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71.
Enthalpies of dilution of aqueous systems containing formamide, dimethyl-formamide, the mixture of these amides, and each amide separately with mannitol, inositol, and cyclohexanol have been determined at 25°C. The data have been treated in terms of the Savage-Wood additivity principle and in combination with literature data. New values for the methylene-amide, carbinol-amide, and amide-amide group interaction enthalpies are presented. These may be used with data on a wider variety of solute systems to obtain interaction enthalpies for new groups. 相似文献
72.
An isotope dilution method for the determination of chloride ion in aqueous samples is described. The method makes use of the isotopic shift in the rotational lines of the 1–0 band of HCl emitted in the near infrared region of the spectrum by vibrationally excited HCl molecules present in a hydrogen/entrained air flame. Chloride ion in the sample is converted to chlorine gas by electrolysis and swept into a hydrogen/entrained air flame where it is converted into HCl. Because isotope dilution is an absolute method of analysis, matrix effects are minimized, and the chlorine generation step need not be quantitative. With the system described in this paper, samples must contain at least 9 mg of chloride ion per ml, and a 2-ml sample is required. Over the range from 10 to 30 mg Cl− ml−1, the average error was −0.96%, and the average relative standard deviation was 3.3% for seven samples using seven of the more intense lines in the P branch. Compared with standard silver nitrate titrations, the isotope dilution procedure was not affected by such common interferences as bromide ion and iodide ion. The technique was applied to several seawater samples from different regions. 相似文献
73.
氯化钙/水-醇溶液稀释热 总被引:3,自引:0,他引:3
电解质溶液稀释热是溶液的重要热性质之一.由它可计算不同浓度下电解质的溶解热、表现相对摩尔焓、溶液中反应热和化合物生成热等.在电解质溶液理论研究中,稀释热也是重要的基础数据.由稀释热可推算溶液中组分的活度系数、渗透系数、相对偏摩尔焓及表观摩尔热容等[1-3].在化工生产中,稀释热是化工过程能量计算不可缺少的数据.电解质水溶液稀释热已有不少研究[2,4].但电解质混合溶剂体系稀释热报导甚少.随着加盐精馏技术、海水淡化技术等研究的进展,急需这方面数据.本文作者已报告了CaCl2/C2H5OH-H2O体系[5]和CaCl2/n-C… 相似文献
74.
W. Zielenkiewicz B. Golankiewicz G. L. Perlovich M. Koźbiał 《Journal of solution chemistry》1999,28(6):731-745
Solubilities of tricyclic analogs of acyclovir have been determined in water at 25, 35, and 45°C and in octanol, water-saturated octanol, and octanol-saturated water at 25°C. Octanol-water partition coefficients were determined at 25°C. Melting temperatures and molar enthalpies of fusion were measured. Activity coefficients in water, octanol, and in aqueous octanol solutions were determined and are discussed. The effect of hydrophilic and hydrophobic substituents in the tricyclic analogs on their thermodynamic properties are discussed. The standard Gibbs energy of transfer between the saturated phases were found to correlate with known values of the melting point of the solvents and the solubilities of the solute. For a number of the compounds examined, correlations between the minimum inhibitory concentration against the herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), varicella-zoster virus (VZV), thymidine kinase-deficient (TK–) strains of VZV and
were established. Detailed conclusions have been derived concerning the relationships between the structure and the thermodynamic parameters of the compounds examined. 相似文献
75.
Summary The separation of two families of plastics additives (phenolic antioxidants and UV absorbers) has been achieved by high performance liquid chromatography with a quaternary gradient. A methodology of separation based on a sequential optimization is described. After a preliminary study of the effects of solvents on retention of compounds, the mobile phase is first chosen for each class of additives (Irganox and Tinuvin), then for the mixture of all the compounds and the separation is finally optimized. The importance of the column phase ratio is also reported. The use of two detectors, UV absorbance and light-scattering, enables all the compounds to be detected. The performance of the detectors has been compared and the effects of the nebulization temperature on the detection of low molecular mass compounds is reported. 相似文献
76.
Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS 总被引:1,自引:0,他引:1
Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the 64Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched 65Cu stable isotope and measurement of 63Cu/65Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of 63Cu/65Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils. 相似文献
77.
78.
Hilary E. Kent Terence H. Lilley Peter J. Milburn Michael Bloemendal Gus Somsen 《Journal of solution chemistry》1985,14(2):101-115
Enthalpies of dilution of the N-acetyl amides of glycine, L-alanine, L-valine, L-leucine, and L-phenylalanine, dissolved in N,N-dimethylformamide (DMF) as a solvent have been measured at 25°C. The results obtained have been analyzed to give the enthalpic interaction (or virial) coefficients of the solutes and these are compared with information previously obtained in aqueous systems. There are marked differences in the interaction properties in the two solvents and, while the additivity approach of Savage and Wood is applicable to the solutes in water it is not suitable for representing the interactions in DMF. A correlation is presented between the enthalpic second virial coefficients in DMF and the propensity of side-chains to be in proximity in globular proteins. 相似文献
79.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
80.
J. -L. Fortier P. -A. Leduc P. Picker J. E. Desnoyers 《Journal of solution chemistry》1973,2(5):467-475
The enthalpies of dilution of NaCl, Me4NBr, andn-Bu4NBr were measured in water at 25°C with a new flow microcalorimeter. The data were analyzed with a polynomial equation, and the derived relative apparent molal enthalpies L are in good agreement with literature values. Provided care is taken that mixing is complete, flow calorimeters are as reliable and much less time-consuming than cell-type instruments for enthalpies of dilution measurements. 相似文献