Enthalpies and temperatures of fusion have been measured by differential scanning calorimetry for urea and a number of its mono- and di-alkyl derivatives. Enthalpies obtained are: urea, 14.79 kj mol−1; monomethylurea, 15.75 kJ mol−1 ; monoethylurea, 13.94 kJ mol−1 ; monopropylurea, 14.63 kJ mol−1 ; monoisopropylurea, 17.40 kJ mol−1 ; monobutylurea, 14.55 kJ mol−1 ; monotertbutylurea, 33.13 kJ mol−1 ; dimethyl-1,1 urea, 29.61 kJ mol−1 ; dimethyl-1,3 urea, 13.62 kJ mol−1; diethyl-1,1 urea, 16/78 kJ mol−1 ; diethyl-1,3 urea, 12.46 kJ mol−1 ; dibutyl-1,3 urea, 14.87 kJ mol−1; trimethyl-1,1,3 urea, 14.30 kJ mol−1. Entropies of fusion have been derived from the experimental results.By temperature scanning starting from r.t. some solid-to-solid transitions for four alkylureas have also been detected, all hitherto unreported. Temperatures and enthalpies of transition are: for monoisopropylurea, 375.5 K and 2.31 kJ mol −1 ; for monobutylurea (two transitions), 313.1 K and 7.02 kJ mol−1 , 344.9 K and 0.88 kJ mol−1 ; for diethyl-1,3 urea, 339.4 K and 1.87 kJ mol−1 ; for dibutyl-1,3 urea, 311.5 K and 11.10 kJ mol−1. 相似文献
The dispersion polymerizations of styrene (St) and methyl methacrylate (MMA) initiated by poly(oxyethylene) macroinimer (PEO-MIM) in ethanol/water were investigated at 50, 60 and 80°C. The polymerisation rate vs. conversion dependence was described by with a maxim at the beginning of polymerisation. Polymerization was faster with MMA than with St. The limiting conversion was inversely proportional to temperature and was much more pronounced with St. The rate of polymerization increased with temperature. The overall initial activation energy increased with conversion and reached value ca. 25 kJ.mol−1 for MMA and 50 kJ.mol−1 for styrene at ca. 60% conversion. The particle size was observed to decrease with increasing the macroinimer concentration. The polymer dispersions were unstable and a large amount of coagulum appeared during the polymerisation especially in the styrene-containing reaction system. 相似文献
The sublimation enthalpies of monophenylurea (MPhU) and diphenyl-1,3 urea (1,3-DPhU) have been derived from the dependence of their vapour pressures on temperature, as measured by the torsion-effusion method. Values obtained are: 136 kj mol−1 for MPhU and 152 kJ mol−1 for 1,3-DPhU, where the estimated errors are comprised within 6 kJ mol−1Enthalpies and temperatures of fusion have been measured by differential scanning calorimetry, leading to 23.7 kJ mol−1 and 420.6 K for MPhU, and 34.6 kJ mol−1 and 512 K for 1,3-DPhU. Poor reproducibility of results for 1,3-DPhU seems be due to the beginning of decomposition. No solid-to-solid transitions have been revealed from r.t. to fusion for both compounds. 相似文献
Summary: An advanced isoconversional method has been applied to determine the effective activation energies (E) for the glass transition in polystyrene (PS), poly(ethylene terephthalate) (PET), and boron oxide (B2O3). The values of E decrease from 280 to 120 kJ · mol−1 in PS, from 1 270 to 550 kJ mol−1 in PET, and from 290 to 200 kJ mol−1 in B2O3. It is suggested that a significant variation in E should be observed for the fragile glasses that typically include polymers.
Variation in the effective activation energy of PS, PET, and B2O3 with temperature. 相似文献
In this paper, the kinetics and mechanism of gold nanoparticles formation during the redox reaction between [AuCl4]− complex and l ‐ascorbic acid under different conditions were described. It was also shown that reagent concentration, chloride ions, and pH influence kinetics of nucleation and growth. To establish rate constants of these stages, the model of Finke and Watzky was applied. From Arrhenius and Eyring dependencies, the values of activation energy (22.5 kJ mol−1 for the nucleation step and 30.3 kJ mol−1 for the growth step), entropy (about −228 J K−1 mol−1 for the nucleation step and −128 J K−1 mol−1 for the growth step), and enthalpy (19.8 kJ mol−1 for nucleation and 27.8 kJ mol−1 for particles growth) were determined. It was also shown that the disproporationation reaction had influence on the rate of nanoparticles formation and may have impact on final particles morphology. 相似文献
The effect on the diffusivity of oxygen of vanadium additions to niobium was investigated by a diffusion couple technique. The addition of vanadium to niobium results in an increase of the activation energy for oxygen diffusion from 107 kJ mol−1 for oxygen in niobium to 176 ± 9 kJ mol−1 for the Nb-0.5at.%V alloy and to 194 ± 9 kJ mol−1 for the Nb-10at.%V alloy. This increase in the activation energy is attributed to the trapping of oxygen by vanadium atoms. Applying Kirchheim's trapping model and the results of internal friction measurements, trapping energies of about −64 and −49 kJ mol−1 were obtained for the Nb-0.5at.%V and the Nb-10at.%V alloys respectively. 相似文献
A new method for the simultaneous determination of the kinetic order and activation energy for atom release under isothermal condition in a graphite furnace has been developed. Tungsten wire probe atomization was employed to examine the validity of the present method. By means of this model, the kinetic parameters for the atomization of Bi, Ge, Pb and Mn at constant temperatures were successfully determined. The values of the kinetic order and activation energy were found to be 0.67 ± 0.01 and 302 ± 8 kJ mol−1 for Bi, 1.01 ± 0.08 and 109 ± 2 kJ mol−1 for Ge, 0.46 ± 0.01 and 159 ± 2 kJ mol−1 for Pb and 0.97 ± 0.03 and 372 ± 5 kJ mol−1 for Mn, respectively. The atomization mechanism for these four elements from the tungsten probe surface was also discussed. 相似文献
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
This paper studies the effect of molecular mass on the melting temperature, enthalpy and entropy of hydroxy-terminated poly(ethylene oxide) (PEO). It aims to correlate the thermal behaviour of PEO polymers and their variation of molecular mass (MW). Samples ranging from 1500 to 200,000 isothermally treated at 373 K during 10 min, were investigated using DSC and Hot Stage Microscopy (HSM). On the basis of DSC and HSM results, melting temperatures were determined, and melting enthalpies and entropies were calculated. Considering the melting temperatures, it was found that the maximum or critical value of MW was found around 4000, and then these remain almost constant. This behaviour was interpreted assuming that lower MW fractions (MW<4000) crystallize in the form of extended chains and higher MW fractions (MW>4000), as folded chains. The melting enthalpies showed a scattering effect at least up to MW 35,000. It was difficult to obtain any relationship between melting enthalpies in J g–1 and MW. These variations seem to be of statistical nature. Corrected enthalpy data on a molar basis (kJ mol–1) exhibited a linear relationship with MW. Considering the solid—liquid equilibrium, the melting entropies (in kJ mol–1) were calculated. These values were more negative as compared with molar enthalpy increases. It was explained because the changes in melting temperatures are much smaller than those observed in the enthalpy values. Linear relationship between enthalpies andentropies as a function of MW was deduced.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
The Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic model was developed for acetylation of glycerol over highly stable and active 2 M SO42−/γ‐Al2O3 catalyst. The apparent reaction rate constants were determined by numerically solving the differential rate equations using ode23 tool in MATLAB coupled with the genetic algorithm optimization technique. The estimated rate constants were used to obtain the activation energy and pre‐exponential factor by using the Arrhenius equation. The estimated activation energy for direct acetylation of glycerol to monoacetylglycerol and diacetylglycerol was 7.2 kJ mol−1, for acetylation of monoacetylglycerol to diacetylglycerol was 37.1 kJ mol−1, and for acetylation of diacetylglycerol to triacetylglycerol was 26.6 kJ mol−1, respectively. 相似文献
Substitution reactions of a Cl− ligand in [SnCl2(tpp)] (tpp=5,10,15,20‐tetraphenyl‐21H,23H‐porphinato(2−)) by five organic bases i.e., butylamine (BuNH2), sec‐butylamine (sBuNH2), tert‐butylamine (tBuNH2), dibutylamine (Bu2NH), and tributylamine (Bu3N), as entering nucleophile in dimethylformamide at I=0.1M (NaNO3) and 30–55° were studied. The second‐order rate constants for the substitution of a Cl− ligand were found to be (36.86±1.14)⋅10−3, (32.91±0.79)⋅10−3, (22.21±0.58)⋅10−3, (19.09±0.66)⋅10−3, and (1.36±0.08)⋅10−3 M −1s−1 at 40° for BuNH2, tBuNH2, sBuNH2, Bu2NH, and Bu3N, respectively. In a temperature‐dependence study, the activation parameters ΔH≠ and ΔS≠ for the reaction of [SnCl2(tpp)] with the organic bases were determined as 38.61±4.79 kJ mol−1 and −150.40±15.46 J K−1mol−1 for BuNH2, 40.95±4.79 kJ mol−1 and −143.75±15.46 J K−1mol−1 for tBuNH2, 30.88±2.43 kJ mol−1 and −179.00±7.82 J K−1mol−1 for sBuNH2, 26.56±2.97 kJ mol−1 and −194.05±9.39 J K−1mol−1 for Bu2NH, and 39.37±2.25 kJ mol−1 and −174.68±7.07 J K−1 mol−1 for Bu3N. From the linear rate dependence on the concentration of the bases, the span of k2 values, and the large negative values of the activation entropy, an associative (A) mechanism is deduced for the ligand substitution. 相似文献
The sublimation enthalpies of bis(2,4-pentanedionato)oxovanadium(IV) and tetrakis(2,4-pentanedionato)zirconium(IV) have been determined by differential scanning calorimetry as 140.7 ± 4.0 and 132.0 ± 6.8 kJ mol−1, respectively. The fusion enthalpy of the latter complex has also been determined as 33.68 ± 2.5 kJ mol−1. A summary of “selected” sublimation enthalpy data for first-row transition metal acetylacetonate complexes is included. 相似文献
Compounds (RO)2 P(:S)SH, RPri, Bun, and Octn, exhibit rotational isomerism about PO and PS bonds. Temperature-dependence studies of band intensities indicate values of ΔH for the equilibria between isomers to be 2.5 kJ mol−1, RPri; 3.0 kJ mol−1, RBun; and ∼4.5 kJ mol−1, ROctn. 相似文献