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1.
The intermediate and LS-coupling schemes for the free lanthanide ions $\text{ Pr }^{3+}$ Pr 3 + and $\text{ Tm }^{3+}$ Tm 3 + have been compared by the matrix elements of the tensor operator ${{\varvec{U}}}^{({\varvec{k}})}, \text{ k } = 2, 4, 6$ U ( k ) , k = 2 , 4 , 6 . The necessary eigenvectors and eigenvalues have been computed with the aid of four parameters, $\text{ F }_{2}, \text{ F }_{4}, \text{ F }_{6}$ F 2 , F 4 , F 6 , and $\zeta _{4\mathrm{f}}$ ζ 4 f , known from free-ion spectra of the same ions. It has been found that both coupling types for each ion lead to close values of ${\vert }{{\varvec{U}}}^{({\varvec{k}})}{\vert }^{2}$ | U ( k ) | 2 only for transitions from the ground level to certain lower-lying energy levels within the $4\text{ f }^\mathrm{N}$ 4 f N configuration.  相似文献   

2.
The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn2+, Tl+, Hg2+ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn2+, Hg2+ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations, but in the case of Tl+ cation, a 1:2 [M:L2] complex is formed in most binary solutions. The thermodynamic parameters ( $ \Delta {\text{H}}^{ \circ }_{{\text{c}}} $ and $ \Delta {\text{S}}^{ \circ }_{{\text{c}}} $ ) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logKf) of these complexes with the composition of AN/DMF binary solutions. The influence of the $ {\text{ClO}}^{ - }_{{\text{4}}} $ , $ {\text{NO}}^{ - }_{{\text{3}}} $ and $ {\text{Cl}}^{ - } $ anions on the stability constant of (18C6-Na+) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na+) complex in the presence of the anions increases in order: $ {\text{ClO}}^{ - }_{{\text{4}}} $  >  $ {\text{NO}}^{ - }_{{\text{3}}} $  >  $ {\text{Cl}}^{ - } $ .  相似文献   

3.
A three-step method to determine the eutectic composition of a binary or ternary mixture is introduced. The method consists in creating a temperature–composition diagram, validating the predicted eutectic composition via differential scanning calorimetry and subsequent T-History measurements. To test the three-step method, we use two novel eutectic phase change materials based on \(\mathrm{Zn}(\hbox {NO}_3)_2\cdot 6\mathrm{H}_{2}{\mathrm O}\) and \(\mathrm{NH}_4\mathrm{NO}_3\)   respectively \(\mathrm{Mn}(\hbox {NO}_3)_2\cdot 6\mathrm{H}_{2}{\hbox {O}}\) and \(\mathrm{NH}_4\mathrm{NO}_3\) with equilibrium liquidus temperatures of 12.4 and 3.9  \(\,^{\circ }\mathrm {C}\) respectively with corresponding melting enthalpies of 135 J \(\mathrm{g}^{-1}\) (237 J \(\mathrm{cm}^{-3}\) ) respectively 133 J \(\mathrm{g}^{-1}\) (225 J \(\mathrm{cm}^{-3}\) ). We find eutectic compositions of 75/25 mass% for \(\mathrm{Zn}(\hbox {NO}_3)_2\cdot \mathrm{6H}_{2}{\mathrm{O}}\) and \(\mathrm{NH}_4\mathrm{NO}_3\) and 73/27 mass% for \(\mathrm{Mn}(\hbox {NO}_3)_2\cdot 6\mathrm{H}_{2}{\mathrm{O}}\) and \(\mathrm{NH}_4\mathrm{NO}_3\) . Considering a temperature range of 15 K around the phase change, a maximum storage capacity of about 172 J \(\mathrm{g}^{-1}\) (302 J \(\mathrm{cm}^{-3}\) ) respectively 162 J \(\mathrm{g}^{-1}\) (274 J \(\mathrm{cm}^{-3}\) ) was determined for \(\mathrm{Zn}(\hbox {NO}_3)_2\cdot \mathrm{6H}_{2}{\mathrm{O}}\) and \(\mathrm{NH}_4\mathrm{NO}_3\) respectively \(\mathrm{Mn}(\hbox {NO}_3)_2\cdot \mathrm{6H}_{2}{\mathrm{O}}\) and \(\mathrm{NH}_4\mathrm{NO}_3\) .  相似文献   

4.
The energies of combustion of chromone-3-carboxylic acid (C3CA), 6-methylchromone-2-carboxylic acid (6MCC), and 6-methyl-4-chromanone (6M4C) were determined using an isoperibolic micro-combustion calorimeter. The calorimeter used in the present work has been assembled, calibrated, and tested in our laboratory with the desired results. Prior to the measurement of the energies of combustion, the purities, heat capacities (C p), fusion temperatures (T fus), and enthalpies of melting (Δfus H) for each compound were determined by differential scanning calorimetry. The values of the energies of combustion were used to derive standard molar enthalpies of combustion ( \( \Delta _{{\text{c}}} H_{{\text{m}}}^{\circ } \) ) and standard molar enthalpies of formation ( \( \Delta _{{\text{f}}} H_{{\text{m}}}^{\circ } \) ) in the crystalline phase at T = 298.15 K. The values found for the \( \Delta _{{\text{f}}} H_{{\text{m}}}^{\circ } \) of C3CA, 6MCC, and 6M4C were ?(619.5 ± 2.6), ?(656.2 ± 2.2), and ?(308.9 ± 3.0) kJ mol?1, respectively.  相似文献   

5.
Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. In this study, the selective uptake of lighter component during liquid phase adsorption of C \(_{14}\) /C \(_{15}\) and C \(_{15}\) /C \(_{16}\) n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand-canonical Monte Carlo molecular simulation technique and a coarse-grained siting analysis. The simulations are conducted under conditions of low and intermediate levels of loading. The siting pattern of the adsorbates inside the zeolite pores explain the selectivity as seen in experiments.  相似文献   

6.
Fourier transform infrared spectroscopy of \(\hbox {CH}_{4}/\hbox {N}_{2}\) and \(\hbox {C}_{2}\hbox {H}_{m}/\hbox {N}_2\) ( \(m = 2, 4, 6\) ) gas mixtures in a medium pressure (300 mbar) dielectric barrier discharge was performed. Consumption of the initial gas and formation of other hydrocarbon and of nitrogen-containing HCN and \(\hbox {NH}_{3}\) molecules was observed. \(\hbox {NH}_{3}\) formation was further confirmed by laser absorption measurements. The experimental result for \(\hbox {NH}_{3}\) is at variance with simulation results.  相似文献   

7.
For some thirty hydrocarbons the s character of hybrids obtained by the application of the maximum overlap method have been correlated with C-H and C-C spin-spin coupling constants. The following relationships were obtained: $$J_{{\text{C}}^{{\text{13}}} - {\text{H}}} = 1079a_{{\text{CH}}}^{\text{2}} /(1 + S_{{\text{CH}}}^{\text{2}} ) - 54.9$$ , $$J_{{\text{C}}_{\text{1}}^{{\text{13}}} - {\text{C}}_{\text{2}}^{{\text{13}}} } = 1020.5a_{{\text{C}}_{\text{1}} }^2 a_{{\text{C}}_{\text{2}} }^{\text{2}} /(1 + S_{{\text{CC}}}^{\text{2}} ) - 8.2$$ . Here the coupling constants are expressed in cps units. In the calculation of the maximum overlap hybrids either the experimental bond lengths or a standard bond lengths were used. For the \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}}\) and \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}} \) coupling constants the standard deviations are 0.9 cps and 1.9 cps respectively. It has been suggested that the large additive constant in the \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}}\) correlation may be attributed to the ionic character of C-H bonds. A good agreement with the experimental data strongly supports the idea that the Fermi contact term and the hybridization are dominant factors in determining carbon-hydrogen and carbon-carbon spin-spin coupling constants across one bond, at least in hydrocarbons.  相似文献   

8.
In this paper we give a sense to the products $${{\left| x \right|^{(n - 2)/2} }} \cdot \frac{{\delta ^{(k - 1)} (x_0 + \left| x \right|)}} {{\left| x \right|^{(n - 2)/2} }}$$ and $\delta ^{(k - 1)} (x_0 - \left| x \right|) \cdot \delta ^{(k - 1)} (x_0 + \left| x \right|)$ . The first of them is a generalization of the product $${{\left| x \right|^{(n - 2)/2} }} \cdot \frac{{\delta (x_0 + \left| x \right|)}} {{\left| x \right|^{(n - 2)/2} }}{\text{ }}$$ given in [1, p. 158].  相似文献   

9.
The effects of bismuth (Bi), antimony (Sb) and strontium (Sr) additions on the characteristic parameters of the evolution of aluminium dendrites in a near eutectic Al–11.3Si–2Cu–0.4Fe alloy during solidification at different cooling rates (0.6–2 °C) were investigated by computer-aided cooling curve thermal analysis (CA-CCTA). Nucleation temperature ( $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ ) is defined with a new approach based on second derivative cooling curve. The results showed that $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ increased with increasing cooling rate but both the growth temperature ( $ T_{\text{G}}^{{\alpha {\text{ - Al}}}} $ ) and the coherency temperature (T DCP) decreased. Increase in the temperature difference for dendrite coherency ( $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} - T_{\text{DCP}} $ ) with increasing cooling rate indicate a wider range of temperature before the dendrite can impinge on each other and higher fraction solid ( $ f_{\text{S}}^{\text{DCP}} $ ). Additions of Bi, Sb and Sr to the base alloy produced only a minor effect on $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ . Additions of Bi and Sb resulted in an increase in fraction solid and an increase of 30 % in the value of $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} \, - \,T_{\text{G}}^{{\alpha {\text{ - Al}}}} $ to almost 13 °C.  相似文献   

10.
Tellurites of CuTeO3 and HgTeO3 are synthesized and their specific molar heat capacities are experimentally determined for the first time. The tellurites discussed in the present paper are used for preparation of optical glasses with special properties for optoelectronics, nuclear and power industries. The tellurites synthesized are prepared for chemical analysis, differential thermal analysis and X-ray analysis. The use of the tellurites studied is related to knowing their thermodynamic properties like specific molar heat capacity (C p,m), enthalpy \( \left( {\Delta_{{{\text {T}}^{\prime}}}^{\text{T}} H_{\text{m}}^{0} } \right), \) entropy \( \left( {\Delta_{{{\text {T}}^{\prime}}}^{\text{T}} S_{\text{m}}^{0} } \right) \) and Gibbs energy \( \left( { - \Delta_{{{\text {T}}^{\prime}}}^{\text{T}} G_{\text{m}}^{0} } \right) \) . The temperature dependences of their molar heat capacities are determined using the least squares method. The thermodynamic properties are calculated: entropy, enthalpy and Gibbs function.  相似文献   

11.
Grid graphs on the plane, torus and cylinder are finite 2-connected bipartite graphs embedded on the plane, torus and cylinder, respectively, whose every interior face is bounded by a quadrangle. Let \(k\) be a positive integer, a grid graph is \(k\) -resonant if the deletion of any \(i \le k\) vertex-disjoint quadrangles from \(G\) results in a graph either having a perfect matching or being empty. If \(G\) is \(k\) -resonant for any integer \(k \ge 1\) , then it is called maximally resonant. In this study, we provide a complete characterization for the \(k\) -resonance of grid graphs \(P_m\times P_n\) on plane, \(C_m\times C_n\) on torus and \(P_m\times C_n\) on cylinder.  相似文献   

12.
A pilot study involving screening measurements of gross alpha/beta activity concentration in drinking water was performed in 12 cities with the highest population density in Albania. The aim of this study was to develop a first insight regarding the radiological quality of drinking and bottled water supplies. The tap and bottled water samples investigated are acceptable for consumption, complying with the WHO recommendations for drinking water. The average gross alpha and beta activity concentrations were \( 36_{ - 18}^{ + 37} \) and \( 269_{ - 150}^{ + 337} \)  mBq/L, respectively in tap waters. While for bottled water the gross alpha and beta activities were respectively \( 39_{ - 23}^{ + 55} \) and \( 220_{ - 132}^{ + 336} \)  mBq/L. The data obtained can provide information for authorities regarding the quality of drinking water and a baseline for future contaminations.  相似文献   

13.
We investigated geometry, energy, ${\nu_{{\text{N--H}}}}$ harmonic frequencies, 14N nuclear quadrupole coupling tensors, and ${n_{\rm O}\to \sigma _{{\text{N--H}}}^\ast}$ charge transfer properties of (acetamide) n clusters, with n = 1 ? 7, by means of second-order Møller-Plesset perturbation theory (MP2) and DFT method. Dependency of dimer stabilization energies and equilibrium geometries on various levels of theory was examined. B3LYP/6-311++G** calculations revealed that for acetamide clusters, the average hydrogen-bonding energy per monomer increases from ?26.85 kJ mol?1 in dimer to ?35.12 kJ mol?1 in heptamer; i.e., 31% cooperativity enhancement. The n-dependent trend of ${\nu_{{\text{N--H}}}\,{and}\,^{14}}$ N nuclear quadrupole coupling values were reasonably correlated with cooperative effects in ${r_{{\text{N--H}}}}$ bond distance. It was also found that intermolecular ${n_{\rm O}\to \sigma_{{\text{N--H}}}^\ast}$ charge transfer plays a key role in cooperative changes of geometry, binding energy, ${\nu_{{\text{N--H}}}}$ harmonic frequencies, and 14N electric field gradient tensors of acetamide clusters. There is a good linear correlation between 14N quadrupole coupling constants, C Q (14N), and the strength of Fock matrix elements (F ij ). Regarding the ${n_{\rm O}\to \sigma_{{\text{N--H}}}^\ast}$ interaction, the capability of the acetamide clusters for electron localization, at the N–H· · ·O bond critical point, depends on the cluster size and thereby leads to cooperative changes in the N–H· · ·O length and strength, N–H stretching frequencies, and 14N quadrupole coupling tensors.  相似文献   

14.
The densities, ρ, refractive indices, n D, and ultrasonic speeds, u, of binary mixtures of acetonitrile (AN) with poly(ethylene glycol) 200 (PEG200), poly(ethylene glycol) 300 (PEG300) and poly(ethylene glycol) 400 (PEG400) were measured over the entire composition range at temperatures (298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. From the experimental data, the excess molar volumes, \( V_{\text{m}}^{\text{E}} \) , deviations in refractive indices, \( \Delta n_{\text{D}} \) , excess molar isentropic compressibility, \( K_{{s , {\text{m}}}}^{\text{E}} \) , excess intermolecular free length, \( L_{\text{f}}^{\text{E}} \) , and excess acoustic impedance, Z E, have been evaluated. The partial molar volumes, \( \overline{V}_{\text{m,1}} \) and \( \overline{V}_{\text{m,2}} \) , partial molar isentropic compressibilities, \( \overline{K}_{{s , {\text{m,1}}}} \) and \( \overline{K}_{{s , {\text{m,2}}}} \) , and their excess values over whole composition range and at infinite dilution have also been calculated. The variations of these properties with composition and temperature are discussed in terms of intermolecular interactions in these mixtures. The results indicate the presence of specific interactions among the AN and PEG molecules, which follow the order PEG200 < PEG300 < PEG400.  相似文献   

15.
Aperiodic oscillations in the sorption of hydrogen and deuterium in palladium have been observed. An expression relating the square of a function, with the derivative and integral with variable upper limit of the same function has been proved and proposed to be used as a base for a chaos-vs.-random test. The result of one “branch” of the test is a real number \(D \in [0,2]\) ; close to zero for the deterministic and smooth datasets, and approaching two for the random or discrete datasets. Another “branch” of the test, based on the same mathematical relation, produces two functions that appear to be convergent for deterministic and smooth datasets, but run totally divergent for random or discrete ones. The \(D\) -values yielded by deterministic time series, recorded in the periodic and quasiperiodic sorptions of H \(_{2}\) or D \(_{2}\) in Pd, are around 0.001. On the other hand, the databases that were presumably random or non-smooth yielded the test results from \(D= 0.2\) to \(D= 1.9\) . Against these benchmarks, the experimental, aperiodic oscillations scored around 0.003 in \(D\) , which is much closer to the deterministic than to a random manner.  相似文献   

16.
We have recently studied by quantum-chemical calculations some fifteen tetrahedral and octahedral molecules. These seemingly disparate numerical tabulations were, it was demonstrated, pulled together by comparison with model semiclassical scaling laws for (i) nuclear–nuclear repulsion energy at the equilibrium geometry and (ii) total energies likewise. Here, we again appeal to such model scaling predictions, but now for positive ions of SiH4. We then report Hartree-Fock equilibrium geometries and MP2 corrections. For ${{\rm SiH}_{4}^{+}}$ , we assumed the symmetry to be C2v , by analogy with ${{\rm CH}_{4}^{+}}$ for which experimental confirmation of this symmetry is available. Larger distortions, but still for C2v symmetry, are found from our quantum-chemical studies in the case of ${{\rm SiH}_{4}^{2+}}$ . But for ${{\rm SiH}_{4}^{3+}}$ there is a marked tendency to return to a configuration quite close to tetrahedral symmetry. But non-convergence is found for ${{\rm SiH}_{4}^{4+}}$ . Finally relations to the admittedly simplistic semiclassical geometry scaling predictions of Lawes and March are conjectured.  相似文献   

17.
The effects of adding an antagonistic salt, sodium tetraphenylborate ( \(\hbox {NaBPh}_4\) ), to a binary mixture of deuterated water and 2,6-dimethylpyridine were investigated by visual inspection, optical microscopy, and small-angle neutron scattering. With increasing salt concentration, the two-phase region shrinks. When the concentration of \(\hbox {NaBPh}_4\) is \(85\hbox { mmol}{\cdot} \hbox {L}^{-1}\) , a temperature-induced lamellar/disorder phase transition is observed at 338 K. These trends are similar to those observed for a mixture of water/3-methylpyridine/ \(\hbox {NaBPh}_4\) (Sadakane et al., Phys. Rev. Lett. 103, 167803 (2009)).  相似文献   

18.
The densities, ρ, speeds of sound, u, and heat capacities, (C P)mix, for binary 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + cyclopentanone or cyclohexanone (2) mixtures within temperature range (293.15–308.15 K) and excess molar enthalpies, H E, at 298.15 K have been measured over the entire composition range. The excess molar volumes, V E, excess isentropic compressibilities, \( \kappa_{\text{S}}^{\text{E}}, \) and excess heat capacities, \( C_{\text{P}}^{\text{E}}, \) have been computed from the experimental results. The V E, \( \kappa_{\text{S}}^{\text{E}} \) , H E, and \( C_{\text{P}}^{\text{E}} \) values have been calculated and compared with calculated values from Graph theory. It has been observed that V E, \( \kappa_{\text{S}}^{\text{E}} \) , H E, and \( C_{\text{P}}^{\text{E}} \) values were predicted by Graph theory compare well with their experimental values. The V E, \( \kappa_{\text{S}}^{\text{E}}, \) and H E thermodynamic properties have also been analyzed in terms of Prigogine–Flory–Patterson theory.  相似文献   

19.
The standard Gibbs energy of formation of Pr2TeO6 $ (\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)) $ was derived from its vapour pressure in the temperature range of 1,400–1,480 K. The vapour pressure of TeO2 (g) was measured by employing a thermogravimetry-based transpiration method. The temperature dependence of the vapour pressure of TeO2 over the mixture Pr2TeO6 (s) + Pr2O3 (s) generated by the incongruent vapourization reaction, Pr2TeO6 (s) = Pr2O3 (s) + TeO2 (g) + ½ O2 (g) could be represented as: $ { \log }\left\{ {{{p\left( {{\text{TeO}}_{ 2} ,\;{\text{g}}} \right)} \mathord{\left/ {\vphantom {{p\left( {{\text{TeO}}_{ 2} ,\;{\text{g}}} \right)} {{\text{Pa}} \pm 0.0 4}}} \right. \kern-0em} {{\text{Pa}} \pm 0.0 4}}} \right\} = 19. 12- 27132\; \left({\rm{{{\text{K}}}}/T} \right) $ . The $ \Updelta_{\text{f}} G^{^\circ } \;\left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} } \right) $ could be represented by the relation $ \left\{ {{{\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)} \mathord{\left/ {\vphantom {{\Updelta_{\text{f}} G^{^\circ } \left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} ,\;{\text{s}}} \right)} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}}} \right. \kern-0em} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}} \pm 5.0} \right\} = - 2 4 1 5. 1+ 0. 5 7 9 3\;\left(T/{\text{K}}\right) .$ Enthalpy increments of Pr2TeO6 were measured by drop calorimetry in the temperature range of 573–1,273 K and heat capacity, entropy and Gibbs energy functions were derived. The $ \Updelta_{\text{f}} H_{{298\;{\text{K}}}}^{^\circ } \;\left( {{ \Pr }_{ 2} {\text{TeO}}_{ 6} } \right) $ was found to be $ {{ - 2, 40 7. 8 \pm 2.0} \mathord{\left/ {\vphantom {{ - 2, 40 7. 8 \pm 2.0} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}}} \right. \kern-0em} {\left( {{\text{kJ}}\,{\text{mol}}^{ - 1} } \right)}} $ .  相似文献   

20.
The crystal structure of ethylenediamine dilauroleate was determined by X-ray crystallography. A thermochemical cycle was designed in accordance with Hess law. The enthalpy change of the synthesis reaction of ethylenediamine dilauroleate was determined to be $ \Updelta_{{\text{r}}} H_{{\text{m}}}^{\Uptheta } $ Δ r H m Θ  = ?(49.07 ± 0.11) kJ mol?1 by an isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the title compound was calculated to be $ \Updelta_{\text{f}} H_{\text{m}}^{\Uptheta } $ Δ f H m Θ  = ?(38.78 ± 0.43) kJ mol?1 by the designed thermochemical cycle, the enthalpies of dissolution and other auxiliary thermodynamic quantities.  相似文献   

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