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1.
By analyzing the topological structures of the three types of icosahedral fullerenes: (1) , (2) and (3) k,\;h,k = 1,2,...} \right)$$ " align="middle" border="0"> , we have obtained theoretically the 13C NMR spectra with natural abundance for 13C of all the icosahedral (Ih and I) fullerenes.  相似文献   

2.
The oxidation of H2NOH is first-order both in [NH3OH+] and [AuCl4 ]. The rate is increased by the increase in [Cl] and decreased with increase in [H+]. The stoichiometry ratio, [NH3OH+]/[AuCl4 ], is 1. The mechanism consists of the following reactions.
The rate law deduced from the reactions (i)–(iv) is given by Equation (v) considering that [H+] K a.
The reaction (iii) is a combination of the following reactions:
The activation parameters for the reactions (ii) and (iii) are consistent with an outer-sphere electron transfer mechanism.  相似文献   

3.
Summary The oxidation of H2O2 by [W(CN)8]3– has been studied in aqueous media between pH 7.87 and 12.10 using both conventional and stopped-flow spectrophotometry. The reaction proceeds without generation of free radicals. The experimental overall rate law, , strongly suggests two types of mechanisms. The first pathway, characterized by the pH-dependent rate constant k s, given by , involves the formation of [W(CN)8· H2O2]3–, [W(CN)8· H2O2·W(CN)8]6– and [W(CN)8· HO]3– intermediates in rapid pre-equilibria steps, and is followed by a one-electron transfer step involving [W(CN)8·HO]3– (k a) and its conjugate base [W(CN)8·O]4– (k b). At 25 °C, I = 0.20 m (NaCl), the rate constant with H a =40±6kJmol–1 and S a =–151±22JK–1mol–1; the rate constant with H b =36±1kJmol–1 and S b =–136±2JK–1mol–1 at 25 °C, I = 0.20 m (NaCl); the acid dissociation constant of [W(CN)8·HO]3–, K 5 =(5.9±1.7)×10–10 m, with and is the first acid dissociation constant of H2O2. The second pathway, with rate constant, k f, involves the formation of [W(CN)8· HO2]4– and is followed by a formal two-electron redox process with [W(CN)8]3–. The pH-dependent rate constant, k f, is given by . The rate constant k 7 =23±6m –1 s –1 with and at 25°C, I = 0.20 m (NaCl).  相似文献   

4.
The solubility of rhodochrosite (MnCO3) at 25°C under constant carbon dioxide partial pressure p(CO2) was determined in NaCl solutions as a function of ionic strength I. The dissolution of MnCO3(s) for the reaction
has been determined as a function of pH. From these values, we have determined the equilibrium constant for the stoichiometric solubility of MnCO3(s) in NaCl solutions
These values have been fitted to the equation
with a standard error of = 0.1 with Iand concentrations in molalities. The extrapolated value of log K o sp(–10.3) in water is in good agreement with literature data (–10.1 to 10.8) determined in solutions of different composition and ionic strength. The measured values of the activity coefficient, T(Mn2+) and T(CO3 2–), have been used to estimate the stability constant for the formation of the MnCO3ion pair, K *(MnCO3 0). The value of K 0(MnCO3 0) calculated from the values of K *(MnCO3) by the Pitzer equation ( = 0.1) in this study (4.8 ± 0.1) is in reasonable agreement with literature data.  相似文献   

5.
Phosphorylation of (S)-prolinol with P(NEt2)3was used to synthesize aminophosphite (2R,5S)- , which was reacted with the corresponding amino alcohols to afford (2S,5R)- (Va) and (2S,5R)- (Vb). Reaction of Vawith [Rh(CO)2Cl]2(P/Rh = 1) yields the mononuclear chelate [Rh(CO)(P^N)Cl] (VIIa), while the analogous reaction with Vbresults in a mixture of products with cis- and trans-orientation of the coordinated phosphorus and nitrogen atoms. Spectral characteristics of the products of coordination of ligands Vaand Vbwere compared with those for the binuclear reference complex [Rh(CO)(L)Cl]2(VIII), where L is P-monodentate ligand (2S,5R)- (VI). The ligands and complexes were studied by IR, NMR, 31P and 13C spectroscopy, mass spectrometry, and elemental analysis methods. X-ray diffraction analysis of crystals VIIIwas performed.  相似文献   

6.
Luminescence Behavior of Polynuclear Alkynylcopper(I) Phosphines   总被引:1,自引:0,他引:1  
A series of soluble trinuclear and tetranuclear copper(I) complexes containing 3-l acetylides , and have been synthesized and shown to exhibit rich photoluminescent behavior at room temperature. The electrochemistry of the trinuclear Cu(I) acetylide complexes and the excited-state redox properties of have been investigated. The X-ray crystal structures of and have been determined.  相似文献   

7.
The enthalpies and entropies of evaporation of Al(CH3)3–Sn(CH3)4and Ga(CH3)3–Sn(CH3)4solutions were determined. It was established that solvates are formed in these systems and that the dissociation energies of specific interactions in them change in the following order: (10.3) > > > (4.08 kJ mol–1), (6.52) > (5.14) > > (4.08 kJ mol–1).  相似文献   

8.
The kinetics of osmium(VIII)-catalyzed oxidation of hypophosphite with hexacyanoferrate(III) in alkaline medium has been studied. The rate is independent of the concentration of the oxidant. The order with respect to hydroxide ion is variable. Rate law (1) conforms with the experimental observations.
The equilibrium constant 'K 1' for step (2)
has been evaluated kinetically to be (21 ± 5.0), (23 ± 5.0), (26 ± 6) and (32 ± 6) at 25, 30, 32 and 35 °C and I = 1.0 mol dm–3 respectively. The energy and entropy of activation were calculated to be (42 ± 2.0) kJ mol–1 and (82 ± 6.0) J K–1 mol–1 respectively. A plausible reaction mechanism has been suggested.  相似文献   

9.
The molecular structure and conformation of p-bis(trimethylsilyl)benzene have been investigated by gas-phase electron diffraction, ab initio MO calculations at the HF/6-31G*, MP2(f.c.)/6-31G*, and B3LYP/6-31G* levels, and MM3 molecular mechanics calculations. The calculations indicate the syn- and anti-coplanar conformations, with two bonds in the plane of the benzene ring, to be energy minima. The perpendicular conformations, with two bonds in a plane orthogonal to the ring plane, are transition states. The two coplanar conformers have nearly the same energy with a low interconversion barrier, 0.3–0.5 kJ mol–1. The calculated lengths of the and bonds differ by only a few thousandths of an angstrom, in agreement with electron diffraction results from molecules containing either or bonds. The geometrical distortion of the benzene ring in p-bis(trimethylsilyl)-benzene may be described by superimposing independent distortions from each of the two SiMe3 groups. The electron diffraction intensities from a previous study (Rozsondai, B.; Zelei, B.; Hargittai, I. J. Mol. Struct. 1982, 95, 187) have been reanalyzed, imposing constraints from the theoretical calculations, and using a model based on a 1:1 mixture of the two coplanar conformers. The effective torsion angles of the SiMe3 groups may indicate nearly free rotation. Important geometrical parameters from the present electron diffraction analysis are , and . While the mean bond lengths are virtually the same from the previous and present analyses, the new ipso angle is in better agreement with the MO calculations [HF, 116.9° MP2(f.c.), 117.1° B3LYP, 116.9°].  相似文献   

10.
The determination of the second dissociation constant of carbonic acid K 2 in 5, 15, and 25 mass% ethanol—water mixed solvents has been made using cell of the type:
at 5 to 45°C. From these data, thermodynamic quantities, dissociation enthalpy, and dissociation entropy were determined. The dependence of pK 2 on dielectric constant of the mixed solvents is discussed in term of the Beveridge model.  相似文献   

11.
The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO3, KBr, KI, KNO3, CaCl2, SrCl2, BaCl2, Li2SO4, K2SO4, Mn(NO3)3)] as a function of concentration at 25°C. The solubilities, mol (kg-H2O)–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg–1)
where A and B are adjustable parameters and the activity coefficient of oxygen )O2) = [O2]0/[O2]. The limiting salting coefficient, k S = (ln / m)m=0 = A, was determined for all salts. The salting coefficients for the chlorides and sodium salts showed a near linear correlation with the crystal molar volume V cryst = 2.52 r 3. The salting coefficients determined from the Scaled Particle Theory were in reasonable agreement with the measured values. The activity coefficients of oxygen in the solutions have been interpreted using the Pitzer equation
where is a parameter that accounts for the interaction of O2 with cations (c) and anions (a) with molalities m a and m c, and accounts for interactions for O2 with the cation and anion pair (c-a). The and coefficients determined for the most of the ions are in reasonable agreement with the tabulations of Clegg and Brimblecombe. The values of for most of the ions are a linear function of the electrostriction molar volume (Velect = V0V cryst).  相似文献   

12.
Activity coefficients for sodium chloride in the NaCl + Na2SO4 + H2O ternary system were determined from emf measurements of the cell
at 15, 25, 35, and 45°C and at total ionic strengths from 0.1 to 6 mol-kg–1. These activity coefficient were analyzed by using the Harned rule and the treatments of Scatchard–Rush–Johnson and Pitzer. The analysis of activity coefficients at trace concentration was also achieved and qualitatively interpreted by considering the ionic interactions that can take place in the mixed system. Finally, the excess Gibbs energy of the mixtures was calculated and qualitatively analyzed against the composition of the system.  相似文献   

13.
The equilibrium constant for the hydrolytic disproportionation of I2
has been determined at 25°C and at ionic strength 0.2 M(NaClO4) in buffered solution. The reaction was followed in the pH range where the equilibrium concentration of I2, I, and IO3 are commensurable, i.e., the fast equilibrium
is also established. The equilibrium concentrations of I2and I3 were determined spectrophotometrically, and the concentrations of all the other species participating in process (1) were calculated from the stoichiometric constraints. The constants determined are \log K_1 = -47.61\pm 0.07 and \log K_2 = 2.86 \pm 0.01.  相似文献   

14.
The constants for the dissociation of citric acid (H3C) have been determined from potentiometric titrations in aqueous NaCl and KCl solutions and their mixtures as a function of ionic strength (0.05–4.5 mol-dm–3) at 25 °C. The stoichiometric dissociation constants (Ki*)
were used to determine Pitzer parameters for citric acid (H3C), and the anions, H2C, HC2–, and C3–. The thermodynamic constants (Ki) needed for these calculations were taken from the work of R. G. Bates and G. D. Pinching (J. Amer. Chem. Soc. 71, 1274; 1949) to fit to the equations (T/K):
The values of Pitzer interaction parameters for Na+ and K+ with H3C, H2C, HC2–, and C3– have been determined from the measured pK values. These parameters represent the values of pK1*, pK2*, and pK3*, respectively, with standard errors of = 0.003–0.006, 0.015–0.016, and 0.019–0.023 for the first, second, and third dissociation constants. A simple mixing of the pK* values for the pure salts in dilute solutions yield values for the mixtures that are in good agreement with the measured values. The full Pitzer equations are necessary to estimate the values of pKi* in the mixtures at high ionic strengths. The interaction parameters found for the mixtures are Na-K – H2C = – 0.00823 ± 0.0009; Na-K – HC = – 0.0233 ± 0.0009, and Na-K – C = 0.0299 ± 0.0055 with standard errors of (pK1) = 0.011, (pK2) = 0.011, and (pK3) = 0.055.  相似文献   

15.
The kinetics of the reaction of CH2O with a quasi-aromatic metal complex (1,1,2,8,9,9-hexamethyl-4,6-dioxa-5-hydro-3,7,10,14-tetraazacyclotetradecane-2,7,10,12-tetraene)copper(II), [Cu(PnAO)-6H]0 (AH), have been studied spectrophotometrically under neutral conditions in 1/3(v/v) MeOH–H2O. The Cu, 2N, 3C quasi-aromatic heterocyclic ring in AH is highly reactive towards CH2O at the central-aromatic-carbon atom, C(12) and the following reaction mechanism is proposed. The compounds AH, A—CH2OH and A—CH2—A were isolated and identified by i.r spectroscopy and by elemental analysis. The kinetic data supported the proposed reaction sequence. All reactions were second order overall. The rate constants and corresponding activation parameters for every step were obtained and are discussed.  相似文献   

16.
The kinetics of alkaline hydrolysis of Co(Asn)2, yielding Co(OH)2, NH3 and aspartic acid, have been studied spectrophotometrically, and the effects of CoII and NaOH concentrations on the reaction rate determined. The rate increases with increasing [NaOH], whereas variation of [CoII] has no significant effect. The kinetics of NH3 evolution conform to the rate law:
It is proposed that the reaction proceeds through formation of a dianionic tetrahedral intermediate.  相似文献   

17.
The kinetics and mechanism of the reduction of enneamolybdonickelate(IV) by arsenite in aqueous acid solution was studied by spectrophotometry. The reaction rate increases with increasing concentrations of H+ and with temperature. The associated rate law is: . The rate constants and activation parameters of the rate-determining step were evaluated. A mechanism related to this reaction was proposed.  相似文献   

18.
Atranes     
Complexes of ferratrane-3,7,10-trione (I) of the composition I · H2O, I · H2O2, I · OS(CH3)2, and I · 2OS(CH3)2 were synthesized. The IR spectra and derivatograms of these compounds were studied.See [1] for communication XXXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 164–170, February, 1973.  相似文献   

19.
The kinetics of oxidation of the chromium(III)-DL- aspartic acid complex, [CrIIIHL]+ by periodate have been investigated in aqueous medium. In the presence of FeII as a catalyst, the following rate law is obeyed:
Catalysis is believed to be due to the oxidation of iron(II) to iron(III), which acts as the oxidizing agent. Thermodynamic activation parameters were calculated. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO 4 - to CrIII.  相似文献   

20.
The thermal decomposition of zirconium oxyhydroxides prepared by the mixture of aqueous zirconium oxychloride solutions and aqueous solutions of sodium hydroxide or ammonium hydroxide under various conditions has been examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectrophotometry. As a result, it is seen that the thermal decomposition of zirconium oxyhydroxide, in which the composition is ZrO2-x(OH)2xyH2O where x2 and 1y<2, proceeds according to the following process:
This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

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