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1.
We performed the analysis of the thermokinetic equations taking into account Kissinger law. The formulas obtained were verified by the use of the so-called isokinetic effect. It was shown that the thermokinetic equation, g(α)=(AT/q)exp(-E/RT), appeared to connect both laws analyzed. Moreover, this approach validates equation km=q/T m which takes a form of Kissinger law, i.e. ln(q/T m) vs. 1/T m. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

2.
合成了稀土(钬, Ho)-氨基酸(甘氨酸, C2H5O2N)二元配合物Ho(NO3)3(C2H5O2N)4·H2O, 并且通过化学分析、元素分析和红外(IR)光谱对配合物进行了表征. 用高精度全自动绝热量热仪, 测定了该配合物在80-390 K温度区间的定压摩尔热容(Cp,m). 利用实验测定的热容数据, 采用最小二乘法, 将热容曲线上热容峰以外的两段平滑区的摩尔热容对折合温度进行拟合, 建立了热容随折合温度变化的多项式方程. 根据热容与焓、熵的热力学关系,计算出了配合物在80-390 K温度区间内,每隔5 K,相对于298.15 K的摩尔热力学函数(HT,m-H298.15,m)和(ST,m-S298.15,m). 通过热容曲线分析, 计算出了350 K附近转变过程的焓变(ΔtrsHm)和熵变(ΔtrsSm). 用差示扫描量热法(DSC)测定了配合物的热稳定性.  相似文献   

3.
The thermal behaviour of Ba[Cu(C2O4)2(H2O)]·5H2O in N2 and in O2 has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol–1 (or 52±5 kJ (mol of H2O)–1). The overall enthalpy change for the decomposition of Ba[Cu(C2O4)2] in N2 was estimated from the combined area of the peaks of the DSC curve as –347 kJ mol–1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the -time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol–1 and (1.38±0.08)×1015 min–1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2.The values ofE a andA were 206±23 kJ mol–1 and (2.2±0.5)×1019 min–1, respectively, for the fast process, and 259±37 kJ mol–1 and (6.3±1.8)×1023 min–1, respectively, for the slow process.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday  相似文献   

4.
Crystallization of 2RbBr · MnBr2 · 2H2O, the only double salt obtained under standard conditions from saturated aqueous rubidium–manganese bromide solutions, was theoretically predicted using the hard and soft Lewis acids and bases concept and Pauling's rules. The RbBr—MnBr2—H2O system was thermodynamically simulated by the Pitzer model assuming a solubility diagram of three branches only: RbBr, 2RbBr · MnBr2 · 2H2O and MnBr2 · 4H2O. The theoretical result was experimentally proved at 25°C by the physicochemical analysis method and formation of the new double salt 2RbBr · MnBr2 · 2H2O was established. It was found to crystallize in a triclinic crystal system, space group –P1, a = 5.890(1) Å, b = 6.885(1) Å, c = 7.367(2) Å, = 66.01(1)°, = 87.78(2)°, = 84.93(2)°, V = 271.8(1) Å3, Z = 1, D x = 3.552 g-cm–3. The binary and ternary ion interaction parameters were calculated and the solubility isotherm was plotted. The standard molar Gibbs energy of the synthesis reaction, rG m o , of the double salt 2RbBr · MnBr2 · 2H2O from the corresponding simple salts RbBr and MnBr2 · 4H2O, as well as the standard molar Gibbs energy of formation, fG m o , and standard molar enthalpy of formation fH m o of the simple and double salts were calculated.  相似文献   

5.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.  相似文献   

6.
Hydrothermal synthesis in the M/Mo/O (M=Co,Ni) system was investigated. Novel transition metal tetramolybdate dihydrates MMo4O13·2H2O (M=Co,Ni), having an interesting pillared layer structure, were found. The molybdates crystallize in the triclinic system with space group P−1, Z=1 with unit cell parameters of a=5.525(3) Å, b=7.058(4) Å, c=7.551(5) Å, α=90.019(10)°, β=105.230(10)°, γ=90.286(10)° for CoMo4O13·2H2O, and a=5.508(2) Å, b=7.017(3) Å, c=7.533(3) Å, α=90.152(6)°, β=105.216(6)°, γ=90.161(6)° for NiMo4O13·2H2O The structure is composed of two-dimensional molybdenum-oxide (2D Mo-O) sheets pillared with CoO6 octahedra. The 2D Mo-O sheet is made up of infinite straight ribbons built up by corner-sharing of four molybdenum octahedra (two MoO6 and two MoO5OH2) sharing edges. These infinite ribbons are similar to the straight ones in triclinic-K2Mo4O13 having 1D chain structure, but are linked one after another by corner-sharing to form a 2D sheet structure, like the twisted ribbons in BaMo4O13·2H2O (or in orthorhombic-K2Mo4O13) are.  相似文献   

7.
The Fourier transform infrared spectra of Cs2CaCl4·2H2O as well as those of a series of its partially deuterated analogues were recorded at room and at liquid-nitrogen temperature (RT and LNT, respectively). The RT Raman spectra of the protiated form and of its almost completely deuterated analogue were also studied. The combined results from the analysis of the spectra were used to assign the observed bands. The mechanical anharmonicity of the OH(D) stretching and bending motions were further analyzed by computing the corresponding anharmonicity constants by several algorithms. The obtained trends in the series of structurally similar compounds were discussed.  相似文献   

8.
Low-temperature heat capacities of the solid compound NaCuAsO4·1.5H2O(s)were measured using a precision automated adiabatic calorimeter over a temperature range of T=78 K to T=390 K.A dehydration process occurred in the temperature range of T=368-374 K.The peak temperature of the dehydration was observed to be TD=(371.828±0.146)K by means of the heat-capacity measurement.The molar enthalpy and entropy of the dehydration were ΔDHm=(18.571±0.142)kJ/mol and ΔDSm=(49.946±0.415)J/(K·mol),respectively.The experimental values of heat capacities for the solid(Ⅰ)and the solid-liquid mixture(Ⅱ)were respectively fitted to two polynomial equations by the least square method.The smoothed values of the molar heat capacities and the fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated at an interval of 5 K.  相似文献   

9.
Thermogravimetric analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion) of 9 different samples were carried out in dynamic conditions at different heating rates. The kinetic parameters (E, A and km) of thermal decomposition were determined and interrelations between the parameters and heating rate q were analyzed. There were also relations between Arrhenius and Eyring equations analyzed for thermal decomposition of solid phase. It was concluded that Eyring theory is an element, which interconnects used thermokinetic equations containing Arrhenius law and suggests considering kinetic quantities in way relative to 3 kinetic constants (E, A and km). Analysis of quantities other than km (i.e. E, A, Δ+H, Δ+S) in relation to heating rate is an incomplete method and does not lead to unambiguous conclusions. It was ascertained that in ideal case, assuming constant values of kinetic parameters (E and A) towards heating rate and satisfying both Kissinger equations, reaction rate constant km should take on values intermediate between constants (km)1 and (km)2 determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation km vs. q in the background of (km)1 and (km)2 made possible classification of differences between thermal decomposition processes taking place in oxidizing and oxygen-free atmosphere.  相似文献   

10.
Thermal and calorimetric studies were carried out on M(IO3)2·6H2O and M(IO3)2·6D2O forM 2+=Ca2+ and Sr2+, using DTA and DSC methods. The thermal behaviour of the ordinary and deuterated hydrates is outlined and the differences observed between them are discussed. The enthalpies of the phase transitions were determined. The H f o for Ca(IO3)2·6H2O, Ca(IO3)2·6H2O(D2O) and Sr(IO3)2·6H2O(D2O) were calculated from the H deh data and comments are made on the isotope effect observed.
Zusammenfassung Mittels DTA- und DSC-Methoden wurden Me(IO3)2·6H2O und Me(IO3)2·6D2O (mitMe 2+=Ca2+ und Sr2+) thermisch und kalorimetrisch untersucht. Es wird ein Überblick über das thermische Verhalten ordentlicher und deuterierter Hydrate gegeben, in dem auch die Unterschiede zwischen beiden diskutiert werden. Die Enthalpien der untersuchten Phasenumwandlungen wurden bestimmt. Aus den Daten für Hdeh wurde Hf von Ca(IO3)2·6H2O, Ca(IO3)2H2O(D2O) und Sr(IO3)2·6H2O(D2O) berechnet und Bemerkungen zum beobachteten Isotopeneffektes gemacht.
  相似文献   

11.
Thermal hazard evaluation of carbon nanotubes with sulfuric acid by DSC   总被引:2,自引:2,他引:0  
Many concerns over unsafe or unknown properties of multi-walled carbon nanotubes (MWNTs) have been raised. The thermal characteristics regarding stability would represent potential hazards during the production or utilization stage and could be determined by calorimetric tests for various thermokinetic parameters. Differential scanning calorimetry (DSC) was employed to evaluate the thermokinetic parameters for MWNTs at various compositions. Thermoanalytical curves showed that the average heat of decomposition (ΔH d) of the MWNTs samples in a manufacturing process was about 31,723 J g−1, by identifying them as an inherently hazardous material. In this study, significant thermal analysis appeared in the presence of sulfuric acid (H2SO4). From the DSC experiments, the purification process of MWNTs could induce an unexpected reaction in the condition of batch addition with reactants of H2SO4. The results can be applied for designing emergency relief system and emergency rescue strategies during a perturbed situation or accident.  相似文献   

12.
Crystals of K2Co3(OH)2(SO4)3·2H2O were synthesized under hydrothermal conditions. The crystal structure [a=17.945 (4) Å,b=7.557 (2) Å,c=9.760 (3) Å, space group Cmc21,Z=4] was determined by direct methods and refined with single crystal X-ray data. The H atoms were located byFourier syntheses. Their structural parameters were refined, too. The finalR-values areR=0.025 andR w =0.028 (w=1/) for 612 reflections withF 0>3 (F 0). Both Co(II) atoms are octahedral six coordinated and form zigzag chains running parallel [001]. These chains are connected via sulfate groups to built up sheets parallel (100). The KO9 polyhedron and one of the four hydrogen bonds link these sheets.
  相似文献   

13.
Summary The crystal structures of the new, hydrothermally synthesized, isotypic compounds Co3(SeO3)3·H2O and Ni3(SeO3)3·H2O were determined by direct and Fourier methods and refined toR w=0.023, 0.032 using single crystal X-ray data up to sin/=0.81 Å–1 [space group P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. The structures are built up from [Me 5(SeO3)6·2H2O]2– sheets containing three crystallographically different types of octahedrally coordinatedMe 2+ and trigonal pyramidal coordinated Se4+ atoms, respectively. These sheets are linked only by a fourth type ofMe 2+[6] atom. All coordination polyhedra deviate significantly from their ideal shapes, bond lengths within the extremly distortedMe(4)O6 polyhedra range from 1.983 (2) Å to 2.403 (2) Å in Co3(SeO3)3·H2O and from 1.987 (4) Å to 2.301 (3) Å in the Ni compound, O-Se-O bond angles were found between 92.8 (2)° and 104.9 (1)°. Hydrogen bond lengths are 2.802 (3)Å and 2.600 (4)Å in the Co compound, and 2.762 (6) Å and 2.561 (6) Å in Ni3(SeO3)3·H2O. The latter is one of the shortest known hydrogen bonds donated by a water molecule.
Die Kristallstrukturen von Co3(SeO3)3·H2O und Ni3(SeO3)3·H2O, zwei neue isotype Verbindungen
Zusammenfassung Die Kristallstrukturen der neuen, hydrothermal synthetisierten, isotypen Verbindungen Co3(SeO3)3·H2O und Ni3(SeO3)3·H2O wurden mit direkten und Fourier-Methoden bestimmt und unter Verwendung von Einkristallröntgendaten bis sin/=0.81 Å–1 aufR w-Werte von 0.023, 0.032 verfeinert [Raumgruppe P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. Die Strukturen werden von [Me 5(SeO3)6·2H2O]2– Schichten aufgebaut, die je drei kristallographisch unterschiedliche Arten von oktaedrisch koordiniertenMe 2+ und trigonal pyramidal koordinierten Se4+ Atomen enthalten. Diese Schichten sind nur durch eine vierte Art vonMe 2+[6] Atomen verknüpft. Alle Koordinationspolyeder weichen deutlich von ihren Idealformen ab, Bindungslängen in den extrem verzerrtenMe(4)O6 Polyedern variieren zwischen 1.983 (2) Å und 2.403 (2) Å in Co3(SeO3)3·H2O und zwischen 1.987 (4) Å und 2.301 (3) Å in der Ni-Verbindung, O-Se-O-Bindungswinkel liegen zwischen 92.8 (2)° und 104.9 (1)°. Wasserstoffbrückenlängen sind 2.802 (3) Å und 2.600 (4) Å in der Co-Verbindung, und 2.762 (6) Å und 2.561 (6) Å in Ni3(SeO3)3·H2O. Letztere ist eine der kürzesten bekannten Wasserstoffbrücken eines Wassermoleküls.
  相似文献   

14.
Intermolecular potential energy curves for the hydrogen bonded systems H2O·H2S, H2O·H2Se and H2S·H2S were calculated with nonempirical pseudopotentials using optimized-in-molecules basis sets augmented by polarization functions. The H2O·H2O interaction energy curve has been also considered as a test case. The present results for H2O·H2S and H2S·H2S indicate much weaker intermolecular interactions than those found in previous ab initio calculations. The H2O·H2Se interaction was found to be quite similar to H2O·H2S.This work was partly supported by the Polish Academy of Sciences within the Project PAN-09, 7.1.1.1On leave from Quantum Chemistry Laboratory, Dept. of Chemistry, University of Warsaw, Pasteura 1, 02-093. Warsaw, Poland  相似文献   

15.
A new magnesium borate Mg2[B2O4(OH)2]·H2O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg2[B2O4(OH)2]·H2O in 0.9764 mol L–1 HCl was determined. With the incorporation of the enthalpies of solution of H3BO3 in HCl (aq), of MgO in (HCl+H3BO3) (aq), and the standard molar enthalpies of formation of MgO(s), H3BO3(s), and H2O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol–1 of Mg2[B2O4(OH)2]·H2O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

16.
Nanometer MgO samples with high surface area, small crystal size and mesoporous texture were synthesized by thermal decomposition of MgC2O4 · 2H2O prepared from solid-state chemical reaction between H2C2O4 · 2H2O and Mg (CH3COO)2 · 4H2O. Steam produced during the decomposition process accelerated the sintering of MgO, and MgO with surface area as high as 412 m2 · g−1 was obtained through calcining its precursor in flowing dry nitrogen at 520°C for 4 h. The samples were characterized by X-ray diffraction, N2 adsorption, transmission electron microscopy, thermogravimetry, and differential thermal analysis. The as-prepared MgO was composed of nanocrystals with a size of about 4–5 nm and formed a wormhole-like porous structure. The MgO also had good thermal stability, and its surface areas remained at 357 and 153 m2·g−1 after calcination at 600 and 800°C for 2 h, respectively. Compared with the MgO sample prepared by the precipitation method, MgO prepared by solid-state chemical reaction has uniform pore size distribution, surface area, and crystal size. The solid-state chemical method has the advantages of low cost, low pollution, and high yield, therefore it appears to be a promising method in the industrial manufacture of nanometer MgO. Translated from Chinese Journal of Catalysis, 2006, 27(9): 793–798 (in Chinese)  相似文献   

17.
邸友莹  高胜利  谭志诚  孙立贤 《化学学报》2007,65(14):1299-1304
利用精密自动绝热热量计直接测定了配合物Zn(Met)SO4•H2O(s) 在78~370 K温区的摩尔热容. 通过热容曲线的解析得到该配合物的起始脱水温度为T0=329.50 K. 将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容 (Cp,m)对温度(T)的多项式方程, 并且在此基础上计算出了它的舒平热容值和各种热力学函数值. 依据Hess定律, 通过设计热化学循环, 选择体积为100 cm3、浓度为2 mol•L-1的盐酸作为量热溶剂, 利用等温环境溶解-反应热量计, 测定和推算出该配合物的标准摩尔生成焓为ΔfHm0=-(2069.30±0.74) kJ•mol-1.  相似文献   

18.
The solid copper l-threonate hydrate, Cu(C4H6O5)·0.5H2O, was synthesized by the reaction of l-threonic acid with copper dihydrocarbonate and characterized by means of chemical and elemental analyses, IR and TG-DTG. Low-temperature heat-capacity of the title compound has been precisely measured with a small sample precise automated adiabatic calorimeter over the temperature range from 77 to 390 K. An obvious process of the dehydration occurred in the temperature range between 353 and 370 K. The peak temperature of the dehydration of the compound has been observed to be 369.304 ± 0.208 K by means of the heat-capacity measurements. The molar enthalpy, ΔdHm, of the dehydration of the resulting compound was of 16.490 ± 0.063 kJ mol−1. The experimental molar heat capacities of the solid from 77 to 353 K and the solid from 370 to 390 K have been, respectively, fitted to tow polynomial equations with the reduced temperatures by least square method. The constant-volume energy of combustion of the compound, ΔcUm, has been determined as being −1616.15 ± 0.72 kJ mol−1 by an RBC-II precision rotating-bomb combustion calorimeter at 298.15 K. The standard molar enthalpy of formation of the compound, , has been calculated to be −1114.76 ± 0.81 kJ mol−1 from the combination of the data of standard molar enthalpy of combustion of the compound with other auxiliary thermodynamic quantities.  相似文献   

19.
Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO2OH) (SeO4) · H2O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 Å3;Z=4, space group P21/c,R=0.029,R w=0.027 for 2430 independent reflections (sin /0.76 Å–1). Isolated FeO5(H2O)-octahedra share five corners with [SeO2OH] and [SeO4] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.
Die Kristallstruktur von Fe(SeO2OH)(SeO4)·H2O
Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO2OH) (SeO4)·H2O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 Å3;Z=4, Raumgruppe P21/c,R=0.029,R w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å–1). Isolierte FeO5(H2O)-Oktaeder teilen fünf Ecken mit [SeO2OH]- und [SeO4]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.
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20.
利用精密绝热热量仪测定了化合物配合物Zn(Met)3(NO3)2·H2O (s) (Met=L-α-蛋氨酸)在78-371 K温区的摩尔热容. 通过热容曲线解析, 得到了该配合物的起始脱水温度为TD=325.10 K. 将该温区的摩尔热容实验值用最小二乘法拟合得到了摩尔热容(Cp)对约化温度(T)的多项式方程, 由此计算得到了配合物的舒平热容值和热力学函数值. 基于设计的热化学循环, 选择100 mL of 2 mol·L-1 HCl为量热溶剂, 利用等温环境溶解-反应热量计, 得到了298.15 K配合物的标准摩尔生成焓为ΔfHm0[Zn(Met)3(NO3)2·H2O(s),s]=-(1472.65±0.76) J·mol-1.  相似文献   

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