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1.
The kinetics of oxidation of malonic acid, studied in aqueous acid perchlorate, conform to the rate law
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2.
The kinetics of substitution of aqua ligands fromcis-diaqua-bis(biguanide)cobalt(III) and chromium(III) ions by aspartic acid in EtOH–H2O media have been studied spectrophotometrically in the 30 to 45°C range. We propose the following rate law for the anation
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3.
The aqueous reactions,
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4.
The kinetics of aqua ligand substitution fromcis-[Ru(bipy)2(H2O)2]2+ by 1, 10-phenanthroline (phen) have been studied spectrophotometrically in the 35 to 50°C temperature range. We propose the following rate law for the reaction within the 3.65 to 5.5 pH range:
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5.
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   

6.
The temperature dependencies of europium carbonate stability constants were examined at 15, 25, and 35°C in 0.68 molal Na+(ClO 4 ? , HCO 3 ? ) using a tributyl phosphate solvent extration technique. Our distribution data can be explained by the equilibria $$\begin{gathered} Eu^{3 + } + H_2 O + CO_2 (g)_ \leftarrow ^ \to EuCO_3^ + + 2H^ + \hfill \\ - log\beta _{12} = 9.607 + 496(t + 273.16)^{ - 1} \hfill \\ Eu^{3 + } + 2H_2 O + 2CO_2 (g)_ \leftarrow ^ \to Eu(CO_3 )_2^ - + 4H^ + \hfill \\ - log\beta _{24} = 21.951 + 670(t + 273.16)^{ - 1} \hfill \\ Eu^{3 + } + H_2 O + CO_2 (g)_ \leftarrow ^ \to EuHCO_3^{2 + } + H^ + \hfill \\ - log\beta _{11} = 1.688 + 1397(t + 273.16)^{ - 1} \hfill \\ \end{gathered}$$   相似文献   

7.
The decomposition of hydrogen peroxide in the presence of hydroxonitrilotri(methylenephosphonato)iron(III), [Fe(NTMP)(OH)4–], was studied in nitrate media (=0.10–0.26 M) over the 0.2–0.5 mM concentration range for the iron complex and the temperature range 26–40°C. The rate law;
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8.
A novel chromium(III) complex of tetraoxalylurea was prepared. In aqueous solutions, [CrIII(H2L)(H2O)]+ (H2L = diprotonated tetraoxalylurea) is oxidized by IO 4 according to the rate law
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9.
The mean diffusion coefficient of 233Pa has been measured simultaneously with those of 22Na and 152Eu in 0.5 M (Na, H)ClO4 solutions with the pH ranging from 0.3 to 13, by the open-end capillary method optimized in order to obtain reproducible and reliable D values at T = 25°C. In the case of Eu(III), the results tend to give higher 13 and 14 hydrolysis constants than the values generally acccepted, but these data are probably affected by the formation of polynuclear or colloidal species as soon as the hydrolysis process is involved. For Pa(V), results are in agreement with the existence of the following two equilibria (I = 0.5 M, T = 25°C):
However, unusual behavior is observed at a pH value around 1.3. A third equilibrium in basic media leads to the formation of a negatively charged species (log K h4 = –9.03 ± 0.1 at I = 0.5 M). Finally, the presence of chloride in solution (0.1 M; pH = 1 and 4) and carbonate-bicarbonate ions (0.1 M; pH = 9.4 and 11.0), which cannot be neglected in most of the natural waters, decreases the measured values for the diffusion coefficient of Pa(V) appreciably compared to noncomplexing media.  相似文献   

10.
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   

11.
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   

12.
The effects of pH, temperature, acetyl acetone (acacH) concentration and substrate complex concentration on the rate of aqua ligand substitution in the title complex in aqueous medium have been studied. The following rate expression is proposed for the 5.0–6.5 pH range.
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13.
The number of parameters in the polynomial is discussed for N components and a polynomial extending up to power n. This number is found to be but may be N less for relative thermodynamic functions. The equation of degree n for an N-component system requires the use of data for each of the i-component systems. Data on the n-component systems suffice if n相似文献   

14.
Summary The mechanical properties of the most aluminium alloys depend strongly on their chemical composition, casting methods and the heat treatment. Alloys of the type G-AlMg5Si are known for good corrosion resistance and mechanical properties at elevated temperatures. Under the trade mark Hydronalium (Hy 511) they are used for the production of cylinder heads for air-cooled Diesel engines. To obtain better chemical characteristics, titanium is added to the alloy. This paper deals with the results obtained during investigations about the distribution of elements in the binary eutectic Mg2Si and the ternary eutectic as well as with the distribution of titanium in samples of Hy 511, obtained during casting of cylinder heads. Studies of the distribution of the elements were performed using EDX/WDX spectrometers, and the distribution of titanium was studied also with Auger electron spectroscopy.  相似文献   

15.
The sulfur-containing biomolecule, cysteine has a role in physiological and natural environment because of its strong interactions with metals. To understand these interactions of metals with cysteine, one needs reliable dissociation constants for the protonated cysteine species [ CH(CH2SH)COOH; H3B+]. The values of dissociated constants, p , for protonated cysteine species (H3B+ H+ + H2B, K 1; H2B H+ + HB,K 2; HB H+ + B2–,K 3) were determined from potentiometric measurements in NaCl solutions as a function of ionic strength, 0.5–6.0 mol-(kgH2O)–1 and between 5, and 45°C. The equations
were fitted to the results with a standard errors of the fits of 0.116, 0.057, and 0.093 for , , and , respectively. The results were used to determine new Pitzer parameters (0, 1, and C) for the interactions of Na+ and Cl with cysteine species. These coefficients can be used to make reasonable estimates of the activity coefficients of the cysteine species and for the dissociation of cysteine in physiological and natural waters containing mostly NaCl.  相似文献   

16.
Electron transfer mediation to an anode, whose potential is judiciously controlled, provides the conceptual basis for the development of novel chronoamperometric biosensors. The mediators are appropriately selected redox couples (Ox/Red) which are amenable to recycling in the following type of enzyme E catalyzed reaction sequence
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17.
Conclusions When alkanesulfenyl chlorides are added to acrylic derivatives CH2=CHR (R=COOH, COOCH3, COOCH3 CN, CONH2 a mixture of the isomers and is formed and the proportions of these depend on the nature of the substituent R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1069–1075, June, 1966.  相似文献   

18.
The reaction between VV and TlI was studied in 4.0 mol dm–3 HCl at an ionic strength of 4.1 mol dm–3 at 25° C. The main active species under the reaction conditions were found to be VO inf2 sup+ and TlCl inf3 sup2– for the oxidant and reductant, respectively. A probable mechanism in terms of these species is given, and follows the rate law:
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19.
Conditional stability constants of 2-[bis(2-hydroxyethyl)amino]-2(hydroxymethyl)-1,3-propanediol (BT) complexes of trivalent rare earth element (Ln) ions (La, Nd, Eu, Gd, Yb, Dy, Er, Lu) and Y were determined potentiometrically in aqueous NaCl solutions at 30°C and 0.1 M ionic strength. Least-squares fitting shows that, at <0.04 molal BT, the complex LnBT3+ is dominant, with LnBT2 3+ forming a secondary complex, where:
Conditional stability constants appear to be directly related to the ionic radius of the trivalent ion in question. The optimal ionic radius, 104–105 pm, yields values of log (Gd) and (Yb). Complexation drops off steeply on either side of the ideal ionic radius. In relating the stability constants to ionic radius, it is assumed that BT complexes with Gd, Dy, Er, and Lu have coordination number eight, whereas those with La, Nd, and Eu have coordination number nine. The smoothest trend of stability constants with ionic radius is obtained if Yb–BT complexes are assumed to have coordination number nine. These results may reflect the ability of BT to form an ionic radius-specific chelate structure.  相似文献   

20.
Two oligomeric proanthocyanidin glycosides have been isolated from the roots ofRhodiola pamiroalaica and their structures and relative configurations have been established: — RP-1 - and — RP-2. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 484–491, July–August, 1998.  相似文献   

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