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1.
The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol?1), followed by babassu biodiesel (E = 76.37 kJ mol?1), and palm biodiesel (E = 87.00 kJ mol?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol?1 K?1, ΔH = +80.38 kJ mol?1 and ΔG = +142.74 kJ mol?1. For palm biodiesel ΔS = ?119.26 J mol?1 K?1, ΔH = + 90.53 kJ mol?1 and ΔG = +141.21 kJ mol?1, and for diesel ΔS = ?131.3 J mol?1 K?1, ΔH = +53.29 kJ mol?1 and ΔG = +115.13 kJ mol?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.  相似文献   

2.
A new chelate (η5-C5H5)2Ti(SB)2, whereSB=O, N donor Schiff base salicylidene-4-methylaniline, was synthesized. The course of thermal degradation of the chelate was studied by thermogravimetric (TG) and differential thermal analysis (DTA) under dynamic conditions of temperature. The order of the thermal decomposition reaction and energy of activation was calculated from TG curve while from DTA curve the change in enthalpy was calculated. Evaluation of the kinetic parameters was performed by Coats-Redfern as well as Piloyan-Novikova methods which gaven=1, ΔH=1.114 kJ·mol?1, ΔE=27.01 kJ·mol?1, ΔS=?340.12 kJ·mol?1·K?1 andn=1, ΔH=1.114 kJ·mol?1, ΔE=20.01 kJ·mol?1, ΔS=?342.60 kJ·mol?1·K?1, respectively. The chelate was also characterized on the basis of different spectral studies viz. conductance, molecular weight, IR, UV-visible and1H NMR, which enabled to propose an octahedral structure to the chelate.  相似文献   

3.
Thermomechanical analysis (TMA) can be used as a sensitive tool to follow crystallization behavior in non-crystalline materials. Newly developed method is based on slowing down of sample deformation caused by viscous flow above the glass transition due to macroscopic crystal growth. It is shown that a typical TMA sigmoidal curve reasonably well corresponds to direct measurement of crystal growth kinetics by means of optical microscopy. The method has been used to study crystallization kinetics in Ge38S62 glass. The TMA measurement is able to detect earlier stages of crystallization than obtained by differential scanning calorimetry measurement. The activation energy obtained from the shift of extrapolated end of TMA curve with heating rate (E = 263 ± 7 kJ mol?1) is similar to the activation energy of ??-GeS2 crystal growth in Ge38S62 glass (E G = 247 ± 23 kJ mol?1) obtained from direct optical microscopy measurements.  相似文献   

4.
A novel complex [Ni(H2O)4(TO)2](NO3)2·2H2O (TO = 1,2,4-triazole-5-one) was synthesized and structurally characterized by X-ray crystal diffraction analysis. The decomposition reaction kinetic of the complex was studied using TG-DTG. A multiple heating rate method was utilized to determine the apparent activation energy (E a) and pre-exponential constant (A) of the former two decomposition stages, and the values are 109.2 kJ mol?1, 1013.80 s?1; 108.0 kJ mol?1, 1023.23 s?1, respectively. The critical temperature of thermal explosion, the entropy of activation (ΔS ), enthalpy of activation (ΔH ) and the free energy of activation (ΔG ) of the initial two decomposition stages of the complex were also calculated. The standard enthalpy of formation of the new complex was determined as being ?1464.55 ± 1.70 kJ mol?1 by a rotating-bomb calorimeter.  相似文献   

5.
The crystal growth kinetics of germanium disulfide in undercooled melts has been studied by optical microscopy under isothermal conditions. The linear growth kinetics of GeS2 has been observed in the temperature range 672 ≤ T ≤ 711 K in thin film samples. The activation energy of crystal growth assuming Arrhenius behavior has been determined as E G = 166 ± 8 kJ mol?1 for thin film samples. From the dependence of reduced growth rate on undercooling, the interface driven 2-D surface nucleated model was estimated.  相似文献   

6.
A new crystalline complex (C8H17NH3)2CuCl4(s) (abbreviated as C8Cu(s)) was synthesized by liquid phase reaction. Chemical analysis, elemental analysis, and X-ray crystallography were applied to characterize the composition and crystal structure of the complex. Low-temperature heat capacities of the complex were measured by a precision automatic adiabatic calorimeter over the temperatures ranging from 78 to 395 K, and two solid–solid phase changes appeared in the heat capacity curve. The temperatures, molar enthalpies and entropies of the two phase transitions of the complex were determined to be: T trs, 1 = 309.4 ± 0.35 K, Δtrs H m, 1 = 16.55 ± 0.41 kJ mol?1, and Δtrs S m, 1 = 53.49 ± 1.3 J K?1 mol?1 for the first peak; T trs, 2 = 338.5 ± 0.63 K, Δtrs H m, 2 = 6.500 ± 0.10 kJ mol?1, and Δtrs S m, 2 = 19.20 ± 0.28 J K?1 mol?1 for the second peak. Two polynomial equations of the heat capacities as a function of the temperature were fitted by least-square method. Smoothed heat capacities and thermodynamic functions of the complex relative to the standard reference temperature of 298.15 K were calculated based on the fitted polynomial equations.  相似文献   

7.
New energetic materials, [Ca(MCZ)3(H2O)2](ClO4)2 and {[Ba2(MCZ)4(H2O)21-ClO4)22-ClO4)2]0.5}n, are synthesized and tried as alternatives to common primary explosives. Both the crystal structures were determined by single-crystal X-ray diffraction. The crystal of [Ca(MCZ)3(H2O)2](ClO4)2 belongs to the monoclinic, P21/c space group, a = 14.168(3) Å, b = 8.5938(18) Å, c = 18.889(4) Å, β = 111.234(2)°, V = 2143.8(8) Å3, ρ = 1.6893 g cm?3, and {[Ba2(MCZ)4(H2O)21-ClO4)22-ClO4)2]0.5}n belongs to the triclinic, P-1 space group, a = 7.166(2) Å, b = 10.461(2) Å, c = 11.738(4) Å, α = 110.563(5)°, β = 93.799(2)°, γ = 96.864(3)°, V = 812.4(4) Å3, ρ = 2.185 g cm?3. Their thermal stabilities were investigated by differential scanning calorimetry (DSC), and exothermic peak temperatures with a heating rate of 10 °C min?1 are 249.7 and 181.7 °C, respectively. Non-isothermal reaction kinetics parameters were calculated via both Kissinger’s method and Ozawa-Doyle’s method to work out EK = 124.6 kJ mol?1, lgAK = 10.38, EO = 126.7 kJ mol?1 for the calcium complex and EK = 100.3 kJ mol?1, lgAK = 9.50, EO = 102.6 kJ mol?1 for the barium complex. Additionally, the critical temperatures of thermal explosion, ΔS, ΔH, and ΔG were calculated as ?231.2 J K?1 mol?1, 120.417 kJ mol?1, 236.728 kJ mol?1 for the calcium complex and ?230.6 J K?1 mol?1, 96.723 kJ mol?1, 195.938 kJ mol?1 for the barium complex. As for their explosive nature, sensitivities toward impact and friction were tested. Both [Ca(MCZ)3(H2O)2](ClO4)2 and {[Ba2(MCZ)4(H2O)21-ClO4)22-ClO4)2]0.5}n are insensitive to friction (>360 N); their impact sensitivities are acceptable (20 and 13 J). Both compounds are energetic complexes.  相似文献   

8.
Thermogravimetric analysis was used to study and compare the combustion of different blends of corn bioresidues with sunflower, rape and algae bioresidues. Non-isothermal thermogravimetric data were used to obtain the combustion kinetics of these bioresidues. This paper reports on the application of the Vyazovkin and Ozawa–Flynn–Wall isoconversional methods for the evaluation of kinetic parameters (energy activation, pre-exponential factor and order of reaction) for the combustion of the biomasses studied. Differences were found in the TG curves in accordance with the proximate analysis results for the cellulose, hemicellulose and lignin content of biomasses. The activation energy obtained from combustion (E ~ 151.6 kJ mol?1) was lower than that from the blends (similar values were obtained for corn–sunflower, E ~ 160.5 kJ mol?1 and corn–rape, E ~ 156.9 kJ mol?1) whereas the activation energy obtained from the microalgae was higher (E ~ 171.5 kJ mol?1). Both the Vyazovkin and Ozawa–Flynn–Wall methods yielded similar results.  相似文献   

9.
Thermal decomposition measurements for lithium borohydride (LiBH4) are performed at non-isothermal and non-equilibrium conditions by means of differential thermal analysis (DTA). A simplified alternative procedure is introduced for evaluating thermodynamic and kinetic parameters simultaneously using a single set of measurements. Rate constant (k) and enthalpy (ΔH = ?102.1 ± 0.7 kJ mol?1 LiBH4) are archived. Temperature dependence for activation energy (E a) is found taking advantage of Guggenheim–Arrhenius method; the mean activation energy is $ \overline{E}_{a} $  93.9 ± 0.9 kJ mol?1 LiBH4 in the range of heating rate β 1–50 K min?1.  相似文献   

10.
Interaction of ammonia with H-MCM-22 zeolite (Si/Al = 24.5) was investigated by temperature-programmed desorption technique in order to obtain information on thermodynamics of the process. Average activation energy for desorption of ammonia from Brønsted acid sites of H-MCM-22 zeolite was estimated from the data obtained under conditions varying in heating rate and also flow rate of carrier gas. It resulted in value of E d = 127 kJ mol?1 for heat rate variation method, whereas flow rate variation led to E d value of 111 kJ mol?1. Obtained E d values are compared with those reported in the literature for other zeolitic materials and discussed in the broader context of zeolite acidity. Comparison of E d values estimated here for H-MCM-22 zeolite with corresponding data for other protonic zeolites shows that H-MCM-22 displays mediocre/lower activation energy for ammonia compared with other high-silica zeolites.  相似文献   

11.
The thermodynamic activation parameters of hindered rotation of the CF3 group in the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF were determined from the temperature dependence of the EPR line widths and spin density distributions calculated by the U-B3LYP method in the 6-31+G* basis set. In the range 293 > T > 199 K, the activation energy of hindered rotation E F depends on the temperature and changes in the range 9.67 < E F < 18.95 kJ·mol?1; the changes in the activation enthalpy and entropy are 7.23 < ΔH < 17.30 kJ·mol?1 and ?53.45 < ΔS < ?11.37 J·(mol·K)?1, respectively. Based on the suggested method for evaluating the inner product of the g tensor and the tensor of anisotropic hfi with the 14N nucleus for nitrobenzene radical anions in the liquid state we calculated the correlation time and determined the activation energy of rotational diffusion of the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF, E r = 20.175±0.54 kJ·mol?1.  相似文献   

12.
The constant-volume combustion energy, △cU (DADE, s, 298.15 K), the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene (DADE) have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared (RSFT-IR) spectroscopy and T-jump/FTIR, respectively. The value of △cHm (DADE, s, 298.15 K) was determined as (-8518.09±4.59) j·g^-1. Its standard enthalpy of combustion, △cU (DADE, s, 298.15 K), and standard enthalpy of formation, △fHm (DADE, s, 298.15 K) were calculated to be (-1254.00±0.68) and (- 103.98±0.73) kJ·mol^-1, respectively The kinetic parameters (the apparent activation energy Ea and pre-exponential factor A) of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger's method and Ozawa's method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.  相似文献   

13.
Adsorption of the gadolinium from H2O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd3+ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd3+ on C100 from H2O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol?1, ΔS = ? 90.27 J mol?1 K?1, ?H = ? 50.93 kJ mol?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd3+ sorption on the C100 resin is reversible second order chemical reaction.  相似文献   

14.
A precision rotating-bomb combustion calorimeter (thermistor of which was constructed in the laboratory) was calibrated using benzoic acid with purity of 99.999 %. The combustion energy of phenanthroline monohydrate (phen·H2O) at 298.15 K was determined to be Δc U m θ  = ?(5,757.45 ± 2.53) kJ mol?1. Then, the standard enthalpy of combustion and the standard enthalpy of formation of phen·H2O were calculated to be Δc H m θ  = ?(5,759.93 ± 2.53) kJ mol?1 and Δf H m θ  = ?(391.34 ± 2.98) kJ mo1?1, respectively. Particularly, the effect of phen·H2O on growth and metabolism of Escherichia coli (E. coli) was also determined by a TAM air isothermal calorimeter at 37 °C. The thermokinetic parameters, including maximum heat output power (P max), growth rate constant (κ), generation times (t G), inhibitive rate (I), and half inhibition concentration (C I,50), were obtained. The results showed that phen·H2O possessed the bi-directional biological effect and Hormesis effect, which stimulated the growth of E. coli at lower concentration, but inhibited the growth at higher concentration. The half inhibition concentration C I,50 of phen·H2O was found to be 7.31 mg L?1.  相似文献   

15.
This study was designed to examine the interaction of histamine H2-receptor antagonist drug ranitidine (RTN) with human serum albumin by multi-spectroscopic methods. The experimental results showed the involvement of dynamic quenching mechanism which was further confirmed by lifetime spectral studies. The binding constants (K a) at three temperatures (288, 298, and 308 K) were 2.058 ± 0.020, 4.160 ± 0.010 and 6.801 ± 0.011 × 104 dm3 mol?1, respectively, and the number of binding sites (m) were 1.169, respectively; thermodynamic parameters ΔH 0 (44.152 ± 0.047 kJ mol?1), ΔG 0 (?26.214 ± 0.040 kJ mol?1), and ΔS 0 (236.130 ± 0.025 J K?1 mol?1) were calculated. The distance r between donor and acceptor was obtained (r = 3.40 nm) according to the Förster theory of non-radiative energy transfer. Synchronous fluorescence, CD, AFM and 3D fluorescence spectral results revealed the changes in secondary structure of the protein upon interaction with RTN. A molecular modeling study further confirmed the binding mode obtained by the experimental studies.  相似文献   

16.
PVA functionalized with vinylphosphonic acid was prepared as a new adsorbent for uranyl (VI) adsorption from aqueous solutions. The vinylphosphonic acid was cografted onto PVA fibers by preirradiation grafting technique. The adsorbent were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorbent was observed to possess a fibrous structure and was bonded with phosphonic acid groups successfully. The adsorbent was used for the adsorption of low levels uranyl (VI) ions from aqueous solutions. The influence of analytical parameters including pH, adsorption time, amount of adsorbent, metal ion concentration, and temperature were investigated on the recovery of uranyl (VI) ion in aqueous solution. The maximum adsorption capacity (32.1 mg g?1) and fast equilibrium time (30 min) were achieved at pH of 4.5 at room temperature. Thermodynamic parameters (ΔH° = 2.695 kJ mol?1; ΔS° = 31.15 J mol?1 K?1; ΔG° = ?6.748 kJ mol?1) show the adsorption of an exothermic process and spontaneous nature, respectively. The possible coordination mechanism was illustrated. Adsorption and desorption coexist in aqueous solutions and then the system becomes equilibrium.  相似文献   

17.
The non-isothermal experiments of limestone decomposition at multi-heating rates in O2/N2 and O2/CO2 atmospheres were studied using thermogravimetry. The limestone decomposition kinetic model function, kinetic parameters of apparent activation energy (E), and pre-exponential factor (A) were evaluated by Bagchi and Malek method. The results shown that in 20 % O2/80 % N2 atmosphere, the limestone decomposed slowly following the contracting sphere volume model controlled by boundary reaction (spherical symmetry) in two stages, and the E increased by about 50 kJ mol?1 in the second decomposition stage. But in 20 % O2/80 % CO2 atmosphere, the presence of high-concentration CO2 significantly inhibited the limestone decomposition, and made the decomposition process occur at high temperature with a rapid rate; the decomposition kinetics was divided into three stages, the first stage was an accelerated decomposition process following the Mampel Power law model with the exponential law equation, the second stage followed the nth order chemical reaction model as an αt deceleration process, and the third stage belonged to the random nucleation and nuclei growth model with the Avrami–Erofeev equation. And with the heating rate increasing, the reaction order n showed a slight rise tendency. The E was about 1,245 kJ mol?1 in 20 % O2/80 % CO2 atmosphere, but was only about 175 kJ mol?1 in 20 % O2/80 % N2 atmosphere. The E and A increased markedly in the O2/CO2 atmosphere.  相似文献   

18.
In this work, the crystallization process of a SiO2–3CaO·P2O5–MgO glass was studied by non-isothermal measurements using differential thermal analysis carried out at various heating rates. X-ray diffraction at room and high temperature was used to identify and follow the evolution of crystalline phases with temperature. The activation energy associated with glass transition, (E g), the activation energy for the crystallization of the primary crystalline phase (E c), and the Avrami exponent (n) were determined under non-isothermal conditions using different equations, namely from Kissinger, Matusita & Sakka, and Osawa. A complex crystallization process was observed with associated activation energies reflecting the change of behavior during in situ crystal precipitation. It was found that the crystallization process was affected by the fraction of crystallization, (x), giving rise to decreasing activation energy values, E c(x), with the increase of x. Values ranging from about 580 kJ mol?1 for the lower crystallized volume fraction to about 480 kJ mol?1 for volume fractions higher than 80 % were found. The Avrami exponents, calculated for the crystallization process at a constant heating rate of 10 °C min?1, increased with the crystallized fraction, from 1.6 to 2, indicating that the number of nucleant sites is temperature dependent and that crystals grow as near needle-like structures.  相似文献   

19.
The thermal and kinetic studies of epoxidized natural rubber (ENR) and its polymer electrolytes, LiX/ENR PEs, (where X = ClO 4 ? , CF3SO 3 ? , COOCF 3 ? , I?, and BF 4 ? ) were carried out using thermogravimetric analysis at different heating rates. The thermal behaviors for LiX/ENR PEs are closely related to the morphology and interactions between the LiX and ENR chains. The LiCF3SO3, LiCOOCF3, and LiI form pseudo-crosslinking within the ENR; their thermal behavior resembled purified ENR. The LiClO4 tends to form aggregates within the ENR. This phenomenon has promoted a much earlier decomposition of epoxide in the ENR. The occurrence of ring-opening and complexation or cross-linking reactions in and between the ENR chains in the LiBF4/ENR has produced a thermally stable macrostructure. The activation energy for the thermal degradation (E d) of purified ENR was 239.8 and 239.9 kJ mol?1 using Kissinger and FWO methods, respectively. According to the Coats–Redfern method, the degradation mechanism of purified ENR follows the F1 type model, while the Criado method revealed that the degradation starts with F1 followed by D3 type models. The E d for LiX/ENR (X = COOCF 3 ? , CF3SO 3 ? , I?, and BF 4 ? ) PE’s obtained via the Kissinger method are 258.5, 257.0, 251.0, and 198.9 kJ mol?1, respectively, and the corresponding E d values obtained by FWO are 236.0, 223.6, 349.7, and 206.6 kJ mol?1, respectively. The degradation of ENR in these PEs followed the D3 type model. However, for LiClO4/ENR, the presence of two distinct degradations of ENR gave two E d values. These are 174.5 and 234.7 kJ mol?1 using Kissinger and 117.8 and 293.6 kJ mol?1 using FWO method. The degradation mechanism of ENR in the LiClO4/ENR PE was similar to purified ENR that is F1 followed by D3 type models.  相似文献   

20.
In this work, the interaction of memantine with human serum albumin (HSA) immobilized on porous silica particles was studied using a biochromatographic approach. The determination of the enthalpy change at different pH values suggested that the protonated group in the memantine–HSA complex exhibits a heat protonation with a magnitude around 65 kJ mol?1. This value agrees with the protonation of a guanidinium group, and confirmed that an arginine group may become protonated in the memantine–HSA complex formation. The thermodynamic data showed that memantine–HSA binding, for low temperature (<293 K), is dominated by a positive entropy change. This result suggests that dehydration at the binding interface and charge–charge interactions contribute to the memantine–HSA complex formation. Above 293 K, the thermodynamic data ΔH and ΔS became negative due to van der Waals interactions and hydrogen bonding which are engaged at the complex interface. The temperature dependence of the free energy of binding is weak because of the enthalpy–entropy compensation caused by a large heat capacity change, ΔC p = ? 3.79 kJ mol?1 K?1 at pH = 7. These results were used to determine the potential binding site of this drug on HSA.  相似文献   

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