首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The heat capacities (C p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at 350.426 K. The melting temperature (T m), the molar enthalpy (Δfus H m0), and the molar entropy (Δfus S m0) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol−1 and 51.676 J K−1 mol−1, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation. The thermodynamic functions (H T-H 298.15 and S T-S 298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU c(C6H8N2,cr)= −3500.15±1.51 kJ mol−1 and Δc H m0 (C6H8N2,cr)= −3502.64±1.51 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δr H m0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1.  相似文献   

2.
The copper(II) complex of 6-benzylaminopurine (6-BAP) has been prepared with dihydrated cupric chloride and 6-benzylaminopurine. Infrared spectrum and thermal stabilities of the solid complex have been discussed. The constant-volume combustion energy, Δc U, has been determined as −12566.92±6.44 kJ mol−1 by a precise rotating-bomb calorimeter at 298.15 K. From the results and other auxiliary quantities, the standard molar enthalpy of combustion, Δc H m θ, and the standard molar of formation of the complex, Δf H m θ, were calculated as −12558.24±6.44 and −842.50±6.47 kJ mol−1, respectively.  相似文献   

3.
The standard enthalpy of combustion of crystalline silver pivalate, (CH3)3CC(O)OAg (AgPiv), was determined in an isoperibolic calorimeter with a self-sealing steel bomb, Δc H 0 (AgPiv, cr)= −2786.9±5.6 kJ mol−1. The value of standard enthalpy of formation was derived for crystalline state: Δf H 0(AgPiv,cr)= −466.9±5.6 kJ mol−1. Using the enthalpy of sublimation, measured earlier, the enthalpy of formation of gaseous dimer was obtained: Δf H 0(Ag2Piv2,g)= −787±14 kJ mol−1. The enthalpy of reaction (CH3)3CC(O)OAg(cr)=Ag(cr)+(CH3)3CC(O)O.(g) was estimated, Δr H 0=202 kJ mol−1.  相似文献   

4.
Thermochemical studies on the thioproline   总被引:3,自引:0,他引:3  
The combustion energy of thioproline was determined by the precision rotating-bomb calorimeter at 298.15 K to be Δc U= –2469.30±1.44 kJ mol–1. From the results and other auxiliary quantities, the standard molar enthalpy of combustion and the standard molar enthalpy of formation of thioproline were calculated to be Δc H m θC4H7NO2S, (s), 298.15 K= –2469.92±1.44 kJ mol–1 and Δf H m θC4H7NO2S, (s), 298.15K= –401.33±1.54 kJ mol–1.  相似文献   

5.
A novel solid complex, formulated as Ho(PDC)3 (o-phen), has been obtained from the reaction of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol, which was characterized by elemental analysis, TG-DTG and IR spectrum. The enthalpy change of the reaction of complex formation from a solution of the reagents, ΔrHmθ (sol), and the molar heat capacity of the complex, cm, were determined as being –19.161±0.051 kJ mol–1 and 79.264±1.218 J mol–1 K–1 at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy change of complex formation from the reaction of the reagents in the solid phase, ΔrHmθ(s), was calculated as being (23.981±0.339) kJ mol–1 on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. The thermodynamics of reaction of formation of the complex was investigated by the reaction in solution at the temperature range of 292.15–301.15 K. The constant-volume combustion energy of the complex, ΔcU, was determined as being –16788.46±7.74 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHmθ, and standard enthalpy of formation, ΔfHmθ, were calculated to be –16803.95±7.74 and –1115.42±8.94 kJ mol–1, respectively.  相似文献   

6.
A solid complex Eu(C5H8NS2)3(C12H8N2) has been obtained from reaction of hydrous europium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen⋅H2O) in absolute ethanol. IR spectrum of the complex indicated that Eu3+ in the complex coordinated with sulfur atoms from the APDC and nitrogen atoms from the o-phen. TG-DTG investigation provided the evidence that the title complex was decomposed into EuS. The enthalpy change of the reaction of formation of the complex in ethanol, Δr H m θ(l), as –22.214±0.081 kJ mol–1, and the molar heat capacity of the complex, c m, as 61.676±0.651 J mol–1 K–1, at 298.15 K were determined by an RD-496 III type microcalorimeter. The enthalpy change of the reaction of formation of the complex in solid, Δr H m θ(s), was calculated as 54.527±0.314 kJ mol–1 through a thermochemistry cycle. Based on the thermodynamics and kinetics on the reaction of formation of the complex in ethanol at different temperatures, fundamental parameters, including the activation enthalpy (ΔH θ), the activation entropy (ΔS θ), the activation free energy (ΔG θ), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained. The constant-volume combustion energy of the complex, Δc U, was determined as –16937.88±9.79 kJ mol–1 by an RBC-II type rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m θ, and standard enthalpy of formation, Δf H m θ, were calculated to be –16953.37±9.79 and –1708.23±10.69 kJ mol–1, respectively.  相似文献   

7.
The low-temperature heat capacity C p,m of erythritol (C4H10O4, CAS 149-32-6) was precisely measured in the temperature range from 80 to 410 K by means of a small sample automated adiabatic calorimeter. A solid-liquid phase transition was found at T=390.254 K from the experimental C p-T curve. The molar enthalpy and entropy of this transition were determined to be 37.92±0.19 kJ mol−1 and 97.17±0.49 J K−1 mol−1, respectively. The thermodynamic functions [H T-H 298.15] and [S T-S 298.15], were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The standard molar enthalpy of combustion and the standard molar enthalpy of formation of the compound have been determined: Δc H m0(C4H10O4, cr)= −2102.90±1.56 kJ mol−1 and Δf H m0(C4H10O4, cr)= − 900.29±0.84 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity measurements.  相似文献   

8.
The standard (p 0=0.1 MPa) molar enthalpy of formation, Δf H 0 m, for crystalline N-phenylphthalimide was derived from its standard molar enthalpy of combustion, in oxygen, at the temperature 298.15 K, measured by static bomb-combustion calorimetry, as –206.0±3.4 kJ mol–1. The standard molar enthalpy of sublimation, Δg cr H 0 m , at T=298.15 K, was derived, from high temperature Calvet microcalorimetry, as 121.3±1.0 kJ mol–1. The derived standard molar enthalpy of formation, in the gaseous state, is analysed in terms of enthalpic increments and interpreted in terms of molecular structure.  相似文献   

9.
The energies of combustion in fluorine of gallium nitride and indium nitride in wurzite crystalline structure have been measured in a two-compartment calorimetric bomb, and new standard molar enthalpies of formation have been calculated: ΔfHm0(GaN(cr) 298.15 K)= –(163.7±4.2) kJ mol–1 and ΔfHm0(InN(cr) 298.15 K)= –(146.5±4.6) kJ mol–1 . Comparison with the recommended values of the ΔfHm0 nitrides from the literature is also presented.  相似文献   

10.
The constant-volume combustion energies of the lead salts of 2-hydroxy-3,5-dinitropyridine (2HDNPPb) and 4-hydroxy-3,5-dinitropyridine (4HDNPPb), ΔU c (2HDNPPb(s) and 4HDNPP(s)), were determined as –4441.92±2.43 and –4515.74±1.92 kJ mol–1 , respectively, at 298.15 K. Their standard enthalpies of combustion, Δc m H θ(2HDNPPb(s) and 4HDNPPb(s), 298.15 K), and standard enthalpies of formation, Δr m H θ(2HDNPPb(s) and 4HDNPPb(s), 298.15 K) were as –4425.81±2.43, –4499.63±1.92 kJ mol–1 and –870.43±2.76, –796.65±2.32 kJ mol–1 , respectively. As two combustion catalysts, 2HDNPPb and 4HDNPPb can enhance the burning rate and reduce the pressure exponent of RDX–CMDB propellant.  相似文献   

11.
The molar heat capacities of the room temperature ionic liquid 1-butylpyridinium tetrafluoroborate (BPBF4) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C p,m [J K−1 mol−1]=181.43+51.297X −4.7816X 2−1.9734X 3+8.1048X 4+11.108X 5 [X=(T−135)/55] for the solid phase (80–190 K), C p,m [J K−1 mol−1]= 349.96+25.106X+9.1320X 2+19.368X 3+2.23X 4−8.8201X 5 [X=(T−225)/27] for the glass state (198–252 K), and C p,m[J K−1 mol−1]= 402.40+21.982X−3.0304X 2+3.6514X 3+3.4585X 4 [X=(T−338)/52] for the liquid phase (286–390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BPBF4 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass transition of BPBF4 was observed at 194.09 K, the enthalpy and entropy of the glass transition were determined to be ΔH g=2.157 kJ mol−1 and ΔS g=11.12 J K−1 mol−1, respectively. The result showed that the melting point of the BPBF4 is 279.79 K, the enthalpy and entropy of phase transition were calculated to be ΔH m = 8.453 kJ mol−1 and ΔS m=30.21 J K−1 mol−1. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BPBF4 was determined to be Δc H m0 = −5451±3 kJ mol−1. The standard molar enthalpy of formation of BPBF4 was evaluated to be Δf H m0 = −1356.3±0.8 kJ mol−1 at T=298.150±0.001 K.  相似文献   

12.
Three samples of silicon dioxide were syhthesized and their surface areas were measured. A thermo-chemical cycle was designed to calculate the molar formation enthalpy. The molar formation enthalpy, Δf H mΦ, for three amorphous silica with the Langmuir surface area 198.0854, 25.1108 and 11.9821 m2 g−1 gave −895.52, −910.86 and −915.67 kJ mol−1, respectively. With the increasing surface area, the values of Δf H mΦ increased accordingly. The results suggest that the silica with larger surface area is more unstable. The wetting heat was also measured by adding the silica powder into water. With the rehydration of the more SiOH groups on the surface, the larger surface areas of silica lead to the more wetting heat. A smaller particle has the more unstable hydroxyl groups and surface energy.  相似文献   

13.
The solid-state coordination reactions of lanthanum chloride with alanine and glycine, and lanthanum nitrate with alanine have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L-1 HCl solvent of these three solid-solid coordination reactions have been measured using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies have been determined to be Δf H m θ[La(Ala)3Cl3·3H2O(s), 298.2 K]= -3716.3 kJ mol-1, Δf H m θ [La(Gly)3Cl3·5H2O(s), 298.2 K]= -4223.0 kJ mol-1 and Δf H m θ [La(Ala)4(NO3)3·H2O(s), 298.2 K]= -3867.57 kJ mol-1, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

14.
The standard molar enthalpy of formation Δf H m 0=–760±12 kJ for amorphous silicon nitride a-Si3N4 has been determined from fluorine combustion calorimetry measurements of the massic energy of the reaction: a-Si3N4(s)+6F2(g)=3SiF4(g)+2N2(g). This value combined with Δf H m 0= –828.9±3.4 kJ for a-Si3N4 indicates that determined for the first time molar enthalpy change for the transition from amorphous to α-crystalline form Δtrs H m 0=69±13 kJ is very evident, in spite of its large uncertainty range resulting from impurity corrections. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

15.
The two complexes, [RE(Gly)4(Im)(H2O)](ClO4)3(s)(RE = Eu, Sm), have been synthesized and characterized. The standard molar enthalpies of reaction for the following reactions, RECl3·6H2O(s)+4Gly(s)+Im(s)+3NaClO4(s) = =[RE(Gly)4(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l), were determined by solution-reaction colorimetry. The standard molar enthalpies of formation of the two complexes at T = 298.15 K were derived as Δf H mΘ {Eu(Gly)4(Im)(H2O)}(ClO4)3(s)} = = −(3396.6±2.3) kJ mol−1 and Δf H mΘ {Sm(Gly)4(Im)(H2O)}(ClO4)3(s)} = −(3472.7±2.3) kJ mol−1, respectively.  相似文献   

16.
The novel ternary solid complex Gd(C5H8NS2)3(C12H8N2) has been obtained from the reaction of hydrous gadolinium chloride, ammonium pyrrolidinedithiocarbamate (APDC), and 1,10-phenanthroline (o-phen · H2O) in absolute ethanol. The complex was described by an elemental analysis, TG-DTG, and an IR spectrum. The enthalpy change of the complex formation reaction from a solution of the reagents, Δr H m ϑ (sol), and the molar heat capacity of the complex, c m , were determined as being − 15.174 ± 0.053 kJ/mol and 72.377 ± 0.636 J/(mol K) at 298.15 K by using an RD496-III heat conduction microcalorimeter. The enthalpy change of a complex formation from the reaction of the reagents in a solid phase, Δr H m ϑ (s), was calculated as being 52.703 ± 0.304 kJ/mol on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. The thermodynamics of the formation reaction of the complex was investigated by the reaction in solution. Fundamental parameters, the activation enthalpy (ΔH ϑ ), the activation entropy (ΔS ϑ ), the activation free energy (ΔG ϑ ), the apparent reaction rate constant (k), the apparent activation energy (E), the preexponential constant (A), and the reaction order (n), were obtained by the combination of the thermochemical data of the reaction and kinetic equations, with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, Δc U, was determined as being −17588.79 ± 8.62 kJ/mol by an RBC-II type rotatingbomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δc H m ϑ , and standard enthalpy of formation, Δf H m ϑ , were calculated to be −17604.28 ± 8.62 and −282.43 ± 9.58 kJ/mol, respectively. The text was submitted by the authors in English.  相似文献   

17.
Heat capacity and enthalpy increments of calcium niobates CaNb2O6 and Ca2Nb2O7 were measured by the relaxation time method (2–300 K), DSC (260–360 K) and drop calorimetry (669–1421 K). Temperature dependencies of the molar heat capacity in the form C pm=200.4+0.03432T−3.450·106/T 2 J K−1 mol−1 for CaNb2O6 and C pm=257.2+0.03621T−4.435·106/T 2 J K−1 mol−1 for Ca2Nb2O7 were derived by the least-squares method from the experimental data. The molar entropies at 298.15 K, S m0(CaNb2O6, 298.15 K)=167.3±0.9 J K−1 mol−1 and S m0(Ca2Nb2O7, 298.15 K)=212.4±1.2 J K−1 mol−1, were evaluated from the low temperature heat capacity measurements. Standard enthalpies of formation at 298.15 K were derived using published values of Gibbs energy of formation and presented heat capacity and entropy data: Δf H 0(CaNb2O6, 298.15 K)= −2664.52 kJ molt-1 and Δf H 0(Ca2Nb2O7, 298.15 K)= −3346.91 kJ mol−1.  相似文献   

18.
A brown and transparent ionic liquid (IL), [C4mim][FeCl4], was prepared by mixing anhydrous FeCl3 with 1-butyl-3-methylimidazolium chloride ([C4mim][Cl]), with molar ratio 1/1 under stirring in a glove box filled with dry argon. The molar enthalpies of solution, Δs H m, of [C4mim][FeCl4], in water with various molalities were determined by a solution-reaction isoperibol calorimeter at 298.15 K. Considering the hydrolyzation of anion [FeCl4] in dissolution process of the IL, a new method of determining the standard molar enthalpy of solution, Δs H m0, was put forward on the bases of Pitzer solution theory of mixed electrolytes. The values of Δs H m0 and the sum of Pitzer parameters: and were obtained, respectively. In terms of thermodynamic cycle and the lattice energy of IL calculated by Glasser’s lattice energy theory of ILs, the dissociation enthalpy of anion [FeCl4], ΔH dis≈5650 kJ mol−1, for the reaction: [FeCl4](g)→Fe3+(g)+4Cl(g), was estimated. It is shown that large hydration enthalpies of ions have been compensated by large the dissociation enthalpy of [FeCl4] anion, Δd H m, in dissolution process of the IL.  相似文献   

19.
The relative enthalpies, ΔHo (0) and ΔHo (298.15), of stationary points (four minimum and three transition structures) on the O3H potential energy surface were calculated with the aid of the G3MP2B3 as well as the CCSD(T)–CBS (W1U) procedures from which we earlier found mean absolute deviations (MAD) of 3.9 kJ mol−1 and 2.3 kJ mol−1, respectively, between experimental and calculated standard enthalpies of the formation of a set of 32 free radicals. For CCSD(T)-CBS (W1U) the well depth from O3 + H to trans-O3H, ΔHowell(298.15) = −339.1 kJ mol−1, as well as the reaction enthalpy of the overall reaction O3 + H→O2 + OH, ΔrHo(298.15) = −333.7 kJ mol−1, and the barrier of bond dissociation of trans-O3H → O2 + OH, ΔHo(298.15) = 22.3 kJ mol−1, affirm the stable short-lived intermediate O3H. In addition, for radicals cis-O3H and trans-O3H, the thermodynamic functions heat capacity Cop(T), entropy So (T), and thermal energy content Ho(T) − Ho(0) are tabulated in the range of 100 − 3000 K. The much debated calculated standard enthalpy of the formation of the trans-O3H resulted to be ΔfHo(298.15) = 31.1 kJ mol −1 and 32.9 kJ mol −1, at the G3MP2B3 and CCSD(T)-CBS (W1U) levels of theory, respectively. In addition, MR-ACPF-CBS calculations were applied to consider possible multiconfiguration effects and yield ΔfHo(298.15) = 21.2 kJ mol −1. The discrepancy between calculated values and the experimental value of −4.2 ± 21 kJ mol−1 is still unresolved. Note added in proof: Yu-Ran Luo and J. Alistair Kerr, based on the discussion in reference 12, recently presented an experimental value of ΔfHo(298.15) = 29.7 ± 8.4 kJ mol−1 in the 85th edition of the CRC Handbook of Chemistry and Physics (in progress).  相似文献   

20.
Summary A ternary solid complex Gd(Et2dtc)3(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, ΔrHΘm(l), was determined as (-11.628±0.0204) kJ mol-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, ΔrHΘm(s), was calculated as (145.306±0.519) kJ mol-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (ΔrHΘ), the activation entropy (ΔrSΘ), the activation free energy (ΔrGΘ) and the enthalpy (ΔrHΘ), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, ΔcU, was determined as (-18673.71±8.15) kJ mol-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHΘm, and standard enthalpy of formation, ΔfHΘm, were calculated to be (-18692.92±8.15) kJ mol-1 and (-51.28±9.17) kJ mol-1, respectively.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号