at temperatures lower than those observed for the free ligand pyrolysis. The composition of intermediates formed during degradation was confirmed by microanalysis and IR spectroscopy. The residues after heating above 740°C corresponded to metal oxide except for Hg(II) complex, which behaved differently. It was found on the basis of thermal analysis that thermal stability of the complexes increased in the following sequence: Hg(II)<Cu(II)<Cd(II).     

Mercury characterisation in urban particulate matter

A five-step sequential extraction procedure was proposed in order to assess the distribution of mercury (Hg) forms in urban particulate matter (PM): exchangeable, HCl-soluble, organic-bound, elemental and other slightly soluble Hg species, mercury(II) sulphide (HgS), and residual Hg. This process was applied to the analysis of urban dust samples collected at locations in Prague (Czech Republic) with high traffic density. In addition to sequential extractions, thermal desorption analysis was performed. The differences in Hg concentrations between untreated and thermally treated samples were indicated as the thermally releasable amount of Hg. For the study of PM-adsorbing capacity, Hg vapours were passed through the samples as long as the enrichment of materials was observed. The retained elemental Hg was readily released by thermal desorption. All Hg analyses were based on the highly sensitive pyrolysis technique of atomic absorption spectrometry using the mercury analyser AMA-254.